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The asymmetric unit of the title compound, [Cu(H2O)6](C7H7O3S)2, contains one half-cation and one anion; the Cu 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 structure; an intra­molecular C—H...O hydrogen bond is also present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049525/hk2341sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049525/hk2341Isup2.hkl
Contains datablock I

CCDC reference: 1273736

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.034
  • wR factor = 0.108
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu1 PLAT245_ALERT_2_C U(iso) H4A Smaller than U(eq) O4 by ... 0.01 AngSq PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A .. S1 .. 3.06 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported O5 .. S1 .. 3.84 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.29 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 5 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 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring La and Cu metals chains by reaction of the lanthanum(III) and copper(II) ions with 4-methylbenzenesulfonic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

The asymmetric unit of the title compound, (I), (Fig. 1) contains one half cation and one anion, in which 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 (Table 1, Fig. 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present.

Related literature top

For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). 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), copper nitrate hexahydrate (295.6 mg, 1 mmol), 4-methylbenzene- sulfonic 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 blue 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 = 0.785 (17)–0.833 (17) Å and Uiso(H) = 0.058 (9) -0.080 (12) 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 = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Structure description top

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring La and Cu metals chains by reaction of the lanthanum(III) and copper(II) ions with 4-methylbenzenesulfonic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

The asymmetric unit of the title compound, (I), (Fig. 1) contains one half cation and one anion, in which 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 (Table 1, Fig. 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present.

For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). 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.
Hexaaquacopper(II) bis(4-methylbenzenesulfonate) top
Crystal data top
[Cu(H2O)6](C7H7O3S)2F(000) = 534
Mr = 514.01Dx = 1.554 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5117 reflections
a = 6.9472 (4) Åθ = 2.4–28.3°
b = 6.2891 (3) ŵ = 1.24 mm1
c = 25.1581 (14) ÅT = 273 K
β = 91.565 (1)°Prism, blue
V = 1098.79 (10) Å30.48 × 0.37 × 0.20 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2349 independent reflections
Radiation source: fine-focus sealed tube2004 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 27.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.588, Tmax = 0.794k = 77
7237 measured reflectionsl = 3231
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0641P)2 + 0.4823P]
where P = (Fo2 + 2Fc2)/3
2349 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.35 e Å3
9 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Cu(H2O)6](C7H7O3S)2V = 1098.79 (10) Å3
Mr = 514.01Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.9472 (4) ŵ = 1.24 mm1
b = 6.2891 (3) ÅT = 273 K
c = 25.1581 (14) Å0.48 × 0.37 × 0.20 mm
β = 91.565 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2349 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2004 reflections with I > 2σ(I)
Tmin = 0.588, Tmax = 0.794Rint = 0.025
7237 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0349 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.35 e Å3
2349 reflectionsΔρmin = 0.42 e Å3
158 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
Cu10.50000.00000.00000.04199 (16)
S10.01464 (9)0.60839 (10)0.90519 (3)0.04218 (18)
O10.1552 (3)0.5134 (3)0.93086 (9)0.0539 (5)
O20.0141 (3)0.8398 (3)0.90896 (8)0.0533 (5)
O30.1925 (3)0.5162 (3)0.92401 (9)0.0544 (5)
O40.7237 (3)0.1026 (4)0.04791 (11)0.0726 (7)
O50.5088 (3)0.2886 (3)0.03508 (9)0.0549 (5)
O60.3032 (4)0.1034 (4)0.05323 (11)0.0727 (7)
C10.0452 (5)0.6350 (7)0.74521 (14)0.0754 (10)
H10.07890.73480.71930.090*
C20.0544 (5)0.6913 (6)0.79850 (13)0.0639 (8)
H20.09460.82670.80810.077*
C30.0035 (4)0.5452 (5)0.83688 (11)0.0462 (6)
C40.0521 (5)0.3430 (5)0.82212 (12)0.0606 (7)
H40.08410.24240.84800.073*
C50.0601 (5)0.2907 (6)0.76879 (13)0.0702 (9)
H50.09850.15470.75920.084*
C60.0123 (5)0.4356 (7)0.72983 (13)0.0694 (9)
C70.0308 (6)0.3770 (9)0.67186 (14)0.0989 (15)
H7B0.16100.33530.66550.148*
H7A0.00250.49750.65010.148*
H7C0.05450.26110.66330.148*
H4A0.763 (4)0.220 (3)0.0485 (12)0.059 (10)*
H5A0.610 (3)0.340 (5)0.0462 (12)0.058 (9)*
H6A0.261 (5)0.220 (3)0.0575 (15)0.080 (12)*
H4B0.814 (4)0.020 (4)0.0558 (15)0.069 (11)*
H5B0.419 (3)0.342 (5)0.0480 (12)0.059 (10)*
H6B0.216 (4)0.017 (4)0.0593 (14)0.065 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0394 (2)0.0311 (3)0.0555 (3)0.00069 (16)0.00176 (18)0.00152 (17)
S10.0414 (3)0.0320 (3)0.0532 (4)0.0005 (2)0.0027 (2)0.0004 (3)
O10.0559 (11)0.0410 (11)0.0641 (12)0.0056 (8)0.0113 (10)0.0018 (8)
O20.0529 (10)0.0318 (10)0.0754 (13)0.0002 (8)0.0044 (9)0.0022 (9)
O30.0536 (11)0.0405 (11)0.0701 (13)0.0043 (8)0.0171 (10)0.0020 (8)
O40.0691 (14)0.0359 (12)0.1105 (19)0.0052 (11)0.0400 (13)0.0005 (12)
O50.0451 (11)0.0380 (11)0.0816 (14)0.0005 (9)0.0052 (10)0.0146 (9)
O60.0746 (15)0.0363 (12)0.1095 (19)0.0008 (11)0.0460 (14)0.0054 (12)
C10.067 (2)0.098 (3)0.0618 (19)0.007 (2)0.0002 (16)0.0239 (19)
C20.0637 (18)0.059 (2)0.0689 (19)0.0101 (15)0.0047 (14)0.0124 (15)
C30.0392 (12)0.0463 (15)0.0532 (15)0.0002 (11)0.0015 (11)0.0022 (11)
C40.074 (2)0.0507 (18)0.0575 (16)0.0096 (14)0.0003 (14)0.0018 (14)
C50.080 (2)0.069 (2)0.0618 (19)0.0039 (18)0.0046 (16)0.0145 (16)
C60.0511 (17)0.099 (3)0.0579 (18)0.0072 (18)0.0023 (14)0.0035 (18)
C70.085 (3)0.156 (5)0.056 (2)0.005 (3)0.0067 (18)0.008 (2)
Geometric parameters (Å, º) top
Cu1—O4i2.045 (2)O6—H6B0.832 (17)
Cu1—O42.045 (2)C1—C61.375 (6)
Cu1—O52.0182 (19)C1—C21.390 (5)
Cu1—O5i2.0182 (19)C1—H10.9300
Cu1—O6i2.046 (2)C2—C31.372 (4)
Cu1—O62.046 (2)C2—H20.9300
S1—O31.456 (2)C3—C41.382 (4)
S1—O11.458 (2)C4—C51.384 (4)
S1—O21.458 (2)C4—H40.9300
S1—C31.768 (3)C5—C61.373 (5)
O4—H4A0.785 (17)C5—H50.9300
O4—H4B0.833 (17)C6—C71.513 (5)
O5—H5A0.813 (17)C7—H7B0.9600
O5—H5B0.786 (17)C7—H7A0.9600
O6—H6A0.796 (17)C7—H7C0.9600
O4i—Cu1—O4180.00 (18)Cu1—O6—H6A129 (3)
O4—Cu1—O5i89.29 (9)Cu1—O6—H6B115 (2)
O4i—Cu1—O5i90.71 (9)H6A—O6—H6B107 (2)
O4—Cu1—O590.71 (9)C6—C1—C2121.7 (3)
O4i—Cu1—O589.29 (9)C6—C1—H1119.2
O4i—Cu1—O688.59 (12)C2—C1—H1119.2
O4—Cu1—O691.41 (12)C3—C2—C1119.4 (3)
O4i—Cu1—O6i91.41 (12)C3—C2—H2120.3
O4—Cu1—O6i88.59 (12)C1—C2—H2120.3
O5—Cu1—O5i180.00 (12)C2—C3—C4119.7 (3)
O5—Cu1—O6i89.29 (9)C2—C3—S1121.1 (2)
O5i—Cu1—O6i90.71 (9)C4—C3—S1119.2 (2)
O5—Cu1—O690.71 (9)C3—C4—C5119.9 (3)
O5i—Cu1—O689.29 (9)C3—C4—H4120.1
O6i—Cu1—O6180.00 (12)C5—C4—H4120.1
O3—S1—O1112.13 (13)C6—C5—C4121.3 (3)
O3—S1—O2112.14 (11)C6—C5—H5119.4
O1—S1—O2112.30 (12)C4—C5—H5119.4
O3—S1—C3106.67 (13)C5—C6—C1118.1 (3)
O1—S1—C3106.39 (12)C5—C6—C7120.1 (4)
O2—S1—C3106.72 (13)C1—C6—C7121.8 (4)
Cu1—O4—H4A124 (2)C6—C7—H7B109.5
Cu1—O4—H4B120 (2)C6—C7—H7A109.5
H4A—O4—H4B109 (2)H7B—C7—H7A109.5
Cu1—O5—H5A122 (2)C6—C7—H7C109.5
Cu1—O5—H5B124 (2)H7B—C7—H7C109.5
H5A—O5—H5B112 (3)H7A—C7—H7C109.5
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O20.932.592.938 (4)103
O4—H4A···O1ii0.79 (2)2.00 (2)2.765 (3)166 (3)
O6—H6A···O3iii0.80 (2)1.98 (2)2.772 (3)171 (4)
O5—H5A···O1iv0.81 (2)1.95 (2)2.761 (3)175 (3)
O5—H5A···S1iv0.81 (2)3.06 (2)3.839 (2)163 (3)
O4—H4B···O2iv0.83 (2)1.98 (2)2.803 (3)167 (4)
O5—H5B···O3v0.79 (2)1.96 (2)2.742 (3)176 (3)
O6—H6B···O2v0.83 (2)1.98 (2)2.791 (3)166 (4)
Symmetry codes: (ii) x+1, y, z+1; (iii) x, y, z+1; (iv) x+1, y+1, z+1; (v) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu(H2O)6](C7H7O3S)2
Mr514.01
Crystal system, space groupMonoclinic, P21/n
Temperature (K)273
a, b, c (Å)6.9472 (4), 6.2891 (3), 25.1581 (14)
β (°) 91.565 (1)
V3)1098.79 (10)
Z2
Radiation typeMo Kα
µ (mm1)1.24
Crystal size (mm)0.48 × 0.37 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.588, 0.794
No. of measured, independent and
observed [I > 2σ(I)] reflections
7237, 2349, 2004
Rint0.025
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.108, 1.03
No. of reflections2349
No. of parameters158
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.42

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

Selected geometric parameters (Å, º) top
Cu1—O4i2.045 (2)Cu1—O5i2.0182 (19)
Cu1—O42.045 (2)Cu1—O6i2.046 (2)
Cu1—O52.0182 (19)Cu1—O62.046 (2)
O4i—Cu1—O4180.00 (18)O4—Cu1—O6i88.59 (12)
O4—Cu1—O5i89.29 (9)O5—Cu1—O5i180.00 (12)
O4i—Cu1—O5i90.71 (9)O5—Cu1—O6i89.29 (9)
O4—Cu1—O590.71 (9)O5i—Cu1—O6i90.71 (9)
O4i—Cu1—O589.29 (9)O5—Cu1—O690.71 (9)
O4i—Cu1—O688.59 (12)O5i—Cu1—O689.29 (9)
O4—Cu1—O691.41 (12)O6i—Cu1—O6180.00 (12)
O4i—Cu1—O6i91.41 (12)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O20.932.592.938 (4)103
O4—H4A···O1ii0.785 (17)1.997 (19)2.765 (3)166 (3)
O6—H6A···O3iii0.796 (17)1.984 (18)2.772 (3)171 (4)
O5—H5A···O1iv0.813 (17)1.950 (18)2.761 (3)175 (3)
O5—H5A···S1iv0.813 (17)3.055 (18)3.839 (2)163 (3)
O4—H4B···O2iv0.833 (17)1.98 (2)2.803 (3)167 (4)
O5—H5B···O3v0.786 (17)1.958 (17)2.742 (3)176 (3)
O6—H6B···O2v0.832 (17)1.98 (2)2.791 (3)166 (4)
Symmetry codes: (ii) x+1, y, z+1; (iii) x, y, z+1; (iv) x+1, y+1, z+1; (v) x, y+1, z+1.
 

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