Di-μ₂-aqua-bis­[aqua­(2,2′-diamino-4,4′-bi-1,3-thia­zole-κ²N,N′)(4-nitro­benzoato-κO)cadmium(II)] bis­(4-nitro­benzoate)

The title compound, [Cd₂(C₇H₄NO₄)₂(C₆H₁₀N₄O₂S₂)₂](C₇H₄NO₄)₂, consists of dimeric Cd^II complex cations and uncoordinated 4-nitro­benzoate anions. Within the complex cation, each Cd^II cation assumes a distorted octa­hedral coordination geometry, formed by a diamino­bithia­zole (DABT) ligand, a 4-nitro­benzoate anion and two coordinated water mol­ecules. Two coordinated water mol­ecules bridge two Cd^II cations to form the dimeric complex cation across an inversion centre. The two thia­zole rings of the chelating DABT ligand are twisted with respect to each other, forming a dihedral angle of 3.91 (18)°. The centroid-to-centroid separation of 3.7601 (19) Å indicates the existence of π–π stacking between nearly parallel thia­zole rings in the crystal structure. O—H...O and N—H...O hydrogen bonding between complex cations and uncoordinated 4-nitro­benzoate anions, and between complex cations, helps to stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.072
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.00 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N21
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.34
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.64
PLAT322_ALERT_2_C Check Hybridisation of  S11    in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S12    in Main Residue .          ?

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd          (2)       2.13

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential application in the field of soft magnetic material (Sun et al., 1997) and biological activities, such as the effective inhibitors of DNA synthesis of the tumor cells (Waring, 1981; Fisher et al., 1985). As part of serial structural investigation of metal complexes with DABT (Liu & Xu, 2004), the title Cd^II complex was recently prepared and its X-ray structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The crystal of the title compound consists of the dimeric Cd^II complex cations and uncoordinated 4-nitrobenzoate anions. Within the complex cation, each Cd^II cation assumes a distorted octahedral coordination geometry (Table 1), formed by DABT, 4-nitrobenzoate anion and two coordinated water molecules. Two coordinated water molecules bridges two Cd^II cations to form the dimeric complex cation across on an inversion center.

Whithin the complex, the DABT molecule shows approximately coplanar configuration with the dihedral angle 3.91 (18)° between two thiazole rings, which comparable to 2.6 (1)° found in [Mn(C₆H₆N₄S₂)(C₈H₄O₄)(H₂O)₂].2H₂O (Liu et al., 2006) and 4.57 (7)° in [Mn(DABT)(oxydiacetate)] (Luo et al., 2004), but different from 17.23 (7)° found in [Cr(C₄H₅NO₄)(C₆H₆N₄S₂)(H₂O)]Cl.H₂O, (Liu et al., 2004) and 20.02 (8)° found in [Ni(DABT)(iminodiacetate)] (Liu & Xu, 2005).

One oxygen atom O21 of carboxyl group of the 4-nitrobenzoate anion chelates to Cd^II atom, and hydrogen bonded to the amino group of DABT within the complex, another uncoordinated oxygen atom(O22) is hydrogen bonded to the coordinated water within the complex (Table 2), which helps to stabilize the crystal structure.

The separations of 3.7601 (19) Å between nearly parallel thiazole rings (1 - x,-y,1 - z) suggests the existence of π-π stacking (Fig. 2).

Related literature

For general background, see: Sun et al. (1997); Waring (1981); Fisher et al. (1985); Liu & Xu (2004). For related structures, see: Luo et al. (2004); Liu et al. (2004, 2006); Liu & Xu (2005).

S2. Experimental

An ethanol solution (20 ml) containing DABT (0.20 g, 1 mmol) and CdCl₂.2.5(H₂O) (0.22 g, 1 mmol) was mixed with an aqueous solution (10 ml) of 4-nitrobenzoic acid (0.34 g, 2 mmol) and NaOH (0.08 g, 2 mmol). The mixture was refluxed for 6 h. After cooling to room temperature the solution was filtered. Single crystals of the title compound were obtained from the filtrate after 7 d.

S3. Refinement

H atoms on carbon atoms were placed in calculated positions with C—H distances = 0.93 Å (aromatic), and were included in the final cycles of refinement in riding mode with U_iso(H) = 1.2U_eq(C). H atoms of amino groups and water molecules were located in a difference Fourier map and included in the structure factor calculations with fixed positional and U_iso(H) = 0.05 Ų.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids (arbitrary spheres for H atoms), dashed lines showing the hydrogen bonding.
	Fig. 2. The unit cell packing diagram showing π-π stacking between the S11-thiazole and S12^i-thiazole rings [symmetry code: (i) 1 - x,-y,1 - z]. H atoms have been omitted for clarity.

Di-µ₂-aqua-bis[aqua(2,2'-diamino-4,4'-bi-1,3-thiazole-κ²N,N')(4- nitrobenzoato-κO)cadmium(II)] bis(4-nitrobenzoate)

Crystal data

[Cd2(C7H4NO4)2(C6H10N4O2S2)2](C7H4NO4)2	Z = 1
Mr = 1357.85	F(000) = 680
Triclinic, P1	Dx = 1.810 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6045 (10) Å	Cell parameters from 4280 reflections
b = 10.7869 (14) Å	θ = 2.0–25.0°
c = 16.118 (2) Å	µ = 1.11 mm^−1
α = 97.741 (1)°	T = 295 K
β = 102.600 (1)°	Prism, red
γ = 100.817 (1)°	0.30 × 0.26 × 0.17 mm
V = 1245.9 (3) Å^3

Data collection

Rigaku R-AXIS RAPID IP diffractometer	4310 independent reflections
Radiation source: fine-focus sealed tube	3751 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 10.0 pixels mm^-1	θmax = 25.0°, θmin = 1.9°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.710, Tmax = 0.825	l = −14→19
6467 measured reflections

Refinement

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.027P)^2 + 0.7682P] where P = (Fo^2 + 2Fc^2)/3
4310 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Ų)

	x	y	z	Uiso*/Ueq
Cd	0.57818 (3)	0.34675 (2)	0.481336 (15)	0.03068 (9)
O1	0.6890 (3)	0.56396 (19)	0.52648 (14)	0.0318 (5)
H1A	0.7300	0.5938	0.4877	0.050*
H1B	0.7772	0.5890	0.5750	0.050*
O2	0.8663 (3)	0.3128 (2)	0.50161 (16)	0.0460 (6)
H2A	0.9032	0.2898	0.4578	0.050*
H2B	0.9550	0.3491	0.5432	0.050*
O21	0.5914 (3)	0.3862 (2)	0.34503 (14)	0.0425 (6)
O22	0.7996 (3)	0.5726 (2)	0.38119 (14)	0.0419 (6)
O23	0.8204 (5)	0.5367 (3)	−0.0475 (2)	0.0797 (10)
O24	0.6407 (6)	0.3528 (4)	−0.0772 (2)	0.0953 (12)
O31	1.1054 (3)	0.3710 (2)	0.32199 (15)	0.0488 (7)
O32	0.9237 (4)	0.2072 (2)	0.35451 (16)	0.0506 (7)
O33	0.6588 (5)	−0.0802 (4)	−0.0749 (2)	0.0964 (13)
O34	0.8323 (6)	0.0790 (4)	−0.1054 (2)	0.0932 (12)
N11	0.3961 (4)	0.1488 (2)	0.42375 (17)	0.0316 (6)
N12	0.3833 (5)	0.1243 (3)	0.27703 (19)	0.0543 (9)
H12A	0.3311	0.0815	0.2257	0.050*
H12B	0.4630	0.1992	0.2858	0.050*
N13	0.5098 (3)	0.2598 (2)	0.59931 (16)	0.0301 (6)
N14	0.6762 (4)	0.4014 (3)	0.72924 (18)	0.0460 (8)
H14A	0.6824	0.4245	0.7832	0.050*
H14B	0.7225	0.4557	0.7000	0.050*
N21	0.7267 (5)	0.4480 (4)	−0.0264 (2)	0.0540 (9)
N31	0.7664 (6)	0.0236 (4)	−0.0541 (2)	0.0660 (11)
S11	0.16984 (14)	−0.05631 (9)	0.33490 (6)	0.0464 (2)
S12	0.44067 (14)	0.18707 (9)	0.73631 (6)	0.0455 (2)
C11	0.3181 (4)	0.0854 (3)	0.4812 (2)	0.0321 (8)
C12	0.1944 (5)	−0.0249 (3)	0.4448 (2)	0.0436 (9)
H12	0.1305	−0.0774	0.4749	0.052*
C13	0.3308 (5)	0.0853 (3)	0.3445 (2)	0.0358 (8)
C14	0.3819 (4)	0.1423 (3)	0.5736 (2)	0.0320 (8)
C15	0.3295 (5)	0.0901 (3)	0.6382 (2)	0.0424 (9)
H15	0.2450	0.0125	0.6308	0.051*
C16	0.5543 (5)	0.2946 (3)	0.6835 (2)	0.0314 (7)
C21	0.7022 (4)	0.4717 (3)	0.2335 (2)	0.0315 (7)
C22	0.8271 (5)	0.5632 (3)	0.2099 (2)	0.0427 (9)
H22	0.9064	0.6296	0.2520	0.051*
C23	0.8349 (5)	0.5569 (4)	0.1256 (2)	0.0483 (10)
H23	0.9192	0.6181	0.1100	0.058*
C24	0.7163 (5)	0.4590 (4)	0.0644 (2)	0.0409 (9)
C25	0.5894 (5)	0.3676 (4)	0.0844 (2)	0.0462 (10)
H25	0.5103	0.3019	0.0418	0.055*
C26	0.5824 (5)	0.3758 (4)	0.1701 (2)	0.0436 (9)
H26	0.4955	0.3157	0.1851	0.052*
C27	0.6992 (5)	0.4782 (3)	0.3278 (2)	0.0339 (8)
C31	0.9354 (5)	0.2001 (3)	0.2088 (2)	0.0357 (8)
C32	1.0135 (5)	0.2538 (4)	0.1488 (2)	0.0475 (10)
H32	1.1044	0.3294	0.1666	0.057*
C33	0.9584 (6)	0.1967 (4)	0.0623 (3)	0.0544 (11)
H33	1.0099	0.2339	0.0218	0.065*
C34	0.8269 (6)	0.0847 (4)	0.0378 (2)	0.0492 (10)
C35	0.7478 (6)	0.0278 (4)	0.0956 (3)	0.0634 (12)
H35	0.6596	−0.0492	0.0777	0.076*
C36	0.8020 (6)	0.0875 (4)	0.1808 (3)	0.0554 (11)
H36	0.7471	0.0511	0.2207	0.067*
C37	0.9909 (5)	0.2639 (3)	0.3028 (2)	0.0368 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.03806 (15)	0.02893 (14)	0.02221 (14)	−0.00009 (10)	0.00893 (10)	0.00328 (10)
O1	0.0354 (12)	0.0313 (12)	0.0234 (12)	−0.0019 (10)	0.0074 (10)	0.0001 (10)
O2	0.0371 (14)	0.0617 (17)	0.0345 (14)	0.0039 (12)	0.0113 (11)	−0.0015 (12)
O21	0.0548 (16)	0.0443 (15)	0.0226 (13)	−0.0031 (12)	0.0102 (11)	0.0050 (11)
O22	0.0441 (14)	0.0511 (15)	0.0238 (13)	−0.0024 (12)	0.0107 (11)	−0.0014 (12)
O23	0.096 (2)	0.102 (3)	0.0470 (19)	0.004 (2)	0.0346 (18)	0.0315 (19)
O24	0.147 (3)	0.094 (3)	0.0289 (18)	−0.008 (2)	0.028 (2)	−0.0048 (18)
O31	0.0586 (17)	0.0476 (16)	0.0267 (14)	−0.0062 (13)	−0.0004 (12)	0.0037 (12)
O32	0.0660 (18)	0.0468 (15)	0.0332 (15)	−0.0044 (13)	0.0203 (13)	−0.0017 (12)
O33	0.095 (3)	0.097 (3)	0.058 (2)	−0.017 (2)	0.0033 (19)	−0.040 (2)
O34	0.132 (3)	0.101 (3)	0.0348 (19)	0.017 (2)	0.015 (2)	−0.0051 (19)
N11	0.0427 (17)	0.0273 (14)	0.0219 (15)	0.0031 (12)	0.0078 (13)	0.0015 (12)
N12	0.077 (2)	0.050 (2)	0.0205 (16)	−0.0115 (17)	0.0068 (16)	−0.0017 (14)
N13	0.0339 (15)	0.0330 (15)	0.0227 (15)	0.0032 (12)	0.0087 (12)	0.0063 (12)
N14	0.065 (2)	0.0427 (18)	0.0246 (16)	−0.0062 (15)	0.0155 (15)	0.0041 (14)
N21	0.066 (2)	0.073 (3)	0.0280 (19)	0.018 (2)	0.0177 (17)	0.0140 (19)
N31	0.070 (3)	0.082 (3)	0.037 (2)	0.019 (2)	0.006 (2)	−0.014 (2)
S11	0.0512 (6)	0.0347 (5)	0.0402 (6)	−0.0036 (4)	0.0019 (5)	−0.0038 (4)
S12	0.0630 (6)	0.0451 (5)	0.0279 (5)	−0.0006 (5)	0.0185 (5)	0.0108 (4)
C11	0.0358 (19)	0.0293 (18)	0.0302 (19)	0.0040 (14)	0.0086 (15)	0.0061 (15)
C12	0.044 (2)	0.038 (2)	0.043 (2)	−0.0046 (16)	0.0094 (18)	0.0060 (17)
C13	0.044 (2)	0.0265 (18)	0.031 (2)	0.0039 (15)	0.0044 (16)	0.0007 (15)
C14	0.0351 (19)	0.0304 (18)	0.0302 (19)	0.0032 (14)	0.0104 (15)	0.0067 (15)
C15	0.050 (2)	0.038 (2)	0.037 (2)	−0.0031 (17)	0.0166 (18)	0.0098 (17)
C16	0.041 (2)	0.0330 (18)	0.0225 (18)	0.0066 (15)	0.0111 (15)	0.0087 (15)
C21	0.0342 (18)	0.0354 (19)	0.0247 (18)	0.0072 (15)	0.0082 (15)	0.0042 (15)
C22	0.049 (2)	0.046 (2)	0.028 (2)	−0.0026 (17)	0.0129 (17)	0.0010 (17)
C23	0.057 (2)	0.054 (2)	0.036 (2)	−0.0010 (19)	0.0230 (19)	0.0121 (19)
C24	0.054 (2)	0.050 (2)	0.0256 (19)	0.0143 (18)	0.0184 (17)	0.0105 (17)
C25	0.060 (2)	0.046 (2)	0.0240 (19)	−0.0029 (18)	0.0064 (18)	0.0024 (17)
C26	0.050 (2)	0.050 (2)	0.0257 (19)	−0.0037 (18)	0.0128 (17)	0.0079 (17)
C27	0.0358 (19)	0.042 (2)	0.0234 (18)	0.0071 (16)	0.0071 (15)	0.0066 (16)
C31	0.0357 (19)	0.039 (2)	0.0279 (19)	0.0058 (15)	0.0035 (15)	0.0001 (15)
C32	0.055 (2)	0.044 (2)	0.033 (2)	−0.0054 (18)	0.0081 (18)	0.0003 (17)
C33	0.074 (3)	0.053 (3)	0.033 (2)	0.007 (2)	0.013 (2)	0.0062 (19)
C34	0.057 (2)	0.053 (2)	0.028 (2)	0.012 (2)	−0.0003 (18)	−0.0077 (18)
C35	0.066 (3)	0.058 (3)	0.047 (3)	−0.014 (2)	0.007 (2)	−0.007 (2)
C36	0.065 (3)	0.049 (2)	0.039 (2)	−0.010 (2)	0.013 (2)	−0.0036 (19)
C37	0.039 (2)	0.037 (2)	0.030 (2)	0.0069 (16)	0.0046 (16)	0.0017 (16)

Geometric parameters (Å, º)

Cd—O1	2.294 (2)	S11—C13	1.734 (3)
Cd—O1^i	2.393 (2)	S12—C15	1.717 (4)
Cd—O2	2.250 (2)	S12—C16	1.740 (3)
Cd—O21	2.313 (2)	C11—C12	1.340 (5)
Cd—N11	2.266 (3)	C11—C14	1.468 (5)
Cd—N13	2.344 (2)	C12—H12	0.9300
O1—H1A	0.8319	C14—C15	1.347 (5)
O1—H1B	0.8843	C15—H15	0.9300
O2—H2A	0.8386	C21—C26	1.379 (5)
O2—H2B	0.8316	C21—C22	1.388 (5)
O21—C27	1.267 (4)	C21—C27	1.516 (4)
O22—C27	1.244 (4)	C22—C23	1.367 (5)
O23—N21	1.216 (4)	C22—H22	0.9300
O24—N21	1.200 (4)	C23—C24	1.370 (5)
O31—C37	1.263 (4)	C23—H23	0.9300
O32—C37	1.239 (4)	C24—C25	1.368 (5)
O33—N31	1.213 (5)	C25—C26	1.386 (5)
O34—N31	1.223 (5)	C25—H25	0.9300
N11—C13	1.306 (4)	C26—H26	0.9300
N11—C11	1.391 (4)	C31—C32	1.377 (5)
N12—C13	1.331 (4)	C31—C36	1.377 (5)
N12—H12A	0.8599	C31—C37	1.510 (5)
N12—H12B	0.8876	C32—C33	1.383 (5)
N13—C16	1.309 (4)	C32—H32	0.9300
N13—C14	1.395 (4)	C33—C34	1.365 (5)
N14—C16	1.342 (4)	C33—H33	0.9300
N14—H14A	0.8607	C34—C35	1.366 (6)
N14—H14B	0.8708	C35—C36	1.374 (5)
N21—C24	1.473 (4)	C35—H35	0.9300
N31—C34	1.472 (5)	C36—H36	0.9300
S11—C12	1.720 (4)
O2—Cd—N11	103.40 (9)	N12—C13—S11	122.6 (3)
O2—Cd—O1	91.73 (8)	C15—C14—N13	115.3 (3)
N11—Cd—O1	164.40 (8)	C15—C14—C11	125.7 (3)
O2—Cd—O21	88.97 (9)	N13—C14—C11	118.9 (3)
N11—Cd—O21	90.87 (9)	C14—C15—S12	110.4 (3)
O1—Cd—O21	85.56 (8)	C14—C15—H15	124.8
O2—Cd—N13	96.10 (9)	S12—C15—H15	124.8
N11—Cd—N13	74.66 (9)	N13—C16—N14	125.9 (3)
O1—Cd—N13	107.87 (8)	N13—C16—S12	113.9 (2)
O21—Cd—N13	165.41 (9)	N14—C16—S12	120.1 (2)
O2—Cd—O1^i	166.01 (8)	C26—C21—C22	118.9 (3)
N11—Cd—O1^i	90.59 (8)	C26—C21—C27	121.0 (3)
O1—Cd—O1^i	74.30 (8)	C22—C21—C27	120.0 (3)
O21—Cd—O1^i	90.54 (8)	C23—C22—C21	120.8 (3)
N13—Cd—O1^i	87.80 (8)	C23—C22—H22	119.6
Cd—O1—Cd^i	105.70 (8)	C21—C22—H22	119.6
Cd—O1—H1A	108.5	C22—C23—C24	118.8 (3)
Cd^i—O1—H1A	100.5	C22—C23—H23	120.6
Cd—O1—H1B	116.5	C24—C23—H23	120.6
Cd^i—O1—H1B	116.7	C25—C24—C23	122.5 (3)
H1A—O1—H1B	107.5	C25—C24—N21	117.9 (3)
Cd—O2—H2A	118.1	C23—C24—N21	119.7 (3)
Cd—O2—H2B	125.5	C24—C25—C26	118.0 (3)
H2A—O2—H2B	110.8	C24—C25—H25	121.0
C27—O21—Cd	126.5 (2)	C26—C25—H25	121.0
C13—N11—C11	111.2 (3)	C21—C26—C25	120.9 (3)
C13—N11—Cd	133.0 (2)	C21—C26—H26	119.5
C11—N11—Cd	115.3 (2)	C25—C26—H26	119.5
C13—N12—H12A	119.8	O22—C27—O21	125.5 (3)
C13—N12—H12B	118.4	O22—C27—C21	118.2 (3)
H12A—N12—H12B	121.4	O21—C27—C21	116.4 (3)
C16—N13—C14	110.8 (3)	C32—C31—C36	118.4 (3)
C16—N13—Cd	136.9 (2)	C32—C31—C37	121.1 (3)
C14—N13—Cd	112.3 (2)	C36—C31—C37	120.4 (3)
C16—N14—H14A	119.9	C31—C32—C33	120.9 (3)
C16—N14—H14B	117.0	C31—C32—H32	119.6
H14A—N14—H14B	120.8	C33—C32—H32	119.6
O24—N21—O23	122.2 (4)	C34—C33—C32	118.6 (4)
O24—N21—C24	119.1 (4)	C34—C33—H33	120.7
O23—N21—C24	118.6 (4)	C32—C33—H33	120.7
O33—N31—O34	123.3 (4)	C33—C34—C35	122.2 (4)
O33—N31—C34	118.8 (4)	C33—C34—N31	119.0 (4)
O34—N31—C34	117.8 (4)	C35—C34—N31	118.8 (4)
C12—S11—C13	89.26 (17)	C34—C35—C36	118.2 (4)
C15—S12—C16	89.57 (16)	C34—C35—H35	120.9
C12—C11—N11	114.9 (3)	C36—C35—H35	120.9
C12—C11—C14	127.1 (3)	C35—C36—C31	121.7 (4)
N11—C11—C14	118.0 (3)	C35—C36—H36	119.1
C11—C12—S11	110.8 (3)	C31—C36—H36	119.1
C11—C12—H12	124.6	O32—C37—O31	125.6 (3)
S11—C12—H12	124.6	O32—C37—C31	118.0 (3)
N11—C13—N12	123.5 (3)	O31—C37—C31	116.3 (3)
N11—C13—S11	113.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O22	0.83	1.90	2.662 (3)	151
O1—H1B···O31^ii	0.88	1.66	2.522 (3)	164
O2—H2A···O32	0.84	1.83	2.650 (4)	164
O2—H2B···O22^ii	0.83	1.95	2.766 (3)	165
N12—H12A···O33^iii	0.86	2.45	3.164 (4)	141
N12—H12A···O34^iii	0.86	2.35	3.192 (5)	165
N12—H12B···O21	0.89	2.07	2.901 (4)	156
N14—H14A···O24^iv	0.86	2.54	3.292 (4)	147
N14—H14B···O31^ii	0.87	2.19	3.014 (4)	158

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) x, y, z+1.