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The asymmetric unit of the title compound, [Cr(H2O)6](C7H7O3S)2, contains one half-cation and one anion; the Cr atom lies on an inversion centre. In the crystal structure, inter­molecular O—H...O and O—H...S hydrogen bonds result in the formation of a supra­molecular network; an intra­molecular C—H...O hydrogen bond is also present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051227/hk2344sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051227/hk2344Isup2.hkl
Contains datablock I

CCDC reference: 1168217

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.049
  • wR factor = 0.142
  • Data-to-parameter ratio = 13.3

checkCIF/PLATON results

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Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cr1 - O5 .. 10.55 su PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for Cr1
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cr1 - O4 .. 6.52 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cr1 - O6 .. 7.54 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A .. S1 .. 2.99 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported O5 .. S1 .. 3.87 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cr1 (3) 2.56 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The crystal structure of hexaaquacopper(II) bis(4-methylbenzenesulfonate), (II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).

The asymmetric unit of the title compound, (I), (Fig. 1) contains one half -cation and one anion; the Cr atom lies on an inversion centre, as in (II). The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).

In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Fig. 2 and Table 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present, as in (II).

The both compounds, (I) and (II), are isostructural.

Related literature top

For a related structure, see: Zhong et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Lanthanum(III) nitrate hexahydrate (216.4 mg, 0.5 mmol), chromium(II) acetate dihydrate (103.1 mg, 0.5 mmol), 4-methyl- benzenesulfonic acid (344.4 mg, 2 mmol), ammonia (0.5 mol/l, 4 ml) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 443 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

H atoms (for H2O) were located in difference syntheses and refined isotropically [O—H = 0.832 (18)–0.89 (4) Å and Uiso(H) = 0.092 (11)–0.12 (2) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93 and 0.96 Å, for aromatic and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.2 for aromatic H and x = 1.5 for methyl H atoms.

Structure description top

The crystal structure of hexaaquacopper(II) bis(4-methylbenzenesulfonate), (II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).

The asymmetric unit of the title compound, (I), (Fig. 1) contains one half -cation and one anion; the Cr atom lies on an inversion centre, as in (II). The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).

In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Fig. 2 and Table 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present, as in (II).

The both compounds, (I) and (II), are isostructural.

For a related structure, see: Zhong et al. (2007). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 3/2 - x, 1/2 - y, 1/2 - z].
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
Hexaaquachromium(II) bis(4-methylbenzenesulfonate) top
Crystal data top
[Cr(H2O)6](C7H7O3S)2F(000) = 524
Mr = 502.47Dx = 1.510 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4992 reflections
a = 7.0181 (11) Åθ = 2.5–28.0°
b = 6.3017 (12) ŵ = 0.76 mm1
c = 24.9978 (15) ÅT = 273 K
β = 91.607 (3)°Prism, colorless
V = 1105.1 (3) Å30.49 × 0.37 × 0.19 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2117 independent reflections
Radiation source: fine-focus sealed tube1842 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ and ω scansθmax = 26.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.709, Tmax = 0.866k = 67
6659 measured reflectionsl = 3030
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)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142 w = 1/[σ2(Fo2) + (0.0803P)2 + 1.3523P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
2117 reflectionsΔρmax = 0.63 e Å3
159 parametersΔρmin = 0.46 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: 0.018 (3)
Crystal data top
[Cr(H2O)6](C7H7O3S)2V = 1105.1 (3) Å3
Mr = 502.47Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.0181 (11) ŵ = 0.76 mm1
b = 6.3017 (12) ÅT = 273 K
c = 24.9978 (15) Å0.49 × 0.37 × 0.19 mm
β = 91.607 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2117 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1842 reflections with I > 2σ(I)
Tmin = 0.709, Tmax = 0.866Rint = 0.023
6659 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0499 restraints
wR(F2) = 0.142H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.63 e Å3
2117 reflectionsΔρmin = 0.46 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
Cr10.50000.00000.00000.0351 (2)
S10.01450 (13)0.60820 (14)0.90526 (4)0.0533 (3)
O10.1535 (4)0.5146 (4)0.93049 (12)0.0677 (7)
O20.0146 (4)0.8388 (4)0.90904 (11)0.0671 (7)
O30.1907 (4)0.5171 (4)0.92380 (13)0.0687 (8)
O40.7234 (5)0.1027 (5)0.04787 (16)0.0866 (10)
O50.5081 (4)0.2891 (5)0.03491 (13)0.0688 (7)
O60.3035 (5)0.1042 (5)0.05307 (16)0.0877 (11)
C10.0456 (7)0.6319 (10)0.7447 (2)0.0888 (15)
H10.08120.72960.71840.107*
C20.0533 (7)0.6920 (8)0.79866 (18)0.0773 (12)
H20.09140.82790.80820.093*
C30.0033 (5)0.5456 (6)0.83687 (16)0.0585 (9)
C40.0535 (7)0.3419 (7)0.82200 (17)0.0734 (11)
H40.08510.24110.84790.088*
C50.0621 (7)0.2926 (9)0.7688 (2)0.0858 (14)
H50.10290.15790.75900.103*
C60.0127 (7)0.4345 (10)0.72959 (18)0.0787 (12)
C70.0319 (9)0.3685 (13)0.6717 (2)0.117 (2)
H7B0.16440.36240.66320.175*
H7A0.03170.47020.64880.175*
H7C0.02490.23130.66630.175*
H4A0.764 (5)0.224 (3)0.0552 (15)0.092 (11)*
H5A0.621 (4)0.330 (8)0.048 (2)0.094 (16)*
H6A0.249 (7)0.226 (4)0.055 (2)0.12 (2)*
H4B0.793 (6)0.024 (5)0.0674 (19)0.095 (18)*
H5B0.456 (8)0.413 (6)0.040 (4)0.11 (4)*
H6B0.210 (5)0.025 (6)0.063 (2)0.10 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0339 (4)0.0249 (4)0.0466 (4)0.0007 (2)0.0015 (2)0.0017 (2)
S10.0534 (5)0.0422 (5)0.0642 (6)0.0006 (4)0.0032 (4)0.0004 (4)
O10.0729 (18)0.0544 (16)0.0750 (17)0.0043 (12)0.0112 (14)0.0023 (12)
O20.0705 (17)0.0440 (14)0.0871 (19)0.0010 (12)0.0058 (14)0.0025 (13)
O30.0705 (17)0.0536 (16)0.0828 (19)0.0049 (12)0.0180 (14)0.0027 (13)
O40.087 (2)0.0471 (17)0.123 (3)0.0055 (16)0.045 (2)0.0009 (17)
O50.0590 (16)0.0508 (16)0.097 (2)0.0011 (13)0.0030 (14)0.0130 (14)
O60.095 (2)0.0483 (18)0.123 (3)0.0001 (16)0.052 (2)0.0048 (17)
C10.084 (3)0.112 (4)0.071 (3)0.009 (3)0.000 (2)0.024 (3)
C20.078 (3)0.076 (3)0.078 (3)0.014 (2)0.006 (2)0.016 (2)
C30.0501 (19)0.056 (2)0.070 (2)0.0002 (16)0.0019 (16)0.0053 (17)
C40.092 (3)0.061 (3)0.066 (2)0.012 (2)0.002 (2)0.003 (2)
C50.090 (3)0.089 (4)0.078 (3)0.007 (3)0.003 (2)0.019 (3)
C60.068 (3)0.105 (4)0.063 (2)0.009 (3)0.002 (2)0.002 (2)
C70.102 (4)0.176 (7)0.073 (3)0.008 (4)0.008 (3)0.009 (4)
Geometric parameters (Å, º) top
Cr1—O42.050 (3)O6—H6B0.87 (4)
Cr1—O52.020 (3)C1—C61.366 (8)
Cr1—O62.048 (3)C1—C21.404 (7)
Cr1—O4i2.050 (3)C1—H10.9300
Cr1—O5i2.020 (3)C2—C31.367 (6)
Cr1—O6i2.048 (3)C2—H20.9300
S1—O11.447 (3)C3—C41.397 (6)
S1—O31.451 (3)C4—C51.370 (6)
S1—O21.456 (3)C4—H40.9300
S1—C31.758 (4)C5—C61.364 (7)
O4—H4A0.832 (18)C5—H50.9300
O4—H4B0.84 (4)C6—C71.516 (7)
O5—H5A0.89 (4)C7—H7B0.9600
O5—H5B0.87 (5)C7—H7A0.9600
O6—H6A0.858 (19)C7—H7C0.9600
O4—Cr1—O4i180H6A—O6—H6B99 (3)
O4—Cr1—O591.19 (13)C6—C1—C2122.1 (5)
O4i—Cr1—O588.81 (13)C6—C1—H1118.9
O4—Cr1—O692.21 (17)C2—C1—H1118.9
O4i—Cr1—O687.79 (17)C3—C2—C1118.2 (5)
O5—Cr1—O5i180C3—C2—H2120.9
O5—Cr1—O691.19 (13)C1—C2—H2120.9
O5i—Cr1—O688.81 (13)C2—C3—C4120.3 (4)
O6—Cr1—O6i180C2—C3—S1120.7 (3)
O4i—Cr1—O5i91.19 (13)C4—C3—S1119.1 (3)
O4i—Cr1—O6i92.21 (17)C5—C4—C3119.2 (4)
O5i—Cr1—O6i91.19 (13)C5—C4—H4120.4
O1—S1—O3112.99 (19)C3—C4—H4120.4
O1—S1—O2112.35 (17)C6—C5—C4122.1 (5)
O3—S1—O2111.85 (17)C6—C5—H5118.9
O1—S1—C3105.91 (18)C4—C5—H5118.9
O3—S1—C3106.48 (19)C5—C6—C1118.1 (4)
O2—S1—C3106.70 (18)C5—C6—C7118.6 (6)
Cr1—O4—H4A132 (2)C1—C6—C7123.3 (5)
Cr1—O4—H4B125 (3)C6—C7—H7B109.5
H4A—O4—H4B103 (3)C6—C7—H7A109.5
Cr1—O5—H5A116 (4)H7B—C7—H7A109.5
Cr1—O5—H5B149 (4)C6—C7—H7C109.5
H5A—O5—H5B94 (3)H7B—C7—H7C109.5
Cr1—O6—H6A130 (3)H7A—C7—H7C109.5
Cr1—O6—H6B122 (3)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O1ii0.83 (2)1.95 (2)2.784 (4)176 (4)
O4—H4B···O2iii0.84 (4)2.02 (3)2.825 (4)160 (6)
O5—H5A···S1iii0.89 (4)2.99 (2)3.871 (3)171 (5)
O5—H5A···O1iii0.89 (4)1.93 (2)2.793 (4)166 (5)
O5—H5B···O3iv0.87 (5)2.14 (6)2.766 (4)128 (7)
O6—H6B···O2iv0.87 (4)1.95 (2)2.813 (4)175 (6)
O6—H6A···O3v0.86 (2)1.96 (2)2.785 (4)162 (6)
C2—H2···O20.932.562.916 (6)103
Symmetry codes: (ii) x+1, y, z+1; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Cr(H2O)6](C7H7O3S)2
Mr502.47
Crystal system, space groupMonoclinic, P21/n
Temperature (K)273
a, b, c (Å)7.0181 (11), 6.3017 (12), 24.9978 (15)
β (°) 91.607 (3)
V3)1105.1 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.76
Crystal size (mm)0.49 × 0.37 × 0.19
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.709, 0.866
No. of measured, independent and
observed [I > 2σ(I)] reflections
6659, 2117, 1842
Rint0.023
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.142, 0.98
No. of reflections2117
No. of parameters159
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.63, 0.46

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).

Selected geometric parameters (Å, º) top
Cr1—O42.050 (3)Cr1—O62.048 (3)
Cr1—O52.020 (3)
O4—Cr1—O4i180O5—Cr1—O5i180
O4—Cr1—O591.19 (13)O5—Cr1—O691.19 (13)
O4i—Cr1—O588.81 (13)O5i—Cr1—O688.81 (13)
O4—Cr1—O692.21 (17)O6—Cr1—O6i180
O4i—Cr1—O687.79 (17)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O1ii0.832 (18)1.953 (19)2.784 (4)176 (4)
O4—H4B···O2iii0.84 (4)2.02 (3)2.825 (4)160 (6)
O5—H5A···S1iii0.89 (4)2.99 (2)3.871 (3)171 (5)
O5—H5A···O1iii0.89 (4)1.93 (2)2.793 (4)166 (5)
O5—H5B···O3iv0.87 (5)2.14 (6)2.766 (4)128 (7)
O6—H6B···O2iv0.87 (4)1.95 (2)2.813 (4)175 (6)
O6—H6A···O3v0.858 (19)1.96 (2)2.785 (4)162 (6)
C2—H2···O20.932.562.916 (6)103
Symmetry codes: (ii) x+1, y, z+1; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1; (v) x, y, z+1.
 

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