The two-dimensional coordination polymer poly[di­aqua­(μ₂-1H-imid­azo[4,5-f][1,10]phenanthroline)-μ₄-sulfato-μ₃-sulfato-dicadmium(II)]

In the title coordination polymer, [Cd₂(SO₄)₂(C₁₃H₈N₄)(H₂O)₂]_n, there are two crystallographically independent Cd^II centres with different coordination geometries. The first Cd^II centre is hexacoordinated by four O atoms of four sulfate ligands, one water O atom and one N atom of a 1H-imid­azo[4,5-f][1,10]phenanthroline (IP) ligand, giving a distorted octa­hedral coordination environment. The second Cd^II centre is heptacoordinated by four O atoms of three sulfate ligands, one water O atom and two N atoms of one chelating IP ligand, resulting in a distorted monocapped anti-trigonal prismatic geometry. The symmetry-independent Cd^II ions are bridged in an alternating fashion by sulfate ligands, forming one-dimensional ladder-like chains which are connected through the IP ligands to form two-dimensional layers. These two-dimensional layers are linked by inter­layer hydrogen bonds, leading to the formation of a three-dimensional supra­molecular network.

S1. Introduction

The design of metal–organic coordination polymers has recently been well developed. Up to now, the control of the architecture still remained a major challenge in this field, due to the fact that the self-assembly process is frequently influenced by many factors. The impact of the anions is important in the coordination process, especially when they can be directly coordinated to the metal centres (Carlucci et al., 2000). In particular, doubly charged anions like sulfate are likely to enter the inner coordination sphere of metal complexes (Rao et al., 2006; Rahmani et al., 1996; Carlucci et al., 2003). Some preternatural examples of coordintion polymers containing sulfate ion have been reported in recent years (Wang et al., 2011). 1H-Imidazo[4,5-f][1,10]phenanthroline (IP) is an important derivative of 1,10-phenanthroline that has been used to recognize the secondary structure of DNA in Ru^II complexes (Xiong et al., 1999). From the viewpoint of crystal engineering, the IP ligand can be a good building block (Huang et al., 2012). In this context, we present the preparation and X-ray characterization of the title Cd^II coordination polymer, [Cd₂(SO₄)₂(IP)(H₂O)₂]_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

1H-Imidazo[4,5-f][1,10]phenanthroline (10 mmol), CdSO₄ (10 mmol) and 2,2-di­thiodi­benzoic acid (10 mmol) were dissolved in an N,N-di­methyl­formamide/water solution (1:100 v/v). The mixture was sealed in a 25 ml Teflon-lined stainless steel bomb and held at 403 K for 120 h. The bomb was allowed to cool naturally to room temperature and brown prismatic crystals were obtained from the filtered solution. Analysis calculated for C₁₃H₁₂Cd₂N₄O₁₀S₂: C 23.19, H 1.80, N 8.32%; found: C 23.10, H 1.76, N 8.30%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å and U_iso(H) = 1.2U_eq(C), and were refined using a riding-model approximation. The H atoms of the water molecule were located in a difference Fourier map and refined with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O).

S3. Results and discussion

As depicted in Fig. 1, each asymmetric unit of (I) consists of two crystallographically independent Cd^II centres with different coordination geometries. The first Cd^II centre (Cd1) is coordinated by four O atoms of two adjacent sulfate molecules, one coordinated water molecule and one N atom of the IP ligand, forming a distorted o­cta­hedral coordination environment. A plane is defined by atoms O6, OW2, O4ⁱⁱ and N3ⁱⁱⁱ [symmetry codes: (ii) -x+3/2, y-1/2, -z+3/2; (iii) -x+1, -y+1, -z+1], while the O1 and O2ⁱ atoms lie mutually trans [O1—Cd1—O2ⁱ = 172.48 (6)°; see Table 2 for details and symmetry code]. The second Cd^II centre (Cd2) is seven-coordinated by four O atoms of two adjacent sulfate ligands, one coordinated water molecule and two N atoms of one chelating IP ligand, exhibiting a distorted monocapped anti-trigonal prismatic geometry. The Cd—O distances fall in the range 2.2408 (18)–2.4782 (18) Å and the Cd—N distances vary from 2.314 (2) to 2.337 (2) Å, which are similar to those in related cadmium coodination polymers with N/O donors (Jacqueline et al., 2010). The bond angles around Cd1 range from 74.56 (6) to 172.48 (6)°, and those around Cd2 range from 56.53 (6) to 157.64 (7) ° (Table 2). As illustrated in Fig. 2, the inorganic ribbon motif substructure consists of two identical one-dimensional chains of distorted Cd1 o­cta­hedra (red polyhedra) and distorted anti-trigonal Cd2 prisms (blue polyhedra), which are linked by sharing corners (O1 from sulfate S2) and edges (O2 from sulfate S2) and O2 from sulfate S1). The ribbon motif observed in this network originates from an aggregation of two one-dimensional chains via ligation of three O atoms of sulfate S2 groups. In the ribbon motif, the Cd1 and Cd2 atoms are alternately bridged by O atoms from two sulfate ligands, the adjacent separations in the same one one-dimensional chains Cd1···Cd1 (and Cd2···Cd2) and Cd1···Cd2 are 6.087 (the unit-cell b dimension) and 4.205 Å, respectively, while the two chain Cd1···Cd1, Cd2···Cd2 and Cd1···Cd2 distances are 5.432, 9.184 and 6.341 Å, respectively. The ribbon motif chains are bridged by the IP ligands, forming the two-dimensional layer structure (Fig. 3). Furthermore, these layers are stabilized by inter­molecular hydrogen bonds, which are formed between the coordinated water molecules and sulfate O atoms, leading to the formation of a three-dimensional supra­molecular network (Fig. 4 and Table 3).

Related literature

For related literature, see: Carlucci et al. (2000, 2003); Huang et al. (2012); Jacqueline et al. (2010); Rahmani et al. (1996); Rao et al. (2006); Wang et al. (2011); Xiong et al. (1999).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), shown with 30% probability displacement ellipsoids. [Symmetry codes: (i) x, y-1, z; (ii) -x+3/2,y-1/2, -z+3/2; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z.]
	Fig. 2. Part of the one-dimensional ribbon motif structure of (I).
	Fig. 3. Part of the two-dimensional layer structure of (I).
	Fig. 4. A packing diagram for (I).

Poly[diaqua(µ₂-1H-imidazo[4,5-f][1,10]phenanthroline)di-µ₄-sulfato-µ₃-sulfato-dicadmium(II)]

Crystal data

[Cd2(SO4)2(C13H8N4)(H2O)2]	F(000) = 1304
Mr = 673.19	Dx = 2.499 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13080 reflections
a = 10.3834 (4) Å	θ = 3.0–28.3°
b = 6.8070 (3) Å	µ = 2.68 mm^−1
c = 25.4684 (10) Å	T = 296 K
β = 96.25 (1)°	Prism, brown
V = 1789.40 (13) Å^3	0.30 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker APEXII diffractometer	4429 independent reflections
Radiation source: fine-focus sealed tube	4042 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10.000 pixels mm^-1	θmax = 28.3°, θmin = 3.0°
ω scans	h = −13→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −8→9
Tmin = 0.500, Tmax = 0.644	l = −33→33
13080 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0224P)^2 + 1.8401P] where P = (Fo^2 + 2Fc^2)/3
4429 reflections	(Δ/σ)max = 0.003
295 parameters	Δρmax = 0.57 e Å^−3
7 restraints	Δρmin = −0.53 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.601890 (16)	0.18001 (2)	0.685949 (6)	0.01611 (5)
Cd2	0.390776 (16)	0.70764 (3)	0.651295 (6)	0.01833 (5)
S1	0.27429 (5)	0.21743 (9)	0.64832 (2)	0.01672 (12)
S2	0.67723 (5)	0.66974 (8)	0.69726 (2)	0.01507 (11)
N1	0.44948 (19)	0.7270 (3)	0.56638 (8)	0.0180 (4)
N2	0.20235 (19)	0.7331 (3)	0.59359 (8)	0.0177 (4)
N3	0.2592 (2)	0.8090 (3)	0.38031 (7)	0.0187 (4)
N4	0.0594 (2)	0.7924 (3)	0.40354 (8)	0.0225 (5)
O1	0.58301 (18)	0.5079 (3)	0.68323 (8)	0.0286 (4)
O9	0.49751 (19)	0.1449 (3)	0.76084 (8)	0.0329 (5)
O2	0.60030 (17)	0.8466 (3)	0.67964 (7)	0.0265 (4)
O3	0.78942 (18)	0.6502 (3)	0.66842 (7)	0.0317 (5)
O4	0.71269 (17)	0.6759 (3)	0.75420 (7)	0.0289 (4)
O5	0.30858 (18)	0.4096 (3)	0.67238 (8)	0.0292 (4)
O6	0.39487 (15)	0.0985 (3)	0.64630 (6)	0.0216 (4)
O7	0.20842 (18)	0.2379 (3)	0.59487 (7)	0.0301 (4)
O8	0.18897 (17)	0.1138 (3)	0.68196 (7)	0.0241 (4)
O10	0.3347 (2)	0.8155 (3)	0.72889 (8)	0.0308 (4)
C1	0.5711 (2)	0.7256 (4)	0.55442 (10)	0.0243 (5)
C2	0.6020 (2)	0.7453 (4)	0.50293 (10)	0.0248 (5)
C3	0.5044 (2)	0.7651 (4)	0.46254 (10)	0.0218 (5)
C4	0.3752 (2)	0.7658 (3)	0.47373 (9)	0.0158 (4)
C5	0.3513 (2)	0.7467 (3)	0.52710 (9)	0.0152 (4)
C6	0.2191 (2)	0.7450 (3)	0.54171 (9)	0.0157 (4)
C7	0.0833 (3)	0.7255 (4)	0.60768 (10)	0.0252 (5)
C8	−0.0274 (3)	0.7295 (4)	0.57096 (11)	0.0286 (6)
C9	−0.0129 (2)	0.7455 (4)	0.51851 (10)	0.0252 (5)
C10	0.1128 (2)	0.7545 (4)	0.50257 (9)	0.0175 (5)
C11	0.1413 (2)	0.7744 (4)	0.44925 (9)	0.0186 (5)
C12	0.2652 (2)	0.7831 (3)	0.43466 (9)	0.0158 (4)
C13	0.1341 (3)	0.8137 (4)	0.36404 (10)	0.0238 (5)
H1	0.6380	0.7109	0.5816	0.029*
H2	0.6881	0.7450	0.4960	0.030*
H3	0.5238	0.7780	0.4279	0.026*
H7	0.0728	0.7173	0.6434	0.030*
H8	−0.1096	0.7214	0.5822	0.034*
H9	−0.0852	0.7504	0.4935	0.030*
H13	0.1011	0.8301	0.3289	0.029*
H10B	0.270 (2)	0.889 (4)	0.7207 (11)	0.036*
H10A	0.324 (3)	0.746 (4)	0.7555 (9)	0.036*
H9B	0.557 (2)	0.138 (4)	0.7860 (9)	0.036*
H9A	0.455 (2)	0.038 (3)	0.7583 (11)	0.036*
H4N	−0.0272 (18)	0.803 (5)	0.4018 (13)	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01689 (9)	0.01553 (9)	0.01560 (9)	−0.00147 (6)	0.00029 (6)	−0.00002 (6)
Cd2	0.01612 (9)	0.02584 (10)	0.01275 (8)	−0.00219 (7)	0.00026 (6)	0.00101 (6)
S1	0.0121 (3)	0.0224 (3)	0.0156 (3)	−0.0005 (2)	0.0009 (2)	0.0019 (2)
S2	0.0141 (3)	0.0157 (3)	0.0147 (3)	0.0004 (2)	−0.00151 (19)	0.0005 (2)
N1	0.0138 (10)	0.0248 (11)	0.0151 (9)	0.0000 (8)	0.0002 (7)	0.0003 (8)
N2	0.0166 (10)	0.0230 (10)	0.0140 (9)	−0.0015 (8)	0.0035 (7)	0.0016 (8)
N3	0.0198 (10)	0.0237 (11)	0.0124 (9)	−0.0012 (8)	0.0010 (7)	0.0004 (8)
N4	0.0133 (10)	0.0380 (13)	0.0154 (9)	0.0003 (9)	−0.0025 (7)	0.0013 (9)
O1	0.0237 (9)	0.0131 (9)	0.0464 (11)	−0.0022 (7)	−0.0080 (8)	0.0000 (8)
O9	0.0226 (10)	0.0529 (13)	0.0225 (9)	−0.0074 (9)	−0.0002 (7)	−0.0037 (9)
O2	0.0246 (10)	0.0165 (9)	0.0357 (10)	0.0015 (7)	−0.0091 (8)	0.0017 (8)
O3	0.0185 (9)	0.0565 (13)	0.0205 (9)	0.0037 (9)	0.0035 (7)	−0.0007 (9)
O4	0.0197 (9)	0.0507 (13)	0.0157 (8)	0.0031 (8)	−0.0009 (7)	0.0019 (8)
O5	0.0303 (10)	0.0219 (10)	0.0350 (10)	−0.0054 (8)	0.0015 (8)	0.0004 (8)
O6	0.0141 (8)	0.0310 (10)	0.0194 (8)	0.0036 (7)	0.0005 (6)	0.0020 (7)
O7	0.0185 (9)	0.0499 (12)	0.0210 (9)	0.0054 (9)	−0.0027 (7)	0.0049 (8)
O8	0.0220 (9)	0.0278 (10)	0.0242 (9)	−0.0048 (7)	0.0105 (7)	−0.0010 (8)
O10	0.0403 (12)	0.0300 (11)	0.0243 (10)	0.0024 (9)	0.0129 (8)	0.0050 (8)
C1	0.0166 (12)	0.0376 (15)	0.0184 (12)	0.0009 (10)	0.0002 (9)	0.0002 (10)
C2	0.0136 (12)	0.0389 (15)	0.0226 (12)	0.0017 (11)	0.0052 (9)	0.0006 (11)
C3	0.0198 (12)	0.0315 (14)	0.0147 (11)	0.0000 (10)	0.0049 (9)	−0.0002 (10)
C4	0.0163 (11)	0.0174 (11)	0.0138 (10)	−0.0003 (9)	0.0020 (8)	−0.0004 (8)
C5	0.0152 (11)	0.0165 (11)	0.0139 (10)	0.0002 (8)	0.0015 (8)	−0.0011 (8)
C6	0.0162 (11)	0.0171 (11)	0.0141 (10)	−0.0002 (9)	0.0026 (8)	0.0009 (8)
C7	0.0219 (13)	0.0360 (15)	0.0186 (12)	−0.0020 (11)	0.0068 (9)	0.0016 (10)
C8	0.0148 (12)	0.0466 (17)	0.0254 (13)	−0.0020 (11)	0.0067 (10)	0.0005 (12)
C9	0.0139 (12)	0.0399 (15)	0.0220 (12)	−0.0005 (11)	0.0024 (9)	0.0012 (11)
C10	0.0166 (12)	0.0215 (12)	0.0148 (10)	0.0005 (9)	0.0031 (8)	−0.0010 (9)
C11	0.0164 (11)	0.0243 (12)	0.0145 (11)	0.0009 (9)	−0.0008 (8)	0.0012 (9)
C12	0.0166 (11)	0.0192 (12)	0.0117 (10)	−0.0007 (9)	0.0019 (8)	−0.0008 (8)
C13	0.0235 (13)	0.0347 (15)	0.0128 (11)	0.0007 (11)	0.0000 (9)	−0.0004 (10)

Geometric parameters (Å, º)

Cd1—N3^i	2.337 (2)	N4—C13	1.343 (3)
Cd1—O1	2.2408 (18)	N4—C11	1.370 (3)
Cd1—O2^ii	2.2748 (18)	N4—H4N	0.899 (18)
Cd1—O4^iii	2.3221 (18)	O2—Cd1^iv	2.2748 (18)
Cd1—O6	2.3400 (16)	O4—Cd1^v	2.3221 (17)
Cd1—O9	2.307 (2)	O9—H9B	0.843 (10)
Cd2—N1	2.314 (2)	O9—H9A	0.852 (10)
Cd2—N2	2.322 (2)	O10—H10B	0.850 (10)
Cd2—O1	2.4782 (18)	O10—H10A	0.844 (10)
Cd2—O2	2.4099 (18)	C1—C2	1.390 (3)
Cd2—O5	2.2875 (19)	C1—H1	0.9300
Cd2—O10	2.2437 (19)	C2—C3	1.370 (3)
Cd2—O6^iv	2.664 (2)	C2—H2	0.9300
S1—O5	1.472 (2)	C3—C4	1.402 (3)
S1—O6	1.4966 (17)	C3—H3	0.9300
S1—O7	1.4619 (18)	C4—C5	1.414 (3)
S1—O8	1.4771 (17)	C4—C12	1.435 (3)
S2—O1	1.4909 (18)	C5—C6	1.460 (3)
S2—O2	1.4871 (18)	C6—C10	1.406 (3)
S2—O3	1.4492 (19)	C7—C8	1.401 (4)
S2—O4	1.4574 (18)	C7—H7	0.9300
N1—C1	1.331 (3)	C8—C9	1.365 (4)
N1—C5	1.355 (3)	C8—H8	0.9300
N2—C7	1.326 (3)	C9—C10	1.410 (3)
N2—C6	1.354 (3)	C9—H9	0.9300
N3—C13	1.321 (3)	C10—C11	1.427 (3)
N3—C12	1.390 (3)	C11—C12	1.379 (3)
N3—Cd1^i	2.337 (2)	C13—H13	0.9300
N1—Cd2—N2	72.16 (7)	N4—C13—H13	123.5
N1—Cd2—O1	93.05 (7)	O2—S2—O1	102.07 (10)
N1—Cd2—O2	86.37 (7)	O3—S2—O4	112.14 (11)
N2—Cd2—O1	147.32 (7)	O3—S2—O2	110.89 (12)
N2—Cd2—O2	146.23 (7)	O3—S2—O1	110.69 (12)
N3^i—Cd1—O6	107.82 (6)	O4—S2—O1	110.35 (12)
O1—Cd1—N3^i	90.27 (7)	O4—S2—O2	110.26 (11)
O1—Cd1—O2^ii	172.48 (6)	O5—S1—O6	109.25 (11)
O1—Cd1—O4^iii	95.50 (7)	O5—S1—O8	108.44 (11)
O1—Cd1—O6	98.61 (7)	O7—S1—O5	111.75 (12)
O1—Cd1—O9	94.67 (8)	O7—S1—O8	109.64 (11)
O2^ii—Cd1—N3^i	88.92 (7)	O7—S1—O6	109.14 (11)
O2^ii—Cd1—O4^iii	91.91 (7)	O8—S1—O6	108.56 (11)
O2^ii—Cd1—O6	74.56 (6)	C1—N1—Cd2	124.51 (16)
O2^ii—Cd1—O9	87.39 (8)	C1—N1—C5	119.2 (2)
O2—Cd2—O1	56.53 (6)	C1—C2—H2	120.3
O4^iii—Cd1—N3^i	86.66 (7)	C2—C1—H1	118.8
O4^iii—Cd1—O6	159.62 (7)	C2—C3—C4	119.6 (2)
O5—Cd2—N1	114.38 (7)	C2—C3—H3	120.2
O5—Cd2—N2	84.52 (7)	C3—C2—C1	119.4 (2)
O5—Cd2—O1	75.17 (6)	C3—C2—H2	120.3
O5—Cd2—O2	128.73 (6)	C3—C4—C5	117.9 (2)
O9—Cd1—N3^i	169.35 (7)	C3—C4—C12	124.5 (2)
O9—Cd1—O4^iii	83.48 (7)	C4—C3—H3	120.2
O9—Cd1—O6	80.79 (6)	C4—C5—C6	120.9 (2)
O10—Cd2—N1	157.64 (7)	C5—N1—Cd2	116.23 (15)
O10—Cd2—N2	104.56 (7)	C5—C4—C12	117.7 (2)
O10—Cd2—O1	99.64 (7)	C6—N2—Cd2	115.67 (15)
O10—Cd2—O2	85.42 (7)	C6—C10—C9	118.3 (2)
O10—Cd2—O5	86.80 (7)	C6—C10—C11	116.8 (2)
Cd1—O1—Cd2	128.41 (8)	C7—N2—C6	119.3 (2)
Cd1^iv—O2—Cd2	114.34 (7)	C7—N2—Cd2	124.91 (16)
Cd1—O9—H9A	108 (2)	C7—C8—H8	120.5
Cd1—O9—H9B	105 (2)	C8—C7—H7	118.7
Cd2—O10—H10B	105 (2)	C8—C9—C10	119.3 (2)
Cd2—O10—H10A	127 (2)	C8—C9—H9	120.4
S1—O5—Cd2	140.37 (12)	C9—C8—C7	119.0 (2)
S1—O6—Cd1	126.12 (10)	C9—C8—H8	120.5
S2—O1—Cd1	132.51 (11)	C9—C10—C11	124.9 (2)
S2—O1—Cd2	99.05 (9)	C10—C6—C5	120.4 (2)
S2—O2—Cd1^iv	141.90 (11)	C10—C9—H9	120.4
S2—O2—Cd2	102.14 (9)	C11—N4—H4N	125 (2)
S2—O4—Cd1^v	139.04 (11)	C11—C12—N3	109.4 (2)
N1—C1—C2	122.5 (2)	C11—C12—C4	120.3 (2)
N1—C1—H1	118.8	C12—N3—Cd1^i	139.35 (16)
N1—C5—C4	121.5 (2)	C12—C11—C10	123.8 (2)
N1—C5—C6	117.6 (2)	C13—N3—C12	104.6 (2)
N2—C6—C10	121.4 (2)	C13—N3—Cd1^i	115.85 (16)
N2—C6—C5	118.2 (2)	C13—N4—C11	106.9 (2)
N2—C7—C8	122.7 (2)	C13—N4—H4N	128 (2)
N2—C7—H7	118.7	H9B—O9—H9A	110.0 (16)
N3—C12—C4	130.3 (2)	H10B—O10—H10A	110.7 (16)
N3—C13—N4	113.0 (2)	O1^iv—Cd2—O6	123.17 (6)
N3—C13—H13	123.5	OW1^iv—Cd2—O6	73.88 (6)
N4—C11—C12	106.1 (2)	O2^iv—Cd2—O6	66.66 (6)
N4—C11—C10	130.1 (2)	O5^iv—Cd2—O6	154.85 (6)
O3—S2—O1—Cd1	55.86 (18)	O5—Cd2—N1—C5	76.45 (18)
O4—S2—O1—Cd1	−68.88 (18)	N2—Cd2—N1—C5	1.28 (17)
O2—S2—O1—Cd1	173.92 (15)	O2—Cd2—N1—C5	−152.29 (18)
O3—S2—O1—Cd2	−122.15 (10)	O1—Cd2—N1—C5	151.55 (17)
O4—S2—O1—Cd2	113.11 (10)	O10—Cd2—N2—C7	−26.7 (2)
O2—S2—O1—Cd2	−4.09 (12)	O5—Cd2—N2—C7	58.5 (2)
O2^ii—Cd1—O1—S2	−150.3 (5)	N1—Cd2—N2—C7	176.3 (2)
O9—Cd1—O1—S2	104.06 (16)	O2—Cd2—N2—C7	−130.6 (2)
O4^iii—Cd1—O1—S2	20.18 (17)	O1—Cd2—N2—C7	109.8 (2)
N3^i—Cd1—O1—S2	−66.49 (16)	O10—Cd2—N2—C6	157.25 (17)
O6—Cd1—O1—S2	−174.56 (15)	O5—Cd2—N2—C6	−117.51 (18)
O2^ii—Cd1—O1—Cd2	27.2 (6)	N1—Cd2—N2—C6	0.30 (16)
O9—Cd1—O1—Cd2	−78.44 (11)	O2—Cd2—N2—C6	53.4 (2)
O4^iii—Cd1—O1—Cd2	−162.33 (11)	O1—Cd2—N2—C6	−66.2 (2)
N3^i—Cd1—O1—Cd2	111.00 (11)	C5—N1—C1—C2	0.5 (4)
O6—Cd1—O1—Cd2	2.93 (12)	Cd2—N1—C1—C2	−177.4 (2)
O10—Cd2—O1—S2	−74.96 (11)	N1—C1—C2—C3	−0.6 (4)
O5—Cd2—O1—S2	−159.01 (11)	C1—C2—C3—C4	0.2 (4)
N1—Cd2—O1—S2	86.56 (10)	C2—C3—C4—C5	0.3 (4)
N2—Cd2—O1—S2	147.55 (10)	C2—C3—C4—C12	−179.2 (2)
O2—Cd2—O1—S2	2.96 (8)	C1—N1—C5—C4	0.0 (4)
O10—Cd2—O1—Cd1	106.91 (11)	Cd2—N1—C5—C4	178.12 (17)
O5—Cd2—O1—Cd1	22.86 (11)	C1—N1—C5—C6	179.2 (2)
N1—Cd2—O1—Cd1	−91.56 (12)	Cd2—N1—C5—C6	−2.7 (3)
N2—Cd2—O1—Cd1	−30.58 (19)	C3—C4—C5—N1	−0.4 (4)
O2—Cd2—O1—Cd1	−175.17 (14)	C12—C4—C5—N1	179.1 (2)
O3—S2—O2—Cd1^iv	−74.6 (2)	C3—C4—C5—C6	−179.6 (2)
O4—S2—O2—Cd1^iv	50.2 (2)	C12—C4—C5—C6	−0.1 (3)
O1—S2—O2—Cd1^iv	167.48 (18)	C7—N2—C6—C10	1.6 (4)
O3—S2—O2—Cd2	122.17 (11)	Cd2—N2—C6—C10	177.90 (18)
O4—S2—O2—Cd2	−113.01 (10)	C7—N2—C6—C5	−178.0 (2)
O1—S2—O2—Cd2	4.25 (12)	Cd2—N2—C6—C5	−1.8 (3)
O10—Cd2—O2—S2	101.75 (11)	N1—C5—C6—N2	3.0 (3)
O5—Cd2—O2—S2	19.57 (14)	C4—C5—C6—N2	−177.8 (2)
N1—Cd2—O2—S2	−99.07 (11)	N1—C5—C6—C10	−176.7 (2)
N2—Cd2—O2—S2	−148.74 (10)	C4—C5—C6—C10	2.6 (4)
O1—Cd2—O2—S2	−2.99 (8)	C6—N2—C7—C8	−0.1 (4)
O10—Cd2—O2—Cd1^iv	−66.99 (9)	Cd2—N2—C7—C8	−176.0 (2)
O5—Cd2—O2—Cd1^iv	−149.17 (8)	N2—C7—C8—C9	−1.3 (5)
N1—Cd2—O2—Cd1^iv	92.19 (9)	C7—C8—C9—C10	1.0 (4)
N2—Cd2—O2—Cd1^iv	42.52 (16)	N2—C6—C10—C9	−1.9 (4)
O1—Cd2—O2—Cd1^iv	−171.73 (12)	C5—C6—C10—C9	177.8 (2)
O3—S2—O4—Cd1^v	4.2 (2)	N2—C6—C10—C11	177.6 (2)
O2—S2—O4—Cd1^v	−119.89 (18)	C5—C6—C10—C11	−2.7 (4)
O1—S2—O4—Cd1^v	128.10 (18)	C8—C9—C10—C6	0.5 (4)
O7—S1—O5—Cd2	−42.1 (2)	C8—C9—C10—C11	−178.9 (3)
O8—S1—O5—Cd2	−163.06 (16)	C13—N4—C11—C12	−0.8 (3)
O6—S1—O5—Cd2	78.79 (19)	C13—N4—C11—C10	177.9 (3)
O10—Cd2—O5—S1	169.53 (19)	C6—C10—C11—N4	−178.0 (3)
N1—Cd2—O5—S1	−3.0 (2)	C9—C10—C11—N4	1.4 (5)
N2—Cd2—O5—S1	64.56 (18)	C6—C10—C11—C12	0.5 (4)
O2—Cd2—O5—S1	−108.94 (18)	C9—C10—C11—C12	179.9 (3)
O1—Cd2—O5—S1	−89.61 (19)	N4—C11—C12—N3	0.8 (3)
O7—S1—O6—Cd1	130.99 (12)	C10—C11—C12—N3	−178.0 (2)
O5—S1—O6—Cd1	8.54 (15)	N4—C11—C12—C4	−179.2 (2)
O8—S1—O6—Cd1	−109.55 (13)	C10—C11—C12—C4	2.0 (4)
O1—Cd1—O6—S1	−29.26 (13)	C13—N3—C12—C11	−0.4 (3)
O2^ii—Cd1—O6—S1	153.94 (13)	Cd1^i—N3—C12—C11	−174.23 (18)
O9—Cd1—O6—S1	64.11 (13)	C13—N3—C12—C4	179.5 (3)
O4^iii—Cd1—O6—S1	104.1 (2)	Cd1^i—N3—C12—C4	5.7 (4)
N3^i—Cd1—O6—S1	−122.34 (12)	C3—C4—C12—C11	177.4 (2)
O10—Cd2—N1—C1	94.3 (3)	C5—C4—C12—C11	−2.2 (3)
O5—Cd2—N1—C1	−105.5 (2)	C3—C4—C12—N3	−2.6 (4)
N2—Cd2—N1—C1	179.3 (2)	C5—C4—C12—N3	177.9 (2)
O2—Cd2—N1—C1	25.7 (2)	C12—N3—C13—N4	−0.2 (3)
O1—Cd2—N1—C1	−30.5 (2)	Cd1^i—N3—C13—N4	175.38 (17)
O10—Cd2—N1—C5	−83.7 (3)	C11—N4—C13—N3	0.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···S1^vi	0.90 (2)	2.74 (2)	3.572 (2)	154 (3)
N4—H4N···O7^vi	0.90 (2)	1.91 (2)	2.794 (3)	166 (3)
N4—H4N···O8^vi	0.90 (2)	2.63 (3)	3.253 (3)	127 (3)
O9—H9B···S2^iii	0.84 (1)	2.75 (2)	3.433 (2)	139 (3)
O9—H9B···O3^iii	0.84 (1)	1.87 (1)	2.697 (3)	168 (3)
O9—H9A···O10^ii	0.85 (1)	2.05 (1)	2.872 (3)	162 (3)
O10—H10A···S1^vii	0.84 (1)	2.76 (2)	3.5037 (19)	148 (3)
O10—H10A···O5^vii	0.84 (1)	2.65 (3)	3.124 (3)	117 (2)
O10—H10A···O8^vii	0.84 (1)	1.85 (1)	2.688 (3)	174 (3)
O10—H10B···S1^iv	0.85 (1)	2.90 (2)	3.437 (2)	123 (2)
O10—H10B···O8^iv	0.85 (1)	1.96 (1)	2.729 (3)	151 (3)

Symmetry codes: (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x, y+1, z; (vi) −x, −y+1, −z+1; (vii) −x+1/2, y+1/2, −z+3/2.