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Acta Cryst. (2007). E63, m1809    [ doi:10.1107/S1600536807026347 ]

Diaquabis[(2-nitrophenylsulfinyl)acetato-[kappa]O]copper(II) tetrahydrate

X.-F. Zhu, L.-M. Zhao, G.-F. Hou and J.-S. Gao

Abstract top

The centrosymmetric title compound, [Cu(C8H6NO5S)2(H2O)2]·4H2O, has a four-coordinate CuII ion in a square-planar geometry defined by two carboxylate O atoms from two (2-nitrophenylsulfinyl)acetate groups and two O atoms from two water molecules. The molecules are linked together by intermolecular hydrogen bonds involving the water molecules, resulting in a layer network.

Comment top

The crystal structure of (2-nitrophenylsulfinyl)acetic acid has been reported (Ma, 2007). Here, we report the structure of the copper derivative. The compound has the copper center being coordinated to two (2-nitrophenylsulfinyl)acetic acid groups and two water molecules in a square-planar geometry. The structure is stabilized by hydrogen bonding interactions (Table 1) that link the molecules into a layer structure (Fig. 2).

Related literature top

For the structure of the parent carboxylic acid, see: Ma (2007). For synthesis of the parent carboxylic acid, see: Nobles & Thompson (1965).

Experimental top

(2-Nitrophenylsulfanyl)acetic acid was prepared by nucleophilic reaction of chloroacetic acid and 2-nitrothiophenol under basic conditions (Nobles & Thompson, 1965). It was then oxidized using 30% aqueous hydrogen peroxide in acetic anhydride solution to produce (2-nitrophenylsulfinyl)acetic acid. Copper(II) nitrate trihydrate (0.482 g, 2 mmol) and (2-nitrophenylsulfinyl)acetic acid (0.458 g, 2 mmol) were dissolved in water and the pH was adjusted to 6 with 0.01 M sodium hydroxide; green crystals separated from the filtered solution after several days.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic C) or C—H = 0.97 Å (methylene C), and with Uiso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H = 0.85 Å and with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms.Dashed lines indicate the hydrogen bonding interactions.
[Figure 2] Fig. 2. A partial packing view,showing the two-dimensional hydrogen-bonding plan.Dashed lines indicate the hydrogen-bonding interactions. H atoms not involved in hydrogen bonds have been omitted.
Diaquabis[(2-nitrophenylsulfinyl)acetato-κO]copper(II) tetrahydrate top
Crystal data top
[Cu(C8H6NO5S)2(H2O)2]·4H2OF(000) = 646
Mr = 628.03Dx = 1.716 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8753 reflections
a = 15.577 (3) Åθ = 6.4–54.9°
b = 5.3724 (11) ŵ = 1.15 mm−1
c = 14.740 (3) ÅT = 293 K
β = 99.79 (3)°Block, green
V = 1215.6 (4) Å30.28 × 0.25 × 0.22 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2762 independent reflections
Radiation source: fine-focus sealed tube2319 reflections with I > 2σ(I)
graphiteRint = 0.034
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −20→16
Tmin = 0.741, Tmax = 0.783k = −6→6
10697 measured reflectionsl = −19→19
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0607P)2 + 0.3938P]
where P = (Fo2 + 2Fc2)/3
2762 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.32 e Å−3
Crystal data top
[Cu(C8H6NO5S)2(H2O)2]·4H2OV = 1215.6 (4) Å3
Mr = 628.03Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.577 (3) ŵ = 1.15 mm−1
b = 5.3724 (11) ÅT = 293 K
c = 14.740 (3) Å0.28 × 0.25 × 0.22 mm
β = 99.79 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2762 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2319 reflections with I > 2σ(I)
Tmin = 0.741, Tmax = 0.783Rint = 0.034
10697 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.115Δρmax = 0.56 e Å−3
S = 1.13Δρmin = −0.32 e Å−3
2762 reflectionsAbsolute structure: ?
169 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
O70.64039 (15)0.3858 (5)0.97093 (15)0.0651 (7)
H90.64870.27701.01340.098*
H100.67540.36070.93350.098*
C10.17597 (14)0.3739 (4)0.65632 (15)0.0305 (5)
C20.19283 (17)0.3735 (5)0.56705 (17)0.0403 (6)
H10.23240.26000.55030.048*
C30.1514 (2)0.5401 (6)0.50240 (18)0.0460 (7)
H20.16420.54000.44300.055*
C40.09128 (18)0.7062 (6)0.52569 (17)0.0453 (6)
H30.06300.81590.48170.054*
C50.07302 (16)0.7100 (5)0.61371 (17)0.0398 (6)
H40.03240.82160.62960.048*
C60.11567 (14)0.5465 (4)0.67806 (15)0.0296 (5)
C70.31452 (16)0.3077 (5)0.79487 (17)0.0359 (5)
H50.35330.36080.75360.043*
H60.29270.45450.82190.043*
C80.36275 (16)0.1415 (5)0.86970 (16)0.0360 (5)
Cu10.50000.00001.00000.03945 (17)
N10.09619 (14)0.5590 (4)0.77139 (14)0.0347 (4)
O10.03918 (14)0.6992 (4)0.78782 (13)0.0532 (5)
O20.13813 (14)0.4272 (4)0.83009 (13)0.0521 (5)
O30.26962 (14)−0.0378 (4)0.67413 (15)0.0488 (5)
O40.44160 (12)0.2006 (3)0.89878 (11)0.0410 (4)
O60.53552 (14)−0.2293 (4)0.91383 (13)0.0541 (6)
H70.5101−0.24190.85820.081*
H80.5606−0.36570.93150.081*
O50.32407 (15)−0.0344 (4)0.89713 (17)0.0638 (7)
S10.22542 (4)0.13019 (11)0.73286 (4)0.03311 (17)
O80.44357 (13)−0.2394 (4)0.74232 (13)0.0526 (5)
H110.4682−0.26540.69600.079*
H120.3902−0.20350.72490.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O70.0726 (15)0.0724 (15)0.0554 (13)0.0386 (13)0.0251 (11)0.0294 (12)
C10.0249 (11)0.0369 (12)0.0283 (11)−0.0008 (9)0.0010 (8)0.0029 (9)
C20.0381 (14)0.0523 (16)0.0314 (12)0.0075 (11)0.0085 (10)−0.0001 (11)
C30.0506 (17)0.0626 (18)0.0251 (12)0.0017 (13)0.0077 (11)0.0043 (12)
C40.0445 (15)0.0592 (17)0.0307 (12)0.0109 (12)0.0021 (10)0.0119 (12)
C50.0352 (13)0.0493 (15)0.0344 (12)0.0090 (11)0.0046 (10)0.0049 (11)
C60.0250 (11)0.0377 (12)0.0256 (10)−0.0025 (9)0.0035 (8)0.0003 (9)
C70.0338 (13)0.0361 (12)0.0355 (12)0.0009 (9)−0.0004 (9)0.0074 (10)
C80.0390 (14)0.0407 (13)0.0289 (11)0.0124 (10)0.0077 (10)0.0051 (10)
Cu10.0463 (3)0.0408 (3)0.0267 (2)0.01786 (18)−0.00671 (18)−0.00255 (17)
N10.0349 (11)0.0406 (11)0.0294 (10)−0.0004 (9)0.0077 (8)0.0003 (9)
O10.0613 (13)0.0607 (12)0.0415 (10)0.0239 (10)0.0198 (9)0.0025 (10)
O20.0545 (12)0.0721 (13)0.0304 (9)0.0210 (11)0.0093 (8)0.0120 (10)
O30.0531 (13)0.0426 (10)0.0509 (12)0.0120 (8)0.0092 (9)−0.0051 (9)
O40.0421 (10)0.0449 (10)0.0319 (9)0.0126 (8)−0.0055 (7)0.0016 (8)
O60.0738 (15)0.0493 (11)0.0339 (9)0.0295 (10)−0.0057 (9)−0.0029 (9)
O50.0549 (14)0.0691 (14)0.0693 (15)0.0095 (11)0.0161 (11)0.0429 (12)
S10.0312 (3)0.0326 (3)0.0356 (3)−0.0001 (2)0.0057 (2)0.0047 (2)
O80.0520 (12)0.0708 (14)0.0353 (9)0.0081 (10)0.0080 (8)−0.0014 (10)
Geometric parameters (Å, °) top
O7—H90.8500C7—H50.9700
O7—H100.8500C7—H60.9700
C1—C21.385 (3)C8—O51.226 (3)
C1—C61.396 (3)C8—O41.271 (3)
C1—S11.812 (2)Cu1—O6i1.9173 (19)
C2—C31.384 (4)Cu1—O61.9173 (19)
C2—H10.9300Cu1—O41.9373 (17)
C3—C41.379 (4)Cu1—O4i1.9373 (17)
C3—H20.9300N1—O21.218 (3)
C4—C51.375 (4)N1—O11.219 (3)
C4—H30.9300O3—S11.497 (2)
C5—C61.378 (3)O6—H70.8499
C5—H40.9300O6—H80.8500
C6—N11.460 (3)O8—H110.8500
C7—C81.515 (3)O8—H120.8501
C7—S11.800 (2)
H9—O7—H10109.6S1—C7—H6110.2
C2—C1—C6117.6 (2)H5—C7—H6108.5
C2—C1—S1117.47 (19)O5—C8—O4125.6 (2)
C6—C1—S1124.64 (17)O5—C8—C7118.9 (2)
C3—C2—C1120.8 (2)O4—C8—C7115.4 (2)
C3—C2—H1119.6O6i—Cu1—O6180.000 (1)
C1—C2—H1119.6O6i—Cu1—O490.12 (8)
C4—C3—C2120.2 (2)O6—Cu1—O489.88 (8)
C4—C3—H2119.9O6i—Cu1—O4i89.88 (8)
C2—C3—H2119.9O6—Cu1—O4i90.12 (8)
C5—C4—C3120.2 (2)O4—Cu1—O4i180.00 (7)
C5—C4—H3119.9O2—N1—O1122.6 (2)
C3—C4—H3119.9O2—N1—C6118.0 (2)
C4—C5—C6119.1 (2)O1—N1—C6119.4 (2)
C4—C5—H4120.4C8—O4—Cu1114.91 (16)
C6—C5—H4120.4Cu1—O6—H7123.4
C5—C6—C1122.0 (2)Cu1—O6—H8121.4
C5—C6—N1117.8 (2)H7—O6—H8109.9
C1—C6—N1120.2 (2)O3—S1—C7102.84 (12)
C8—C7—S1107.53 (17)O3—S1—C1105.31 (11)
C8—C7—H5110.2C7—S1—C198.20 (11)
S1—C7—H5110.2H11—O8—H12110.3
C8—C7—H6110.2
Symmetry codes: (i) −x+1, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H9···O5i0.851.852.699 (3)175
O7—H10···O3ii0.852.002.779 (3)152
O8—H11···O4iii0.852.152.982 (3)166
O8—H12···O30.852.102.933 (3)167
O6—H7···O80.851.842.686 (3)172
O6—H8···O7iv0.851.852.680 (3)165
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H9···O5i0.851.852.699 (3)175
O7—H10···O3ii0.852.002.779 (3)152
O8—H11···O4iii0.852.152.982 (3)166
O8—H12···O30.852.102.933 (3)167
O6—H7···O80.851.842.686 (3)172
O6—H8···O7iv0.851.852.680 (3)165
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, y−1, z.
Acknowledgements top

The authors thank the Daqing New Century Industrial Co. Ltd and Heilongjiang University for supporting this study.

references
References top

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

Ma, D.-S. (2007). Acta Cryst. E63, o658–o659.

Nobles, W. L. & Thompson, B. B. (1965). J. Pharm. Sci. 54, 709–713.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

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

Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.