metal-organic compounds
catena-Poly[[diaqua[(4-tolylsulfanyl)acetato-κO]cadmium(II)]-μ-4,4′-bipyridine-κ2N:N′]
aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
*Correspondence e-mail: sky37@zjnu.cn
The title complex, [Cd(C9H9O2S)2(C10H8N2)(H2O)2]n, has a linear chain structure. The central CdII ion is in a slightly disorted octahedral environment, coordinated by two aqua ligands, two (4-tolylsulfanyl)acetate ligands and two bridging 4,4′-bipyridine ligands. The CdII ion lies on a twofold rotation axis. Intermolecular O—H⋯O hydrogen bonds connect adjacent chains, forming a layer structure. An intramolecular O—H⋯O hydrogen bond is also present.
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808024720/at2595sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808024720/at2595Isup2.hkl
CdSO4.8/3H2O (0.128 g, 0.5 mmol), (4-tolylsulfanyl)acetic acid (0.091 g, 0.5 mmol), 4,4'-bipy (0.039 g, 0.25 mmol) and H2O (18 ml) were sealed in a 25 ml stainless-steel reactor with a Teflon-lined stainless steel reactor and the solution was heated at 433 K for 72 h and then cooled to room temperature over a period of 72 h. Colourless crystals suitable for X-ray analysis were obtained.
The methyl groups were allowed to rotate to fit the electron density [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)]; the other H atoms were positioned geometrically [aromatic C—H = 0.93 Å and aliphatic C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C)]. Water H atom H1WA was positioned geometrically, with O—H = 0.82 Å, and the other water H atoms H1WB was located from a difference Fourier map, and they were refined with distance restraints of O—H = 0.85 (2) Å and H···H = 1.30 (2) Å; their displacement parameters were set to 1.5Ueq(O).
Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cd(C9H9O2S)2(C10H8N2)(H2O)2] | F(000) = 1360 |
Mr = 667.09 | Dx = 1.589 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7745 reflections |
a = 21.659 (4) Å | θ = 2.7–27.5° |
b = 11.590 (2) Å | µ = 0.98 mm−1 |
c = 11.137 (2) Å | T = 296 K |
β = 93.88 (3)° | Block, colourless |
V = 2789.3 (9) Å3 | 0.40 × 0.35 × 0.17 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 3154 independent reflections |
Radiation source: fine-focus sealed tube | 2937 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −27→27 |
Tmin = 0.68, Tmax = 0.85 | k = −14→14 |
12185 measured reflections | l = −14→14 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0658P)2 + 5.8321P] where P = (Fo2 + 2Fc2)/3 |
3154 reflections | (Δ/σ)max < 0.001 |
184 parameters | Δρmax = 0.60 e Å−3 |
3 restraints | Δρmin = −0.37 e Å−3 |
[Cd(C9H9O2S)2(C10H8N2)(H2O)2] | V = 2789.3 (9) Å3 |
Mr = 667.09 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.659 (4) Å | µ = 0.98 mm−1 |
b = 11.590 (2) Å | T = 296 K |
c = 11.137 (2) Å | 0.40 × 0.35 × 0.17 mm |
β = 93.88 (3)° |
Bruker APEXII area-detector diffractometer | 3154 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2937 reflections with I > 2σ(I) |
Tmin = 0.68, Tmax = 0.85 | Rint = 0.017 |
12185 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 3 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.60 e Å−3 |
3154 reflections | Δρmin = −0.37 e Å−3 |
184 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 | 0.05131 (2) | 0.2500 | 0.03198 (12) | |
S1 | 0.14880 (4) | 0.21253 (9) | −0.05125 (7) | 0.0514 (2) | |
O1 | 0.08144 (10) | 0.05635 (16) | 0.1325 (2) | 0.0353 (5) | |
O1W | 0.06445 (12) | 0.0644 (2) | 0.4169 (2) | 0.0415 (5) | |
H1WA | 0.0990 | 0.0836 | 0.3982 | 0.062* | |
H1WB | 0.0700 (14) | 0.012 (3) | 0.464 (3) | 0.047 (11)* | |
O2 | 0.15198 (12) | 0.1218 (3) | 0.2705 (2) | 0.0632 (8) | |
N1 | 0.0000 | −0.1422 (3) | 0.2500 | 0.0290 (6) | |
N2 | 0.0000 | −0.7537 (3) | 0.2500 | 0.0303 (7) | |
C1 | 0.16190 (13) | 0.3534 (3) | 0.0059 (3) | 0.0422 (7) | |
C2 | 0.19048 (16) | 0.3817 (4) | 0.1177 (3) | 0.0506 (9) | |
H2A | 0.2025 | 0.3234 | 0.1717 | 0.061* | |
C3 | 0.20102 (17) | 0.4945 (4) | 0.1488 (3) | 0.0544 (9) | |
H3A | 0.2210 | 0.5109 | 0.2234 | 0.065* | |
C4 | 0.18302 (16) | 0.5854 (4) | 0.0730 (3) | 0.0520 (8) | |
C5 | 0.15375 (18) | 0.5566 (3) | −0.0382 (3) | 0.0508 (9) | |
H5A | 0.1407 | 0.6152 | −0.0910 | 0.061* | |
C6 | 0.14372 (16) | 0.4440 (3) | −0.0715 (3) | 0.0469 (9) | |
H6A | 0.1245 | 0.4275 | −0.1468 | 0.056* | |
C7 | 0.1952 (2) | 0.7075 (5) | 0.1109 (4) | 0.0714 (12) | |
H7A | 0.2389 | 0.7186 | 0.1271 | 0.107* | |
H7B | 0.1742 | 0.7236 | 0.1822 | 0.107* | |
H7C | 0.1803 | 0.7586 | 0.0476 | 0.107* | |
C8 | 0.17850 (15) | 0.1165 (4) | 0.0670 (3) | 0.0495 (8) | |
H8A | 0.1879 | 0.0426 | 0.0316 | 0.059* | |
H8B | 0.2169 | 0.1481 | 0.1029 | 0.059* | |
C9 | 0.13410 (13) | 0.0967 (3) | 0.1664 (3) | 0.0385 (6) | |
C10 | −0.02550 (18) | −0.2021 (3) | 0.3350 (3) | 0.0470 (8) | |
H10A | −0.0435 | −0.1619 | 0.3959 | 0.056* | |
C11 | −0.02676 (18) | −0.3207 (3) | 0.3379 (3) | 0.0441 (8) | |
H11A | −0.0457 | −0.3584 | 0.3992 | 0.053* | |
C12 | 0.0000 | −0.3838 (3) | 0.2500 | 0.0259 (7) | |
C13 | 0.0000 | −0.5111 (3) | 0.2500 | 0.0250 (7) | |
C14 | −0.02533 (15) | −0.5744 (3) | 0.3404 (3) | 0.0357 (6) | |
H14A | −0.0432 | −0.5363 | 0.4029 | 0.043* | |
C15 | −0.02423 (15) | −0.6931 (3) | 0.3382 (3) | 0.0365 (6) | |
H15A | −0.0410 | −0.7331 | 0.4006 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03971 (19) | 0.02551 (18) | 0.03160 (18) | 0.000 | 0.00893 (12) | 0.000 |
S1 | 0.0526 (5) | 0.0682 (6) | 0.0343 (4) | −0.0107 (4) | 0.0090 (3) | 0.0052 (4) |
O1 | 0.0353 (11) | 0.0355 (11) | 0.0362 (11) | −0.0019 (7) | 0.0104 (9) | −0.0040 (8) |
O1W | 0.0525 (13) | 0.0448 (12) | 0.0281 (10) | 0.0011 (10) | 0.0085 (9) | 0.0047 (9) |
O2 | 0.0444 (13) | 0.107 (2) | 0.0385 (13) | −0.0222 (15) | 0.0024 (10) | 0.0066 (14) |
N1 | 0.0354 (16) | 0.0245 (15) | 0.0280 (15) | 0.000 | 0.0076 (13) | 0.000 |
N2 | 0.0364 (16) | 0.0283 (16) | 0.0272 (15) | 0.000 | 0.0089 (13) | 0.000 |
C1 | 0.0259 (13) | 0.071 (2) | 0.0310 (14) | −0.0051 (13) | 0.0104 (11) | 0.0042 (14) |
C2 | 0.0409 (16) | 0.080 (3) | 0.0311 (15) | −0.0024 (17) | 0.0043 (12) | 0.0064 (16) |
C3 | 0.0416 (17) | 0.088 (3) | 0.0336 (16) | −0.0069 (19) | 0.0047 (13) | −0.0062 (18) |
C4 | 0.0392 (16) | 0.074 (2) | 0.0447 (18) | −0.0076 (17) | 0.0169 (14) | −0.0093 (18) |
C5 | 0.0455 (19) | 0.068 (3) | 0.0399 (18) | 0.0016 (15) | 0.0091 (15) | 0.0059 (15) |
C6 | 0.0368 (16) | 0.074 (3) | 0.0302 (15) | −0.0021 (14) | 0.0025 (12) | 0.0062 (14) |
C7 | 0.070 (3) | 0.080 (3) | 0.066 (3) | −0.010 (2) | 0.023 (2) | −0.014 (2) |
C8 | 0.0342 (15) | 0.067 (2) | 0.0492 (18) | 0.0037 (15) | 0.0146 (13) | 0.0072 (16) |
C9 | 0.0321 (13) | 0.0426 (16) | 0.0417 (16) | 0.0027 (12) | 0.0084 (12) | 0.0068 (13) |
C10 | 0.073 (2) | 0.0307 (15) | 0.0411 (16) | 0.0028 (15) | 0.0315 (16) | −0.0034 (13) |
C11 | 0.069 (2) | 0.0292 (14) | 0.0374 (15) | 0.0012 (14) | 0.0306 (15) | 0.0021 (12) |
C12 | 0.0284 (16) | 0.0253 (17) | 0.0245 (16) | 0.000 | 0.0048 (13) | 0.000 |
C13 | 0.0260 (16) | 0.0236 (17) | 0.0259 (16) | 0.000 | 0.0047 (13) | 0.000 |
C14 | 0.0510 (17) | 0.0298 (13) | 0.0289 (13) | −0.0056 (12) | 0.0207 (12) | −0.0053 (11) |
C15 | 0.0506 (16) | 0.0293 (14) | 0.0320 (13) | −0.0068 (12) | 0.0198 (12) | −0.0030 (11) |
Cd1—N1 | 2.243 (3) | C4—C5 | 1.393 (5) |
Cd1—O1W | 2.253 (2) | C4—C7 | 1.495 (6) |
Cd1—O1Wi | 2.253 (2) | C5—C6 | 1.371 (5) |
Cd1—N2ii | 2.259 (3) | C5—H5A | 0.9300 |
Cd1—O1 | 2.267 (2) | C6—H6A | 0.9300 |
Cd1—O1i | 2.267 (2) | C7—H7A | 0.9600 |
S1—C1 | 1.769 (4) | C7—H7B | 0.9600 |
S1—C8 | 1.809 (4) | C7—H7C | 0.9600 |
O1—C9 | 1.266 (4) | C8—C9 | 1.532 (4) |
O1W—H1WA | 0.8200 | C8—H8A | 0.9700 |
O1W—H1WB | 0.805 (17) | C8—H8B | 0.9700 |
O2—C9 | 1.232 (4) | C10—C11 | 1.375 (4) |
N1—C10i | 1.325 (3) | C10—H10A | 0.9300 |
N1—C10 | 1.325 (3) | C11—C12 | 1.381 (3) |
N2—C15 | 1.343 (3) | C11—H11A | 0.9300 |
N2—C15i | 1.343 (3) | C12—C11i | 1.381 (3) |
N2—Cd1iii | 2.259 (3) | C12—C13 | 1.475 (5) |
C1—C2 | 1.391 (5) | C13—C14i | 1.389 (3) |
C1—C6 | 1.398 (5) | C13—C14 | 1.389 (3) |
C2—C3 | 1.367 (7) | C14—C15 | 1.376 (4) |
C2—H2A | 0.9300 | C14—H14A | 0.9300 |
C3—C4 | 1.389 (6) | C15—H15A | 0.9300 |
C3—H3A | 0.9300 | ||
N1—Cd1—O1W | 93.87 (6) | C6—C5—H5A | 119.2 |
N1—Cd1—O1Wi | 93.87 (6) | C4—C5—H5A | 119.2 |
O1W—Cd1—O1Wi | 172.26 (12) | C5—C6—C1 | 121.0 (3) |
N1—Cd1—N2ii | 180.0 | C5—C6—H6A | 119.5 |
O1W—Cd1—N2ii | 86.13 (6) | C1—C6—H6A | 119.5 |
O1Wi—Cd1—N2ii | 86.13 (6) | C4—C7—H7A | 109.5 |
N1—Cd1—O1 | 91.48 (5) | C4—C7—H7B | 109.5 |
O1W—Cd1—O1 | 90.67 (9) | H7A—C7—H7B | 109.5 |
O1Wi—Cd1—O1 | 89.13 (9) | C4—C7—H7C | 109.5 |
N2ii—Cd1—O1 | 88.52 (5) | H7A—C7—H7C | 109.5 |
N1—Cd1—O1i | 91.48 (5) | H7B—C7—H7C | 109.5 |
O1W—Cd1—O1i | 89.13 (9) | C9—C8—S1 | 114.1 (2) |
O1Wi—Cd1—O1i | 90.67 (9) | C9—C8—H8A | 108.7 |
N2ii—Cd1—O1i | 88.52 (5) | S1—C8—H8A | 108.7 |
O1—Cd1—O1i | 177.04 (10) | C9—C8—H8B | 108.7 |
C1—S1—C8 | 105.40 (18) | S1—C8—H8B | 108.7 |
C9—O1—Cd1 | 123.9 (2) | H8A—C8—H8B | 107.6 |
Cd1—O1W—H1WA | 109.5 | O2—C9—O1 | 126.0 (3) |
Cd1—O1W—H1WB | 123 (3) | O2—C9—C8 | 118.2 (3) |
H1WA—O1W—H1WB | 105.7 | O1—C9—C8 | 115.9 (3) |
C10i—N1—C10 | 116.8 (4) | N1—C10—C11 | 123.4 (3) |
C10i—N1—Cd1 | 121.62 (18) | N1—C10—H10A | 118.3 |
C10—N1—Cd1 | 121.62 (18) | C11—C10—H10A | 118.3 |
C15—N2—C15i | 116.8 (4) | C10—C11—C12 | 120.2 (3) |
C15—N2—Cd1iii | 121.58 (18) | C10—C11—H11A | 119.9 |
C15i—N2—Cd1iii | 121.58 (18) | C12—C11—H11A | 119.9 |
C2—C1—C6 | 117.7 (4) | C11i—C12—C11 | 116.0 (4) |
C2—C1—S1 | 126.2 (3) | C11i—C12—C13 | 122.02 (18) |
C6—C1—S1 | 116.1 (3) | C11—C12—C13 | 122.02 (18) |
C3—C2—C1 | 120.6 (4) | C14i—C13—C14 | 116.2 (3) |
C3—C2—H2A | 119.7 | C14i—C13—C12 | 121.89 (17) |
C1—C2—H2A | 119.7 | C14—C13—C12 | 121.89 (17) |
C2—C3—C4 | 122.4 (3) | C15—C14—C13 | 120.4 (3) |
C2—C3—H3A | 118.8 | C15—C14—H14A | 119.8 |
C4—C3—H3A | 118.8 | C13—C14—H14A | 119.8 |
C3—C4—C5 | 116.8 (4) | N2—C15—C14 | 123.0 (3) |
C3—C4—C7 | 120.6 (4) | N2—C15—H15A | 118.5 |
C5—C4—C7 | 122.6 (4) | C14—C15—H15A | 118.5 |
C6—C5—C4 | 121.5 (4) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y+1, z; (iii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2 | 0.82 | 1.94 | 2.667 (4) | 148 |
O1W—H1WB···O1iv | 0.81 (2) | 2.04 (2) | 2.782 (3) | 154 (4) |
Symmetry code: (iv) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C9H9O2S)2(C10H8N2)(H2O)2] |
Mr | 667.09 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 21.659 (4), 11.590 (2), 11.137 (2) |
β (°) | 93.88 (3) |
V (Å3) | 2789.3 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.40 × 0.35 × 0.17 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.68, 0.85 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12185, 3154, 2937 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.112, 1.12 |
No. of reflections | 3154 |
No. of parameters | 184 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.37 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2 | 0.82 | 1.94 | 2.667 (4) | 147.5 |
O1W—H1WB···O1i | 0.805 (17) | 2.04 (2) | 2.782 (3) | 154 (4) |
Symmetry code: (i) x, −y, z+1/2. |
Footnotes
‡Current address: Wenzhou Medical College Pharmacy School, Wenzhou Medical College, Wenzhou, Zhejiang 325035, People's Republic of China.
References
Bruker (2006). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lin, H., Su, H. & Feng, Y. (2006). Acta Cryst. E62, m747–m749. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, X.-Y., Su, H. & Feng, Y.-L. (2006). Acta Cryst. E62, m1393–m1394. Web of Science CSD CrossRef IUCr Journals Google Scholar
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The title compound, (I), is isostructural with the NiII (Lin et al., 2006) and CoII analogues (Zheng et al., 2006). The structure of (I) (Fig.1) consists of linear chains formed through 4,4'-bipy ligands linking six-coordinated CdII ions which lie on twofold rotation axes. Intermolecular O—H···O hydrogen bonds link neighboring chains to form a two-dimensional network. It is notable that these chains are arranged alternately and the 4-tolysulfanyl groups are almost coplanar. There is no signifcant π-π interactions between the planes of adjacent chains with centroid-centroid distance of 6.19 (1)Å and plane-to-plane distance of 3.64 (1) Å.