Copper(II) and cadmium(II) isothio­cyanate coordination polymers with 4,4'-bi-1,2,4-triazole

The coordination polymers catena-poly[[[(4,4'-bi-1,2,4-triazole-[kappa]N¹)bis­(thio­cyanato-[kappa]N)copper(II)]-[mu]-4,4'-bi-1,2,4-triazole-[kappa]²N¹:N^1'] dihydrate], {[Cu(NCS)₂(C₄H₄N₆)₂]·2H₂O}_n, (I), and poly[tetra­kis([mu]-4,4'-bi-1,2,4-triazole-[kappa]²N¹:N^1')bis­([mu]-thio­cyanato-[kappa]²N:S)tetra­kis(thio­cyanato-[kappa]N)tricadmium(II)], [Cd₃(NCS)₆(C₄H₄N₆)₄]_n, (II), exhibit chain and two-dimensional layer structures, respectively. The differentiation of the Lewis acidic nature of Cu^II and Cd^II has an influence on the coordination modes of the triazole and thio­cyanate ligands, leading to topologically different polymeric motifs. In (I), copper ions are linked by bitriazole N:N'-bridges into zigzag chains and the tetra­gonal-pyramidal CuN₅ environment is composed of two thio­cyanate N atoms and three triazole N atoms [basal Cu-N = 1.9530 (18)-2.0390 (14) Å and apical Cu-N = 2.2637 (15) Å]. The structure of (II) contains two types of crystallographically unique Cd^II atoms. One type lies on an inversion center in a distorted CdN₆ octa­hedral environment, with bitriazole ligands in the equatorial plane and terminal isothio­cyanate N atoms in the axial positions. The other type lies on a general position and forms centrosymmetric binuclear [Cd₂([mu]-NCS-[kappa]²N:S)₂(NCS)₂] units (tetra­gonal-pyramidal CdN₄S coordination). N:N'-Bridging bitriazole ligands link the Cd centers into a flat (4,4)-network.

S1. Comment

The growing interest in the structural design of M^II–bi(1,2,4-triazole) coordination polymers (where M = Fe^II, Cu^II and Cd^II) has been dictated by their importance in the fields of magnetism and fluorescence (Janiak, 2000). The bitopic bitriazoles propagate local coordination environments around either discrete metal ions or polynuclear secondary building units (SBU) as nodes, forming metal-organic frameworks (MOFs). The adjacent N atoms (N1 and N2) in 1,2,4-triazole derivatives are well suited for binding together transition metal cations, leading to characteristic polynuclear clusters, viz. dimers (Drabent et al., 2004), linear (Liu et al., 1999) and triangular trimers (Virovets et al., 1997), etc. Recently, for the Cu^II–btr–X^- (X = Cl and Br; btr is 4,4'-bi-1,2,4-triazole) systems, we have demonstrated how such cluster motifs may be rationally integrated in the MOFs (Lysenko et al., 2006, 2007). Obviously, the nature of the anion is a crucial factor that determines the resultant structure and net topology of the M^II–btr polymers. In this context, a very interesting situation could be realised in the case of pseudohalide anions, e.g. NCS^-, which are complementary to a short triazole linker, and such a combination of neutral and anionic bridges can support formation of triangular Cu^II {[Cu₃(µ₃-OH)(µ₂-L)₄(H₂O)(NCS)₃](ClO₄)₂·H₂O; Liu et al., 2003} as well as linear trinuclear Cd^II cores {[{Cd₃(µ₂-L)₄(µ₂-NCS)₂}(µ₂-NCS)₂(NCS)₂]; L is 4-amino-3,5-dimethyltriazole; Yi et al., 2004}. We report here the crystal structures of two new coordination polymers, [Cu(btr)₂(NCS)₂](H₂O)₂, (I), and [Cd₃(btr)₄(NCS)₆], (II), that build on these ideas.

In (I), the Cu1 centers are located in general positions and possess a distorted tetragonal–pyramidal environment of five N atoms. The basal sites of the pyramid are occupied by two terminal trans-coordinated isothiocyanate groups and one N atom each from one terminal and one N¹,N^1'-bidentate btr molecule, while the apical position is occupied by the other N atom of the bidentate btr ligand (Fig. 1 and Table 1). These Cu—N_NCS bond lengths are slightly shorter than those observed in the similar five-coordinate complexes Cu(3-methylpyridine)₃(NCS)₂ [1.973 (9) and 2.194 (13) Å] and Cu(3,4-dimethylpyridine)₃(NCS)₂ [1.981 (13) and 2.215 (17) Å; Kabesova & Koziskova, 1989].

The N,N'-bidentate btr molecules link the adjacent Cu atoms [related by the symmetry operation (-x, y + 1/2, -z + 3/2)] at a distance of 9.1198 (5) Å. Their cis-location around the metal center leads to the formation of zigzag [Cu(µ₂-btr)]_n²ⁿ⁺ chains running along the b axis (Fig. 2), with corresponding Cu···Cu···Cu angles of 86.81 (1)° and separations between the translating units (x, y + 1, z) of 12.5332 (9) Å. The neighboring chains, which are related by translation along the a axis, afford tight packing with a closest Cu1···Cu1(x + 1, y, z) distance of 6.9047 (4) Å. The N¹,N¹'-coordination mode of btr is widely found (Vreugdenhil et al., 1985); however, the polymeric motif with two kinds of mono- and bidentate-coordinated btr molecules similar to (I) is uncommon. The only structural precedent is [Mn(µ₂-btr)(btr)₂(H₂O)(NCS)]NCS (Zilverentant et al., 1998).

The noncoordinated water molecules in (I) are involved in hydrogen-bonding interactions with each other [O1···O2ⁱⁱ = 2.899 (0) Å; symmetry code: (ii) x, y + 1, z] (Fig. 2). This `dimer' can be considered as a donor of two hydrogen bonds towards two btr molecules [O1···N11 = 2.997 (3) Å and O2···N2 = 2.933 (3) Å) with one weak hydrogen bond towards the S atom of an NCS^- anion [O1···S2ⁱⁱⁱ = 3.331 (2) Å; symmetry code: (iii) x + 1, y, z] (Table 2) (Desiraju & Steiner, 1999). These interactions lead to interconnection of the coordination chains into two-dimensional hydrogen-bonded layers aligned parallel to the bc plane.

The Lewis softness of the Cd²⁺ centers in (II) and their higher affinity towards NCS^- anions either as N– or as S-atom donors effects the formation of an even more complicated polymeric motif, as compared with the copper(II) complex. The structure of (II) involves two types of coordination environments (Fig. 3). Two equivalent Cd1 ions [related by the symmetry operation (i) (-x + 2, -y + 1, -z + 1)] are linked by a pair of thiocyanate-N,S bridges into centrosymmetric dimers and the distorted tetragonal–pyramidal N₄S environment of the Cd1 center is completed with two triazole-N donors and a terminal thiocyanate-N group in the apical position (Fig. 4). Within these double bridged Cd₂(µ₂-NCS)₂ dimers the Cd···Cd distance [5.7044 (9) Å] is similar to those observed in the related complex [N(C₃H₇)₄][Cd(µ₂-NCS)₂(NCS)] (5.715 and 5.856 Å; Taniguchi & Ouch, 1989). The eight-membered Cd₂(µ₂-NCS)₂ cycle possesses a "chair" conformation (displacement of the Cd1 atom out of the (NCS)₂ plane is 0.544 Å), and two terminal NCS^- anions are attached to the Cd1 ions at the opposite sides of the metallocycle. This Cd₂(µ₂-NCS)₂(NCS)₂ arrangement is scarcely found and has only two precedents in [{Cd₃(µ₂-tr)₄(µ₂-Cl)₂}(µ₂-NCS)₂(NCS)₂]·2H₂O (tr is 4-amino-3,5-diethyltriazole) (Yi et al., 2004) and (N(C₃H₇)₄)[Cd(µ₂-NCS)₂(NCS)] (Taniguchi & Ouch, 1989), with octahedral and tetragonal–pyramidal metal atoms, respectively.

The coordination environment of the second unique Cd ion is much simpler. Atom Cd2 is located on a center of inversion and has a slightly distorted octahedral environment involving four triazole N-donors in the equatorial plane and two isothiocyanates in the axial positions (Table 3).

Each (Cd1)₂(µ-NCS)₂ moiety and discrete Cd2 ion coordinates four triazole groups and this predetermines parity of their structural functions: both of them (in a 1:1 proportion) provide four-connected nodes for a planar (4,4)-network and the corresponding diagonal Cd2···Cd2^iv [symmetry code: (iv) x, y, 1 + z] separations are 13.836 Å (c parameter of the unit cell) (Figs. 3 and 4). Adjacent layers are shifted and stacked at a distance of 5.20 Å. The terminal coordinating isothiocyanates containing atoms S1 and S2 are directed inside the pores of the adjacent layer (x + 1, y, z) to afford interdigitation of the successive nets.

In both structures, the btr molecules display almost orthogonal orientation of two triazole groups, which does not depend upon coordination modes of the ligand. The dihedral angles between the planes of the triazole heterocycles lie in the range 77.58 (4)–89.99 (4)°, in good agreement with those reported for the free 4,4'-bi-1,2,4-triazole [88.12 (1)°; Domiano, 1977].

These results demonstrate that the btr molecule in combination with the nucleophilic isothiocyanate anion (N-terminal and N,S-bidentate roles) as coligand adopts monodentate and N¹,N^1'-bidentate coordination behavior toward Cu^II and Cd^II, leading to formation of low-dimensional coordination polymers.

Related literature

For related literature, see: Bartlett & Humphrey (1967); Desiraju & Steiner (1999); Domiano (1977); Drabent et al. (2004); Kabesova & Koziskova (1989); Liu et al. (1999, 2003); Lysenko et al. (2006, 2007); Taniguchi & Ouch (1989); Virovets et al. (1997); Vreugdenhil et al. (1985); Yi et al. (2004); Zilverentant et al. (1998).

S2. Experimental

All materials were of reagent grade and were used as received. The btr ligand was prepared according to the reported procedure (Bartlett et al., 1967). The precipitate obtained by mixing aqueous CuSO₄·5H₂O (0.0250 g, 0.100 mmol), CsSCN (0.0382 g, 0.200 mmol) and btr (0.0136 g, 0.100 mmol) solutions was recrystallized from water to afford green prisms of (I) (yield 83%). Evaporation of an aqueous solution (3 ml) of Cd(SCN)₂ (0.0457 g, 0.200 mmol) and btr (0.0136 g, 0.100 mmol) in a desiccator over CaCl₂ for a few days afforded colorless prisms of (II) (yield 98%).######

S3. Refinement

All H atoms were located in difference maps and included as riding atoms, with O—H distances constrained to 0.85 Å and C—H distances constrained to 0.94 Å, and with U_iso(H) values of 1.2U_eq(C) and 1.5U_eq(O).

Computing details

Data collection: IPDS Software (Stoe & Cie, 2000) for (I); CAD-4 EXPRESS (Enraf–Nonius, 1994) for (II). Cell refinement: IPDS Software (Stoe & Cie, 2000) for (I); CAD-4 EXPRESS (Enraf–Nonius, 1994) for (II). Data reduction: IPDS Software (Stoe & Cie, 2000) for (I); XCAD4 (Harms & Wocadlo, 1995) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999). Software used to prepare material for publication: WinGX (Version 1.700.00; Farrugia, 1999) for (I); SHELXL97 (Sheldrick, 2008) for (II).

Figures

	Fig. 1. A portion of the structure of (I), showing the atom-labelling scheme and copper coordination environment. Displacement ellipsoids are drawn at the 40% probability level. The dashed line represents an intermolecular hydrogen bond. [Symmetry code: (i) -x, y + 1/2, -z + 3/2.]
	Fig. 2. Intermolecular hydrogen bonds (dashed lines) in the structure of (I), providing the connection of the zigzag-like chains into two-dimensional hydrogen-bonded layers. [Symmetry codes: (iii) x + 1, y, z; (iv) x, y - 1, z.]
	Fig. 3. A portion of the structure of (II), showing the atom-labelling scheme and cadmium coordination environments. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) x, y, z - 1; (iii) -x, -y, -z; (iv) x, y, z + 1.]
	Fig. 4. The two-dimensional network in the structure of (II) contains two kinds of nodal units, [(Cd1)2(µ-NCS)2(NCS)2] and Cd2, linked by N^1,N^1'-bidentate bitriazole bridges.

(I) catena-poly[[(4,4'-bi-1,2,4-triazole-κN¹)bis(thiocyanato-κN)copper(II)]- µ-4,4'-bi-1,2,4-triazole-κ²N¹:N^1' dihydrate]

Crystal data

[Cu(NCS)2(C4H4N6)2]·2H2O	Dx = 1.713 Mg m^−3
Mr = 488.00	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 8000 reflections
a = 6.9047 (4) Å	θ = 1.9–28.0°
b = 12.5332 (9) Å	µ = 1.42 mm^−1
c = 21.8652 (18) Å	T = 213 K
V = 1892.2 (2) Å^3	Prism, green
Z = 4	0.20 × 0.18 × 0.18 mm
F(000) = 988

Data collection

Stoe IPDS diffractometer	4019 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 28.0°, θmin = 1.9°
ϕ oscillation scans	h = −8→8
18528 measured reflections	k = −16→16
4417 independent reflections	l = −28→28

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)] = 0.022	H-atom parameters constrained
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0307P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.001
4417 reflections	Δρmax = 0.26 e Å^−3
262 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1806 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (8)

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
Cu1	0.40468 (3)	0.220250 (15)	0.831398 (9)	0.01950 (5)
S1	0.79981 (9)	0.09578 (5)	0.68072 (3)	0.03784 (13)
S2	−0.13170 (9)	0.26397 (5)	0.96452 (3)	0.04031 (14)
O1	0.6274 (4)	0.94852 (15)	1.03402 (10)	0.0701 (7)
H1W	0.5809	0.8858	1.0353	0.105*
H2W	0.6482	0.9643	0.9968	0.105*
O2	0.7618 (4)	0.01984 (15)	0.91451 (11)	0.0643 (6)
H3W	0.7561	0.0841	0.9268	0.097*
H4W	0.6810	0.0121	0.8855	0.097*
N1	0.3141 (2)	0.06553 (11)	0.82787 (8)	0.0241 (3)
N2	0.4377 (2)	−0.02263 (11)	0.83130 (8)	0.0255 (3)
N3	0.1425 (2)	−0.07576 (11)	0.81393 (7)	0.0218 (3)
N4	−0.2701 (3)	−0.24093 (12)	0.81414 (7)	0.0264 (4)
N5	−0.2307 (2)	−0.22949 (12)	0.75148 (7)	0.0246 (3)
N6	−0.0146 (3)	−0.14111 (12)	0.80226 (7)	0.0227 (3)
N7	0.5203 (3)	0.36161 (12)	0.85532 (7)	0.0217 (3)
N8	0.6754 (3)	0.41012 (13)	0.82639 (8)	0.0326 (4)
N9	0.6022 (3)	0.49857 (11)	0.90889 (7)	0.0239 (3)
N10	0.6811 (3)	0.64115 (16)	1.04494 (8)	0.0407 (5)
N11	0.5754 (3)	0.71456 (14)	1.01082 (8)	0.0378 (4)
N12	0.6122 (3)	0.57128 (12)	0.95664 (7)	0.0255 (3)
N13	0.6402 (3)	0.17816 (13)	0.78821 (8)	0.0288 (4)
N14	0.1825 (3)	0.24998 (13)	0.88514 (8)	0.0298 (4)
C1	0.1385 (3)	0.03238 (14)	0.81808 (9)	0.0266 (4)
H1	0.0279	0.0757	0.8145	0.032*
C2	0.3286 (3)	−0.10618 (14)	0.82260 (9)	0.0255 (4)
H2	0.3727	−0.1771	0.8224	0.031*
C3	−0.1371 (3)	−0.18731 (15)	0.84297 (8)	0.0268 (4)
H3	−0.1272	−0.1814	0.8857	0.032*
C4	−0.0788 (3)	−0.17001 (14)	0.74566 (8)	0.0273 (4)
H4	−0.0217	−0.1499	0.7084	0.033*
C5	0.4781 (3)	0.41586 (14)	0.90471 (8)	0.0234 (4)
H5	0.3784	0.3999	0.9325	0.028*
C6	0.7224 (4)	0.49264 (17)	0.85969 (10)	0.0359 (5)
H6	0.8236	0.5405	0.8510	0.043*
C7	0.7026 (4)	0.55633 (18)	1.01149 (10)	0.0361 (5)
H7	0.7699	0.4944	1.0232	0.043*
C8	0.5355 (4)	0.67114 (16)	0.95857 (10)	0.0340 (5)
H8	0.4647	0.7036	0.9269	0.041*
C9	0.7048 (3)	0.14259 (14)	0.74378 (9)	0.0248 (4)
C10	0.0517 (3)	0.25614 (14)	0.91798 (8)	0.0256 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01990 (11)	0.01771 (9)	0.02089 (9)	−0.00181 (8)	0.00063 (9)	−0.00212 (8)
S1	0.0364 (3)	0.0397 (3)	0.0374 (3)	0.0022 (2)	0.0087 (2)	−0.0123 (2)
S2	0.0360 (4)	0.0467 (3)	0.0382 (3)	0.0068 (2)	0.0163 (2)	0.0070 (2)
O1	0.0974 (19)	0.0427 (10)	0.0704 (13)	0.0047 (11)	−0.0371 (14)	−0.0124 (9)
O2	0.0622 (15)	0.0491 (11)	0.0817 (15)	−0.0008 (10)	−0.0313 (12)	−0.0055 (10)
N1	0.0220 (9)	0.0172 (6)	0.0331 (8)	−0.0026 (5)	−0.0033 (7)	−0.0001 (6)
N2	0.0207 (9)	0.0222 (6)	0.0336 (8)	−0.0018 (6)	−0.0036 (7)	−0.0005 (7)
N3	0.0227 (10)	0.0181 (7)	0.0247 (7)	−0.0051 (6)	−0.0048 (6)	−0.0005 (5)
N4	0.0269 (10)	0.0273 (8)	0.0250 (7)	−0.0052 (6)	0.0008 (6)	−0.0005 (6)
N5	0.0266 (9)	0.0242 (7)	0.0229 (7)	−0.0049 (7)	−0.0021 (6)	−0.0002 (7)
N6	0.0219 (9)	0.0222 (7)	0.0240 (8)	−0.0076 (6)	−0.0042 (6)	−0.0023 (6)
N7	0.0245 (9)	0.0189 (7)	0.0218 (7)	−0.0023 (6)	0.0007 (6)	−0.0030 (6)
N8	0.0390 (11)	0.0279 (8)	0.0309 (9)	−0.0113 (7)	0.0149 (8)	−0.0082 (8)
N9	0.0260 (9)	0.0220 (7)	0.0238 (7)	−0.0035 (7)	0.0031 (7)	−0.0073 (5)
N10	0.0497 (14)	0.0435 (10)	0.0290 (9)	−0.0039 (9)	−0.0021 (9)	−0.0108 (8)
N11	0.0473 (13)	0.0311 (8)	0.0350 (8)	−0.0018 (9)	0.0000 (8)	−0.0152 (7)
N12	0.0290 (10)	0.0227 (7)	0.0246 (7)	−0.0013 (7)	−0.0001 (7)	−0.0090 (6)
N13	0.0263 (11)	0.0226 (7)	0.0374 (9)	−0.0014 (7)	0.0072 (7)	−0.0040 (7)
N14	0.0274 (10)	0.0336 (9)	0.0284 (8)	−0.0064 (7)	0.0061 (7)	−0.0053 (6)
C1	0.0269 (12)	0.0204 (8)	0.0326 (10)	−0.0012 (7)	−0.0035 (8)	−0.0003 (7)
C2	0.0246 (11)	0.0204 (8)	0.0315 (10)	−0.0005 (7)	−0.0013 (8)	−0.0002 (7)
C3	0.0302 (12)	0.0272 (8)	0.0230 (9)	−0.0063 (7)	−0.0005 (7)	−0.0002 (7)
C4	0.0315 (12)	0.0291 (9)	0.0213 (8)	−0.0071 (9)	−0.0027 (9)	−0.0002 (7)
C5	0.0258 (11)	0.0212 (8)	0.0232 (8)	−0.0018 (7)	0.0029 (7)	−0.0028 (7)
C6	0.0398 (15)	0.0300 (10)	0.0378 (12)	−0.0121 (9)	0.0161 (10)	−0.0097 (9)
C7	0.0454 (16)	0.0337 (11)	0.0293 (11)	0.0014 (10)	−0.0060 (10)	−0.0044 (9)
C8	0.0464 (15)	0.0246 (9)	0.0309 (10)	0.0019 (9)	−0.0032 (10)	−0.0051 (8)
C9	0.0229 (11)	0.0175 (8)	0.0339 (10)	0.0002 (7)	−0.0005 (9)	0.0005 (7)
C10	0.0284 (12)	0.0261 (9)	0.0222 (8)	−0.0018 (7)	−0.0032 (7)	0.0005 (7)

Geometric parameters (Å, º)

Cu1—N13	1.9530 (18)	N6—C4	1.364 (2)
Cu1—N14	1.9678 (18)	N7—C5	1.309 (2)
Cu1—N7	2.0124 (15)	N7—N8	1.385 (2)
Cu1—N1	2.0390 (14)	N8—C6	1.306 (3)
Cu1—N5^i	2.2637 (15)	N9—C5	1.348 (2)
S1—C9	1.636 (2)	N9—C6	1.361 (3)
S2—C10	1.627 (2)	N9—N12	1.387 (2)
O1—H1W	0.8500	N10—C7	1.299 (3)
O1—H2W	0.8500	N10—N11	1.391 (3)
O2—H3W	0.8500	N11—C8	1.295 (3)
O2—H4W	0.8500	N12—C8	1.359 (3)
N1—C1	1.299 (3)	N12—C7	1.365 (3)
N1—N2	1.398 (2)	N13—C9	1.158 (3)
N2—C2	1.304 (2)	N14—C10	1.157 (3)
N3—C2	1.354 (3)	C1—H1	0.9400
N3—C1	1.359 (2)	C2—H2	0.9400
N3—N6	1.383 (2)	C3—H3	0.9400
N4—C3	1.301 (3)	C4—H4	0.9400
N4—N5	1.404 (2)	C5—H5	0.9400
N5—C4	1.293 (3)	C6—H6	0.9400
N5—Cu1^ii	2.2637 (15)	C7—H7	0.9400
N6—C3	1.358 (3)	C8—H8	0.9400
N13—Cu1—N14	171.45 (8)	C7—N10—N11	107.43 (18)
N13—Cu1—N7	91.90 (7)	C8—N11—N10	107.86 (17)
N14—Cu1—N7	89.27 (7)	C8—N12—C7	106.08 (16)
N13—Cu1—N1	88.87 (7)	C8—N12—N9	127.49 (17)
N14—Cu1—N1	87.91 (7)	C7—N12—N9	126.42 (17)
N7—Cu1—N1	165.65 (7)	C9—N13—Cu1	146.11 (18)
N13—Cu1—N5^i	97.47 (7)	C10—N14—Cu1	172.84 (16)
N14—Cu1—N5^i	90.67 (7)	N1—C1—N3	108.12 (17)
N7—Cu1—N5^i	100.00 (6)	N1—C1—H1	125.9
N1—Cu1—N5^i	94.09 (6)	N3—C1—H1	125.9
H1W—O1—H2W	108.1	N2—C2—N3	110.04 (16)
H3W—O2—H4W	108.3	N2—C2—H2	125.0
C1—N1—N2	109.01 (15)	N3—C2—H2	125.0
C1—N1—Cu1	126.63 (13)	N4—C3—N6	110.02 (16)
N2—N1—Cu1	124.20 (12)	N4—C3—H3	125.0
C2—N2—N1	105.91 (15)	N6—C3—H3	125.0
C2—N3—C1	106.91 (16)	N5—C4—N6	109.11 (17)
C2—N3—N6	127.12 (15)	N5—C4—H4	125.4
C1—N3—N6	125.96 (17)	N6—C4—H4	125.4
C3—N4—N5	106.45 (16)	N7—C5—N9	108.31 (17)
C4—N5—N4	108.19 (15)	N7—C5—H5	125.8
C4—N5—Cu1^ii	120.80 (12)	N9—C5—H5	125.8
N4—N5—Cu1^ii	130.53 (12)	N8—C6—N9	109.40 (19)
C3—N6—C4	106.22 (16)	N8—C6—H6	125.3
C3—N6—N3	128.33 (16)	N9—C6—H6	125.3
C4—N6—N3	125.44 (17)	N10—C7—N12	109.3 (2)
C5—N7—N8	108.72 (15)	N10—C7—H7	125.4
C5—N7—Cu1	125.70 (14)	N12—C7—H7	125.4
N8—N7—Cu1	125.07 (12)	N11—C8—N12	109.36 (19)
C6—N8—N7	106.58 (16)	N11—C8—H8	125.3
C5—N9—C6	106.98 (15)	N12—C8—H8	125.3
C5—N9—N12	126.01 (17)	N13—C9—S1	178.21 (18)
C6—N9—N12	126.89 (17)	N14—C10—S2	179.5 (2)
N13—Cu1—N1—C1	−140.90 (18)	N7—Cu1—N13—C9	−132.5 (3)
N14—Cu1—N1—C1	47.02 (18)	N1—Cu1—N13—C9	61.8 (3)
N7—Cu1—N1—C1	125.8 (3)	N5^i—Cu1—N13—C9	−32.2 (3)
N5^i—Cu1—N1—C1	−43.49 (18)	N2—N1—C1—N3	−1.0 (2)
N13—Cu1—N1—N2	34.10 (15)	Cu1—N1—C1—N3	174.67 (13)
N14—Cu1—N1—N2	−137.97 (16)	C2—N3—C1—N1	0.9 (2)
N7—Cu1—N1—N2	−59.2 (4)	N6—N3—C1—N1	−178.35 (17)
N5^i—Cu1—N1—N2	131.51 (15)	N1—N2—C2—N3	−0.1 (2)
C1—N1—N2—C2	0.7 (2)	C1—N3—C2—N2	−0.5 (2)
Cu1—N1—N2—C2	−175.09 (14)	N6—N3—C2—N2	178.76 (17)
C3—N4—N5—C4	−0.3 (2)	N5—N4—C3—N6	0.5 (2)
C3—N4—N5—Cu1^ii	−172.24 (14)	C4—N6—C3—N4	−0.4 (2)
C2—N3—N6—C3	90.5 (3)	N3—N6—C3—N4	178.33 (17)
C1—N3—N6—C3	−90.4 (3)	N4—N5—C4—N6	0.0 (2)
C2—N3—N6—C4	−91.0 (3)	Cu1^ii—N5—C4—N6	172.90 (12)
C1—N3—N6—C4	88.1 (3)	C3—N6—C4—N5	0.2 (2)
N13—Cu1—N7—C5	−150.32 (17)	N3—N6—C4—N5	−178.59 (17)
N14—Cu1—N7—C5	21.21 (18)	N8—N7—C5—N9	−0.1 (2)
N1—Cu1—N7—C5	−57.4 (4)	Cu1—N7—C5—N9	172.04 (13)
N5^i—Cu1—N7—C5	111.75 (17)	C6—N9—C5—N7	0.1 (2)
N13—Cu1—N7—N8	20.63 (16)	N12—N9—C5—N7	−176.06 (18)
N14—Cu1—N7—N8	−167.84 (16)	N7—N8—C6—N9	−0.1 (3)
N1—Cu1—N7—N8	113.5 (3)	C5—N9—C6—N8	0.0 (3)
N5^i—Cu1—N7—N8	−77.29 (16)	N12—N9—C6—N8	176.12 (19)
C5—N7—N8—C6	0.2 (2)	N11—N10—C7—N12	−0.7 (3)
Cu1—N7—N8—C6	−172.07 (16)	C8—N12—C7—N10	0.5 (3)
C7—N10—N11—C8	0.7 (3)	N9—N12—C7—N10	−179.6 (2)
C5—N9—N12—C8	−99.4 (3)	N10—N11—C8—N12	−0.3 (3)
C6—N9—N12—C8	85.2 (3)	C7—N12—C8—N11	−0.1 (3)
C5—N9—N12—C7	80.8 (3)	N9—N12—C8—N11	−179.9 (2)
C6—N9—N12—C7	−94.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···N11	0.85	2.21	2.997 (3)	154
O1—H2W···O2^iii	0.85	2.08	2.914 (3)	166
O2—H3W···S2^iv	0.85	2.52	3.331 (2)	159
O2—H4W···N2	0.85	2.10	2.933 (3)	166

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

(II) poly[bis(µ-thiocyanato-κ²N:S)tetrakis(thiocyanato-κN)tetrakis(µ-4,4'- bi-1,2,4-triazole-κ²N¹:N^1')tricadmium(II)]

Crystal data

[Cd3(NCS)6(C4H4N6)4]	Z = 1
Mr = 1230.21	F(000) = 598
Triclinic, P1	Dx = 2.026 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.092 (1) Å	Cell parameters from 22 reflections
b = 10.4867 (18) Å	θ = 12.1–17.8°
c = 13.836 (2) Å	µ = 1.94 mm^−1
α = 87.440 (18)°	T = 298 K
β = 81.158 (16)°	Prism, colorless
γ = 82.847 (11)°	0.40 × 0.25 × 0.12 mm
V = 1008.5 (3) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	3813 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
non–profiled ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
Tmin = 0.511, Tmax = 0.800	l = −18→18
5237 measured reflections	3 standard reflections every 120 min
4853 independent reflections	intensity decay: none

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.079P] where P = (Fo^2 + 2Fc^2)/3
4853 reflections	(Δ/σ)max = 0.001
277 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.63 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
Cd1	0.74354 (3)	0.37189 (2)	0.409603 (15)	0.02879 (7)
Cd2	0.0000	0.0000	0.0000	0.02410 (8)
S1	0.44852 (19)	−0.32200 (10)	0.14859 (8)	0.0595 (3)
S2	1.14967 (16)	−0.04039 (12)	0.33967 (11)	0.0635 (3)
S3	1.05782 (13)	0.46097 (9)	0.69250 (6)	0.03770 (19)
N1	0.4891 (4)	0.2901 (3)	0.51075 (19)	0.0366 (6)
N2	0.3557 (5)	0.2315 (4)	0.4704 (2)	0.0563 (10)
N3	0.3515 (4)	0.1684 (3)	0.62208 (17)	0.0291 (5)
N4	0.3156 (4)	0.0950 (2)	0.70704 (17)	0.0283 (5)
N5	0.1980 (4)	0.0290 (3)	0.85035 (19)	0.0333 (6)
N6	0.3276 (4)	−0.0699 (3)	0.8073 (2)	0.0387 (7)
N7	0.6982 (4)	0.3887 (3)	0.19224 (18)	0.0317 (6)
N8	0.5744 (4)	0.3779 (3)	0.27976 (18)	0.0302 (6)
N9	0.4234 (4)	0.3403 (2)	0.16256 (17)	0.0258 (5)
N10	0.2841 (4)	0.3071 (2)	0.11294 (18)	0.0264 (5)
N11	0.1116 (4)	0.1904 (3)	0.04664 (19)	0.0314 (6)
N12	0.0499 (4)	0.3191 (3)	0.02676 (19)	0.0322 (6)
N13	0.2451 (5)	−0.1146 (3)	0.0635 (2)	0.0452 (7)
N14	0.9291 (6)	0.1925 (4)	0.3776 (3)	0.0641 (10)
N15	0.8231 (5)	0.4194 (4)	0.5548 (2)	0.0513 (9)
C1	0.4844 (4)	0.2503 (3)	0.6014 (2)	0.0311 (7)
H1	0.5614	0.2749	0.6452	0.037*
C2	0.2750 (6)	0.1589 (4)	0.5384 (2)	0.0524 (11)
H2	0.1787	0.1076	0.5312	0.063*
C3	0.1929 (5)	0.1262 (3)	0.7895 (2)	0.0350 (7)
H3	0.1163	0.2055	0.8008	0.042*
C4	0.3938 (5)	−0.0277 (3)	0.7209 (3)	0.0387 (8)
H4	0.4829	−0.0753	0.6747	0.046*
C5	0.6043 (4)	0.3643 (3)	0.1238 (2)	0.0299 (6)
H5	0.6537	0.3632	0.0568	0.036*
C6	0.4110 (4)	0.3484 (3)	0.2609 (2)	0.0283 (6)
H6	0.3032	0.3352	0.3074	0.034*
C7	0.2519 (5)	0.1862 (3)	0.0968 (2)	0.0347 (7)
H7	0.3208	0.1108	0.1186	0.042*
C8	0.1557 (4)	0.3861 (3)	0.0677 (2)	0.0309 (6)
H8	0.1454	0.4764	0.0663	0.037*
C9	0.3274 (5)	−0.2004 (3)	0.1001 (2)	0.0316 (7)
C10	1.0222 (5)	0.0961 (4)	0.3610 (2)	0.0382 (8)
C11	0.9227 (5)	0.4352 (3)	0.6101 (2)	0.0355 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02856 (12)	0.03616 (14)	0.02446 (11)	−0.01177 (10)	−0.00723 (8)	0.00183 (9)
Cd2	0.02865 (15)	0.02530 (15)	0.02016 (14)	−0.00849 (12)	−0.00617 (11)	0.00327 (11)
S1	0.0860 (8)	0.0392 (5)	0.0544 (6)	0.0126 (5)	−0.0307 (6)	0.0032 (4)
S2	0.0403 (5)	0.0506 (6)	0.0990 (9)	0.0011 (5)	−0.0085 (6)	−0.0191 (6)
S3	0.0413 (5)	0.0449 (5)	0.0318 (4)	−0.0181 (4)	−0.0121 (3)	0.0057 (3)
N1	0.0338 (14)	0.0518 (18)	0.0283 (13)	−0.0206 (13)	−0.0074 (11)	0.0084 (12)
N2	0.061 (2)	0.092 (3)	0.0277 (14)	−0.051 (2)	−0.0154 (14)	0.0186 (16)
N3	0.0301 (13)	0.0384 (15)	0.0202 (11)	−0.0133 (11)	−0.0031 (9)	0.0069 (10)
N4	0.0306 (13)	0.0324 (14)	0.0216 (11)	−0.0088 (11)	−0.0011 (10)	0.0057 (10)
N5	0.0401 (15)	0.0331 (14)	0.0268 (13)	−0.0100 (12)	−0.0023 (11)	0.0036 (11)
N6	0.0457 (17)	0.0319 (15)	0.0351 (14)	−0.0044 (13)	0.0021 (12)	0.0073 (12)
N7	0.0316 (14)	0.0383 (15)	0.0273 (12)	−0.0114 (12)	−0.0061 (10)	0.0014 (11)
N8	0.0315 (13)	0.0384 (15)	0.0229 (12)	−0.0092 (11)	−0.0077 (10)	0.0013 (10)
N9	0.0283 (12)	0.0272 (13)	0.0242 (12)	−0.0065 (10)	−0.0095 (10)	0.0004 (9)
N10	0.0295 (13)	0.0231 (12)	0.0296 (12)	−0.0057 (10)	−0.0122 (10)	0.0001 (9)
N11	0.0370 (14)	0.0282 (13)	0.0326 (13)	−0.0084 (11)	−0.0129 (11)	−0.0007 (10)
N12	0.0307 (13)	0.0332 (14)	0.0350 (14)	−0.0057 (11)	−0.0116 (11)	0.0014 (11)
N13	0.0476 (18)	0.0438 (18)	0.0463 (17)	0.0010 (15)	−0.0202 (14)	0.0026 (14)
N14	0.069 (3)	0.052 (2)	0.073 (3)	0.0107 (19)	−0.027 (2)	−0.0078 (19)
N15	0.058 (2)	0.070 (2)	0.0351 (16)	−0.0385 (18)	−0.0091 (14)	−0.0026 (15)
C1	0.0305 (15)	0.0382 (18)	0.0269 (14)	−0.0117 (13)	−0.0065 (12)	0.0048 (12)
C2	0.056 (2)	0.084 (3)	0.0261 (16)	−0.044 (2)	−0.0120 (16)	0.0114 (17)
C3	0.0389 (18)	0.0356 (17)	0.0266 (15)	−0.0011 (14)	0.0029 (13)	0.0039 (13)
C4	0.0439 (19)	0.0346 (18)	0.0345 (17)	−0.0020 (15)	0.0015 (14)	0.0007 (14)
C5	0.0322 (16)	0.0331 (16)	0.0254 (14)	−0.0091 (13)	−0.0038 (12)	−0.0004 (12)
C6	0.0291 (15)	0.0339 (16)	0.0236 (13)	−0.0065 (13)	−0.0068 (11)	−0.0007 (11)
C7	0.0425 (18)	0.0260 (16)	0.0402 (17)	−0.0064 (13)	−0.0190 (14)	0.0002 (13)
C8	0.0315 (16)	0.0255 (15)	0.0374 (16)	−0.0042 (12)	−0.0104 (13)	0.0015 (12)
C9	0.0367 (17)	0.0331 (17)	0.0265 (14)	−0.0051 (14)	−0.0079 (12)	−0.0033 (12)
C10	0.0339 (17)	0.049 (2)	0.0352 (17)	−0.0096 (16)	−0.0119 (14)	0.0002 (15)
C11	0.0414 (18)	0.0387 (18)	0.0288 (15)	−0.0198 (15)	−0.0002 (13)	−0.0005 (13)

Geometric parameters (Å, º)

Cd1—N14	2.178 (4)	N5—Cd2^v	2.347 (3)
Cd1—N15	2.261 (3)	N6—C4	1.294 (4)
Cd1—N8	2.303 (2)	N7—C5	1.289 (4)
Cd1—N1	2.335 (3)	N7—N8	1.391 (3)
Cd1—S3^i	2.6142 (10)	N8—C6	1.302 (4)
Cd2—N13	2.256 (3)	N9—C6	1.356 (4)
Cd2—N13^ii	2.256 (3)	N9—C5	1.361 (4)
Cd2—N5^iii	2.347 (3)	N9—N10	1.373 (3)
Cd2—N5^iv	2.347 (3)	N10—C7	1.350 (4)
Cd2—N11	2.386 (3)	N10—C8	1.359 (4)
Cd2—N11^ii	2.386 (3)	N11—C7	1.293 (4)
S1—C9	1.625 (3)	N11—N12	1.395 (4)
S2—C10	1.609 (4)	N12—C8	1.294 (4)
S3—C11	1.649 (3)	N13—C9	1.152 (4)
S3—Cd1^i	2.6142 (10)	N14—C10	1.148 (5)
N1—C1	1.300 (4)	N15—C11	1.148 (4)
N1—N2	1.386 (4)	C1—H1	0.9400
N2—C2	1.292 (4)	C2—H2	0.9400
N3—C1	1.344 (4)	C3—H3	0.9400
N3—C2	1.365 (4)	C4—H4	0.9400
N3—N4	1.384 (3)	C5—H5	0.9400
N4—C3	1.351 (4)	C6—H6	0.9400
N4—C4	1.354 (4)	C7—H7	0.9400
N5—C3	1.293 (4)	C8—H8	0.9400
N5—N6	1.387 (4)
N14—Cd1—N15	101.05 (14)	C6—N8—Cd1	139.2 (2)
N14—Cd1—N8	98.51 (12)	N7—N8—Cd1	109.84 (18)
N15—Cd1—N8	159.79 (13)	C6—N9—C5	106.4 (2)
N14—Cd1—N1	98.97 (14)	C6—N9—N10	126.4 (2)
N15—Cd1—N1	82.24 (10)	C5—N9—N10	127.1 (2)
N8—Cd1—N1	89.75 (9)	C7—N10—C8	105.9 (2)
N14—Cd1—S3^i	101.73 (12)	C7—N10—N9	125.9 (3)
N15—Cd1—S3^i	95.07 (8)	C8—N10—N9	128.2 (2)
N8—Cd1—S3^i	85.87 (7)	C7—N11—N12	108.2 (3)
N1—Cd1—S3^i	159.25 (8)	C7—N11—Cd2	122.0 (2)
N13—Cd2—N13^ii	180.0	N12—N11—Cd2	129.83 (18)
N13—Cd2—N5^iii	88.62 (11)	C8—N12—N11	106.3 (2)
N13^ii—Cd2—N5^iii	91.38 (11)	C9—N13—Cd2	158.1 (3)
N13—Cd2—N5^iv	91.38 (11)	C10—N14—Cd1	178.0 (4)
N13^ii—Cd2—N5^iv	88.62 (11)	C11—N15—Cd1	157.0 (3)
N5^iii—Cd2—N5^iv	180.0	N1—C1—N3	108.9 (3)
N13—Cd2—N11	88.09 (11)	N1—C1—H1	125.6
N13^ii—Cd2—N11	91.91 (11)	N3—C1—H1	125.6
N5^iii—Cd2—N11	94.85 (9)	N2—C2—N3	109.4 (3)
N5^iv—Cd2—N11	85.15 (9)	N2—C2—H2	125.3
N13—Cd2—N11^ii	91.91 (11)	N3—C2—H2	125.3
N13^ii—Cd2—N11^ii	88.09 (11)	N5—C3—N4	108.8 (3)
N5^iii—Cd2—N11^ii	85.15 (9)	N5—C3—H3	125.6
N5^iv—Cd2—N11^ii	94.85 (9)	N4—C3—H3	125.6
N11—Cd2—N11^ii	180.0	N6—C4—N4	110.0 (3)
C11—S3—Cd1^i	97.73 (11)	N6—C4—H4	125.0
C1—N1—N2	108.2 (3)	N4—C4—H4	125.0
C1—N1—Cd1	127.3 (2)	N7—C5—N9	110.3 (3)
N2—N1—Cd1	120.2 (2)	N7—C5—H5	124.8
C2—N2—N1	107.0 (3)	N9—C5—H5	124.8
C1—N3—C2	106.5 (3)	N8—C6—N9	108.0 (3)
C1—N3—N4	127.0 (2)	N8—C6—H6	126.0
C2—N3—N4	126.0 (3)	N9—C6—H6	126.0
C3—N4—C4	106.3 (3)	N11—C7—N10	109.4 (3)
C3—N4—N3	128.4 (3)	N11—C7—H7	125.3
C4—N4—N3	125.2 (3)	N10—C7—H7	125.3
C3—N5—N6	108.6 (3)	N12—C8—N10	110.2 (3)
C3—N5—Cd2^v	128.8 (2)	N12—C8—H8	124.9
N6—N5—Cd2^v	122.09 (19)	N10—C8—H8	124.9
C4—N6—N5	106.4 (3)	N13—C9—S1	178.2 (3)
C5—N7—N8	106.2 (2)	N14—C10—S2	178.8 (4)
C6—N8—N7	109.0 (2)	N15—C11—S3	177.6 (4)
N14—Cd1—N1—C1	75.6 (3)	C7—N11—N12—C8	−0.9 (4)
N15—Cd1—N1—C1	−24.4 (3)	Cd2—N11—N12—C8	−179.8 (2)
N8—Cd1—N1—C1	174.2 (3)	N5^iii—Cd2—N13—C9	56.1 (8)
S3^i—Cd1—N1—C1	−108.2 (3)	N5^iv—Cd2—N13—C9	−123.9 (8)
N14—Cd1—N1—N2	−78.2 (3)	N11—Cd2—N13—C9	151.0 (8)
N15—Cd1—N1—N2	−178.3 (3)	N11^ii—Cd2—N13—C9	−29.0 (8)
N8—Cd1—N1—N2	20.3 (3)	N14—Cd1—N15—C11	49.6 (8)
S3^i—Cd1—N1—N2	97.9 (3)	N8—Cd1—N15—C11	−145.2 (7)
C1—N1—N2—C2	0.2 (5)	N1—Cd1—N15—C11	147.3 (8)
Cd1—N1—N2—C2	158.6 (3)	S3^i—Cd1—N15—C11	−53.4 (8)
C1—N3—N4—C3	90.0 (4)	N2—N1—C1—N3	−0.4 (4)
C2—N3—N4—C3	−99.0 (5)	Cd1—N1—C1—N3	−156.8 (2)
C1—N3—N4—C4	−93.5 (4)	C2—N3—C1—N1	0.5 (4)
C2—N3—N4—C4	77.6 (5)	N4—N3—C1—N1	172.9 (3)
C3—N5—N6—C4	−0.8 (4)	N1—N2—C2—N3	0.1 (5)
Cd2^v—N5—N6—C4	171.6 (2)	C1—N3—C2—N2	−0.3 (5)
C5—N7—N8—C6	−0.5 (4)	N4—N3—C2—N2	−172.9 (3)
C5—N7—N8—Cd1	166.8 (2)	N6—N5—C3—N4	−0.1 (4)
N14—Cd1—N8—C6	97.4 (4)	Cd2^v—N5—C3—N4	−171.8 (2)
N15—Cd1—N8—C6	−67.8 (5)	C4—N4—C3—N5	0.8 (4)
N1—Cd1—N8—C6	−1.6 (4)	N3—N4—C3—N5	177.9 (3)
S3^i—Cd1—N8—C6	−161.3 (3)	N5—N6—C4—N4	1.3 (4)
N14—Cd1—N8—N7	−64.0 (2)	C3—N4—C4—N6	−1.3 (4)
N15—Cd1—N8—N7	130.7 (3)	N3—N4—C4—N6	−178.5 (3)
N1—Cd1—N8—N7	−163.0 (2)	N8—N7—C5—N9	1.1 (4)
S3^i—Cd1—N8—N7	37.30 (19)	C6—N9—C5—N7	−1.4 (4)
C6—N9—N10—C7	−83.6 (4)	N10—N9—C5—N7	−178.0 (3)
C5—N9—N10—C7	92.4 (4)	N7—N8—C6—N9	−0.4 (4)
C6—N9—N10—C8	98.7 (4)	Cd1—N8—C6—N9	−161.8 (2)
C5—N9—N10—C8	−85.3 (4)	C5—N9—C6—N8	1.0 (3)
N13—Cd2—N11—C7	−5.5 (3)	N10—N9—C6—N8	177.7 (3)
N13^ii—Cd2—N11—C7	174.6 (3)	N12—N11—C7—N10	1.2 (4)
N5^iii—Cd2—N11—C7	83.0 (3)	Cd2—N11—C7—N10	−179.8 (2)
N5^iv—Cd2—N11—C7	−97.0 (3)	C8—N10—C7—N11	−1.0 (4)
N13—Cd2—N11—N12	173.3 (3)	N9—N10—C7—N11	−179.1 (3)
N13^ii—Cd2—N11—N12	−6.7 (3)	N11—N12—C8—N10	0.2 (3)
N5^iii—Cd2—N11—N12	−98.2 (3)	C7—N10—C8—N12	0.5 (4)
N5^iv—Cd2—N11—N12	81.8 (3)	N9—N10—C8—N12	178.5 (3)

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