Acta Cryst. (2007). E63, m2414 [ doi:10.1107/S1600536807041190 ]
The title complex, [Cu(H2O)6](C6H5SO4)2, was synthesized hydrothermally. The [Cu(H2O)6]2+ cations lie on centres of symmetry and exhibit tetragonally elongated coordination geometry, typical of Jahn-Teller-distorted CuII complexes. An extensive network of O-H
O hydrogen bonds between the coordinated water molecules and the sulfonate groups of the anions links the molecules into layers. The hydroxy groups of the anions form O-HO hydrogen bonds that link between layers.
A mixture of 4-hydroxybenzenesulfonic acid (0.348 g, 0.002 mol) and CuO (0.079, 0.001 mol) was added to 20 ml water and the mixture was sealed in a teflon-lined steel autoclave and heated at 418 K for 4 days. Single crystals of the title compound formed on cooling in air.
H atoms bound to C atoms and of the OH group were placed geometrically and refined as riding with C—H = 0.93 Å and O—H = 0.82 Å, and with Ueq(H) = 1.2 Ueq(C) or 1.5 Ueq(O). The H atoms of the water molecules were located in difference Fourier maps and refined with the O—H bond lengths restrained to 0.83 (2) Å and with Uiso(H) refined freely.
Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./bi2224fig1thm.gif)
| Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids. H atoms are omitted. The suffix A denotes symmetry code 1 − x, 2 − y, −z. |
![[Figure 2]](./bi2224fig2thm.gif)
| Fig. 2. Packing diagram viewed along the a axis showing a layer in the (002) plane. Hydrogen bonds are shown as dashed lines. |
| [Cu(H2O)6](C6H5SO4)2 | F000 = 534.0 |
| Mr = 517.99 | Dx = 1.706 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 6039 reflections |
| a = 6.9299 (13) Å | θ = 2.6–28.3º |
| b = 6.1868 (12) Å | µ = 1.36 mm−1 |
| c = 23.531 (4) Å | T = 293 (2) K |
| β = 91.528 (2)º | Block, blue |
| V = 1008.5 (3) Å3 | 0.48 × 0.48 × 0.35 mm |
| Z = 2 |
| Bruker SMART APEX II CCD diffractometer | 1833 independent reflections |
| Radiation source: fine-focus sealed tube | 1734 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.052 |
| T = 293(2) K | θmax = 25.5º |
| φ and ω scans | θmin = 3.1º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.530, Tmax = 0.620 | k = −7→7 |
| 5886 measured reflections | l = −27→28 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.2229P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max = 0.002 |
| 1833 reflections | Δρmax = 0.35 e Å−3 |
| 159 parameters | Δρmin = −0.29 e Å−3 |
| 9 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.073 (4) |
| [Cu(H2O)6](C6H5SO4)2 | V = 1008.5 (3) Å3 |
| Mr = 517.99 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.9299 (13) Å | µ = 1.36 mm−1 |
| b = 6.1868 (12) Å | T = 293 (2) K |
| c = 23.531 (4) Å | 0.48 × 0.48 × 0.35 mm |
| β = 91.528 (2)º |
| Bruker SMART APEX II CCD diffractometer | 1833 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1734 reflections with I > 2σ(I) |
| Tmin = 0.530, Tmax = 0.620 | Rint = 0.052 |
| 5886 measured reflections |
| R[F2 > 2σ(F2)] = 0.027 | 9 restraints |
| wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.09 | Δρmax = 0.35 e Å−3 |
| 1833 reflections | Δρmin = −0.29 e Å−3 |
| 159 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 > 2sigma(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 | 0.5000 | 1.0000 | 0.0000 | 0.03006 (16) | |
| S1 | 0.00308 (6) | 0.60798 (7) | 0.098056 (18) | 0.03163 (17) | |
| C3 | −0.0610 (3) | 0.6358 (4) | 0.26714 (9) | 0.0446 (5) | |
| H3 | −0.1090 | 0.7334 | 0.2933 | 0.053* | |
| C6 | 0.0787 (3) | 0.3434 (3) | 0.18887 (8) | 0.0391 (4) | |
| H6 | 0.1254 | 0.2455 | 0.1626 | 0.047* | |
| C2 | −0.0607 (3) | 0.6884 (3) | 0.21002 (9) | 0.0415 (5) | |
| H2 | −0.1075 | 0.8219 | 0.1978 | 0.050* | |
| C1 | 0.0092 (3) | 0.5428 (3) | 0.17107 (8) | 0.0330 (4) | |
| C5 | 0.0783 (3) | 0.2909 (4) | 0.24607 (9) | 0.0430 (5) | |
| H5 | 0.1238 | 0.1566 | 0.2582 | 0.052* | |
| C4 | 0.0103 (3) | 0.4375 (4) | 0.28548 (9) | 0.0427 (5) | |
| O3 | 0.4870 (2) | 0.7127 (2) | 0.03289 (6) | 0.0377 (3) | |
| O6 | 0.1696 (2) | 0.5037 (2) | 0.07292 (7) | 0.0407 (4) | |
| O1 | 0.6894 (2) | 1.1065 (2) | 0.08131 (6) | 0.0424 (4) | |
| O2 | 0.2623 (2) | 1.0915 (2) | 0.03679 (7) | 0.0476 (4) | |
| O5 | −0.1792 (2) | 0.5252 (2) | 0.07440 (7) | 0.0431 (4) | |
| O4 | 0.0127 (2) | 0.8432 (2) | 0.09386 (6) | 0.0416 (4) | |
| O7 | 0.0198 (3) | 0.3770 (3) | 0.34066 (6) | 0.0596 (5) | |
| H7 | −0.0249 | 0.4731 | 0.3604 | 0.089* | |
| H1A | 0.7892 (16) | 1.032 (3) | 0.0829 (13) | 0.053 (8)* | |
| H2A | 0.234 (3) | 1.2081 (16) | 0.0517 (9) | 0.062 (8)* | |
| H3A | 0.395 (2) | 0.662 (4) | 0.0504 (9) | 0.052 (7)* | |
| H1B | 0.741 (3) | 1.2271 (14) | 0.0803 (14) | 0.069 (9)* | |
| H2B | 0.193 (3) | 1.012 (2) | 0.0558 (10) | 0.052 (8)* | |
| H3B | 0.575 (2) | 0.653 (4) | 0.0513 (10) | 0.079 (10)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0321 (2) | 0.0257 (2) | 0.0325 (2) | 0.00063 (11) | 0.00330 (13) | 0.00130 (11) |
| S1 | 0.0316 (3) | 0.0290 (3) | 0.0342 (3) | −0.00129 (17) | −0.00018 (17) | 0.00307 (17) |
| C3 | 0.0422 (11) | 0.0510 (12) | 0.0407 (11) | 0.0057 (9) | 0.0051 (8) | −0.0053 (9) |
| C6 | 0.0415 (11) | 0.0383 (10) | 0.0374 (10) | 0.0047 (8) | −0.0003 (7) | −0.0003 (8) |
| C2 | 0.0396 (11) | 0.0403 (11) | 0.0447 (11) | 0.0068 (8) | 0.0012 (8) | 0.0002 (9) |
| C1 | 0.0291 (9) | 0.0353 (9) | 0.0344 (9) | −0.0009 (7) | −0.0011 (7) | 0.0019 (8) |
| C5 | 0.0438 (11) | 0.0420 (11) | 0.0431 (11) | 0.0061 (9) | −0.0025 (8) | 0.0074 (9) |
| C4 | 0.0365 (11) | 0.0554 (12) | 0.0359 (10) | −0.0004 (10) | −0.0005 (7) | 0.0036 (9) |
| O3 | 0.0354 (7) | 0.0305 (7) | 0.0474 (8) | −0.0011 (6) | 0.0016 (6) | 0.0074 (6) |
| O6 | 0.0424 (9) | 0.0372 (8) | 0.0430 (8) | 0.0019 (5) | 0.0085 (6) | 0.0007 (5) |
| O1 | 0.0402 (8) | 0.0347 (8) | 0.0519 (8) | −0.0026 (6) | −0.0046 (6) | −0.0013 (6) |
| O2 | 0.0479 (9) | 0.0306 (8) | 0.0654 (10) | 0.0017 (7) | 0.0241 (7) | 0.0018 (7) |
| O5 | 0.0400 (8) | 0.0415 (8) | 0.0469 (9) | −0.0062 (6) | −0.0113 (6) | 0.0066 (6) |
| O4 | 0.0435 (8) | 0.0305 (7) | 0.0511 (8) | −0.0011 (5) | 0.0032 (6) | 0.0058 (6) |
| O7 | 0.0698 (11) | 0.0737 (12) | 0.0353 (8) | 0.0148 (9) | 0.0028 (7) | 0.0072 (8) |
| Cu1—O1 | 2.3842 (14) | C6—C1 | 1.385 (3) |
| Cu1—O2 | 1.9645 (14) | C6—H6 | 0.930 |
| Cu1—O3 | 1.9415 (13) | C2—C1 | 1.382 (3) |
| Cu1—O1i | 2.3842 (14) | C2—H2 | 0.930 |
| Cu1—O2i | 1.9645 (14) | C5—C4 | 1.389 (3) |
| Cu1—O3i | 1.9415 (13) | C5—H5 | 0.930 |
| S1—O4 | 1.4605 (15) | C4—O7 | 1.351 (3) |
| S1—O5 | 1.4595 (15) | O3—H3A | 0.83 (2) |
| S1—O6 | 1.4608 (16) | O3—H3B | 0.83 (2) |
| S1—C1 | 1.7641 (19) | O1—H1A | 0.83 (1) |
| C3—C2 | 1.383 (3) | O1—H1B | 0.83 (1) |
| C3—C4 | 1.387 (3) | O2—H2A | 0.83 (1) |
| C3—H3 | 0.930 | O2—H2B | 0.83 (2) |
| C6—C5 | 1.385 (3) | O7—H7 | 0.820 |
| O3i—Cu1—O3 | 180.00 (8) | C5—C6—H6 | 120.2 |
| O3i—Cu1—O2i | 92.28 (6) | C1—C6—H6 | 120.2 |
| O3—Cu1—O2i | 87.72 (6) | C1—C2—C3 | 120.05 (19) |
| O3i—Cu1—O2 | 87.72 (6) | C1—C2—H2 | 120.0 |
| O3—Cu1—O2 | 92.28 (6) | C3—C2—H2 | 120.0 |
| O2i—Cu1—O2 | 180.00 (12) | C2—C1—C6 | 120.34 (18) |
| O3i—Cu1—O1 | 92.10 (6) | C2—C1—S1 | 119.81 (15) |
| O3—Cu1—O1 | 87.90 (6) | C6—C1—S1 | 119.82 (15) |
| O2i—Cu1—O1 | 89.03 (6) | C4—C5—C6 | 120.3 (2) |
| O2—Cu1—O1 | 90.97 (6) | C4—C5—H5 | 119.8 |
| O3i—Cu1—O1i | 87.90 (6) | C6—C5—H5 | 119.8 |
| O3—Cu1—O1i | 92.10 (6) | O7—C4—C5 | 116.9 (2) |
| O2i—Cu1—O1i | 90.97 (6) | O7—C4—C3 | 123.5 (2) |
| O2—Cu1—O1i | 89.03 (6) | C5—C4—C3 | 119.64 (19) |
| O1—Cu1—O1i | 180.0 | Cu1—O3—H3A | 126.0 (16) |
| O4—S1—O5 | 111.39 (8) | Cu1—O3—H3B | 125.3 (17) |
| O4—S1—O6 | 112.00 (8) | H3A—O3—H3B | 97.9 (19) |
| O5—S1—O6 | 112.05 (9) | Cu1—O1—H1A | 108.8 (19) |
| O4—S1—C1 | 107.08 (9) | Cu1—O1—H1B | 117 (2) |
| O5—S1—C1 | 106.82 (9) | H1A—O1—H1B | 98.1 (18) |
| O6—S1—C1 | 107.14 (9) | Cu1—O2—H2A | 130.5 (15) |
| C2—C3—C4 | 120.05 (19) | Cu1—O2—H2B | 125.1 (15) |
| C2—C3—H3 | 120.0 | H2A—O2—H2B | 98.1 (18) |
| C4—C3—H3 | 120.0 | C4—O7—H7 | 109.5 |
| C5—C6—C1 | 119.58 (19) |
| Symmetry codes: (i) −x+1, −y+2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O7—H7···O1ii | 0.82 | 1.99 | 2.763 (2) | 158 |
| O1—H1A···O4iii | 0.83 (1) | 1.95 (2) | 2.779 (2) | 174 (3) |
| O1—H1B···O5iv | 0.83 (1) | 1.93 (1) | 2.752 (2) | 171 (2) |
| O2—H2B···O4 | 0.83 (2) | 1.87 (2) | 2.698 (2) | 174 (3) |
| O2—H2A···O6v | 0.83 (1) | 1.95 (1) | 2.769 (2) | 170 (2) |
| O3—H3B···O5iii | 0.83 (2) | 1.94 (2) | 2.744 (2) | 164 (2) |
| O3—H3A···O6 | 0.83 (2) | 1.93 (2) | 2.740 (2) | 165 (3) |
| Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) x+1, y+1, z; (v) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O7—H7···O1i | 0.82 | 1.99 | 2.763 (2) | 158 |
| O1—H1A···O4ii | 0.83 (1) | 1.95 (2) | 2.779 (2) | 174 (3) |
| O1—H1B···O5iii | 0.83 (1) | 1.93 (1) | 2.752 (2) | 171 (2) |
| O2—H2B···O4 | 0.83 (2) | 1.87 (2) | 2.698 (2) | 174 (3) |
| O2—H2A···O6iv | 0.83 (1) | 1.95 (1) | 2.769 (2) | 170 (2) |
| O3—H3B···O5ii | 0.83 (2) | 1.94 (2) | 2.744 (2) | 164 (2) |
| O3—H3A···O6 | 0.83 (2) | 1.93 (2) | 2.740 (2) | 165 (3) |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) x, y+1, z. |
The authors are grateful for the support of this work by the Natural Science Foundation of JiangXi Province (grant Nos. 0520036 and 0620029).
Bruker (1997). SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2000). (DATE?). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Kosnic, E. J., McClymont, E. L., Hodder, R. A. & Squattrito, P. J. (1992). Inorg. Chim. Acta, 201, 143–151.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
In the title complex (Fig. 1), the [Cu(H2O)6]2+ cations lies on centres of symmetry and exhibit tetragonally elongated coordination geometry, with atoms O2, O3, O2i and O3i forming the equatorial plane and atoms O1 and O1i lying in the axial positions [symmetry code (i): 1 − x, 2 − y, −z]. The Cu1—O1 bond length of 2.3842 (14) Å is significantly longer than the Cu1—O2 and Cu1—O3 bond lengths of 1.9645 (14) and 1.9615 (13) Å, respectively.
An extensive network of O—H···O hydrogen bonds between the coordinated water molecules and the sulfonate groups of the anions link the molecules into layers lying in the (002) planes (Fig. 2). The hydroxy groups of the anions form O—H···O hydrogen bonds between layers.