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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026347/ng2272sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026347/ng2272Isup2.hkl
Contains datablock I

CCDC reference: 654704

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.039
  • wR factor = 0.115
  • Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O5 PLAT430_ALERT_2_C Short Inter D...A Contact O1 .. N1 .. 2.88 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 H2 O
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) 2.05
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 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 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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).

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.034
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 2016
Tmin = 0.741, Tmax = 0.783k = 66
10697 measured reflectionsl = 1919
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 Å3
0 restraintsΔρmin = 0.32 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.115H-atom parameters constrained
S = 1.13Δρmax = 0.56 e Å3
2762 reflectionsΔρmin = 0.32 e Å3
169 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
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)
H70.51010.24190.85820.081*
H80.56060.36570.93150.081*
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)
H110.46820.26540.69600.079*
H120.39020.20350.72490.079*
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, º) 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 code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) 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, y1/2, z+3/2; (iv) x, y1, z.

Experimental details

Crystal data
Chemical formula[Cu(C8H6NO5S)2(H2O)2]·4H2O
Mr628.03
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)15.577 (3), 5.3724 (11), 14.740 (3)
β (°) 99.79 (3)
V3)1215.6 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.15
Crystal size (mm)0.28 × 0.25 × 0.22
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.741, 0.783
No. of measured, independent and
observed [I > 2σ(I)] reflections
10697, 2762, 2319
Rint0.034
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.115, 1.13
No. of reflections2762
No. of parameters169
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.32

Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.

Hydrogen-bond geometry (Å, º) 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, y1/2, z+3/2; (iv) x, y1, z.
 

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