Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107051670/tr3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051670/tr3018Isup2.hkl |
CCDC reference: 677082
For related literature, see: Chui et al. (1999); Cremer & Pople (1975); Danish & Rajendraprasad (2003); Desiraju (1995); Etter (1990); Fariati, Craig & Phillips (1998); Fujita et al. (1994); Ganley et al. (2001); Hu et al. (2003); Hussain (1996); Kumaresan et al. (2006); Matsumoto et al. (1999); Ramasubramanian et al. (2007); Zou et al. (1998).
A mixture of CuSO4·5H2O (0.0624 g, 0.25 mmol), HOPTP (0.0995 g, 0.50 mmol) and NaOH (0.040 g, 0.50 mmol) in ethanol (20 ml) was stirred for 10 h at room temperature. The stirred solution was filtered and kept for slow evaporation. After a week, peacock-blue coloured [Red in CIF - please clarify] crystalline blocks of [Cu(C8H8O3NS)2(H2O)]n.2nH2O appeared. The crystals were collected by filtration, washed with deionized water followed by diethyl ether, and then dried (yield 0.090 g, 70%).
Water H atoms were located and refined subject to O—H distance restraints of 0.82 (1) Å. The remaining H atoms were refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.5Ueq(C) for idealized secondary CH2, and with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).
[Cu(C8H8NO3S)2(H2O)]·2H2O | F(000) = 1060 |
Mr = 514.02 | Dx = 1.632 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5123 reflections |
a = 6.9091 (5) Å | θ = 2.3–25.0° |
b = 8.6855 (7) Å | µ = 1.30 mm−1 |
c = 34.899 (3) Å | T = 298 K |
β = 92.974 (1)° | Block, blue |
V = 2091.4 (3) Å3 | 0.36 × 0.22 × 0.14 mm |
Z = 4 |
Bruker APEX CCD area-detector diffractometer | 3769 independent reflections |
Radiation source: fine-focus sealed tube | 3567 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→7 |
Tmin = 0.653, Tmax = 0.839 | k = −10→9 |
10850 measured reflections | l = −41→41 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0548P)2 + 2.1602P] where P = (Fo2 + 2Fc2)/3 |
3769 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 0.78 e Å−3 |
9 restraints | Δρmin = −0.28 e Å−3 |
[Cu(C8H8NO3S)2(H2O)]·2H2O | V = 2091.4 (3) Å3 |
Mr = 514.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9091 (5) Å | µ = 1.30 mm−1 |
b = 8.6855 (7) Å | T = 298 K |
c = 34.899 (3) Å | 0.36 × 0.22 × 0.14 mm |
β = 92.974 (1)° |
Bruker APEX CCD area-detector diffractometer | 3769 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3567 reflections with I > 2σ(I) |
Tmin = 0.653, Tmax = 0.839 | Rint = 0.021 |
10850 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 9 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | Δρmax = 0.78 e Å−3 |
3769 reflections | Δρmin = −0.28 e Å−3 |
289 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 | ||
Cu1 | 0.95692 (6) | 0.87437 (5) | 0.147830 (11) | 0.02869 (15) | |
S1 | 0.98543 (13) | 0.81422 (11) | 0.25851 (2) | 0.0345 (2) | |
S2 | 0.76836 (14) | 0.34348 (12) | 0.01097 (3) | 0.0420 (2) | |
O1 | 0.8147 (4) | 0.7737 (3) | 0.18764 (7) | 0.0375 (6) | |
O2 | 1.0496 (3) | 0.5728 (3) | 0.32722 (7) | 0.0324 (5) | |
O3 | 1.2928 (4) | 0.6147 (3) | 0.36954 (8) | 0.0489 (7) | |
O4 | 0.7569 (4) | 0.1764 (4) | −0.05276 (9) | 0.0627 (9) | |
O5 | 0.9776 (3) | 0.6844 (3) | 0.12055 (7) | 0.0366 (6) | |
O6 | 0.6608 (4) | 0.6647 (3) | 0.10854 (8) | 0.0448 (6) | |
O7 | 1.1583 (5) | 0.9511 (3) | 0.11680 (9) | 0.0617 (9) | |
O8 | 0.6717 (4) | 0.0348 (4) | 0.36558 (11) | 0.0641 (9) | |
O9 | 0.6673 (5) | 0.7248 (4) | 0.38212 (12) | 0.0692 (10) | |
N1 | 0.7013 (4) | 0.8632 (3) | 0.20840 (8) | 0.0319 (6) | |
N2 | 0.5847 (4) | 0.1671 (4) | −0.03813 (9) | 0.0377 (7) | |
C1 | 0.7630 (5) | 0.8959 (4) | 0.24509 (9) | 0.0294 (7) | |
C2 | 0.6413 (5) | 0.9823 (4) | 0.26747 (10) | 0.0359 (8) | |
H2 | 0.6795 | 1.0070 | 0.2927 | 0.043* | |
C3 | 0.4645 (6) | 1.0307 (4) | 0.25203 (12) | 0.0428 (9) | |
H3 | 0.3823 | 1.0870 | 0.2670 | 0.051* | |
C4 | 0.4081 (5) | 0.9958 (5) | 0.21415 (12) | 0.0456 (9) | |
H4 | 0.2898 | 1.0304 | 0.2035 | 0.055* | |
C5 | 0.5277 (6) | 0.9106 (4) | 0.19292 (11) | 0.0413 (9) | |
H5 | 0.4905 | 0.8848 | 0.1677 | 0.050* | |
C6 | 1.0202 (5) | 0.8859 (4) | 0.30723 (10) | 0.0348 (8) | |
H6A | 1.0299 | 0.9973 | 0.3070 | 0.042* | |
H6B | 0.9102 | 0.8577 | 0.3219 | 0.042* | |
C7 | 1.2059 (5) | 0.8166 (4) | 0.32586 (11) | 0.0368 (8) | |
H7A | 1.3028 | 0.8117 | 0.3068 | 0.044* | |
H7B | 1.2546 | 0.8852 | 0.3461 | 0.044* | |
C8 | 1.1821 (5) | 0.6575 (4) | 0.34270 (10) | 0.0318 (7) | |
C9 | 0.5595 (5) | 0.2460 (4) | −0.00514 (10) | 0.0330 (8) | |
C10 | 0.3816 (5) | 0.2391 (4) | 0.01102 (11) | 0.0424 (9) | |
H10 | 0.3618 | 0.2925 | 0.0336 | 0.051* | |
C11 | 0.2331 (6) | 0.1534 (5) | −0.00615 (13) | 0.0481 (10) | |
H11 | 0.1131 | 0.1489 | 0.0047 | 0.058* | |
C12 | 0.2640 (6) | 0.0752 (5) | −0.03926 (13) | 0.0484 (10) | |
H12 | 0.1653 | 0.0161 | −0.0509 | 0.058* | |
C13 | 0.4397 (6) | 0.0839 (5) | −0.05510 (11) | 0.0450 (9) | |
H13 | 0.4597 | 0.0320 | −0.0779 | 0.054* | |
C14 | 0.6951 (5) | 0.4274 (4) | 0.05541 (10) | 0.0383 (8) | |
H14A | 0.5920 | 0.5017 | 0.0504 | 0.046* | |
H14B | 0.6489 | 0.3482 | 0.0723 | 0.046* | |
C15 | 0.8727 (5) | 0.5056 (4) | 0.07359 (11) | 0.0395 (8) | |
H15A | 0.9434 | 0.5546 | 0.0536 | 0.047* | |
H15B | 0.9566 | 0.4280 | 0.0856 | 0.047* | |
C16 | 0.8265 (5) | 0.6255 (4) | 0.10336 (9) | 0.0310 (7) | |
H7C | 1.192 (5) | 1.042 (2) | 0.1184 (9) | 0.037* | |
H7D | 1.184 (5) | 0.911 (3) | 0.0958 (7) | 0.037* | |
H9C | 0.556 (3) | 0.696 (4) | 0.3784 (11) | 0.037* | |
H9D | 0.691 (5) | 0.814 (2) | 0.3799 (12) | 0.037* | |
H8C | 0.567 (3) | 0.071 (4) | 0.3727 (10) | 0.037* | |
H8D | 0.767 (3) | 0.079 (4) | 0.3772 (10) | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0300 (2) | 0.0272 (2) | 0.0287 (2) | 0.00117 (15) | 0.00023 (17) | −0.00681 (16) |
S1 | 0.0336 (5) | 0.0378 (5) | 0.0319 (5) | 0.0097 (4) | 0.0008 (4) | −0.0004 (4) |
S2 | 0.0402 (5) | 0.0477 (6) | 0.0386 (5) | −0.0093 (4) | 0.0063 (4) | −0.0179 (4) |
O1 | 0.0514 (15) | 0.0292 (12) | 0.0325 (12) | 0.0044 (11) | 0.0086 (11) | −0.0012 (10) |
O2 | 0.0381 (13) | 0.0258 (12) | 0.0332 (12) | −0.0046 (10) | −0.0001 (10) | 0.0067 (10) |
O3 | 0.0509 (17) | 0.0465 (16) | 0.0475 (16) | −0.0011 (13) | −0.0144 (13) | 0.0155 (13) |
O4 | 0.0521 (18) | 0.085 (2) | 0.0533 (18) | −0.0226 (16) | 0.0200 (14) | −0.0373 (17) |
O5 | 0.0335 (13) | 0.0324 (13) | 0.0443 (14) | −0.0013 (10) | 0.0050 (11) | −0.0165 (11) |
O6 | 0.0346 (15) | 0.0496 (16) | 0.0504 (16) | 0.0034 (12) | 0.0037 (12) | −0.0125 (13) |
O7 | 0.077 (2) | 0.0455 (17) | 0.067 (2) | −0.0287 (16) | 0.0422 (17) | −0.0309 (16) |
O8 | 0.0381 (17) | 0.0564 (19) | 0.098 (3) | −0.0045 (14) | 0.0092 (17) | −0.0187 (18) |
O9 | 0.0418 (17) | 0.0453 (18) | 0.120 (3) | 0.0050 (14) | 0.0011 (19) | 0.010 (2) |
N1 | 0.0378 (16) | 0.0302 (15) | 0.0279 (14) | −0.0017 (12) | 0.0042 (12) | −0.0003 (12) |
N2 | 0.0394 (17) | 0.0399 (17) | 0.0339 (16) | −0.0025 (13) | 0.0020 (13) | −0.0073 (14) |
C1 | 0.0316 (18) | 0.0247 (16) | 0.0321 (17) | 0.0002 (13) | 0.0024 (14) | 0.0038 (14) |
C2 | 0.039 (2) | 0.0338 (19) | 0.0348 (18) | 0.0041 (15) | 0.0048 (15) | 0.0012 (15) |
C3 | 0.040 (2) | 0.039 (2) | 0.051 (2) | 0.0049 (16) | 0.0131 (18) | 0.0031 (18) |
C4 | 0.031 (2) | 0.052 (2) | 0.054 (2) | 0.0031 (17) | −0.0032 (18) | 0.011 (2) |
C5 | 0.041 (2) | 0.044 (2) | 0.038 (2) | −0.0051 (17) | −0.0052 (16) | 0.0084 (17) |
C6 | 0.044 (2) | 0.0258 (17) | 0.0339 (18) | 0.0040 (15) | −0.0025 (16) | −0.0006 (14) |
C7 | 0.041 (2) | 0.0296 (18) | 0.0388 (19) | −0.0052 (15) | −0.0087 (16) | 0.0028 (15) |
C8 | 0.0345 (19) | 0.0313 (17) | 0.0300 (17) | 0.0036 (14) | 0.0042 (15) | 0.0016 (14) |
C9 | 0.037 (2) | 0.0308 (18) | 0.0310 (17) | 0.0021 (14) | −0.0008 (15) | −0.0020 (15) |
C10 | 0.042 (2) | 0.041 (2) | 0.044 (2) | 0.0055 (17) | 0.0030 (17) | −0.0054 (18) |
C11 | 0.030 (2) | 0.048 (2) | 0.066 (3) | 0.0027 (17) | −0.0002 (19) | 0.004 (2) |
C12 | 0.046 (2) | 0.037 (2) | 0.060 (3) | −0.0063 (17) | −0.016 (2) | 0.0033 (19) |
C13 | 0.053 (2) | 0.043 (2) | 0.038 (2) | −0.0046 (18) | −0.0070 (18) | −0.0068 (17) |
C14 | 0.045 (2) | 0.039 (2) | 0.0319 (18) | −0.0029 (16) | 0.0041 (16) | −0.0109 (16) |
C15 | 0.040 (2) | 0.040 (2) | 0.0387 (19) | −0.0019 (16) | 0.0046 (16) | −0.0108 (17) |
C16 | 0.039 (2) | 0.0252 (16) | 0.0291 (17) | −0.0047 (14) | 0.0011 (15) | −0.0011 (14) |
Cu1—O5 | 1.914 (2) | C2—C3 | 1.375 (5) |
Cu1—O7 | 1.926 (3) | C2—H2 | 0.9300 |
Cu1—O2i | 1.933 (2) | C3—C4 | 1.392 (6) |
Cu1—O3i | 2.755 (1) | C3—H3 | 0.9300 |
Cu1—O1 | 1.950 (2) | C4—C5 | 1.358 (6) |
S1—C1 | 1.735 (3) | C4—H4 | 0.9300 |
S1—C6 | 1.815 (3) | C5—H5 | 0.9300 |
S2—C9 | 1.741 (4) | C6—C7 | 1.531 (5) |
S2—C14 | 1.810 (3) | C6—H6A | 0.9700 |
O1—N1 | 1.342 (4) | C6—H6B | 0.9700 |
O2—C8 | 1.273 (4) | C7—C8 | 1.514 (5) |
O2—Cu1ii | 1.933 (2) | C7—H7A | 0.9700 |
O3—C8 | 1.235 (4) | C7—H7B | 0.9700 |
O4—N2 | 1.321 (4) | C9—C10 | 1.380 (5) |
O5—C16 | 1.283 (4) | C10—C11 | 1.379 (6) |
O6—C16 | 1.217 (4) | C10—H10 | 0.9300 |
O7—H7C | 0.822 (17) | C11—C12 | 1.367 (6) |
O7—H7D | 0.839 (17) | C11—H11 | 0.9300 |
O8—H8C | 0.837 (17) | C12—C13 | 1.362 (6) |
O8—H8D | 0.847 (18) | C12—H12 | 0.9300 |
O9—H9C | 0.811 (17) | C13—H13 | 0.9300 |
O9—H9D | 0.798 (17) | C14—C15 | 1.513 (5) |
N1—C5 | 1.353 (5) | C14—H14A | 0.9700 |
N1—C1 | 1.358 (4) | C14—H14B | 0.9700 |
N2—C13 | 1.347 (5) | C15—C16 | 1.517 (5) |
N2—C9 | 1.359 (4) | C15—H15A | 0.9700 |
C1—C2 | 1.396 (5) | C15—H15B | 0.9700 |
O5—Cu1—O7 | 86.80 (11) | C7—C6—H6B | 109.8 |
O5—Cu1—O2i | 175.57 (11) | S1—C6—H6B | 109.8 |
O7—Cu1—O2i | 88.78 (11) | H6A—C6—H6B | 108.3 |
O5—Cu1—O1 | 91.22 (10) | C8—C7—C6 | 114.7 (3) |
O7—Cu1—O1 | 164.02 (14) | C8—C7—H7A | 108.6 |
O1—Cu1—O2i | 93.12 (10) | C6—C7—H7A | 108.6 |
O7—Cu1—O3i | 94.38 (1) | C8—C7—H7B | 108.6 |
O1—Cu1—O3i | 99.40 (1) | C6—C7—H7B | 108.6 |
C1—S1—C6 | 100.66 (16) | H7A—C7—H7B | 107.6 |
C9—S2—C14 | 102.04 (17) | O3—C8—O2 | 123.4 (3) |
N1—O1—Cu1 | 117.08 (19) | O3—C8—C7 | 119.6 (3) |
C8—O2—Cu1ii | 110.9 (2) | O2—C8—C7 | 116.9 (3) |
C16—O5—Cu1 | 119.8 (2) | N2—C9—C10 | 118.7 (3) |
Cu1—O7—H7C | 120 (2) | N2—C9—S2 | 112.2 (3) |
Cu1—O7—H7D | 123 (2) | C10—C9—S2 | 129.0 (3) |
H7C—O7—H7D | 113 (2) | C11—C10—C9 | 120.3 (4) |
H8C—O8—H8D | 110 (2) | C11—C10—H10 | 119.9 |
H9C—O9—H9D | 119 (3) | C9—C10—H10 | 119.9 |
O1—N1—C5 | 119.4 (3) | C12—C11—C10 | 119.4 (4) |
O1—N1—C1 | 117.8 (3) | C12—C11—H11 | 120.3 |
C5—N1—C1 | 122.7 (3) | C10—C11—H11 | 120.3 |
O4—N2—C13 | 121.8 (3) | C13—C12—C11 | 119.8 (4) |
O4—N2—C9 | 117.0 (3) | C13—C12—H12 | 120.1 |
C13—N2—C9 | 121.2 (3) | C11—C12—H12 | 120.1 |
N1—C1—C2 | 118.1 (3) | N2—C13—C12 | 120.7 (4) |
N1—C1—S1 | 113.5 (2) | N2—C13—H13 | 119.7 |
C2—C1—S1 | 128.3 (3) | C12—C13—H13 | 119.7 |
C3—C2—C1 | 119.6 (3) | C15—C14—S2 | 106.5 (2) |
C3—C2—H2 | 120.2 | C15—C14—H14A | 110.4 |
C1—C2—H2 | 120.2 | S2—C14—H14A | 110.4 |
C2—C3—C4 | 120.3 (4) | C15—C14—H14B | 110.4 |
C2—C3—H3 | 119.8 | S2—C14—H14B | 110.4 |
C4—C3—H3 | 119.8 | H14A—C14—H14B | 108.6 |
C5—C4—C3 | 119.2 (4) | C14—C15—C16 | 113.6 (3) |
C5—C4—H4 | 120.4 | C14—C15—H15A | 108.8 |
C3—C4—H4 | 120.4 | C16—C15—H15A | 108.8 |
N1—C5—C4 | 120.0 (3) | C14—C15—H15B | 108.8 |
N1—C5—H5 | 120.0 | C16—C15—H15B | 108.8 |
C4—C5—H5 | 120.0 | H15A—C15—H15B | 107.7 |
C7—C6—S1 | 109.3 (2) | O6—C16—O5 | 124.6 (3) |
C7—C6—H6A | 109.8 | O6—C16—C15 | 121.8 (3) |
S1—C6—H6A | 109.8 | O5—C16—C15 | 113.5 (3) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7C···O9i | 0.82 (2) | 1.86 (2) | 2.664 (4) | 164 (4) |
O7—H7D···O4iii | 0.84 (2) | 1.75 (2) | 2.589 (4) | 178 (4) |
O9—H9C···O3iv | 0.81 (2) | 1.96 (2) | 2.772 (4) | 177 (4) |
O9—H9D···O8v | 0.80 (2) | 1.98 (2) | 2.754 (5) | 162 (3) |
O8—H8C···O6vi | 0.84 (2) | 1.92 (2) | 2.754 (4) | 176 (3) |
O8—H8D···O5ii | 0.85 (2) | 1.99 (2) | 2.770 (4) | 154 (3) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+2, −y+1, −z; (iv) x−1, y, z; (v) x, y+1, z; (vi) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H8NO3S)2(H2O)]·2H2O |
Mr | 514.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 6.9091 (5), 8.6855 (7), 34.899 (3) |
β (°) | 92.974 (1) |
V (Å3) | 2091.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.36 × 0.22 × 0.14 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.653, 0.839 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10850, 3769, 3567 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.117, 1.19 |
No. of reflections | 3769 |
No. of parameters | 289 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.78, −0.28 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004).
Cu1—O5 | 1.914 (2) | O1—N1 | 1.342 (4) |
Cu1—O7 | 1.926 (3) | O2—C8 | 1.273 (4) |
Cu1—O2i | 1.933 (2) | O3—C8 | 1.235 (4) |
Cu1—O3i | 2.755 (1) | O4—N2 | 1.321 (4) |
Cu1—O1 | 1.950 (2) | ||
O5—Cu1—O7 | 86.80 (11) | O1—Cu1—O2i | 93.12 (10) |
O5—Cu1—O2i | 175.57 (11) | O7—Cu1—O3i | 94.38 (1) |
O7—Cu1—O2i | 88.78 (11) | O1—Cu1—O3i | 99.40 (1) |
O5—Cu1—O1 | 91.22 (10) | C8—O2—Cu1ii | 110.9 (2) |
O7—Cu1—O1 | 164.02 (14) | C16—O5—Cu1 | 119.8 (2) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7C···O9i | 0.822 (17) | 1.86 (2) | 2.664 (4) | 164 (4) |
O7—H7D···O4iii | 0.839 (17) | 1.750 (18) | 2.589 (4) | 178 (4) |
O9—H9C···O3iv | 0.811 (17) | 1.961 (18) | 2.772 (4) | 177 (4) |
O9—H9D···O8v | 0.798 (17) | 1.98 (2) | 2.754 (5) | 162 (3) |
O8—H8C···O6vi | 0.837 (17) | 1.919 (19) | 2.754 (4) | 176 (3) |
O8—H8D···O5ii | 0.847 (18) | 1.99 (2) | 2.770 (4) | 154 (3) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) −x+2, −y+1, −z; (iv) x−1, y, z; (v) x, y+1, z; (vi) −x+1, y−1/2, −z+1/2. |
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In recent years, intense research activity has been directed towards the design and construction of novel coordination polymers based on covalent interactions (Fujita et al., 1994) or supramolecular contacts, such as hydrogen bonds and π–π stacking interactions (Desiraju, 1995). They are of interest not only due to their fascinating structures, but also because of their unexpected properties for potential application in areas such as gas adsorption, catalysis and optoelectronic devices (Matsumoto et al., 1999; Chui et al., 1999). The key step in the design of coordination polymers is to select suitable multidentate bridging ligands and spacers. Many pyridine-based carboxylate ligands (Kumaresan et al., 2006; Hussain, 1996; Fariati et al., 1998) have been used to obtain coordination polymers but, to the best of our knowledge, very little is known about the coordination chemistry of 1-oxopyridinium-2-thiopropionic acid, HOPTP (Ramasubramanian et al., 2007). The HOPTP ligand possesses several features. It is a polydentate ligand with up to four donor atoms. The N-oxide group has proved to be more versatile in its coordination mode than the pyridine, because the lone pairs of the O atom of the N-oxide provide more coordination flexibility than the N atom of the pyridine, which affords only a straight coordination geometry. Steric hindrance is much smaller for N-oxide and, in addition, it has the capability of forming hydrogen bonds. Finally, some N-oxides possess important antimicrobial activity (Danish & Rajendraprasad, 2003) and they are also recognized as potential DNA-cleaving agents (Ganley et al., 2001). In view of the above facts and our interest in the synthesis and characterization of coordination complexes, we report here the synthesis and single-crystal characterization of the title complex, (I).
Complex (I) is a one-dimensional polymer, the dimeric units [Cu(C8H8O3NS)(H2O)]+ and [C8H8O3NS]- being the elemental links that define the chain structure. The CuII metal centre is strongly bonded to four O atoms and weakly bonded to a fifth O atom, displaying a distorted square-pyramidal geometry, as evidenced by the bond angles around atom Cu1 (Fig. 1, Table 1): the dihedral angle between the planes of O1/Cu1/O2(-x + 2, y + 1/2, -z + 1/2) and O5/Cu1/O7 is 49.66 (8)°. The O atoms involved in the coordination of the CuII ion belong to the [C8H8O3NS]- anions (O2, O3 and O5), the pyridine N-oxide (O1) and the water molcule (O7) (Fig. 1). Two water molecules (O8 and O9) are left uncoordinated in the crystal structure.
An infinite three-dimensional coordination polymer with a zigzag chain structure is formed by the CuII cations, µ3-bridging and terminal OPTP- anions, and one terminal water molecule (Fig. 2). The Cu—O carboxylate bond lengths are in the range 1.914 (2)–2.755 (1) Å (Table 1), within which the semi-coordinating Cu1—O3 distance [2.755 (1) Å] is considerably longer than the Cu—O distance reported earlier (2.010 Å; Zou et al., 1998), while the Cu1—O5 distance of 1.914 (2) Å is shorter than the normal literature value (1.927 Å; Hu et al., 2003). The pyridine N-oxide rings are non-planar. The puckering parameters (ϕ2, θ2 and Q; Cremer & Pople, 1975) for the rings N1/C1–C5 and N2/C9–C13 indicate that these rings are in envelope (5E) and half-chair (5H4) conformations, respectively.
Overall, the structure of (I) does not depart from what might be expected, but its most interesting feature is its self-assembly into a three-dimensional structure. This process is achieved through a dense network of C—H···O hydrogen bonds involving most of the available H atoms of the [Cu(C8H8O3NS)(H2O)]+ units and only one H atom of the [C8H8O3NS]- units (Table 2). The two solvent water molecules interlink neighbouring [Cu(C8H8O3NS)(H2O)]+ units through O—H···O hydrogen-bond interactions (Table 2). The O atom of the coordinated water molecule (O7) is involved in intermolecular hydrogen-bond interactions with the N—O group of the OPTP- ion and with solvent water molecule O9. These interactions stabilize the crystal packing (Fig. 2). On the whole, the network of C—H···O and O—H···O hydrogen bonds can be described by Etter's hydrogen-bond notation (Etter, 1990) as R22(22), R68(30), R33(28), R32(11), R22(19) and R22(18). Among these, the two adjacent hydrogen-bonded rings R22(22) and R68(30) form an infinite ladder in the crystal structure via O—H···O interactions.