Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026347/ng2272sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026347/ng2272Isup2.hkl |
CCDC reference: 654704
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
(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.
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).
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).
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.
[Cu(C8H6NO5S)2(H2O)2]·4H2O | F(000) = 646 |
Mr = 628.03 | Dx = 1.716 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8753 reflections |
a = 15.577 (3) Å | θ = 6.4–54.9° |
b = 5.3724 (11) Å | µ = 1.15 mm−1 |
c = 14.740 (3) Å | T = 293 K |
β = 99.79 (3)° | Block, green |
V = 1215.6 (4) Å3 | 0.28 × 0.25 × 0.22 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 2762 independent reflections |
Radiation source: fine-focus sealed tube | 2319 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −20→16 |
Tmin = 0.741, Tmax = 0.783 | k = −6→6 |
10697 measured reflections | l = −19→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-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 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu(C8H6NO5S)2(H2O)2]·4H2O | V = 1215.6 (4) Å3 |
Mr = 628.03 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.577 (3) Å | µ = 1.15 mm−1 |
b = 5.3724 (11) Å | T = 293 K |
c = 14.740 (3) Å | 0.28 × 0.25 × 0.22 mm |
β = 99.79 (3)° |
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 = 0.783 | Rint = 0.034 |
10697 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.56 e Å−3 |
2762 reflections | Δρmin = −0.32 e Å−3 |
169 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O7 | 0.64039 (15) | 0.3858 (5) | 0.97093 (15) | 0.0651 (7) | |
H9 | 0.6487 | 0.2770 | 1.0134 | 0.098* | |
H10 | 0.6754 | 0.3607 | 0.9335 | 0.098* | |
C1 | 0.17597 (14) | 0.3739 (4) | 0.65632 (15) | 0.0305 (5) | |
C2 | 0.19283 (17) | 0.3735 (5) | 0.56705 (17) | 0.0403 (6) | |
H1 | 0.2324 | 0.2600 | 0.5503 | 0.048* | |
C3 | 0.1514 (2) | 0.5401 (6) | 0.50240 (18) | 0.0460 (7) | |
H2 | 0.1642 | 0.5400 | 0.4430 | 0.055* | |
C4 | 0.09128 (18) | 0.7062 (6) | 0.52569 (17) | 0.0453 (6) | |
H3 | 0.0630 | 0.8159 | 0.4817 | 0.054* | |
C5 | 0.07302 (16) | 0.7100 (5) | 0.61371 (17) | 0.0398 (6) | |
H4 | 0.0324 | 0.8216 | 0.6296 | 0.048* | |
C6 | 0.11567 (14) | 0.5465 (4) | 0.67806 (15) | 0.0296 (5) | |
C7 | 0.31452 (16) | 0.3077 (5) | 0.79487 (17) | 0.0359 (5) | |
H5 | 0.3533 | 0.3608 | 0.7536 | 0.043* | |
H6 | 0.2927 | 0.4545 | 0.8219 | 0.043* | |
C8 | 0.36275 (16) | 0.1415 (5) | 0.86970 (16) | 0.0360 (5) | |
Cu1 | 0.5000 | 0.0000 | 1.0000 | 0.03945 (17) | |
N1 | 0.09619 (14) | 0.5590 (4) | 0.77139 (14) | 0.0347 (4) | |
O1 | 0.03918 (14) | 0.6992 (4) | 0.78782 (13) | 0.0532 (5) | |
O2 | 0.13813 (14) | 0.4272 (4) | 0.83009 (13) | 0.0521 (5) | |
O3 | 0.26962 (14) | −0.0378 (4) | 0.67413 (15) | 0.0488 (5) | |
O4 | 0.44160 (12) | 0.2006 (3) | 0.89878 (11) | 0.0410 (4) | |
O6 | 0.53552 (14) | −0.2293 (4) | 0.91383 (13) | 0.0541 (6) | |
H7 | 0.5101 | −0.2419 | 0.8582 | 0.081* | |
H8 | 0.5606 | −0.3657 | 0.9315 | 0.081* | |
O5 | 0.32407 (15) | −0.0344 (4) | 0.89713 (17) | 0.0638 (7) | |
S1 | 0.22542 (4) | 0.13019 (11) | 0.73286 (4) | 0.03311 (17) | |
O8 | 0.44357 (13) | −0.2394 (4) | 0.74232 (13) | 0.0526 (5) | |
H11 | 0.4682 | −0.2654 | 0.6960 | 0.079* | |
H12 | 0.3902 | −0.2035 | 0.7249 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O7 | 0.0726 (15) | 0.0724 (15) | 0.0554 (13) | 0.0386 (13) | 0.0251 (11) | 0.0294 (12) |
C1 | 0.0249 (11) | 0.0369 (12) | 0.0283 (11) | −0.0008 (9) | 0.0010 (8) | 0.0029 (9) |
C2 | 0.0381 (14) | 0.0523 (16) | 0.0314 (12) | 0.0075 (11) | 0.0085 (10) | −0.0001 (11) |
C3 | 0.0506 (17) | 0.0626 (18) | 0.0251 (12) | 0.0017 (13) | 0.0077 (11) | 0.0043 (12) |
C4 | 0.0445 (15) | 0.0592 (17) | 0.0307 (12) | 0.0109 (12) | 0.0021 (10) | 0.0119 (12) |
C5 | 0.0352 (13) | 0.0493 (15) | 0.0344 (12) | 0.0090 (11) | 0.0046 (10) | 0.0049 (11) |
C6 | 0.0250 (11) | 0.0377 (12) | 0.0256 (10) | −0.0025 (9) | 0.0035 (8) | 0.0003 (9) |
C7 | 0.0338 (13) | 0.0361 (12) | 0.0355 (12) | 0.0009 (9) | −0.0004 (9) | 0.0074 (10) |
C8 | 0.0390 (14) | 0.0407 (13) | 0.0289 (11) | 0.0124 (10) | 0.0077 (10) | 0.0051 (10) |
Cu1 | 0.0463 (3) | 0.0408 (3) | 0.0267 (2) | 0.01786 (18) | −0.00671 (18) | −0.00255 (17) |
N1 | 0.0349 (11) | 0.0406 (11) | 0.0294 (10) | −0.0004 (9) | 0.0077 (8) | 0.0003 (9) |
O1 | 0.0613 (13) | 0.0607 (12) | 0.0415 (10) | 0.0239 (10) | 0.0198 (9) | 0.0025 (10) |
O2 | 0.0545 (12) | 0.0721 (13) | 0.0304 (9) | 0.0210 (11) | 0.0093 (8) | 0.0120 (10) |
O3 | 0.0531 (13) | 0.0426 (10) | 0.0509 (12) | 0.0120 (8) | 0.0092 (9) | −0.0051 (9) |
O4 | 0.0421 (10) | 0.0449 (10) | 0.0319 (9) | 0.0126 (8) | −0.0055 (7) | 0.0016 (8) |
O6 | 0.0738 (15) | 0.0493 (11) | 0.0339 (9) | 0.0295 (10) | −0.0057 (9) | −0.0029 (9) |
O5 | 0.0549 (14) | 0.0691 (14) | 0.0693 (15) | 0.0095 (11) | 0.0161 (11) | 0.0429 (12) |
S1 | 0.0312 (3) | 0.0326 (3) | 0.0356 (3) | −0.0001 (2) | 0.0057 (2) | 0.0047 (2) |
O8 | 0.0520 (12) | 0.0708 (14) | 0.0353 (9) | 0.0081 (10) | 0.0080 (8) | −0.0014 (10) |
O7—H9 | 0.8500 | C7—H5 | 0.9700 |
O7—H10 | 0.8500 | C7—H6 | 0.9700 |
C1—C2 | 1.385 (3) | C8—O5 | 1.226 (3) |
C1—C6 | 1.396 (3) | C8—O4 | 1.271 (3) |
C1—S1 | 1.812 (2) | Cu1—O6i | 1.9173 (19) |
C2—C3 | 1.384 (4) | Cu1—O6 | 1.9173 (19) |
C2—H1 | 0.9300 | Cu1—O4 | 1.9373 (17) |
C3—C4 | 1.379 (4) | Cu1—O4i | 1.9373 (17) |
C3—H2 | 0.9300 | N1—O2 | 1.218 (3) |
C4—C5 | 1.375 (4) | N1—O1 | 1.219 (3) |
C4—H3 | 0.9300 | O3—S1 | 1.497 (2) |
C5—C6 | 1.378 (3) | O6—H7 | 0.8499 |
C5—H4 | 0.9300 | O6—H8 | 0.8500 |
C6—N1 | 1.460 (3) | O8—H11 | 0.8500 |
C7—C8 | 1.515 (3) | O8—H12 | 0.8501 |
C7—S1 | 1.800 (2) | ||
H9—O7—H10 | 109.6 | S1—C7—H6 | 110.2 |
C2—C1—C6 | 117.6 (2) | H5—C7—H6 | 108.5 |
C2—C1—S1 | 117.47 (19) | O5—C8—O4 | 125.6 (2) |
C6—C1—S1 | 124.64 (17) | O5—C8—C7 | 118.9 (2) |
C3—C2—C1 | 120.8 (2) | O4—C8—C7 | 115.4 (2) |
C3—C2—H1 | 119.6 | O6i—Cu1—O6 | 180.000 (1) |
C1—C2—H1 | 119.6 | O6i—Cu1—O4 | 90.12 (8) |
C4—C3—C2 | 120.2 (2) | O6—Cu1—O4 | 89.88 (8) |
C4—C3—H2 | 119.9 | O6i—Cu1—O4i | 89.88 (8) |
C2—C3—H2 | 119.9 | O6—Cu1—O4i | 90.12 (8) |
C5—C4—C3 | 120.2 (2) | O4—Cu1—O4i | 180.00 (7) |
C5—C4—H3 | 119.9 | O2—N1—O1 | 122.6 (2) |
C3—C4—H3 | 119.9 | O2—N1—C6 | 118.0 (2) |
C4—C5—C6 | 119.1 (2) | O1—N1—C6 | 119.4 (2) |
C4—C5—H4 | 120.4 | C8—O4—Cu1 | 114.91 (16) |
C6—C5—H4 | 120.4 | Cu1—O6—H7 | 123.4 |
C5—C6—C1 | 122.0 (2) | Cu1—O6—H8 | 121.4 |
C5—C6—N1 | 117.8 (2) | H7—O6—H8 | 109.9 |
C1—C6—N1 | 120.2 (2) | O3—S1—C7 | 102.84 (12) |
C8—C7—S1 | 107.53 (17) | O3—S1—C1 | 105.31 (11) |
C8—C7—H5 | 110.2 | C7—S1—C1 | 98.20 (11) |
S1—C7—H5 | 110.2 | H11—O8—H12 | 110.3 |
C8—C7—H6 | 110.2 |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H9···O5i | 0.85 | 1.85 | 2.699 (3) | 175 |
O7—H10···O3ii | 0.85 | 2.00 | 2.779 (3) | 152 |
O8—H11···O4iii | 0.85 | 2.15 | 2.982 (3) | 166 |
O8—H12···O3 | 0.85 | 2.10 | 2.933 (3) | 167 |
O6—H7···O8 | 0.85 | 1.84 | 2.686 (3) | 172 |
O6—H8···O7iv | 0.85 | 1.85 | 2.680 (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. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H6NO5S)2(H2O)2]·4H2O |
Mr | 628.03 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.577 (3), 5.3724 (11), 14.740 (3) |
β (°) | 99.79 (3) |
V (Å3) | 1215.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.28 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.741, 0.783 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10697, 2762, 2319 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.115, 1.13 |
No. of reflections | 2762 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H9···O5i | 0.85 | 1.85 | 2.699 (3) | 175 |
O7—H10···O3ii | 0.85 | 2.00 | 2.779 (3) | 152 |
O8—H11···O4iii | 0.85 | 2.15 | 2.982 (3) | 166 |
O8—H12···O3 | 0.85 | 2.10 | 2.933 (3) | 167 |
O6—H7···O8 | 0.85 | 1.84 | 2.686 (3) | 172 |
O6—H8···O7iv | 0.85 | 1.85 | 2.680 (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. |
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).