Related literature   {#sec1}
====================

For the synthesis of 2-acetyl­pyridine-(4-phenyl­thio­semi­carbazone), see: Offiong & Martelli (1997[@bb7]). For thio­semi­carbazone complexes with similar coordination environments, see: Ali *et al.* (2002[@bb1]); Kovala-Demertzi *et al.* (2005[@bb6]). For the anti­bacterial and anti­fungal activity of Cd^II^ thio­semicarbazone complexes, see: Alomar *et al.* (2010[@bb2]). For the bioinorganic chemistry of the Cd^II^ ion and its relation to biologically important ions, namely Zn^II^ and Ca^II^, see: Kaim & Schwederski (1995[@bb5]).

Experimental   {#sec2}
==============

 {#sec2.1}

### Crystal data   {#sec2.1.1}

\[Cd(C~14~H~13~N~4~S)~2~\]*M* *~r~* = 651.09Triclinic,*a* = 9.8452 (2) Å*b* = 13.0116 (3) Å*c* = 13.1736 (5) Åα = 116.495 (1)°β = 105.757 (1)°γ = 96.122 (1)°*V* = 1401.81 (7) Å^3^*Z* = 2Mo *K*α radiationμ = 0.96 mm^−1^*T* = 296 K0.22 × 0.14 × 0.11 mm

### Data collection   {#sec2.1.2}

Bruker APEXII CCD diffractometerAbsorption correction: multi-scan (*SADABS*; Bruker, 2009[@bb4]) *T* ~min~ = 0.816, *T* ~max~ = 0.90229421 measured reflections8199 independent reflections5975 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.044

### Refinement   {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.038*wR*(*F* ^2^) = 0.080*S* = 1.068199 reflections362 parametersH atoms treated by a mixture of independent and constrained refinementΔρ~max~ = 0.75 e Å^−3^Δρ~min~ = −0.49 e Å^−3^

 {#d5e506}

Data collection: *APEX2* (Bruker, 2009[@bb4]); cell refinement: *SAINT* (Bruker, 2009[@bb4]); data reduction: *SAINT*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb8]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb8]); molecular graphics: *DIAMOND* (Brandenburg, 2006[@bb3]); software used to prepare material for publication: *publCIF* (Westrip, 2010[@bb9]).

Supplementary Material
======================

Crystal structure: contains datablock(s) I, global. DOI: [10.1107/S1600536812016558/bt5877sup1.cif](http://dx.doi.org/10.1107/S1600536812016558/bt5877sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S1600536812016558/bt5877Isup2.hkl](http://dx.doi.org/10.1107/S1600536812016558/bt5877Isup2.hkl)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?bt5877&file=bt5877sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?bt5877sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?bt5877&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [BT5877](http://scripts.iucr.org/cgi-bin/sendsup?bt5877)).

We gratefully thank Professor Dr Manfredo Hörner (Federal University of Santa Maria, Brazil) for his help and support with the X-ray measurements. We also acknowledge the financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-\# 11/2029--1 and PRONEX-CNPq-FAPERGS projects.

Comment
=======

Thiosemicarbazone derivatives have a wide range of applications on biological inorganic chemistry. For example, some Cd^II^ thiosemicarbazone complexes show important antibacterial and antifungal activity against *Acinetobacter baumannii* and *Aspergillus fumigatus*, respectively (Alomar *et al.*, 2010). In addition, the Cd^II^ ion has similarity with two biologically important elements, namely Zn^II^ and Ca^II^. The ionic radii for these cations are 0,95 Å, 0,74 Å and 1,00 Å, respectively, and the chemical similarity suggests that Cd^II^ may displace Zn^II^ and Ca^II^ from critical biological sites (Kaim & Schwederski, 1995), making the cadmium coordination chemistry very attractive. As part of our study of thiosemicarbazone derivatives, we report herein the synthesis and the crystal structure of a new Cd^II^ complex with 2-acetylpyridine-(4-phenylthiosemicarbazone).

In the title compound, in which the molecular structure unit matches the asymmetric unit, the Cd^II^ ion is six-coordinated in a distorted octahedral environment by two deprotonated 2-acetylpyridine-(4-phenylthiosemicarbazone) ligands acting in a tridentate chelating mode, forming five-membered rings (Fig. 1). The selected bond angles formed between donor atoms trough the Cd1 atom are N6---Cd1---N2 = 151.43 (7)°, N1---Cd1---S1 = 134.61 (5)° and N5---Cd1---S2 = 143.06 (5)° and show clearly a distorted octahedral environment. The displacement from ideal coordination geometry is probably a consequence of the geometrical requirements of the ligand and of crystal packing interactions.

The acidic hydrogen of the hydrazine fragment is lost by the reaction with KOH, which is in agreement for thiosemicarbazone derivatives prepared from aldehydes or ketones. The negative charge is delocalized over the C---N---N---C---S fragment as indicated by their intermediate bond distances. The imine and thioamide C---N distances indicate considerable double bond character, while the C---S distance is consistent with increased single bond character. For the first ligand, these distances are C6---N2 = 1.285 (3) Å, N2---N3 = 1.385 (2) Å, N3---C8 = 1.311 (3) Å and C8---S1 = 1.748 (2) Å and for the second ligand, they are C20---N6 = 1.291 (3) Å, N6---N7 = 1.373 (3) Å, N7---C22 = 1.305 (3) Å and C22---S2 = 1.738 (2) Å.

The two ligands are coordinated to the Cd^II^ ion in their meridional conformations with the S1/S2 thiolate and the N1/N5 pyridyl atoms *cis* to each other, while the N2/N6 azomethine atoms are *trans* to each other. A similar meridional conformation has also been observed in the Mn^II^ complex with the same thiosemicarbazone ligand (Kovala-Demertzi *et al.*, 2005) and in several Cd^II^ complexes with tridentate \"NNS\"-chelating ligands derived from thiosemicarbazones (Ali *et al.*, 2002). The two ligands show a Z---E---*Z* conformation for the donor atoms about the C1---C6/C6---N2/N3---C8 and the C15---C20/C20---N6/N7---C22 bonds, respectively.

The ligands are not planar (Fig. 1 and Fig. 2), the mean deviations from the least squares planes for the chelated fragments Cd1/N1/C1/C6/N2 and Cd1/N2/N3/C8/S1 amount to -0,0644 (16) ° for C1 and -0,2702 (12) ° for N2, respectively, and the dihedral angle between the two planes is 20,15 (10)°. The maximal deviation from the least squares plane through all non-hydrogen atoms for the acetylpyridine derivative fragment C1/C2/C3/C4/C5/C6/C7/N1 and for the phenyl-thiosemicarbazone derivative fragment C8/C9/C10/C11/C12/C13/C14/N2/N3/N4/S1 amount to 0,1120 (19) Å for C7 and 0,1301 (16) Å for N2, respectively, and the dihedral angle between the two planes is 30,76 (08)°.

Additionally, the mean deviations from the least squares planes for the chelated fragments Cd1/N5/C15/C20/N6 and Cd1/N6/N7/C22/S2 amount to 0,0489 (13) Å for N5 and 0,0371 (12) Å for N6, respectively, and the dihedral angle between the two planes is 4,31 (07)°. The maximal deviation from the least squares plane through all non-hydrogen atoms for the acetylpyridine derivative fragment C15/C16/C17/C18/C19/C20/C21/N5 and for the phenyl-thiosemicarbazone derivative fragment C22/C23/C24/C25/C26/C27/C28/N6/N7/N8/S2 amount to 0,0457 (17) Å for C21 and -0,5623 (31) Å for C28, respectively, and the dihedral angle between the two planes is 14,77 (11)°. The displacement from planarity, for both of the ligands, is probably a consequence of the coordination with the Cd^II^ ion and of crystal packing interactions.

The crystal packing is stabilized by intermolecular hydrogen bonding. The molecules are connected through inversion centers *via* pairs of N---H···S interactions (Table 1; N4---H8···S1^i^ and N8---H21···S2^ii^), building a one-dimensional H-bonded polymer along the (0 11) direction (Fig. 2). Symmetry codes: (i) -*x*, -*y* + 1, -*z* + 1; (ii) -*x*, -*y*, -*z*.

Experimental {#experimental}
============

Starting materials were commercially available and were used without further purification. The synthesis of 2-acetylpyridine-(4-phenylthiosemicarbazone) was adapted from a procedure reported previously (Offiong & Martelli, 1997). 2-Acetylpyridine-(4-phenylthiosemicarbazone) (2 mmol) was dissolved in ethanol and treated with one KOH pellet. Stirring was maintained for 30 min, while the reaction mixture turns yellow. A solution of cadmium acetate dihydrate (1 mmol) also in ethanol was added under continuous stirring and under slight warming to 60 °C. After 3 h a yellow solid was formed. This solid was filtered-off, washed with small portions of cool ethanol and dried at room conditions. Yellow crystals of the complex, suitable for X-ray analysis, were obtained by recrystallization from a 2:1 mixture of acetone and dimethylformamide.

Refinement {#refinement}
==========

H atoms attached to C atoms were positioned with idealized geometry and were refined isotropic with *U*~eq~(H) set to 1.2 times of the *U*~eq~(C) for the aromatic and 1.5 times of the *U*~eq~(C) for methyl H atoms using a riding model with C---H = 0.93 Å and C---H = 0.96 Å, respectively. H atoms attached to N atoms were located in difference Fourier maps. Their positional and isotropic displacement parameters were refined.

Figures
=======

![: The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level.](e-68-0m635-fig1){#Fap1}

![: The crystal structure of the title compound showing the molecules connected through N---H···S interactions and building a one-dimensional H-bonded polymer along the (0 11) direction. Hydrogen bonding is indicated as dashed lines and the figure is simplified for clarity. Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x, -y, -z.](e-68-0m635-fig2){#Fap2}

Crystal data {#tablewrapcrystaldatalong}
============

  ---------------------------- ---------------------------------------
  \[Cd(C~14~H~13~N~4~S)~2~\]   *Z* = 2
  *M~r~* = 651.09              *F*(000) = 660
  Triclinic, *P*1              *D*~x~ = 1.543 Mg m^−3^
  Hall symbol: -P 1            Mo *K*α radiation, λ = 0.71073 Å
  *a* = 9.8452 (2) Å           Cell parameters from 5467 reflections
  *b* = 13.0116 (3) Å          θ = 2.3--23.9°
  *c* = 13.1736 (5) Å          µ = 0.96 mm^−1^
  α = 116.495 (1)°             *T* = 296 K
  β = 105.757 (1)°             Block, yellow
  γ = 96.122 (1)°              0.22 × 0.14 × 0.11 mm
  *V* = 1401.81 (7) Å^3^       
  ---------------------------- ---------------------------------------

Data collection {#tablewrapdatacollectionlong}
===============

  ------------------------------------------------------------ --------------------------------------
  Bruker APEXII CCD diffractometer                             8199 independent reflections
  Radiation source: fine-focus sealed tube                     5975 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                       *R*~int~ = 0.044
  φ and ω scans                                                θ~max~ = 30.1°, θ~min~ = 2.7°
  Absorption correction: multi-scan (*SADABS*; Bruker, 2009)   *h* = −13→13
  *T*~min~ = 0.816, *T*~max~ = 0.902                           *k* = −18→17
  29421 measured reflections                                   *l* = −16→18
  ------------------------------------------------------------ --------------------------------------

Refinement {#tablewraprefinementdatalong}
==========

  ------------------------------------- -------------------------------------------------------------------------------------------------
  Refinement on *F*^2^                  Primary atom site location: structure-invariant direct methods
  Least-squares matrix: full            Secondary atom site location: difference Fourier map
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.038   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.080                  H atoms treated by a mixture of independent and constrained refinement
  *S* = 1.06                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0314*P*)^2^ + 0.0548*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  8199 reflections                      (Δ/σ)~max~ = 0.001
  362 parameters                        Δρ~max~ = 0.75 e Å^−3^
  0 restraints                          Δρ~min~ = −0.49 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------------------

Special details {#specialdetails}
===============

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  Geometry. All e.s.d.\'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.\'s are taken into account individually in the estimation of e.s.d.\'s in distances, angles and torsion angles; correlations between e.s.d.\'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.\'s is used for estimating e.s.d.\'s involving l.s. planes.
  Refinement. Refinement of *F*^2^ against ALL reflections. The weighted *R*-factor *wR* and goodness of fit *S* are based on *F*^2^, conventional *R*-factors *R* are based on *F*, with *F* set to zero for negative *F*^2^. The threshold expression of *F*^2^ \> σ(*F*^2^) is used only for calculating *R*-factors(gt) *etc*. and is not relevant to the choice of reflections for refinement. *R*-factors based on *F*^2^ are statistically about twice as large as those based on *F*, and *R*- factors based on ALL data will be even larger.
  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å^2^) {#tablewrapcoords}
==================================================================================================

  ----- --------------- --------------- --------------- -------------------- --
        *x*             *y*             *z*             *U*~iso~\*/*U*~eq~   
  Cd1   0.226151 (19)   0.208486 (15)   0.431225 (15)   0.03261 (6)          
  S1    0.04751 (7)     0.34127 (6)     0.45863 (5)     0.03845 (15)         
  S2    0.11139 (7)     0.07311 (6)     0.19832 (6)     0.04311 (16)         
  C1    0.2081 (3)      0.0380 (2)      0.5482 (2)      0.0349 (5)           
  C5    0.3030 (3)      −0.0431 (2)     0.3973 (3)      0.0542 (7)           
  H4    0.3389          −0.0363         0.3415          0.065\*              
  C2    0.1985 (3)      −0.0638 (2)     0.5583 (3)      0.0468 (7)           
  H1    0.1624          −0.0695         0.6145          0.056\*              
  C3    0.2432 (4)      −0.1567 (3)     0.4838 (3)      0.0582 (8)           
  H2    0.2360          −0.2261         0.4886          0.070\*              
  C4    0.2977 (4)      −0.1462 (3)     0.4035 (3)      0.0622 (9)           
  H3    0.3306          −0.2071         0.3541          0.075\*              
  C8    0.0828 (3)      0.3844 (2)      0.6114 (2)      0.0319 (5)           
  C6    0.1612 (3)      0.1410 (2)      0.6249 (2)      0.0334 (5)           
  C9    0.0826 (3)      0.5625 (2)      0.8007 (2)      0.0356 (5)           
  C10   0.0613 (3)      0.6755 (2)      0.8373 (2)      0.0436 (6)           
  H9    0.0400          0.7026          0.7818          0.052\*              
  C14   0.1168 (4)      0.5245 (3)      0.8844 (2)      0.0536 (8)           
  H13   0.1325          0.4495          0.8618          0.064\*              
  C7    0.1277 (4)      0.1484 (3)      0.7318 (3)      0.0550 (8)           
  H5    0.2132          0.1489          0.7887          0.083\*              
  H6    0.0495          0.0807          0.7050          0.083\*              
  H7    0.0989          0.2201          0.7704          0.083\*              
  C12   0.1050 (3)      0.7096 (3)      1.0382 (2)      0.0526 (7)           
  H11   0.1124          0.7584          1.1179          0.063\*              
  C11   0.0713 (3)      0.7478 (2)      0.9550 (2)      0.0521 (7)           
  H10   0.0551          0.8229          0.9782          0.063\*              
  C13   0.1275 (4)      0.5989 (3)      1.0025 (3)      0.0610 (8)           
  H12   0.1505          0.5730          1.0589          0.073\*              
  N2    0.1521 (2)      0.22010 (16)    0.59191 (17)    0.0324 (4)           
  N4    0.0634 (3)      0.49398 (19)    0.67666 (19)    0.0402 (5)           
  N3    0.1191 (2)      0.32216 (17)    0.66504 (17)    0.0348 (4)           
  N1    0.2593 (2)      0.04738 (17)    0.46709 (19)    0.0399 (5)           
  C22   0.2505 (3)      0.1299 (2)      0.1648 (2)      0.0337 (5)           
  C20   0.5236 (3)      0.3367 (2)      0.4314 (2)      0.0334 (5)           
  C15   0.5532 (3)      0.3897 (2)      0.5636 (2)      0.0340 (5)           
  C23   0.3274 (3)      0.0925 (2)      −0.0112 (2)     0.0405 (6)           
  C24   0.3295 (3)      −0.0091 (3)     −0.1097 (2)     0.0503 (7)           
  H22   0.2653          −0.0818         −0.1376         0.060\*              
  C16   0.6781 (3)      0.4789 (2)      0.6492 (2)      0.0489 (7)           
  H14   0.7463          0.5080          0.6250          0.059\*              
  C28   0.4211 (3)      0.1993 (3)      0.0278 (3)      0.0581 (8)           
  H26   0.4193          0.2683          0.0927          0.070\*              
  C19   0.4774 (3)      0.3928 (2)      0.7153 (2)      0.0489 (7)           
  H17   0.4083          0.3634          0.7385          0.059\*              
  C18   0.5999 (3)      0.4811 (3)      0.8043 (3)      0.0600 (8)           
  H16   0.6133          0.5106          0.8860          0.072\*              
  C17   0.7008 (3)      0.5246 (3)      0.7713 (3)      0.0642 (9)           
  H15   0.7845          0.5845          0.8300          0.077\*              
  C25   0.4256 (4)      −0.0030 (4)     −0.1660 (3)     0.0688 (10)          
  H23   0.4262          −0.0715         −0.2320         0.083\*              
  C27   0.5184 (4)      0.2041 (4)      −0.0295 (3)     0.0795 (11)          
  H25   0.5827          0.2764          −0.0026         0.095\*              
  C26   0.5200 (4)      0.1022 (4)      −0.1263 (3)     0.0835 (12)          
  H24   0.5858          0.1054          −0.1644         0.100\*              
  N6    0.3994 (2)      0.25909 (17)    0.35954 (17)    0.0327 (4)           
  N5    0.4528 (2)      0.34715 (18)    0.59691 (18)    0.0389 (5)           
  N7    0.3738 (2)      0.21135 (18)    0.23768 (18)    0.0374 (5)           
  N8    0.2265 (3)      0.0800 (2)      0.0431 (2)      0.0429 (5)           
  C21   0.6341 (3)      0.3730 (2)      0.3876 (3)      0.0480 (7)           
  H18   0.6029          0.3237          0.3010          0.072\*              
  H19   0.7266          0.3639          0.4253          0.072\*              
  H20   0.6440          0.4548          0.4081          0.072\*              
  H8    0.041 (3)       0.531 (2)       0.639 (2)       0.035 (7)\*          
  H21   0.152 (3)       0.024 (2)       −0.002 (2)      0.042 (8)\*          
  ----- --------------- --------------- --------------- -------------------- --

Atomic displacement parameters (Å^2^) {#tablewrapadps}
=====================================

  ----- -------------- -------------- -------------- -------------- -------------- -------------
        *U*^11^        *U*^22^        *U*^33^        *U*^12^        *U*^13^        *U*^23^
  Cd1   0.03545 (10)   0.03298 (10)   0.03154 (10)   0.00908 (7)    0.01550 (7)    0.01576 (8)
  S1    0.0509 (4)     0.0407 (3)     0.0317 (3)     0.0229 (3)     0.0181 (3)     0.0201 (3)
  S2    0.0417 (4)     0.0439 (4)     0.0312 (3)     −0.0027 (3)    0.0145 (3)     0.0108 (3)
  C1    0.0361 (13)    0.0341 (13)    0.0347 (13)    0.0098 (10)    0.0081 (11)    0.0196 (11)
  C5    0.071 (2)      0.0504 (17)    0.0535 (18)    0.0301 (15)    0.0326 (16)    0.0266 (15)
  C2    0.0517 (17)    0.0423 (15)    0.0526 (17)    0.0155 (13)    0.0159 (14)    0.0295 (14)
  C3    0.070 (2)      0.0413 (16)    0.067 (2)      0.0229 (15)    0.0158 (17)    0.0325 (16)
  C4    0.076 (2)      0.0465 (17)    0.065 (2)      0.0355 (17)    0.0270 (18)    0.0236 (16)
  C8    0.0342 (13)    0.0356 (12)    0.0323 (12)    0.0132 (10)    0.0161 (10)    0.0190 (11)
  C6    0.0325 (13)    0.0377 (13)    0.0355 (13)    0.0118 (10)    0.0128 (10)    0.0217 (11)
  C9    0.0387 (14)    0.0384 (13)    0.0318 (13)    0.0139 (11)    0.0160 (11)    0.0164 (11)
  C10   0.0548 (17)    0.0375 (14)    0.0387 (15)    0.0139 (12)    0.0167 (13)    0.0188 (12)
  C14   0.083 (2)      0.0494 (17)    0.0436 (16)    0.0323 (16)    0.0317 (16)    0.0268 (14)
  C7    0.077 (2)      0.0605 (18)    0.0552 (18)    0.0314 (16)    0.0366 (17)    0.0407 (16)
  C12   0.0600 (19)    0.0539 (18)    0.0330 (15)    0.0100 (15)    0.0200 (14)    0.0120 (14)
  C11   0.0620 (19)    0.0373 (15)    0.0437 (16)    0.0114 (13)    0.0199 (14)    0.0092 (13)
  C13   0.089 (3)      0.066 (2)      0.0376 (16)    0.0265 (18)    0.0281 (16)    0.0293 (16)
  N2    0.0367 (11)    0.0310 (10)    0.0342 (11)    0.0130 (9)     0.0156 (9)     0.0176 (9)
  N4    0.0582 (15)    0.0395 (12)    0.0352 (12)    0.0258 (11)    0.0220 (11)    0.0227 (11)
  N3    0.0424 (12)    0.0341 (11)    0.0337 (11)    0.0164 (9)     0.0181 (9)     0.0177 (9)
  N1    0.0485 (13)    0.0358 (11)    0.0429 (12)    0.0161 (10)    0.0226 (10)    0.0210 (10)
  C22   0.0372 (13)    0.0355 (13)    0.0295 (12)    0.0119 (11)    0.0142 (10)    0.0151 (11)
  C20   0.0298 (12)    0.0322 (12)    0.0374 (13)    0.0096 (10)    0.0113 (10)    0.0167 (11)
  C15   0.0286 (12)    0.0319 (12)    0.0383 (14)    0.0100 (10)    0.0085 (10)    0.0164 (11)
  C23   0.0376 (14)    0.0546 (16)    0.0310 (13)    0.0150 (12)    0.0143 (11)    0.0208 (12)
  C24   0.0570 (18)    0.0598 (18)    0.0364 (15)    0.0242 (15)    0.0189 (13)    0.0225 (14)
  C16   0.0342 (14)    0.0499 (16)    0.0455 (16)    0.0017 (12)    0.0088 (12)    0.0151 (14)
  C28   0.066 (2)      0.0600 (19)    0.0418 (16)    0.0029 (16)    0.0255 (15)    0.0190 (15)
  C19   0.0475 (17)    0.0543 (17)    0.0359 (15)    0.0064 (13)    0.0106 (13)    0.0193 (13)
  C18   0.0511 (18)    0.070 (2)      0.0342 (15)    0.0070 (16)    0.0053 (14)    0.0136 (15)
  C17   0.0414 (17)    0.068 (2)      0.0418 (17)    −0.0061 (15)   −0.0007 (14)   0.0074 (16)
  C25   0.062 (2)      0.103 (3)      0.0435 (18)    0.043 (2)      0.0279 (17)    0.0286 (19)
  C27   0.067 (2)      0.099 (3)      0.058 (2)      −0.012 (2)     0.0248 (18)    0.034 (2)
  C26   0.062 (2)      0.142 (4)      0.050 (2)      0.024 (3)      0.0331 (19)    0.043 (2)
  N6    0.0313 (11)    0.0344 (10)    0.0318 (11)    0.0082 (9)     0.0121 (9)     0.0156 (9)
  N5    0.0353 (11)    0.0407 (12)    0.0343 (12)    0.0056 (9)     0.0088 (9)     0.0164 (10)
  N7    0.0334 (11)    0.0444 (12)    0.0315 (11)    0.0061 (9)     0.0134 (9)     0.0164 (10)
  N8    0.0394 (13)    0.0470 (13)    0.0313 (12)    0.0009 (11)    0.0133 (10)    0.0124 (11)
  C21   0.0370 (15)    0.0528 (17)    0.0535 (17)    0.0046 (12)    0.0173 (13)    0.0268 (14)
  ----- -------------- -------------- -------------- -------------- -------------- -------------

Geometric parameters (Å, º) {#tablewrapgeomlong}
===========================

  ----------------------- -------------- ----------------------- --------------
  Cd1---N6                2.3288 (19)    C11---H10               0.9300
  Cd1---N2                2.3691 (18)    C13---H12               0.9300
  Cd1---N1                2.381 (2)      N2---N3                 1.385 (2)
  Cd1---N5                2.446 (2)      N4---H8                 0.84 (2)
  Cd1---S1                2.5778 (6)     C22---N7                1.305 (3)
  Cd1---S2                2.5814 (7)     C22---N8                1.371 (3)
  S1---C8                 1.748 (2)      C20---N6                1.291 (3)
  S2---C22                1.738 (2)      C20---C15               1.484 (3)
  C1---N1                 1.344 (3)      C20---C21               1.489 (3)
  C1---C2                 1.385 (3)      C15---N5                1.346 (3)
  C1---C6                 1.487 (3)      C15---C16               1.380 (3)
  C5---N1                 1.332 (3)      C23---C28               1.371 (4)
  C5---C4                 1.376 (4)      C23---C24               1.386 (3)
  C5---H4                 0.9300         C23---N8                1.407 (3)
  C2---C3                 1.381 (4)      C24---C25               1.367 (4)
  C2---H1                 0.9300         C24---H22               0.9300
  C3---C4                 1.360 (4)      C16---C17               1.383 (4)
  C3---H2                 0.9300         C16---H14               0.9300
  C4---H3                 0.9300         C28---C27               1.383 (4)
  C8---N3                 1.311 (3)      C28---H26               0.9300
  C8---N4                 1.365 (3)      C19---N5                1.335 (3)
  C6---N2                 1.285 (3)      C19---C18               1.373 (4)
  C6---C7                 1.498 (3)      C19---H17               0.9300
  C9---C14                1.377 (4)      C18---C17               1.353 (4)
  C9---C10                1.387 (3)      C18---H16               0.9300
  C9---N4                 1.413 (3)      C17---H15               0.9300
  C10---C11               1.376 (3)      C25---C26               1.355 (5)
  C10---H9                0.9300         C25---H23               0.9300
  C14---C13               1.383 (4)      C27---C26               1.375 (5)
  C14---H13               0.9300         C27---H25               0.9300
  C7---H5                 0.9600         C26---H24               0.9300
  C7---H6                 0.9600         N6---N7                 1.373 (3)
  C7---H7                 0.9600         N8---H21                0.83 (3)
  C12---C13               1.365 (4)      C21---H18               0.9600
  C12---C11               1.373 (4)      C21---H19               0.9600
  C12---H11               0.9300         C21---H20               0.9600
                                                                 
  N6---Cd1---N2           151.43 (7)     N3---N2---Cd1           120.07 (13)
  N6---Cd1---N1           111.91 (7)     C8---N4---C9            132.0 (2)
  N2---Cd1---N1           67.80 (6)      C8---N4---H8            116.0 (16)
  N6---Cd1---N5           68.06 (7)      C9---N4---H8            111.9 (16)
  N2---Cd1---N5           83.38 (7)      C8---N3---N2            112.35 (18)
  N1---Cd1---N5           94.00 (7)      C5---N1---C1            118.4 (2)
  N6---Cd1---S1           113.46 (5)     C5---N1---Cd1           122.97 (18)
  N2---Cd1---S1           71.90 (5)      C1---N1---Cd1           117.63 (15)
  N1---Cd1---S1           134.61 (5)     N7---C22---N8           115.7 (2)
  N5---Cd1---S1           101.36 (5)     N7---C22---S2           129.77 (18)
  N6---Cd1---S2           75.54 (5)      N8---C22---S2           114.48 (18)
  N2---Cd1---S2           132.65 (5)     N6---C20---C15          116.4 (2)
  N1---Cd1---S2           93.71 (5)      N6---C20---C21          123.3 (2)
  N5---Cd1---S2           143.06 (5)     C15---C20---C21         120.3 (2)
  S1---Cd1---S2           98.58 (2)      N5---C15---C16          121.1 (2)
  C8---S1---Cd1           95.23 (8)      N5---C15---C20          117.2 (2)
  C22---S2---Cd1          96.70 (8)      C16---C15---C20         121.7 (2)
  N1---C1---C2            121.2 (2)      C28---C23---C24         119.2 (3)
  N1---C1---C6            116.9 (2)      C28---C23---N8          123.3 (2)
  C2---C1---C6            121.9 (2)      C24---C23---N8          117.5 (2)
  N1---C5---C4            123.3 (3)      C25---C24---C23         120.3 (3)
  N1---C5---H4            118.3          C25---C24---H22         119.9
  C4---C5---H4            118.3          C23---C24---H22         119.9
  C3---C2---C1            119.0 (3)      C15---C16---C17         119.3 (3)
  C3---C2---H1            120.5          C15---C16---H14         120.3
  C1---C2---H1            120.5          C17---C16---H14         120.3
  C4---C3---C2            119.8 (3)      C23---C28---C27         119.9 (3)
  C4---C3---H2            120.1          C23---C28---H26         120.1
  C2---C3---H2            120.1          C27---C28---H26         120.1
  C3---C4---C5            118.2 (3)      N5---C19---C18          123.1 (3)
  C3---C4---H3            120.9          N5---C19---H17          118.5
  C5---C4---H3            120.9          C18---C19---H17         118.5
  N3---C8---N4            119.1 (2)      C17---C18---C19         118.8 (3)
  N3---C8---S1            127.34 (17)    C17---C18---H16         120.6
  N4---C8---S1            113.48 (17)    C19---C18---H16         120.6
  N2---C6---C1            115.1 (2)      C18---C17---C16         119.3 (3)
  N2---C6---C7            124.1 (2)      C18---C17---H15         120.3
  C1---C6---C7            120.7 (2)      C16---C17---H15         120.3
  C14---C9---C10          119.0 (2)      C26---C25---C24         120.6 (3)
  C14---C9---N4           125.1 (2)      C26---C25---H23         119.7
  C10---C9---N4           115.9 (2)      C24---C25---H23         119.7
  C11---C10---C9          120.7 (3)      C26---C27---C28         120.0 (3)
  C11---C10---H9          119.7          C26---C27---H25         120.0
  C9---C10---H9           119.7          C28---C27---H25         120.0
  C9---C14---C13          119.5 (3)      C25---C26---C27         120.0 (3)
  C9---C14---H13          120.3          C25---C26---H24         120.0
  C13---C14---H13         120.3          C27---C26---H24         120.0
  C6---C7---H5            109.5          C20---N6---N7           115.53 (19)
  C6---C7---H6            109.5          C20---N6---Cd1          122.35 (16)
  H5---C7---H6            109.5          N7---N6---Cd1           122.07 (14)
  C6---C7---H7            109.5          C19---N5---C15          118.3 (2)
  H5---C7---H7            109.5          C19---N5---Cd1          125.71 (18)
  H6---C7---H7            109.5          C15---N5---Cd1          115.53 (15)
  C13---C12---C11         119.2 (3)      C22---N7---N6           115.70 (19)
  C13---C12---H11         120.4          C22---N8---C23          127.6 (2)
  C11---C12---H11         120.4          C22---N8---H21          114.8 (18)
  C12---C11---C10         120.2 (3)      C23---N8---H21          115.6 (18)
  C12---C11---H10         119.9          C20---C21---H18         109.5
  C10---C11---H10         119.9          C20---C21---H19         109.5
  C12---C13---C14         121.5 (3)      H18---C21---H19         109.5
  C12---C13---H12         119.3          C20---C21---H20         109.5
  C14---C13---H12         119.3          H18---C21---H20         109.5
  C6---N2---N3            117.64 (19)    H19---C21---H20         109.5
  C6---N2---Cd1           121.55 (15)                            
                                                                 
  N6---Cd1---S1---C8      −124.64 (10)   N6---Cd1---N1---C1      155.39 (17)
  N2---Cd1---S1---C8      25.28 (9)      N2---Cd1---N1---C1      6.27 (17)
  N1---Cd1---S1---C8      53.53 (11)     N5---Cd1---N1---C1      87.45 (18)
  N5---Cd1---S1---C8      −53.81 (10)    S1---Cd1---N1---C1      −22.8 (2)
  S2---Cd1---S1---C8      157.47 (8)     S2---Cd1---N1---C1      −128.71 (17)
  N6---Cd1---S2---C22     −2.87 (9)      Cd1---S2---C22---N7     2.4 (2)
  N2---Cd1---S2---C22     −177.49 (10)   Cd1---S2---C22---N8     −178.32 (17)
  N1---Cd1---S2---C22     −114.55 (10)   N6---C20---C15---N5     4.1 (3)
  N5---Cd1---S2---C22     −12.87 (12)    C21---C20---C15---N5    −175.7 (2)
  S1---Cd1---S2---C22     109.27 (8)     N6---C20---C15---C16    −176.0 (2)
  N1---C1---C2---C3       0.3 (4)        C21---C20---C15---C16   4.3 (4)
  C6---C1---C2---C3       179.7 (2)      C28---C23---C24---C25   1.0 (4)
  C1---C2---C3---C4       1.0 (4)        N8---C23---C24---C25    −179.6 (3)
  C2---C3---C4---C5       −1.6 (5)       N5---C15---C16---C17    0.4 (4)
  N1---C5---C4---C3       1.0 (5)        C20---C15---C16---C17   −179.6 (2)
  Cd1---S1---C8---N3      −31.2 (2)      C24---C23---C28---C27   −1.3 (5)
  Cd1---S1---C8---N4      151.43 (17)    N8---C23---C28---C27    179.3 (3)
  N1---C1---C6---N2       11.0 (3)       N5---C19---C18---C17    0.2 (5)
  C2---C1---C6---N2       −168.4 (2)     C19---C18---C17---C16   −0.1 (5)
  N1---C1---C6---C7       −169.2 (2)     C15---C16---C17---C18   −0.1 (5)
  C2---C1---C6---C7       11.4 (4)       C23---C24---C25---C26   0.1 (5)
  C14---C9---C10---C11    −1.3 (4)       C23---C28---C27---C26   0.7 (5)
  N4---C9---C10---C11     177.3 (3)      C24---C25---C26---C27   −0.8 (6)
  C10---C9---C14---C13    0.7 (4)        C28---C27---C26---C25   0.4 (6)
  N4---C9---C14---C13     −177.7 (3)     C15---C20---N6---N7     179.82 (18)
  C13---C12---C11---C10   −0.4 (5)       C21---C20---N6---N7     −0.4 (3)
  C9---C10---C11---C12    1.1 (4)        C15---C20---N6---Cd1    2.1 (3)
  C11---C12---C13---C14   −0.1 (5)       C21---C20---N6---Cd1    −178.17 (17)
  C9---C14---C13---C12    0.0 (5)        N2---Cd1---N6---C20     −6.2 (3)
  C1---C6---N2---N3       −175.47 (19)   N1---Cd1---N6---C20     −89.70 (19)
  C7---C6---N2---N3       4.7 (4)        N5---Cd1---N6---C20     −4.35 (17)
  C1---C6---N2---Cd1      −5.3 (3)       S1---Cd1---N6---C20     88.90 (18)
  C7---C6---N2---Cd1      174.9 (2)      S2---Cd1---N6---C20     −177.89 (19)
  N6---Cd1---N2---C6      −95.5 (2)      N2---Cd1---N6---N7      176.23 (14)
  N1---Cd1---N2---C6      −0.13 (18)     N1---Cd1---N6---N7      92.71 (17)
  N5---Cd1---N2---C6      −97.20 (19)    N5---Cd1---N6---N7      178.06 (18)
  S1---Cd1---N2---C6      158.52 (19)    S1---Cd1---N6---N7      −88.69 (16)
  S2---Cd1---N2---C6      73.6 (2)       S2---Cd1---N6---N7      4.52 (15)
  N6---Cd1---N2---N3      74.4 (2)       C18---C19---N5---C15    0.1 (4)
  N1---Cd1---N2---N3      169.78 (18)    C18---C19---N5---Cd1    −171.9 (2)
  N5---Cd1---N2---N3      72.71 (16)     C16---C15---N5---C19    −0.4 (4)
  S1---Cd1---N2---N3      −31.57 (15)    C20---C15---N5---C19    179.6 (2)
  S2---Cd1---N2---N3      −116.53 (15)   C16---C15---N5---Cd1    172.36 (19)
  N3---C8---N4---C9       4.0 (4)        C20---C15---N5---Cd1    −7.6 (3)
  S1---C8---N4---C9       −178.4 (2)     N6---Cd1---N5---C19     178.4 (2)
  C14---C9---N4---C8      −5.7 (5)       N2---Cd1---N5---C19     −2.5 (2)
  C10---C9---N4---C8      175.8 (3)      N1---Cd1---N5---C19     −69.6 (2)
  N4---C8---N3---N2       −172.7 (2)     S1---Cd1---N5---C19     67.5 (2)
  S1---C8---N3---N2       10.1 (3)       S2---Cd1---N5---C19     −171.19 (17)
  C6---N2---N3---C8       −166.8 (2)     N6---Cd1---N5---C15     6.18 (15)
  Cd1---N2---N3---C8      23.0 (2)       N2---Cd1---N5---C15     −174.70 (17)
  C4---C5---N1---C1       0.4 (4)        N1---Cd1---N5---C15     118.22 (17)
  C4---C5---N1---Cd1      −168.1 (2)     S1---Cd1---N5---C15     −104.72 (16)
  C2---C1---N1---C5       −1.0 (4)       S2---Cd1---N5---C15     16.6 (2)
  C6---C1---N1---C5       179.6 (2)      N8---C22---N7---N6      −178.4 (2)
  C2---C1---N1---Cd1      168.07 (19)    S2---C22---N7---N6      0.8 (3)
  C6---C1---N1---Cd1      −11.3 (3)      C20---N6---N7---C22     177.8 (2)
  N6---Cd1---N1---C5      −36.1 (2)      Cd1---N6---N7---C22     −4.5 (3)
  N2---Cd1---N1---C5      174.8 (2)      N7---C22---N8---C23     10.8 (4)
  N5---Cd1---N1---C5      −104.0 (2)     S2---C22---N8---C23     −168.6 (2)
  S1---Cd1---N1---C5      145.7 (2)      C28---C23---N8---C22    −44.0 (4)
  S2---Cd1---N1---C5      39.8 (2)       C24---C23---N8---C22    136.6 (3)
  ----------------------- -------------- ----------------------- --------------

Hydrogen-bond geometry (Å, º) {#tablewraphbondslong}
=============================

  ------------------- ---------- ---------- ----------- ---------------
  *D*---H···*A*       *D*---H    H···*A*    *D*···*A*   *D*---H···*A*
  N4---H8···S1^i^     0.84 (2)   2.60 (3)   3.437 (2)   172 (2)
  N8---H21···S2^ii^   0.83 (3)   2.79 (3)   3.513 (2)   147 (2)
  ------------------- ---------- ---------- ----------- ---------------

Symmetry codes: (i) −*x*, −*y*+1, −*z*+1; (ii) −*x*, −*y*, −*z*.

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*       *D*---H    H⋯*A*      *D*⋯*A*     *D*---H⋯*A*
  ----------------- ---------- ---------- ----------- -------------
  N4---H8⋯S1^i^     0.84 (2)   2.60 (3)   3.437 (2)   172 (2)
  N8---H21⋯S2^ii^   0.83 (3)   2.79 (3)   3.513 (2)   147 (2)

Symmetry codes: (i) ; (ii) .
