A two-dimensional cadmium(II) coordination polymer based on 1-cyano­methyl-4-aza-1-azonia­bicyclo­[2.2.2]octane and thio­cyanate ligands

A cadmium–thio­cyanate complex, poly[(1-cyano­methyl-4-aza-1-azonia­bicyclo[2.2.2]octane-κ⁴N)octa­kis-μ₂-thio­cyanato-κ⁸N:S;κ⁸S:N-tricadmium(II)], [Cd₃(C₈H₁₄N₃)₂(NCS)₈]_n, was synthesized by the reaction of 1-cyano­methyl-4-aza-1-azonia­bicyclo­[2.2.2]octane chloride, cadmium nitrate tetra­hydrate and potassium thio­cyanide in aqueous solution. In the crystal structure, there are two independent types of Cd^II cation (one on a centre of inversion and one in a general position) and both are in distorted octa­hedral coordination environments, coordinated by N and S atoms from different ligands. Neighbouring Cd^II cations are linked together by thio­cyanate bridges to form a two-dimensional network. Hydrogen-bonding inter­actions are involved in the formation of a three-dimensional supra­molecular network.

S1. Introduction

\ Metal–organic coordination polymers have attracted considerable attention, not only owing to their intriguing architectures, but also due to their unique chemical and physical properties and potential applications (Lin et al., 1999; Moulton & Zaworotko, 2001; Gao et al., 2008). There are some reports in which N- and S-donor bridging ligands are used to form infinite polymeric frameworks (Kuniyasu et al., 1987; Liu et al., 2002; Zhang et al., 1999). Cadmium(II) is a rather soft metal ion. Therefore, it is expected that both the N and the S atoms of a thio­cyanate ion (SCN^-) are able to bond easily with cadmium(II). The anionic thio­cyanate ligand is a highly versatile ambidentate ligand with a polarizable π-system and can coordinate to metal ions through either/both the N or/and the S atom (Eichele & Wasylishen, 1994). Different bridging modes of the thio­cyanate ligand and cadmium(II) cation can generate various types of dimensional structures with particular properties such as nonlinear optical (NLO) behaviour (Liu et al., 2002).

Many of the reported framework structures of polymeric cadmium complexes are one-dimensional zigzag chains. In contrast, two-dimensional Cd^II networks are quite rare. Recently, however, a particularly inter­esting two-dimensional honeycomb-like {[Cd(NCS)]^-}_n anionic polymeric framework was observed, in which the Cd—NCS—Cd units link to form eight-membered rings (Lai et al., 2007). Furthermore, the structure of an {[N(CH₃)₄]₂[Cd(NCS)₂S]}_n complex, composed of eight-membered (Cd—NCS—Cd links) and four-membered (Cd—S—Cd links) rings combining to form a novel two-dimensional polymeric network structure, was reported (Li et al., 2003). Recently, we have investigated the synthesis of metal DABCO-based (DABCO is 1,4-di­aza­bicyclo­[2.2.2]o­ctane) coordination polymers, because DABCO, its derivatives and its metal complexes have exhibited excellent dielectric properties (Liao et al., 2013; Ye et al., 2012). In the present paper, we report a two-dimensional Cd^II coordination polymer using the 1-cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane cation (L) as a template, namely poly[(1-cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane-κ⁴N)o­cta­kis-\ µ₂-thio­cyanato-κ⁸N:S;κ⁸S:N-\ tricadmium(II)], [Cd₃(L)₂(NCS)₈], (I).

S2. Experimental

S2.1. Synthesis and crystallization

1-Cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane chloride was prepared according to the literature procedure of Li et al. (2015). An aqueous solution (10 ml) of 1-cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane chloride (0.282 g, 1.5 mmol) was added slowly to an aqueous solution containing cadmium nitrate tetra­hydrate (0.462 g, 1.5 mmol) and potassium thio­cyanide (0.582 g, 6 mmol), affording a colourless solution. Upon standing at room temperature for several days, suitable colourless single crystals of (I) were obtained by slow solvent evaporation.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in idealized positions (C—H = 0.97 Å) and refined as a riding model, with isotropic displacement parameters set at 1.2U_eq of the appropriate carrier atoms.

S3. Results and discussion

\ Compound (I) crystallizes in the monoclinic space group P2₁/c. The asymmetric unit is composed of one-and-a-half Cd^II cations (one in a special position), one cationic 1-cyano­methyl-4-aza-1-azoniabi­cyclo­[2.2.2]o­ctane (L) organic ligand and four anionic thio­cyanate (SCN^-) ligands (Fig. 1).

As shown in Fig. 1, there are two crystallographically unique Cd^II cations in (I), i.e. the Cd1 ion lies on an inversion centre, while the Cd2 ion is in a general position. Both of the Cd^II centres are six-coordinated with distorted o­cta­hedral geometries, but with different coordination environments. The Cd1 ion is symmetrically coordinated by two N atoms from two terminal L ligands, an dby two N atoms and two S atoms from four different thio­cyanate bridging ligands, while the Cd2 ion is surrounded by three N atoms and three S atoms from six thio­cyanate bridging ligands. Each of the Cd^II cations is joined to neighbouring Cd^II cations through double thio­cyanate bridges. The Cd—N bond lengths range from 2.244 (3) to 2.349 (3) Å and the Cd—S bond lengths vary from 2.7148 (11) to 2.7634 (13) Å (Table 2), and these are within the typical ranges for such bonds (Gao et al., 2008; Wei et al., 2007). There are two sorts of angle around each Cd^II centre, namely orthogonal cis [84.34 (9)–98.21 (9)°] and linear trans angles [172.98 (9)–180.00 (16)°]. In general, all the bond lengths and angles are in the normal ranges, and the Cd—S—C and Cd—N—C bond angles are consistent with those in other reported cadmium–thio­cyanate compounds (Wang et al., 2004; Liu et al., 2002).

The two-dimensional network of (I) is a new coordination polymer in which each of the six-coordinated Cd^II centres adopts a distorted o­cta­hedral coordination geometry. It displays a novel coordination architecture compared with the related structure (BMIM)₂[Cd₂(SCN)₆], (II) (BMIM is 1-butyl-3-methyl­imidazolium; Gao et al., 2008), in which each Cd^II centre is located at the node position and o­cta­hedrally coordinated by N atoms from three bridging SCN^- ligands and S atoms from three bridging NCS^- ligands, forming a distorted two-dimensional honeycomb-like structure. In (I), two independent Cd^II centres are linked by bridging thio­cyanate ligands, forming an infinite two-dimensional puckered re­cta­ngular network with coordinated L ligands (Fig. 2). The corrugated two-dimensional net has a puckered re­cta­ngular structure where each loop within the grid is composed of Cd₈(NCS)₈ rings, with eight additional thio­cyanate ligands involved in double bridges between pairs of Cd^II cations, thus involving 16 thio­cyanate ligands and two coordinated L ligands in total per grid in the bc plane (Fig. 2). It is worth noting that, in one direction, the Cd^II cations alternate so that there is a Cd2···Cd1···Cd2 sequence, connected by thio­cyanate bridges, with a Cd···Cd distance of 5.7571 (10) Å, while in the other direction, the sequence is Cd2···Cd2···Cd2, also connected by thio­cyanate bridges, forming an inorganic zigzag anionic chain, with a Cd···Cd distance of 5.6982 (10) Å. This is different from what we found in our previous report on poly[4-(di­methyl­amino)­pyridin-1-ium [di-µ-thio­cyanato-κ²N:S;κ²S:N-thio­cyanato-\ κN-cadmium(II)]], (C₇H₁₁N₂)[Cd(NCS)₃] (Wang & Wang, 2015), where the Cd^II cations are linked by two N:S-bridging and two S:N-bridging thio­cyanate ligands, forming an infinite two-dimensional sandwich-like network.

The crystal structure of (I) exhibits two distinct metal-ion coordination modes: one is N₄S₂-coordinated doubly bridging and the other is N₃S₃-coordinated doubly bridging. Thus, the title polymer can be considered as the first example of a cadmium–thio­cyanate complex having various coordination modes. Additionally, the cations occur in centrosymmetrically related pairs within the cavities in this network and present two different orientations, as shown in Fig. 2.

The van der Waals radii of H and S atoms are 1.20 and 1.80 Å (Bondi, 1964), respectively. Any H···S contact shorter than 3.00 Å may therefore potentially be considered significant (Zhou et al., 2006). In complex (I), the H···S distances are 2.86 and 2.82 Å, which indicates the formation of C—H···S hydrogen bonds. The C—H···S hydrogen bond is very important in supra­molecular self-assembly. It should be pointed out that the two-dimensional anionic framework is filled by L cations through electrostatic and hydrogen-bonding inter­actions (C5—H5A···S2 and C7—H7A···N5; Table 3). Inter­molecular hydrogen-bonding inter­actions between the L cations and the bridging thio­cyanate ligands further stabilize the corrugated two-dimensional network (Fig. 3). The undulating networks are stacked by C7—H7B···S3 inter­actions along the a axis, with a spacing between the layers of 3.632 (4) Å (the a-axis length). C7—H7B···S3 hydrogen-bonding inter­actions again serve as important driving forces to crosslink the puckered two-dimensional networks into a three-dimensional architecture in the ab plane (Fig. 4).

In summary, a new cadmium–thio­cyanate coordination polymer with an inter­esting structural architecture has been prepared in aqueous solution. The Cd^II cations are linked by bridging thio­cyanate ligands to form a two-dimensional coordination polymer which lies parallel to the bc plane. Hydrogen-bonding inter­actions are involved in forming the three-dimensional architecture.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment of the Cd1 and Cd2 atoms in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y + 1, -z + 2; (ii) x, -y + 1/2, -z + 2; (iii) x, -y + 1/2, z + 1/2.]
	Fig. 2. The puckered rectangular net structure of complex (I), formed by the Cd^II centres, viewed in the bc plane.
	Fig. 3. The crystal packing of (I), showing the hydrogen-bonding interactions (dashed lines) among the cations and the inorganic coordination polymer.
	Fig. 4. An illustration of the three-dimensional supramolecular network of (I) in the ab plane, formed by the cations via hydrogen-bonding interactions (dashed lines).

Poly[(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κ⁴N)octakis-µ₂-thiocyanato-κ⁸N:S;κ⁸S:N-tricadmium(II)]

Crystal data

[Cd3(C8H14N3)2(NCS)8]	F(000) = 1084
Mr = 1106.28	Dx = 1.975 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4249 reflections
a = 7.1457 (14) Å	θ = 3.1–27.5°
b = 26.002 (5) Å	µ = 2.19 mm^−1
c = 10.043 (2) Å	T = 293 K
β = 94.36 (3)°	Prismatic, colourless
V = 1860.6 (6) Å^3	0.54 × 0.38 × 0.25 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer	3356 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −30→33
Tmin = 0.384, Tmax = 0.611	l = −13→12
12484 measured reflections	3 standard reflections every 180 reflections
4249 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0174P)^2 + 1.0538P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
4249 reflections	Δρmax = 0.48 e Å^−3
223 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0819 (12)

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
N3	0.7421 (5)	0.57229 (15)	0.4979 (4)	0.0525 (10)
Cd2	0.02622 (4)	0.301789 (11)	0.74665 (3)	0.03336 (9)
Cd1	0.0000	0.5000	1.0000	0.02908 (10)
S2	−0.26035 (13)	0.47545 (4)	0.79683 (10)	0.0331 (2)
S3	0.21742 (15)	0.21181 (4)	0.77700 (10)	0.0375 (2)
S4	−0.29430 (15)	0.25357 (5)	0.63757 (12)	0.0486 (3)
N1	0.1698 (4)	0.55127 (11)	0.8336 (3)	0.0265 (7)
N2	0.3462 (4)	0.59756 (11)	0.6547 (3)	0.0255 (6)
N7	0.1443 (5)	0.30370 (12)	0.5436 (3)	0.0400 (8)
C6	0.3036 (5)	0.54266 (14)	0.6129 (4)	0.0336 (9)
H6A	0.4197	0.5241	0.6032	0.040*
H6B	0.2302	0.5422	0.5276	0.040*
N5	−0.1089 (5)	0.38314 (13)	0.7054 (3)	0.0439 (9)
C1	0.0664 (5)	0.59678 (15)	0.7841 (4)	0.0403 (10)
H1A	0.0541	0.6205	0.8576	0.048*
H1B	−0.0588	0.5866	0.7501	0.048*
C9	0.2498 (5)	0.39627 (15)	0.9236 (4)	0.0313 (8)
C10	−0.1729 (5)	0.42065 (16)	0.7462 (4)	0.0344 (9)
C11	0.1752 (5)	0.20396 (13)	0.9342 (4)	0.0291 (8)
N6	−0.1185 (5)	0.29984 (15)	0.9401 (3)	0.0510 (10)
C3	0.3556 (5)	0.56799 (17)	0.8884 (4)	0.0387 (10)
H3A	0.4286	0.5381	0.9179	0.046*
H3B	0.3417	0.5897	0.9657	0.046*
C4	0.4612 (5)	0.59766 (15)	0.7867 (3)	0.0325 (9)
H4A	0.4826	0.6327	0.8170	0.039*
H4B	0.5820	0.5817	0.7770	0.039*
N4	0.1875 (4)	0.43272 (12)	0.9669 (3)	0.0351 (8)
C12	−0.1924 (5)	0.22277 (16)	0.5199 (4)	0.0376 (10)
C7	0.4469 (5)	0.62521 (14)	0.5505 (4)	0.0341 (9)
H7A	0.3635	0.6293	0.4704	0.041*
H7B	0.4834	0.6592	0.5828	0.041*
C2	0.1636 (5)	0.62431 (15)	0.6732 (4)	0.0380 (10)
H2A	0.0839	0.6234	0.5906	0.046*
H2B	0.1865	0.6600	0.6975	0.046*
C8	0.6146 (6)	0.59640 (16)	0.5185 (4)	0.0364 (9)
C5	0.1949 (6)	0.51719 (15)	0.7184 (4)	0.0410 (10)
H5A	0.0726	0.5070	0.6786	0.049*
H5B	0.2607	0.4863	0.7496	0.049*
S1	0.34782 (16)	0.34544 (5)	0.86551 (14)	0.0639 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3	0.056 (2)	0.046 (2)	0.058 (2)	−0.012 (2)	0.018 (2)	−0.0027 (19)
Cd2	0.04479 (18)	0.02826 (16)	0.02734 (15)	0.00671 (13)	0.00474 (13)	0.00026 (12)
Cd1	0.0279 (2)	0.0272 (2)	0.0323 (2)	0.00311 (17)	0.00366 (16)	−0.00541 (16)
S2	0.0303 (5)	0.0313 (6)	0.0369 (5)	0.0051 (4)	−0.0021 (4)	−0.0056 (4)
S3	0.0486 (6)	0.0324 (6)	0.0330 (5)	0.0116 (5)	0.0128 (5)	0.0038 (4)
S4	0.0391 (6)	0.0535 (8)	0.0543 (7)	0.0008 (5)	0.0101 (5)	−0.0043 (5)
N1	0.0247 (15)	0.0238 (17)	0.0307 (16)	0.0001 (13)	−0.0006 (13)	−0.0028 (13)
N2	0.0238 (15)	0.0221 (16)	0.0296 (16)	−0.0003 (13)	−0.0039 (13)	0.0037 (13)
N7	0.054 (2)	0.034 (2)	0.0329 (19)	−0.0043 (17)	0.0079 (16)	0.0015 (15)
C6	0.042 (2)	0.029 (2)	0.030 (2)	−0.0065 (18)	0.0030 (17)	−0.0048 (16)
N5	0.056 (2)	0.027 (2)	0.046 (2)	0.0099 (17)	−0.0145 (18)	−0.0058 (16)
C1	0.035 (2)	0.037 (3)	0.050 (3)	0.0044 (19)	0.0032 (19)	0.0040 (19)
C9	0.0262 (19)	0.034 (2)	0.032 (2)	−0.0020 (17)	−0.0075 (16)	−0.0023 (17)
C10	0.037 (2)	0.037 (2)	0.028 (2)	−0.0062 (19)	−0.0071 (17)	0.0046 (18)
C11	0.0281 (19)	0.020 (2)	0.039 (2)	0.0021 (16)	0.0011 (17)	−0.0018 (16)
N6	0.058 (2)	0.062 (3)	0.0339 (19)	0.017 (2)	0.0102 (18)	0.0073 (18)
C3	0.027 (2)	0.053 (3)	0.035 (2)	−0.0101 (19)	−0.0021 (17)	0.0040 (19)
C4	0.0266 (19)	0.038 (2)	0.031 (2)	−0.0049 (17)	−0.0078 (16)	0.0041 (17)
N4	0.0331 (18)	0.0299 (19)	0.0411 (19)	0.0055 (15)	−0.0044 (15)	−0.0090 (15)
C12	0.038 (2)	0.043 (3)	0.032 (2)	−0.011 (2)	−0.0017 (19)	0.0073 (19)
C7	0.037 (2)	0.032 (2)	0.033 (2)	−0.0089 (18)	−0.0052 (17)	0.0082 (17)
C2	0.029 (2)	0.033 (2)	0.051 (3)	0.0075 (18)	−0.0031 (18)	0.0084 (19)
C8	0.047 (2)	0.035 (2)	0.028 (2)	−0.018 (2)	0.0034 (19)	0.0037 (17)
C5	0.054 (3)	0.031 (2)	0.039 (2)	−0.011 (2)	0.015 (2)	−0.0101 (18)
S1	0.0428 (7)	0.0518 (8)	0.0943 (10)	0.0180 (6)	−0.0130 (7)	−0.0378 (7)

Geometric parameters (Å, º)

N3—C8	1.138 (5)	C6—C5	1.513 (5)
Cd2—N7	2.266 (3)	C6—H6A	0.9700
Cd2—N6	2.269 (3)	C6—H6B	0.9700
Cd2—N5	2.349 (3)	N5—C10	1.165 (5)
Cd2—S3	2.7148 (11)	C1—C2	1.534 (5)
Cd2—S1	2.7528 (14)	C1—H1A	0.9700
Cd2—S4	2.7634 (13)	C1—H1B	0.9700
Cd1—N4	2.244 (3)	C9—N4	1.147 (4)
Cd1—N4^i	2.244 (3)	C9—S1	1.625 (4)
Cd1—N1^i	2.520 (3)	C11—N7^iii	1.154 (4)
Cd1—N1	2.520 (3)	N6—C12^iii	1.154 (5)
Cd1—S2	2.7305 (13)	C3—C4	1.525 (5)
Cd1—S2^i	2.7305 (13)	C3—H3A	0.9700
S2—C10	1.652 (4)	C3—H3B	0.9700
S3—C11	1.642 (4)	C4—H4A	0.9700
S4—C12	1.643 (4)	C4—H4B	0.9700
N1—C1	1.462 (4)	C12—N6^ii	1.154 (5)
N1—C3	1.464 (4)	C7—C8	1.469 (6)
N1—C5	1.480 (4)	C7—H7A	0.9700
N2—C7	1.498 (4)	C7—H7B	0.9700
N2—C2	1.503 (4)	C2—H2A	0.9700
N2—C4	1.505 (4)	C2—H2B	0.9700
N2—C6	1.513 (4)	C5—H5A	0.9700
N7—C11^ii	1.154 (4)	C5—H5B	0.9700
N7—Cd2—N6	174.76 (12)	N2—C6—H6B	109.9
N7—Cd2—N5	89.87 (12)	C5—C6—H6B	109.9
N6—Cd2—N5	87.88 (13)	H6A—C6—H6B	108.3
N7—Cd2—S3	84.34 (9)	C10—N5—Cd2	149.2 (3)
N6—Cd2—S3	98.21 (9)	N1—C1—C2	112.3 (3)
N5—Cd2—S3	172.98 (9)	N1—C1—H1A	109.1
N7—Cd2—S1	91.47 (9)	C2—C1—H1A	109.1
N6—Cd2—S1	93.31 (11)	N1—C1—H1B	109.1
N5—Cd2—S1	91.35 (9)	C2—C1—H1B	109.1
S3—Cd2—S1	84.85 (4)	H1A—C1—H1B	107.9
N7—Cd2—S4	90.41 (9)	N4—C9—S1	177.2 (3)
N6—Cd2—S4	84.91 (10)	N5—C10—S2	177.0 (4)
N5—Cd2—S4	91.23 (9)	N7^iii—C11—S3	177.1 (3)
S3—Cd2—S4	92.77 (4)	C12^iii—N6—Cd2	150.3 (3)
S1—Cd2—S4	176.81 (4)	N1—C3—C4	112.3 (3)
N4—Cd1—N4^i	180.00 (16)	N1—C3—H3A	109.1
N4—Cd1—N1^i	90.50 (11)	C4—C3—H3A	109.1
N4^i—Cd1—N1^i	89.50 (11)	N1—C3—H3B	109.1
N4—Cd1—N1	89.50 (11)	C4—C3—H3B	109.1
N4^i—Cd1—N1	90.50 (11)	H3A—C3—H3B	107.9
N1^i—Cd1—N1	180.00 (11)	N2—C4—C3	108.9 (3)
N4—Cd1—S2	95.03 (8)	N2—C4—H4A	109.9
N4^i—Cd1—S2	84.97 (8)	C3—C4—H4A	109.9
N1^i—Cd1—S2	92.11 (7)	N2—C4—H4B	109.9
N1—Cd1—S2	87.89 (7)	C3—C4—H4B	109.9
N4—Cd1—S2^i	84.97 (8)	H4A—C4—H4B	108.3
N4^i—Cd1—S2^i	95.03 (8)	C9—N4—Cd1	162.5 (3)
N1^i—Cd1—S2^i	87.89 (7)	N6^ii—C12—S4	178.0 (4)
N1—Cd1—S2^i	92.11 (7)	C8—C7—N2	110.5 (3)
S2—Cd1—S2^i	180.0	C8—C7—H7A	109.5
C10—S2—Cd1	100.34 (13)	N2—C7—H7A	109.5
C11—S3—Cd2	95.02 (13)	C8—C7—H7B	109.5
C12—S4—Cd2	96.14 (14)	N2—C7—H7B	109.5
C1—N1—C3	107.9 (3)	H7A—C7—H7B	108.1
C1—N1—C5	107.9 (3)	N2—C2—C1	108.6 (3)
C3—N1—C5	108.2 (3)	N2—C2—H2A	110.0
C1—N1—Cd1	113.4 (2)	C1—C2—H2A	110.0
C3—N1—Cd1	112.1 (2)	N2—C2—H2B	110.0
C5—N1—Cd1	107.2 (2)	C1—C2—H2B	110.0
C7—N2—C2	109.4 (3)	H2A—C2—H2B	108.4
C7—N2—C4	110.8 (3)	N3—C8—C7	176.7 (4)
C2—N2—C4	108.1 (3)	N1—C5—C6	112.6 (3)
C7—N2—C6	110.9 (3)	N1—C5—H5A	109.1
C2—N2—C6	108.2 (3)	C6—C5—H5A	109.1
C4—N2—C6	109.3 (3)	N1—C5—H5B	109.1
C11^ii—N7—Cd2	164.6 (3)	C6—C5—H5B	109.1
N2—C6—C5	108.8 (3)	H5A—C5—H5B	107.8
N2—C6—H6A	109.9	C9—S1—Cd2	97.04 (13)
C5—C6—H6A	109.9
N4—Cd1—S2—C10	3.38 (16)	C3—N1—C1—C2	60.7 (4)
N4^i—Cd1—S2—C10	−176.62 (16)	C5—N1—C1—C2	−55.9 (4)
N1^i—Cd1—S2—C10	−87.31 (15)	Cd1—N1—C1—C2	−174.4 (3)
N1—Cd1—S2—C10	92.69 (15)	Cd2—N5—C10—S2	155 (6)
S2^i—Cd1—S2—C10	140 (100)	Cd1—S2—C10—N5	−108 (7)
N7—Cd2—S3—C11	173.31 (15)	Cd2—S3—C11—N7^iii	138 (7)
N6—Cd2—S3—C11	−11.29 (17)	N7—Cd2—N6—C12^iii	81.2 (15)
N5—Cd2—S3—C11	138.8 (7)	N5—Cd2—N6—C12^iii	145.8 (7)
S1—Cd2—S3—C11	81.32 (14)	S3—Cd2—N6—C12^iii	−37.7 (7)
S4—Cd2—S3—C11	−96.55 (13)	S1—Cd2—N6—C12^iii	−123.0 (7)
N7—Cd2—S4—C12	30.90 (17)	S4—Cd2—N6—C12^iii	54.4 (7)
N6—Cd2—S4—C12	−151.46 (17)	C1—N1—C3—C4	−56.1 (4)
N5—Cd2—S4—C12	120.78 (17)	C5—N1—C3—C4	60.4 (4)
S3—Cd2—S4—C12	−53.46 (15)	Cd1—N1—C3—C4	178.3 (2)
S1—Cd2—S4—C12	−95.2 (6)	C7—N2—C4—C3	−178.6 (3)
N4—Cd1—N1—C1	162.7 (2)	C2—N2—C4—C3	61.6 (4)
N4^i—Cd1—N1—C1	−17.3 (2)	C6—N2—C4—C3	−56.1 (4)
N1^i—Cd1—N1—C1	−52 (76)	N1—C3—C4—N2	−4.2 (4)
S2—Cd1—N1—C1	67.7 (2)	S1—C9—N4—Cd1	157 (7)
S2^i—Cd1—N1—C1	−112.3 (2)	N4^i—Cd1—N4—C9	−115 (34)
N4—Cd1—N1—C3	−74.7 (2)	N1^i—Cd1—N4—C9	95.1 (11)
N4^i—Cd1—N1—C3	105.3 (2)	N1—Cd1—N4—C9	−84.9 (11)
N1^i—Cd1—N1—C3	71 (76)	S2—Cd1—N4—C9	2.9 (11)
S2—Cd1—N1—C3	−169.8 (2)	S2^i—Cd1—N4—C9	−177.1 (11)
S2^i—Cd1—N1—C3	10.2 (2)	Cd2—S4—C12—N6^ii	74 (12)
N4—Cd1—N1—C5	43.8 (2)	C2—N2—C7—C8	−173.1 (3)
N4^i—Cd1—N1—C5	−136.2 (2)	C4—N2—C7—C8	67.8 (4)
N1^i—Cd1—N1—C5	−171 (76)	C6—N2—C7—C8	−53.8 (4)
S2—Cd1—N1—C5	−51.2 (2)	C7—N2—C2—C1	−177.7 (3)
S2^i—Cd1—N1—C5	128.8 (2)	C4—N2—C2—C1	−56.9 (4)
N6—Cd2—N7—C11^ii	−47 (2)	C6—N2—C2—C1	61.4 (4)
N5—Cd2—N7—C11^ii	−111.2 (12)	N1—C1—C2—N2	−3.7 (5)
S3—Cd2—N7—C11^ii	72.8 (12)	N2—C7—C8—N3	2 (8)
S1—Cd2—N7—C11^ii	157.5 (12)	C1—N1—C5—C6	60.2 (4)
S4—Cd2—N7—C11^ii	−19.9 (12)	C3—N1—C5—C6	−56.3 (4)
C7—N2—C6—C5	−177.6 (3)	Cd1—N1—C5—C6	−177.4 (3)
C2—N2—C6—C5	−57.6 (4)	N2—C6—C5—N1	−3.0 (5)
C4—N2—C6—C5	59.9 (4)	N4—C9—S1—Cd2	177 (100)
N7—Cd2—N5—C10	−160.7 (6)	N7—Cd2—S1—C9	120.40 (17)
N6—Cd2—N5—C10	24.0 (6)	N6—Cd2—S1—C9	−57.46 (17)
S3—Cd2—N5—C10	−126.4 (7)	N5—Cd2—S1—C9	30.50 (17)
S1—Cd2—N5—C10	−69.2 (6)	S3—Cd2—S1—C9	−155.41 (15)
S4—Cd2—N5—C10	108.9 (6)	S4—Cd2—S1—C9	−113.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···S2	0.97	2.86	3.574 (4)	131
C7—H7A···N5^iv	0.97	2.46	3.397 (5)	163
C7—H7B···S3^v	0.97	2.82	3.632 (4)	142

Symmetry codes: (iv) −x, −y+1, −z+1; (v) −x+1, y+1/2, −z+3/2.