Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614015514/em3069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015514/em3069Isup2.hkl |
CCDC reference: 1011887
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 RuII 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 CdII coordination polymer, [Cd2(SO4)2(IP)(H2O)2]n, (I).
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%.
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 Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.5Ueq(O).
As depicted in Fig. 1, each asymmetric unit of (I) consists of two crystallographically independent CdII centres with different coordination geometries. The first CdII 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 CdII 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).
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).
[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) Å3 | 0.30 × 0.20 × 0.18 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0224P)2 + 1.8401P] where P = (Fo2 + 2Fc2)/3 |
4429 reflections | (Δ/σ)max = 0.003 |
295 parameters | Δρmax = 0.57 e Å−3 |
7 restraints | Δρmin = −0.53 e Å−3 |
[Cd2(SO4)2(C13H8N4)(H2O)2] | V = 1789.40 (13) Å3 |
Mr = 673.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.3834 (4) Å | µ = 2.68 mm−1 |
b = 6.8070 (3) Å | T = 296 K |
c = 25.4684 (10) Å | 0.30 × 0.20 × 0.18 mm |
β = 96.25 (1)° |
Bruker APEXII diffractometer | 4429 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 4042 reflections with I > 2σ(I) |
Tmin = 0.500, Tmax = 0.644 | Rint = 0.025 |
13080 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 7 restraints |
wR(F2) = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.57 e Å−3 |
4429 reflections | Δρmin = −0.53 e Å−3 |
295 parameters |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Cd1—N3i | 2.337 (2) | N4—C13 | 1.343 (3) |
Cd1—O1 | 2.2408 (18) | N4—C11 | 1.370 (3) |
Cd1—O2ii | 2.2748 (18) | N4—H4N | 0.899 (18) |
Cd1—O4iii | 2.3221 (18) | O2—Cd1iv | 2.2748 (18) |
Cd1—O6 | 2.3400 (16) | O4—Cd1v | 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—O6iv | 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—Cd1i | 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) |
N3i—Cd1—O6 | 107.82 (6) | O4—S2—O1 | 110.35 (12) |
O1—Cd1—N3i | 90.27 (7) | O4—S2—O2 | 110.26 (11) |
O1—Cd1—O2ii | 172.48 (6) | O5—S1—O6 | 109.25 (11) |
O1—Cd1—O4iii | 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) |
O2ii—Cd1—N3i | 88.92 (7) | O7—S1—O6 | 109.14 (11) |
O2ii—Cd1—O4iii | 91.91 (7) | O8—S1—O6 | 108.56 (11) |
O2ii—Cd1—O6 | 74.56 (6) | C1—N1—Cd2 | 124.51 (16) |
O2ii—Cd1—O9 | 87.39 (8) | C1—N1—C5 | 119.2 (2) |
O2—Cd2—O1 | 56.53 (6) | C1—C2—H2 | 120.3 |
O4iii—Cd1—N3i | 86.66 (7) | C2—C1—H1 | 118.8 |
O4iii—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—N3i | 169.35 (7) | C3—C4—C12 | 124.5 (2) |
O9—Cd1—O4iii | 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) |
Cd1iv—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—Cd1iv | 141.90 (11) | C10—C9—H9 | 120.4 |
S2—O2—Cd2 | 102.14 (9) | C11—N4—H4N | 125 (2) |
S2—O4—Cd1v | 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—Cd1i | 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—Cd1i | 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) | O1iv—Cd2—O6 | 123.17 (6) |
N3—C13—H13 | 123.5 | OW1iv—Cd2—O6 | 73.88 (6) |
N4—C11—C12 | 106.1 (2) | O2iv—Cd2—O6 | 66.66 (6) |
N4—C11—C10 | 130.1 (2) | O5iv—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) |
O2ii—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) |
O4iii—Cd1—O1—S2 | 20.18 (17) | O1—Cd2—N2—C7 | 109.8 (2) |
N3i—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) |
O2ii—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) |
O4iii—Cd1—O1—Cd2 | −162.33 (11) | O1—Cd2—N2—C6 | −66.2 (2) |
N3i—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—Cd1iv | −74.6 (2) | C3—C4—C5—C6 | −179.6 (2) |
O4—S2—O2—Cd1iv | 50.2 (2) | C12—C4—C5—C6 | −0.1 (3) |
O1—S2—O2—Cd1iv | 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—Cd1iv | −66.99 (9) | Cd2—N2—C7—C8 | −176.0 (2) |
O5—Cd2—O2—Cd1iv | −149.17 (8) | N2—C7—C8—C9 | −1.3 (5) |
N1—Cd2—O2—Cd1iv | 92.19 (9) | C7—C8—C9—C10 | 1.0 (4) |
N2—Cd2—O2—Cd1iv | 42.52 (16) | N2—C6—C10—C9 | −1.9 (4) |
O1—Cd2—O2—Cd1iv | −171.73 (12) | C5—C6—C10—C9 | 177.8 (2) |
O3—S2—O4—Cd1v | 4.2 (2) | N2—C6—C10—C11 | 177.6 (2) |
O2—S2—O4—Cd1v | −119.89 (18) | C5—C6—C10—C11 | −2.7 (4) |
O1—S2—O4—Cd1v | 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) |
O2ii—Cd1—O6—S1 | 153.94 (13) | Cd1i—N3—C12—C11 | −174.23 (18) |
O9—Cd1—O6—S1 | 64.11 (13) | C13—N3—C12—C4 | 179.5 (3) |
O4iii—Cd1—O6—S1 | 104.1 (2) | Cd1i—N3—C12—C4 | 5.7 (4) |
N3i—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) | Cd1i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4N···S1vi | 0.90 (2) | 2.74 (2) | 3.572 (2) | 154 (3) |
N4—H4N···O7vi | 0.90 (2) | 1.91 (2) | 2.794 (3) | 166 (3) |
N4—H4N···O8vi | 0.90 (2) | 2.63 (3) | 3.253 (3) | 127 (3) |
O9—H9B···S2iii | 0.84 (1) | 2.75 (2) | 3.433 (2) | 139 (3) |
O9—H9B···O3iii | 0.84 (1) | 1.87 (1) | 2.697 (3) | 168 (3) |
O9—H9A···O10ii | 0.85 (1) | 2.05 (1) | 2.872 (3) | 162 (3) |
O10—H10A···S1vii | 0.84 (1) | 2.76 (2) | 3.5037 (19) | 148 (3) |
O10—H10A···O5vii | 0.84 (1) | 2.65 (3) | 3.124 (3) | 117 (2) |
O10—H10A···O8vii | 0.84 (1) | 1.85 (1) | 2.688 (3) | 174 (3) |
O10—H10B···S1iv | 0.85 (1) | 2.90 (2) | 3.437 (2) | 123 (2) |
O10—H10B···O8iv | 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. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(SO4)2(C13H8N4)(H2O)2] |
Mr | 673.19 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 10.3834 (4), 6.8070 (3), 25.4684 (10) |
β (°) | 96.25 (1) |
V (Å3) | 1789.40 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.68 |
Crystal size (mm) | 0.30 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.500, 0.644 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13080, 4429, 4042 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.053, 1.02 |
No. of reflections | 4429 |
No. of parameters | 295 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.53 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2004).
Cd1—N3i | 2.337 (2) | Cd2—N2 | 2.322 (2) |
Cd1—O1 | 2.2408 (18) | Cd2—O1 | 2.4782 (18) |
Cd1—O2ii | 2.2748 (18) | Cd2—O2 | 2.4099 (18) |
Cd1—O4iii | 2.3221 (18) | Cd2—O5 | 2.2875 (19) |
Cd1—O6 | 2.3400 (16) | Cd2—O10 | 2.2437 (19) |
Cd1—O9 | 2.307 (2) | Cd2—O6iv | 2.664 (2) |
Cd2—N1 | 2.314 (2) | ||
N1—Cd2—N2 | 72.16 (7) | O4iii—Cd1—O6 | 159.62 (7) |
N1—Cd2—O1 | 93.05 (7) | O5—Cd2—N1 | 114.38 (7) |
N1—Cd2—O2 | 86.37 (7) | O5—Cd2—N2 | 84.52 (7) |
N2—Cd2—O1 | 147.32 (7) | O5—Cd2—O1 | 75.17 (6) |
N2—Cd2—O2 | 146.23 (7) | O5—Cd2—O2 | 128.73 (6) |
N3i—Cd1—O6 | 107.82 (6) | O9—Cd1—N3i | 169.35 (7) |
O1—Cd1—N3i | 90.27 (7) | O9—Cd1—O4iii | 83.48 (7) |
O1—Cd1—O2ii | 172.48 (6) | O9—Cd1—O6 | 80.79 (6) |
O1—Cd1—O4iii | 95.50 (7) | O10—Cd2—N1 | 157.64 (7) |
O1—Cd1—O6 | 98.61 (7) | O10—Cd2—N2 | 104.56 (7) |
O1—Cd1—O9 | 94.67 (8) | O10—Cd2—O1 | 99.64 (7) |
O2ii—Cd1—N3i | 88.92 (7) | O10—Cd2—O2 | 85.42 (7) |
O2ii—Cd1—O4iii | 91.91 (7) | O10—Cd2—O5 | 86.80 (7) |
O2ii—Cd1—O6 | 74.56 (6) | O1iv—Cd2—O6 | 123.17 (6) |
O2ii—Cd1—O9 | 87.39 (8) | OW1iv—Cd2—O6 | 73.88 (6) |
O2—Cd2—O1 | 56.53 (6) | O2iv—Cd2—O6 | 66.66 (6) |
O4iii—Cd1—N3i | 86.66 (7) | O5iv—Cd2—O6 | 154.85 (6) |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4N···O7v | 0.899 (18) | 1.913 (19) | 2.794 (3) | 166 (3) |
O9—H9B···O3iii | 0.843 (10) | 1.868 (11) | 2.697 (3) | 168 (3) |
O9—H9A···O10ii | 0.852 (10) | 2.050 (12) | 2.872 (3) | 162 (3) |
O10—H10A···O8vi | 0.844 (10) | 1.847 (11) | 2.688 (3) | 174 (3) |
O10—H10B···O8iv | 0.850 (10) | 1.956 (14) | 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; (v) −x, −y+1, −z+1; (vi) −x+1/2, y+1/2, −z+3/2. |