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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—H...O hydrogen bonds that link between layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041190/bi2224sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041190/bi2224Isup2.hkl
Contains datablock I

CCDC reference: 660162

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.027
  • wR factor = 0.079
  • Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1 .. 7.92 su
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.20 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

For the structure of a related complex [Ni(H2O)6](C6H5SO4)2·2H2O, see: Kosnic et al. (1992).

Experimental top

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.

Refinement top

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.

Structure description top

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.

For the structure of a related complex [Ni(H2O)6](C6H5SO4)2·2H2O, see: Kosnic et al. (1992).

Computing details top

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).

Figures top
[Figure 1] 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] Fig. 2. Packing diagram viewed along the a axis showing a layer in the (002) plane. Hydrogen bonds are shown as dashed lines.
Hexaaquacopper(II) bis(4-hydroxybenzenesulfonate) top
Crystal data top
[Cu(H2O)6](C6H5SO4)2F(000) = 534.0
Mr = 517.99Dx = 1.706 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6039 reflections
a = 6.9299 (13) Åθ = 2.6–28.3°
b = 6.1868 (12) ŵ = 1.36 mm1
c = 23.531 (4) ÅT = 293 K
β = 91.528 (2)°Block, blue
V = 1008.5 (3) Å30.48 × 0.48 × 0.35 mm
Z = 2
Data collection top
Bruker SMART APEX II CCD
diffractometer
1833 independent reflections
Radiation source: fine-focus sealed tube1734 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
φ and ω scansθmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.530, Tmax = 0.620k = 77
5886 measured reflectionsl = 2728
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H 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 reflectionsΔρmax = 0.35 e Å3
159 parametersΔρmin = 0.29 e Å3
9 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.073 (4)
Crystal data top
[Cu(H2O)6](C6H5SO4)2V = 1008.5 (3) Å3
Mr = 517.99Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.9299 (13) ŵ = 1.36 mm1
b = 6.1868 (12) ÅT = 293 K
c = 23.531 (4) Å0.48 × 0.48 × 0.35 mm
β = 91.528 (2)°
Data collection top
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 = 0.620Rint = 0.052
5886 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0279 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.35 e Å3
1833 reflectionsΔρmin = 0.29 e Å3
159 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50001.00000.00000.03006 (16)
S10.00308 (6)0.60798 (7)0.098056 (18)0.03163 (17)
C30.0610 (3)0.6358 (4)0.26714 (9)0.0446 (5)
H30.10900.73340.29330.053*
C60.0787 (3)0.3434 (3)0.18887 (8)0.0391 (4)
H60.12540.24550.16260.047*
C20.0607 (3)0.6884 (3)0.21002 (9)0.0415 (5)
H20.10750.82190.19780.050*
C10.0092 (3)0.5428 (3)0.17107 (8)0.0330 (4)
C50.0783 (3)0.2909 (4)0.24607 (9)0.0430 (5)
H50.12380.15660.25820.052*
C40.0103 (3)0.4375 (4)0.28548 (9)0.0427 (5)
O30.4870 (2)0.7127 (2)0.03289 (6)0.0377 (3)
O60.1696 (2)0.5037 (2)0.07292 (7)0.0407 (4)
O10.6894 (2)1.1065 (2)0.08131 (6)0.0424 (4)
O20.2623 (2)1.0915 (2)0.03679 (7)0.0476 (4)
O50.1792 (2)0.5252 (2)0.07440 (7)0.0431 (4)
O40.0127 (2)0.8432 (2)0.09386 (6)0.0416 (4)
O70.0198 (3)0.3770 (3)0.34066 (6)0.0596 (5)
H70.02490.47310.36040.089*
H1A0.7892 (16)1.032 (3)0.0829 (13)0.053 (8)*
H2A0.234 (3)1.2081 (16)0.0517 (9)0.062 (8)*
H3A0.395 (2)0.662 (4)0.0504 (9)0.052 (7)*
H1B0.741 (3)1.2271 (14)0.0803 (14)0.069 (9)*
H2B0.193 (3)1.012 (2)0.0558 (10)0.052 (8)*
H3B0.575 (2)0.653 (4)0.0513 (10)0.079 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0321 (2)0.0257 (2)0.0325 (2)0.00063 (11)0.00330 (13)0.00130 (11)
S10.0316 (3)0.0290 (3)0.0342 (3)0.00129 (17)0.00018 (17)0.00307 (17)
C30.0422 (11)0.0510 (12)0.0407 (11)0.0057 (9)0.0051 (8)0.0053 (9)
C60.0415 (11)0.0383 (10)0.0374 (10)0.0047 (8)0.0003 (7)0.0003 (8)
C20.0396 (11)0.0403 (11)0.0447 (11)0.0068 (8)0.0012 (8)0.0002 (9)
C10.0291 (9)0.0353 (9)0.0344 (9)0.0009 (7)0.0011 (7)0.0019 (8)
C50.0438 (11)0.0420 (11)0.0431 (11)0.0061 (9)0.0025 (8)0.0074 (9)
C40.0365 (11)0.0554 (12)0.0359 (10)0.0004 (10)0.0005 (7)0.0036 (9)
O30.0354 (7)0.0305 (7)0.0474 (8)0.0011 (6)0.0016 (6)0.0074 (6)
O60.0424 (9)0.0372 (8)0.0430 (8)0.0019 (5)0.0085 (6)0.0007 (5)
O10.0402 (8)0.0347 (8)0.0519 (8)0.0026 (6)0.0046 (6)0.0013 (6)
O20.0479 (9)0.0306 (8)0.0654 (10)0.0017 (7)0.0241 (7)0.0018 (7)
O50.0400 (8)0.0415 (8)0.0469 (9)0.0062 (6)0.0113 (6)0.0066 (6)
O40.0435 (8)0.0305 (7)0.0511 (8)0.0011 (5)0.0032 (6)0.0058 (6)
O70.0698 (11)0.0737 (12)0.0353 (8)0.0148 (9)0.0028 (7)0.0072 (8)
Geometric parameters (Å, º) top
Cu1—O12.3842 (14)C6—C11.385 (3)
Cu1—O21.9645 (14)C6—H60.930
Cu1—O31.9415 (13)C2—C11.382 (3)
Cu1—O1i2.3842 (14)C2—H20.930
Cu1—O2i1.9645 (14)C5—C41.389 (3)
Cu1—O3i1.9415 (13)C5—H50.930
S1—O41.4605 (15)C4—O71.351 (3)
S1—O51.4595 (15)O3—H3A0.83 (2)
S1—O61.4608 (16)O3—H3B0.83 (2)
S1—C11.7641 (19)O1—H1A0.83 (1)
C3—C21.383 (3)O1—H1B0.83 (1)
C3—C41.387 (3)O2—H2A0.83 (1)
C3—H30.930O2—H2B0.83 (2)
C6—C51.385 (3)O7—H70.820
O3i—Cu1—O3180.00 (8)C5—C6—H6120.2
O3i—Cu1—O2i92.28 (6)C1—C6—H6120.2
O3—Cu1—O2i87.72 (6)C1—C2—C3120.05 (19)
O3i—Cu1—O287.72 (6)C1—C2—H2120.0
O3—Cu1—O292.28 (6)C3—C2—H2120.0
O2i—Cu1—O2180.00 (12)C2—C1—C6120.34 (18)
O3i—Cu1—O192.10 (6)C2—C1—S1119.81 (15)
O3—Cu1—O187.90 (6)C6—C1—S1119.82 (15)
O2i—Cu1—O189.03 (6)C4—C5—C6120.3 (2)
O2—Cu1—O190.97 (6)C4—C5—H5119.8
O3i—Cu1—O1i87.90 (6)C6—C5—H5119.8
O3—Cu1—O1i92.10 (6)O7—C4—C5116.9 (2)
O2i—Cu1—O1i90.97 (6)O7—C4—C3123.5 (2)
O2—Cu1—O1i89.03 (6)C5—C4—C3119.64 (19)
O1—Cu1—O1i180.0Cu1—O3—H3A126.0 (16)
O4—S1—O5111.39 (8)Cu1—O3—H3B125.3 (17)
O4—S1—O6112.00 (8)H3A—O3—H3B97.9 (19)
O5—S1—O6112.05 (9)Cu1—O1—H1A108.8 (19)
O4—S1—C1107.08 (9)Cu1—O1—H1B117 (2)
O5—S1—C1106.82 (9)H1A—O1—H1B98.1 (18)
O6—S1—C1107.14 (9)Cu1—O2—H2A130.5 (15)
C2—C3—C4120.05 (19)Cu1—O2—H2B125.1 (15)
C2—C3—H3120.0H2A—O2—H2B98.1 (18)
C4—C3—H3120.0C4—O7—H7109.5
C5—C6—C1119.58 (19)
Symmetry code: (i) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O1ii0.821.992.763 (2)158
O1—H1A···O4iii0.83 (1)1.95 (2)2.779 (2)174 (3)
O1—H1B···O5iv0.83 (1)1.93 (1)2.752 (2)171 (2)
O2—H2B···O40.83 (2)1.87 (2)2.698 (2)174 (3)
O2—H2A···O6v0.83 (1)1.95 (1)2.769 (2)170 (2)
O3—H3B···O5iii0.83 (2)1.94 (2)2.744 (2)164 (2)
O3—H3A···O60.83 (2)1.93 (2)2.740 (2)165 (3)
Symmetry codes: (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y, z; (iv) x+1, y+1, z; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu(H2O)6](C6H5SO4)2
Mr517.99
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.9299 (13), 6.1868 (12), 23.531 (4)
β (°) 91.528 (2)
V3)1008.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.36
Crystal size (mm)0.48 × 0.48 × 0.35
Data collection
DiffractometerBruker SMART APEX II CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.530, 0.620
No. of measured, independent and
observed [I > 2σ(I)] reflections
5886, 1833, 1734
Rint0.052
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.079, 1.09
No. of reflections1833
No. of parameters159
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.29

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Selected bond lengths (Å) top
Cu1—O12.3842 (14)Cu1—O31.9415 (13)
Cu1—O21.9645 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O1i0.821.992.763 (2)157.6
O1—H1A···O4ii0.83 (1)1.95 (2)2.779 (2)174 (3)
O1—H1B···O5iii0.83 (1)1.93 (1)2.752 (2)171 (2)
O2—H2B···O40.83 (2)1.87 (2)2.698 (2)174 (3)
O2—H2A···O6iv0.83 (1)1.95 (1)2.769 (2)170 (2)
O3—H3B···O5ii0.83 (2)1.94 (2)2.744 (2)164 (2)
O3—H3A···O60.83 (2)1.93 (2)2.740 (2)165 (3)
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) x, y+1, z.
 

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