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Acta Cryst. (2007). E63, m2001    [ doi:10.1107/S1600536807030711 ]

Tetraamminediaquacopper(II) 4-amino-2,5-dichlorobenzenesulfonate

W.-L. Zhang, J.-F. Ma and H. Jiang

Abstract top

In the title compound, [Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2, the CuII cation lies on an inversion centre and is six-coordinated by four NH3 molecules and two water molecules in an enlongated octahedral coordination geometry. The anion is free from coordination but is linked to the CuII complex cation via O-H...O and N-H...O hydrogen bonding.

Comment top

As metal sulfonates are a class of novel materials showing interesting properties, such as exchange, guest sorption (Côté & Shimizu, 2003; Yang et al., 2006), several studies on the coordination chemistry of transition metal sulfonates and their solid-state properties have been reported. In some cases, sulfonate group can compete with water molecule and coordinate to metal ion (Markku & Reijo, 1993). As part of an investigation of the structure of transition metal sulfonate compounds, we present here the structure of the title compound.

The crystal of the compound is composed of [Cu(NH3)4(H2O)2]2+ cations and 4-amino-2,5-dichlorobenzenesulfonate anions (Fig. 1). The CuII cation lies on an inversion center and is six-coordinated by four NH3 molecules and two water molecules. The Cu—O1W bond in the axial direction is much longer than Cu—N bonds in the equatorial plane (Table 1), showing the typical Jahn-Teller distortion. The anions act as counterions and are hydrogen-bonded to the complex cations, forming a three dimensional supra-molecular structure (Fig. 2).

Related literature top

For general background, see: Côté & Shimizu (2003); Markku & Reijo (1993); Yang et al. (2006).

Experimental top

A mixture of CuCl2·2H2O (0.171 g, 1 mmol) and NaOH (0.080 g, 2 mmol) in water (10 ml) was stirred for 10 min at room temperature, then the Cu(OH)2 precipitate was collected by filtration and washed with water. 4-Amino-2,5-dichlorobenzenesulfonic acid (0.484 g, 2 mmol) was added to the Cu(OH)2 suspension in water (10 ml) with stirring, and a blue precipitate was obtained. A minimum amount of ammonia solution (14 M) was added to give a blue, clear solution. Suitable crystals of the title compound were obtained after several days.

Refinement top

H atoms bonded to N and O atoms were located in a difference Fourier map and refined as riding in their as-found relative positions, Uiso(H) = 1.5Ueq(N,O). Aromatic H atoms were poisitioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (i) −x + 2, −y, −z + 2].
[Figure 2] Fig. 2. View of the two-dimensional network formed by the L− anions and [Cu(NH3)4(H2O)2]2+ cations. The hydrogen bonds are drawn as dashed lines.
Tetraamminediaquacopper(II) 4-amino-2,5-dichlorobenzenesulfonate top
Crystal data top
[Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2Z = 1
Mr = 649.83F000 = 331
Triclinic, P1Dx = 1.808 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.367 (6) ÅCell parameters from 5673 reflections
b = 7.380 (5) Åθ = 3.2–27.5º
c = 12.689 (10) ŵ = 1.59 mm−1
α = 96.22 (4)ºT = 293 (2) K
β = 94.62 (4)ºBlock, blue
γ = 118.33 (3)º0.44 × 0.37 × 0.27 mm
V = 596.8 (8) Å3
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2715 independent reflections
Radiation source: rotor target2518 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.1º
ω scansh = −9→9
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −9→9
Tmin = 0.521, Tmax = 0.650l = −16→16
5849 measured reflections
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)] = 0.029H-atom parameters constrained
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0461P)2 + 0.1532P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
2715 reflectionsΔρmax = 0.43 e Å−3
151 parametersΔρmin = −0.42 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(H2O)2(NH3)4](C6H4Cl2NO3S)2γ = 118.33 (3)º
Mr = 649.83V = 596.8 (8) Å3
Triclinic, P1Z = 1
a = 7.367 (6) ÅMo Kα
b = 7.380 (5) ŵ = 1.59 mm−1
c = 12.689 (10) ÅT = 293 (2) K
α = 96.22 (4)º0.44 × 0.37 × 0.27 mm
β = 94.62 (4)º
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2715 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2518 reflections with I > 2σ(I)
Tmin = 0.521, Tmax = 0.650Rint = 0.020
5849 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029151 parameters
wR(F2) = 0.076H-atom parameters constrained
S = 1.10Δρmax = 0.43 e Å−3
2715 reflectionsΔρmin = −0.42 e Å−3
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu11.00000.00001.00000.02605 (10)
Cl10.12744 (6)0.22744 (8)0.68358 (3)0.03803 (12)
Cl20.80402 (7)0.27818 (7)0.40904 (3)0.03640 (12)
S10.57643 (6)0.30274 (6)0.80181 (3)0.02445 (11)
C10.5153 (2)0.2819 (2)0.66165 (12)0.0231 (3)
C20.3236 (2)0.2471 (2)0.61119 (13)0.0248 (3)
C30.2789 (2)0.2209 (3)0.50137 (13)0.0279 (3)
H30.14960.19830.47040.033*
C40.4238 (3)0.2275 (3)0.43586 (12)0.0270 (3)
C50.6171 (2)0.2647 (2)0.48716 (13)0.0256 (3)
C60.6623 (2)0.2912 (2)0.59713 (12)0.0246 (3)
H60.79210.31550.62840.030*
N10.3790 (3)0.1971 (3)0.32678 (12)0.0384 (4)
H1N0.26200.17980.29620.058*
H2N0.46890.20390.29100.058*
O10.4554 (2)0.0939 (2)0.82788 (10)0.0357 (3)
O20.79984 (18)0.3761 (2)0.82209 (10)0.0357 (3)
O1W1.0063 (2)−0.1798 (2)0.81528 (12)0.0445 (3)
H1A0.9705−0.31360.80540.067*
H1B1.1262−0.11500.80140.067*
N20.6962 (2)−0.0932 (2)0.95054 (12)0.0317 (3)
H2A0.6650−0.02150.91040.048*
H2B0.6300−0.10331.00890.048*
H2C0.6394−0.22090.92110.048*
O30.5222 (2)0.4502 (2)0.85509 (10)0.0362 (3)
N31.0992 (2)0.2790 (2)0.95026 (11)0.0314 (3)
H3A1.00380.27910.91150.047*
H3B1.14470.37591.00250.047*
H3C1.19790.30350.91400.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02468 (15)0.02976 (17)0.02568 (15)0.01440 (12)0.00308 (11)0.00729 (11)
Cl10.0261 (2)0.0597 (3)0.0322 (2)0.0231 (2)0.00693 (16)0.01044 (19)
Cl20.0330 (2)0.0446 (3)0.0305 (2)0.01790 (19)0.01035 (16)0.00277 (17)
S10.02302 (18)0.0277 (2)0.02057 (18)0.01111 (15)0.00088 (14)0.00409 (14)
C10.0238 (7)0.0231 (7)0.0216 (7)0.0110 (6)0.0017 (6)0.0046 (5)
C20.0227 (7)0.0256 (8)0.0270 (7)0.0116 (6)0.0045 (6)0.0074 (6)
C30.0238 (7)0.0302 (8)0.0286 (8)0.0127 (6)−0.0011 (6)0.0062 (6)
C40.0301 (8)0.0242 (8)0.0236 (7)0.0110 (6)0.0015 (6)0.0047 (6)
C50.0264 (7)0.0242 (8)0.0256 (7)0.0115 (6)0.0065 (6)0.0045 (6)
C60.0220 (6)0.0251 (7)0.0264 (7)0.0115 (6)0.0015 (6)0.0046 (6)
N10.0371 (8)0.0530 (10)0.0225 (7)0.0205 (7)0.0008 (6)0.0062 (6)
O10.0392 (7)0.0336 (7)0.0297 (6)0.0128 (5)0.0042 (5)0.0122 (5)
O20.0250 (6)0.0494 (8)0.0300 (6)0.0167 (5)−0.0017 (5)0.0074 (5)
O1W0.0394 (7)0.0418 (8)0.0477 (8)0.0143 (6)0.0165 (6)0.0087 (6)
N20.0298 (7)0.0364 (8)0.0317 (7)0.0185 (6)0.0024 (6)0.0062 (6)
O30.0378 (6)0.0382 (7)0.0310 (6)0.0198 (6)0.0014 (5)−0.0042 (5)
N30.0328 (7)0.0339 (8)0.0286 (7)0.0169 (6)0.0028 (6)0.0073 (6)
Geometric parameters (Å, °) top
Cu1—N22.024 (2)C3—H30.9300
Cu1—N2i2.024 (2)C4—N11.365 (2)
Cu1—N32.025 (2)C4—C51.403 (3)
Cu1—N3i2.025 (2)C5—C61.379 (2)
Cu1—O1W2.580 (2)C6—H60.9300
Cl1—C21.731 (2)N1—H1N0.8605
Cl2—C51.732 (2)N1—H2N0.8179
S1—O31.4482 (15)O1W—H1A0.8836
S1—O21.4574 (17)O1W—H1B0.8260
S1—O11.4608 (17)N2—H2A0.8642
S1—C11.771 (2)N2—H2B0.9089
C1—C61.390 (2)N2—H2C0.8531
C1—C21.395 (2)N3—H3A0.8251
C2—C31.377 (2)N3—H3B0.8346
C3—C41.391 (3)N3—H3C0.8488
N2—Cu1—N2i180.000 (1)C3—C4—C5116.84 (15)
N2—Cu1—N392.99 (7)C6—C5—C4122.08 (15)
N2i—Cu1—N387.01 (7)C6—C5—Cl2119.39 (13)
N2—Cu1—N3i87.01 (7)C4—C5—Cl2118.53 (14)
N2i—Cu1—N3i92.99 (7)C5—C6—C1120.52 (15)
N3—Cu1—N3i180.000 (1)C5—C6—H6119.7
O3—S1—O2112.05 (9)C1—C6—H6119.7
O3—S1—O1112.11 (10)C4—N1—H1N120.9
O2—S1—O1111.67 (9)C4—N1—H2N118.6
O3—S1—C1108.15 (8)H1N—N1—H2N120.3
O2—S1—C1105.56 (8)H1A—O1W—H1B107.3
O1—S1—C1106.89 (9)Cu1—N2—H2A119.1
C6—C1—C2117.67 (15)Cu1—N2—H2B109.0
C6—C1—S1118.57 (12)H2A—N2—H2B108.1
C2—C1—S1123.70 (12)Cu1—N2—H2C106.8
C3—C2—C1121.70 (15)H2A—N2—H2C111.0
C3—C2—Cl1116.75 (13)H2B—N2—H2C101.4
C1—C2—Cl1121.53 (13)Cu1—N3—H3A110.6
C2—C3—C4121.18 (15)Cu1—N3—H3B110.9
C2—C3—H3119.4H3A—N3—H3B109.9
C4—C3—H3119.4Cu1—N3—H3C110.4
N1—C4—C3121.51 (16)H3A—N3—H3C107.6
N1—C4—C5121.65 (16)H3B—N3—H3C107.4
O3—S1—C1—C6133.25 (13)Cl1—C2—C3—C4−178.05 (13)
O2—S1—C1—C613.16 (15)C2—C3—C4—N1178.56 (16)
O1—S1—C1—C6−105.86 (14)C2—C3—C4—C5−0.8 (2)
O3—S1—C1—C2−49.74 (16)N1—C4—C5—C6−178.61 (16)
O2—S1—C1—C2−169.83 (14)C3—C4—C5—C60.7 (2)
O1—S1—C1—C271.15 (16)N1—C4—C5—Cl21.6 (2)
C6—C1—C2—C30.6 (2)C3—C4—C5—Cl2−179.06 (12)
S1—C1—C2—C3−176.48 (13)C4—C5—C6—C10.0 (3)
C6—C1—C2—Cl1178.68 (12)Cl2—C5—C6—C1179.77 (12)
S1—C1—C2—Cl11.6 (2)C2—C1—C6—C5−0.6 (2)
C1—C2—C3—C40.2 (3)S1—C1—C6—C5176.58 (13)
Symmetry codes: (i) −x+2, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O2ii0.882.072.900 (3)156
O1W—H1B···O1iii0.832.142.925 (3)159
N1—H1N···O1Wiv0.862.343.179 (4)166
N1—H2N···Cl20.822.562.967 (3)112
N2—H2A···O10.862.323.134 (3)157
N2—H2B···O1v0.912.223.108 (3)166
N2—H2C···O3ii0.852.193.038 (3)174
N3—H3A···O20.822.233.033 (3)164
N3—H3B···O2vi0.842.593.412 (3)166
N3—H3B···O3vi0.842.593.226 (3)133
N3—H3C···O3iii0.852.333.157 (3)164
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y, −z+1; (v) −x+1, −y, −z+2; (vi) −x+2, −y+1, −z+2.
Selected geometric parameters (Å) top
Cu1—N22.024 (2)Cu1—O1W2.580 (2)
Cu1—N32.025 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O2i0.882.072.900 (3)156
O1W—H1B···O1ii0.832.142.925 (3)159
N1—H1N···O1Wiii0.862.343.179 (4)166
N1—H2N···Cl20.822.562.967 (3)112
N2—H2A···O10.862.323.134 (3)157
N2—H2B···O1iv0.912.223.108 (3)166
N2—H2C···O3i0.852.193.038 (3)174
N3—H3A···O20.822.233.033 (3)164
N3—H3B···O2v0.842.593.412 (3)166
N3—H3B···O3v0.842.593.226 (3)133
N3—H3C···O3ii0.852.333.157 (3)164
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z+2; (v) −x+2, −y+1, −z+2.
Acknowledgements top

The authors thank the National Natural Science Foundation of China (grant No. 20471014), the Programme for New Century Excellent Talents in Chinese Universities (grant No. NCET-05–0320), the Fok Ying Tung Education Foundation, and the Analysis and Testing Foundation of Northeast Normal University, China, for supporting this work.

references
References top

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Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Markku, R. S. & Reijo, S. (1993). Acta Chem. Scand. 47, 1173–1178.

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Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Yang, J., Li, L., Ma, J.-F., Liu, Y.-Y. & Ma, J.-C. (2006). J. Mol. Struct. 788, 43–48.