Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028434/gd1351sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028434/gd1351Isup2.hkl |
CCDC reference: 263023
Cd(CH3COO)2·2H2O (0.2 mmol, 0.053 g), 4,4'-bipyridine (0.2 mmol, 0.031 g) and 2-sulfobenzoic acid (0.2 mmol, 0.040 g) were dissolved in H2O (8 ml). The mixture was then sealed in a 25 ml stainless steel vessel with a Teflon liner and heated to 433 K for 72 h. After cooling to room temperature, the reaction mixture was filtered and transparent crystals of (I) were obtained in 67.3% yield (based on Cd).
All of the water H atoms were found in difference Fourier maps at an intermediate stage of the refinement and were refined with an O—H restraint of 0.85 (5) Å. H atoms bonded to C atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). Please check added text.
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
[Cd2(C7H4O5S)2(C10H8N2)2(H2O)2]·2H2O | F(000) = 2016 |
Mr = 1009.6 | Dx = 1.809 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6223 reflections |
a = 16.888 (5) Å | θ = 2.2–27.5° |
b = 11.722 (5) Å | µ = 1.34 mm−1 |
c = 20.258 (7) Å | T = 173 K |
β = 112.483 (5)° | Prism, white |
V = 3706 (2) Å3 | 0.50 × 0.10 × 0.05 mm |
Z = 4 |
Rigaku Mercury70 (2x2 bin mode) diffractometer | 4254 independent reflections |
Radiation source: Rotating anode | 4059 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5°, θmin = 2.2° |
dtprofit.ref scans | h = −21→19 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −15→15 |
Tmin = 0.613, Tmax = 0.935 | l = −13→26 |
14147 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0244P)2 + 6.0536P] where P = (Fo2 + 2Fc2)/3 |
4254 reflections | (Δ/σ)max = 0.001 |
273 parameters | Δρmax = 0.86 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Cd2(C7H4O5S)2(C10H8N2)2(H2O)2]·2H2O | V = 3706 (2) Å3 |
Mr = 1009.6 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.888 (5) Å | µ = 1.34 mm−1 |
b = 11.722 (5) Å | T = 173 K |
c = 20.258 (7) Å | 0.50 × 0.10 × 0.05 mm |
β = 112.483 (5)° |
Rigaku Mercury70 (2x2 bin mode) diffractometer | 4254 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4059 reflections with I > 2σ(I) |
Tmin = 0.613, Tmax = 0.935 | Rint = 0.028 |
14147 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.86 e Å−3 |
4254 reflections | Δρmin = −0.61 e Å−3 |
273 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.0000 | 0.328102 (17) | 0.2500 | 0.01377 (6) | |
Cd2 | 0.2500 | 0.2500 | 0.5000 | 0.00967 (6) | |
S1 | 0.39639 (3) | 0.25100 (4) | 0.42586 (3) | 0.01275 (11) | |
O3 | 0.34224 (10) | 0.16938 (13) | 0.37541 (9) | 0.0203 (3) | |
N3 | 0.24497 (10) | 0.05305 (15) | 0.48461 (10) | 0.0120 (3) | |
C23 | 0.0000 | −0.2331 (2) | 0.2500 | 0.0156 (6) | |
N1 | 0.0000 | 0.1341 (2) | 0.2500 | 0.0157 (5) | |
C31 | 0.17469 (13) | −0.00748 (18) | 0.47798 (12) | 0.0148 (4) | |
H31 | 0.1226 | 0.0326 | 0.4686 | 0.018* | |
C47 | 0.36340 (13) | 0.38939 (18) | 0.38914 (11) | 0.0134 (4) | |
O4 | 0.48678 (10) | 0.24235 (14) | 0.44034 (10) | 0.0222 (4) | |
C46 | 0.42829 (14) | 0.46993 (19) | 0.40212 (13) | 0.0187 (5) | |
H46 | 0.4861 | 0.4484 | 0.4283 | 0.022* | |
O5 | 0.38295 (9) | 0.25162 (12) | 0.49445 (8) | 0.0136 (3) | |
C13 | 0.0000 | −0.1063 (2) | 0.2500 | 0.0160 (6) | |
C11 | 0.07185 (14) | 0.07367 (18) | 0.28599 (13) | 0.0197 (5) | |
H11 | 0.1232 | 0.1142 | 0.3117 | 0.024* | |
C33 | 0.24876 (12) | −0.18712 (17) | 0.49634 (11) | 0.0115 (4) | |
C35 | 0.31677 (13) | −0.00709 (18) | 0.49580 (12) | 0.0165 (4) | |
H35 | 0.3672 | 0.0335 | 0.5002 | 0.020* | |
C32 | 0.17405 (13) | −0.12485 (18) | 0.48402 (12) | 0.0145 (4) | |
H32 | 0.1228 | −0.1631 | 0.4798 | 0.017* | |
C22 | 0.04668 (15) | −0.29460 (19) | 0.31107 (13) | 0.0202 (5) | |
H22 | 0.0803 | −0.2559 | 0.3538 | 0.024* | |
C34 | 0.32127 (13) | −0.12451 (18) | 0.50127 (13) | 0.0166 (4) | |
H34 | 0.3735 | −0.1627 | 0.5084 | 0.020* | |
C12 | 0.07424 (15) | −0.04458 (19) | 0.28722 (13) | 0.0200 (5) | |
H12 | 0.1263 | −0.0833 | 0.3133 | 0.024* | |
N2 | 0.0000 | −0.4720 (2) | 0.2500 | 0.0151 (5) | |
C41 | 0.19983 (13) | 0.34380 (17) | 0.33406 (12) | 0.0126 (4) | |
C42 | 0.27777 (13) | 0.41981 (18) | 0.34950 (11) | 0.0140 (4) | |
C43 | 0.26117 (15) | 0.53133 (19) | 0.32333 (13) | 0.0202 (5) | |
H43 | 0.2040 | 0.5526 | 0.2949 | 0.024* | |
C21 | 0.04395 (15) | −0.41230 (19) | 0.30933 (12) | 0.0196 (5) | |
H21 | 0.0746 | −0.4529 | 0.3521 | 0.023* | |
C45 | 0.40980 (15) | 0.5813 (2) | 0.37745 (14) | 0.0233 (5) | |
H45 | 0.4544 | 0.6360 | 0.3877 | 0.028* | |
C44 | 0.32578 (16) | 0.6116 (2) | 0.33774 (14) | 0.0251 (5) | |
H44 | 0.3124 | 0.6873 | 0.3204 | 0.030* | |
O1 | 0.14417 (9) | 0.34923 (13) | 0.27122 (8) | 0.0163 (3) | |
O2 | 0.18963 (9) | 0.28660 (13) | 0.38228 (8) | 0.0156 (3) | |
O7 | 0.01040 (12) | 0.34649 (16) | 0.36865 (10) | 0.0225 (4) | |
O6 | 0.14492 (13) | 0.42967 (17) | 0.14342 (11) | 0.0295 (4) | |
H7B | 0.040 (2) | 0.316 (3) | 0.4027 (19) | 0.038 (9)* | |
H6A | 0.161 (2) | 0.415 (3) | 0.188 (2) | 0.059 (11)* | |
H7A | −0.032 (2) | 0.373 (3) | 0.3760 (18) | 0.046 (10)* | |
H6B | 0.157 (3) | 0.500 (4) | 0.142 (2) | 0.078 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01550 (11) | 0.00625 (10) | 0.02060 (12) | 0.000 | 0.00808 (9) | 0.000 |
Cd2 | 0.01001 (10) | 0.00630 (10) | 0.01257 (11) | −0.00025 (7) | 0.00416 (8) | 0.00053 (8) |
S1 | 0.0107 (2) | 0.0113 (2) | 0.0172 (3) | 0.00090 (17) | 0.0064 (2) | 0.0012 (2) |
O3 | 0.0225 (8) | 0.0122 (7) | 0.0247 (9) | 0.0001 (6) | 0.0073 (7) | −0.0028 (7) |
N3 | 0.0116 (8) | 0.0105 (8) | 0.0134 (9) | 0.0000 (6) | 0.0042 (7) | 0.0020 (7) |
C23 | 0.0231 (15) | 0.0075 (13) | 0.0190 (16) | 0.000 | 0.0110 (13) | 0.000 |
N1 | 0.0157 (12) | 0.0172 (13) | 0.0156 (13) | 0.000 | 0.0075 (11) | 0.000 |
C31 | 0.0126 (9) | 0.0107 (10) | 0.0204 (11) | 0.0019 (8) | 0.0055 (9) | −0.0018 (9) |
C47 | 0.0155 (10) | 0.0123 (10) | 0.0142 (10) | −0.0008 (8) | 0.0076 (8) | 0.0017 (8) |
O4 | 0.0126 (7) | 0.0255 (9) | 0.0315 (10) | 0.0042 (6) | 0.0117 (7) | 0.0054 (7) |
C46 | 0.0134 (10) | 0.0194 (11) | 0.0228 (12) | −0.0039 (8) | 0.0065 (9) | 0.0016 (9) |
O5 | 0.0112 (7) | 0.0139 (7) | 0.0162 (8) | 0.0011 (5) | 0.0059 (6) | 0.0035 (6) |
C13 | 0.0265 (16) | 0.0070 (13) | 0.0170 (15) | 0.000 | 0.0112 (13) | 0.000 |
C11 | 0.0222 (11) | 0.0107 (10) | 0.0239 (12) | −0.0018 (8) | 0.0061 (10) | −0.0021 (9) |
C33 | 0.0127 (9) | 0.0087 (10) | 0.0127 (10) | −0.0001 (7) | 0.0044 (8) | −0.0001 (8) |
C35 | 0.0147 (10) | 0.0097 (10) | 0.0260 (12) | −0.0018 (8) | 0.0090 (9) | 0.0009 (9) |
C32 | 0.0106 (9) | 0.0106 (10) | 0.0224 (11) | −0.0007 (7) | 0.0064 (9) | −0.0017 (9) |
C22 | 0.0294 (12) | 0.0109 (10) | 0.0185 (12) | −0.0020 (9) | 0.0071 (10) | −0.0016 (9) |
C34 | 0.0135 (10) | 0.0105 (10) | 0.0269 (12) | 0.0011 (8) | 0.0091 (9) | 0.0020 (9) |
C12 | 0.0241 (11) | 0.0126 (10) | 0.0206 (12) | 0.0012 (8) | 0.0055 (10) | 0.0013 (9) |
N2 | 0.0205 (13) | 0.0053 (11) | 0.0212 (14) | 0.000 | 0.0098 (11) | 0.000 |
C41 | 0.0109 (9) | 0.0107 (10) | 0.0156 (10) | 0.0021 (7) | 0.0045 (8) | −0.0002 (8) |
C42 | 0.0160 (10) | 0.0130 (10) | 0.0146 (10) | −0.0018 (8) | 0.0077 (8) | 0.0002 (8) |
C43 | 0.0215 (11) | 0.0147 (11) | 0.0216 (12) | 0.0016 (8) | 0.0053 (10) | 0.0052 (9) |
C21 | 0.0269 (11) | 0.0120 (10) | 0.0171 (11) | 0.0014 (9) | 0.0054 (10) | 0.0029 (9) |
C45 | 0.0239 (12) | 0.0174 (11) | 0.0296 (13) | −0.0096 (9) | 0.0112 (10) | 0.0014 (10) |
C44 | 0.0318 (13) | 0.0111 (11) | 0.0313 (14) | −0.0024 (9) | 0.0109 (11) | 0.0069 (10) |
O1 | 0.0138 (7) | 0.0184 (8) | 0.0144 (8) | −0.0008 (6) | 0.0027 (6) | 0.0031 (6) |
O2 | 0.0142 (7) | 0.0171 (8) | 0.0127 (7) | −0.0035 (6) | 0.0018 (6) | 0.0032 (6) |
O7 | 0.0217 (9) | 0.0244 (9) | 0.0190 (9) | 0.0054 (7) | 0.0051 (8) | 0.0065 (7) |
O6 | 0.0443 (11) | 0.0241 (10) | 0.0224 (10) | −0.0102 (8) | 0.0152 (9) | −0.0001 (8) |
Cd1—N1 | 2.274 (3) | C13—C12 | 1.393 (3) |
Cd1—O1 | 2.3182 (16) | C11—C12 | 1.387 (3) |
Cd1—O1i | 2.3182 (16) | C11—H11 | 0.9500 |
Cd1—N2ii | 2.343 (3) | C33—C32 | 1.395 (3) |
Cd1—O7 | 2.352 (2) | C33—C34 | 1.398 (3) |
Cd1—O7i | 2.352 (2) | C33—C33iv | 1.481 (4) |
Cd2—O2iii | 2.2475 (16) | C35—C34 | 1.381 (3) |
Cd2—O2 | 2.2475 (16) | C35—H35 | 0.9500 |
Cd2—O5iii | 2.2907 (15) | C32—H32 | 0.9500 |
Cd2—O5 | 2.2907 (15) | C22—C21 | 1.380 (3) |
Cd2—N3iii | 2.327 (2) | C22—H22 | 0.9500 |
Cd2—N3 | 2.327 (2) | C34—H34 | 0.9500 |
S1—O3 | 1.4428 (17) | C12—H12 | 0.9500 |
S1—O4 | 1.4437 (16) | N2—C21 | 1.343 (3) |
S1—O5 | 1.4912 (17) | N2—C21i | 1.343 (3) |
S1—C47 | 1.783 (2) | N2—Cd1v | 2.343 (3) |
N3—C31 | 1.345 (3) | C41—O2 | 1.250 (3) |
N3—C35 | 1.345 (3) | C41—O1 | 1.262 (3) |
C23—C22i | 1.388 (3) | C41—C42 | 1.520 (3) |
C23—C22 | 1.388 (3) | C42—C43 | 1.398 (3) |
C23—C13 | 1.486 (4) | C43—C44 | 1.384 (3) |
N1—C11i | 1.352 (3) | C43—H43 | 0.9500 |
N1—C11 | 1.352 (3) | C21—H21 | 0.9500 |
C31—C32 | 1.382 (3) | C45—C44 | 1.383 (3) |
C31—H31 | 0.9500 | C45—H45 | 0.9500 |
C47—C46 | 1.393 (3) | C44—H44 | 0.9500 |
C47—C42 | 1.405 (3) | O7—H7B | 0.77 (4) |
C46—C45 | 1.390 (3) | O7—H7A | 0.85 (4) |
C46—H46 | 0.9500 | O6—H6A | 0.86 (4) |
C13—C12i | 1.393 (3) | O6—H6B | 0.85 (5) |
N1—Cd1—O1 | 96.13 (4) | C47—C46—H46 | 119.5 |
N1—Cd1—O1i | 96.13 (4) | S1—O5—Cd2 | 123.16 (9) |
O1—Cd1—O1i | 167.74 (8) | C12i—C13—C12 | 117.4 (3) |
N1—Cd1—N2ii | 180.0 | C12i—C13—C23 | 121.29 (14) |
O1—Cd1—N2ii | 83.87 (4) | C12—C13—C23 | 121.29 (14) |
O1i—Cd1—N2ii | 83.87 (4) | N1—C11—C12 | 123.2 (2) |
N1—Cd1—O7 | 95.26 (4) | N1—C11—H11 | 118.4 |
O1—Cd1—O7 | 97.94 (6) | C12—C11—H11 | 118.4 |
O1i—Cd1—O7 | 80.93 (6) | C32—C33—C34 | 116.47 (19) |
N2ii—Cd1—O7 | 84.74 (4) | C32—C33—C33iv | 121.9 (2) |
N1—Cd1—O7i | 95.26 (4) | C34—C33—C33iv | 121.7 (2) |
O1—Cd1—O7i | 80.93 (6) | N3—C35—C34 | 123.68 (19) |
O1i—Cd1—O7i | 97.94 (6) | N3—C35—H35 | 118.2 |
N2ii—Cd1—O7i | 84.74 (4) | C34—C35—H35 | 118.2 |
O7—Cd1—O7i | 169.48 (9) | C31—C32—C33 | 119.98 (19) |
O2iii—Cd2—O2 | 180.0 | C31—C32—H32 | 120.0 |
O2iii—Cd2—O5iii | 90.10 (5) | C33—C32—H32 | 120.0 |
O2—Cd2—O5iii | 89.90 (5) | C21—C22—C23 | 119.6 (2) |
O2iii—Cd2—O5 | 89.90 (5) | C21—C22—H22 | 120.2 |
O2—Cd2—O5 | 90.10 (5) | C23—C22—H22 | 120.2 |
O5iii—Cd2—O5 | 180.00 (8) | C35—C34—C33 | 119.85 (19) |
O2iii—Cd2—N3iii | 93.94 (6) | C35—C34—H34 | 120.1 |
O2—Cd2—N3iii | 86.06 (6) | C33—C34—H34 | 120.1 |
O5iii—Cd2—N3iii | 89.30 (5) | C11—C12—C13 | 119.7 (2) |
O5—Cd2—N3iii | 90.70 (5) | C11—C12—H12 | 120.2 |
O2iii—Cd2—N3 | 86.06 (6) | C13—C12—H12 | 120.2 |
O2—Cd2—N3 | 93.94 (6) | C21—N2—C21i | 117.2 (3) |
O5iii—Cd2—N3 | 90.70 (5) | C21—N2—Cd1v | 121.41 (13) |
O5—Cd2—N3 | 89.30 (5) | C21i—N2—Cd1v | 121.41 (13) |
N3iii—Cd2—N3 | 180.0 | O2—C41—O1 | 122.91 (19) |
O3—S1—O4 | 115.59 (10) | O2—C41—C42 | 121.40 (19) |
O3—S1—O5 | 112.47 (9) | O1—C41—C42 | 115.49 (19) |
O4—S1—O5 | 109.70 (10) | C43—C42—C47 | 117.85 (19) |
O3—S1—C47 | 107.19 (10) | C43—C42—C41 | 115.97 (19) |
O4—S1—C47 | 106.62 (10) | C47—C42—C41 | 126.15 (19) |
O5—S1—C47 | 104.46 (9) | C44—C43—C42 | 121.8 (2) |
C31—N3—C35 | 116.41 (18) | C44—C43—H43 | 119.1 |
C31—N3—Cd2 | 121.50 (13) | C42—C43—H43 | 119.1 |
C35—N3—Cd2 | 120.88 (13) | N2—C21—C22 | 123.0 (2) |
C22i—C23—C22 | 117.4 (3) | N2—C21—H21 | 118.5 |
C22i—C23—C13 | 121.30 (14) | C22—C21—H21 | 118.5 |
C22—C23—C13 | 121.30 (14) | C44—C45—C46 | 119.3 (2) |
C11i—N1—C11 | 116.8 (3) | C44—C45—H45 | 120.3 |
C11i—N1—Cd1 | 121.59 (14) | C46—C45—H45 | 120.3 |
C11—N1—Cd1 | 121.59 (14) | C45—C44—C43 | 119.9 (2) |
N3—C31—C32 | 123.58 (19) | C45—C44—H44 | 120.0 |
N3—C31—H31 | 118.2 | C43—C44—H44 | 120.0 |
C32—C31—H31 | 118.2 | C41—O1—Cd1 | 120.39 (13) |
C46—C47—C42 | 119.94 (19) | C41—O2—Cd2 | 142.14 (14) |
C46—C47—S1 | 116.11 (16) | Cd1—O7—H7B | 130 (2) |
C42—C47—S1 | 123.95 (16) | Cd1—O7—H7A | 118 (2) |
C45—C46—C47 | 121.1 (2) | H7B—O7—H7A | 108 (3) |
C45—C46—H46 | 119.5 | H6A—O6—H6B | 104 (4) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y+1, z; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1/2, −y−1/2, −z+1; (v) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O1 | 0.86 (4) | 1.97 (4) | 2.760 (3) | 153 (4) |
O6—H6B···O3vi | 0.85 (5) | 2.02 (5) | 2.855 (3) | 167 (5) |
O7—H7A···O6i | 0.84 (4) | 1.91 (4) | 2.720 (3) | 160 (3) |
O7—H7B···O5iii | 0.77 (4) | 2.14 (4) | 2.905 (3) | 172 (4) |
Symmetry codes: (i) −x, y, −z+1/2; (iii) −x+1/2, −y+1/2, −z+1; (vi) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C7H4O5S)2(C10H8N2)2(H2O)2]·2H2O |
Mr | 1009.6 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 16.888 (5), 11.722 (5), 20.258 (7) |
β (°) | 112.483 (5) |
V (Å3) | 3706 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.50 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Rigaku Mercury70 (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.613, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14147, 4254, 4059 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.060, 1.10 |
No. of reflections | 4254 |
No. of parameters | 273 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.86, −0.61 |
Computer programs: CrystalClear (Rigaku, 2002), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cd1—N1 | 2.274 (3) | Cd2—O2 | 2.2475 (16) |
Cd1—O1 | 2.3182 (16) | Cd2—O5 | 2.2907 (15) |
Cd1—N2i | 2.343 (3) | Cd2—N3 | 2.327 (2) |
Cd1—O7 | 2.352 (2) |
Symmetry code: (i) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O1 | 0.86 (4) | 1.97 (4) | 2.760 (3) | 153 (4) |
O6—H6B···O3ii | 0.85 (5) | 2.02 (5) | 2.855 (3) | 167 (5) |
O7—H7A···O6iii | 0.84 (4) | 1.91 (4) | 2.720 (3) | 160 (3) |
O7—H7B···O5iv | 0.77 (4) | 2.14 (4) | 2.905 (3) | 172 (4) |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+1/2, −z+1. |
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Recently, the design and synthesis of novel inorganic-organic supramolecular complexes have attracted considerable attention (Robson et al., 1992; Subramanian & Zaworotko, 1995), due to their potential applications in many areas (Zheng et al., 2003). Many cadmium(II)-carboxylate complexes (Shi et al., 2001; Eringathodi et al., 2001) have been synthesized, exhibiting a variety of coordination modes for the carboxylate group (Vaidhyanathan et al., 2000). On the other hand, few cadmium(II)-sulfonate complexes have been reported. Because organosulfonates, (RSO3)−, are poor ligands, they have typically been employed as `non-coordinating' anions. This has prompted us to search for such complexes. Here, we report the hydrothermal synthesis and characterization of the title compound, (I), a new cadmium(II)-sulfonatobenzoate coordination compound. \sch
Fig. 1 depicts the different coordination spheres and atom-numbering schemes of the two CdII atoms in the structure of (I). Atom Cd1 is six-coordinated by two N atoms [N1 and N2ii; symmetry code: (ii) x, 1 + y, z] from two 4,4'-bipyridine (4,4'-bipy) ligands which occupy the axial positions, two O atoms [O7 and O7i; symmetry code: (i) −x, y, 1/2 − z] from two different water molecules and two O atoms [O1 and O1i] from the carboxylic acid groups of two different 2-sulfonatobenzoate ligands, forming the square base. Another metal centre, atom Cd2, is also six-coordinated, in this case by two N atoms [N3 and N3iii; symmetry code: (iii) 1/2 − x, 1/2 − y, 1 − z] from two 4,4'-bipy, two O atoms [O2 and O2iii] from the carboxylic acid groups of two different 2-sulfonatobenzoate ligands and two O atoms [O5 and O5iii] from two different sulfonate groups. In the structure of (I), there are two different coordination spheres of the Cd atoms: atom Cd1 lies on a twofold axis and atom Cd2 lies on an inversion centre. Correspondingly, atoms N1 and N2 lie on a twofold axis by connecting Cd1 atoms, and atom N3 lies across an inversion centre by connecting Cd2 atoms. Therefore, the coordination geometry of both CdII atoms can be regarded as distorted hexahedral.
There are two distinct types of chain generated by the CdII atoms and 4,4'-bipy units alone (Fig. 2). Each CdII atom is connected by two trans 4,4'-bipy ligands, forming [010] chains. One chain type only contains Cd1 and 4,4'-bipy, while the other is composed of Cd2 and 4,4'-bipy units. The carboxylic acid groups act as bridges, by connecting the different CdII-4,4'-bipy chains along [100]. These three types of chain generate a two-dimensional coordination polymer sheet.
The Cd—N distances in (I) are in accord with other bonds found in cadmium(II)-4,4'-bipy complexes. The Cd—O distances involving the anion are slightly shorter than the Cd—O(water) distance and consistent with the average Cd—O bond distance reported for similar compounds (Hagrman et al., 1999). In the coordination polymer, the sulfonate group serves as a monodentate ligand.
It should be noted that both the carboxylic acid and the sulfonate groups are not only employed as coordinative groups, but also take part in the formation of hydrogen bonds. In the presence of solvent water molecules, coordinated water molecules, carboxylic acid groups and sulfonate groups, four different kinds of hydrogen bonds are observed in the structure of (I) (Table 2), namely hydrogen bonds between solvent water molecules and sulfonate O atoms, hydrogen bonds between coordinated water molecules and solvent water molecules, hydrogen bonds between solvent water molecules and carboxylic acid O atoms, and hydrogen bonds between coordinated water molecules and sulfonate O atoms. The effect of these hydrogen bonds is to link the two-dimensional coordination polymer layers into a three-dimensional framework (Fig. 3).