Triaqua­bis[(2-nitro­phenyl­sulfan­yl)acetato-κ²O,O′]cadmium(II) dihydrate

The title compound, [Cd(C₈H₆NO₄S)₂(H₂O)₃]·2H₂O, has a seven-coordinate Cd^II atom in a distorted penta­gonal–bipyramidal geometry defined by four carboxylate O atoms from two (2-nitro­phenyl­sulfan­yl)acetate groups and three O atoms from three water mol­ecules. The complex mol­ecules are linked together by inter­molecular hydrogen bonds involving the uncoordinated water mol­ecules, resulting in a two-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.075
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cd4    -   O4      ..      13.59 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cd4    -   O7      ..      12.13 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.85 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cd4    -   O3      ..       5.62 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cd4    -   O8      ..       6.72 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H22    ..  S1      ..       2.97 Ang.

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

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 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
   0 ALERT type 5 Informative message, check

---

S1. Comment

The structures of the metal derivative sof 4-nitrophenylsulfanylacetic acid are known for nickel and cobalt (Gao et al., 2006; Shi et al., 2006). The structures of the 2-nitrophenylsulfanylacetic acid analogs are yet unknown.

The asymmetric unit of (I) consists of a cadmium(II) atom, two 2-nitrophenylsulfanylacetate groups, three coordinated water molecules and two uncoordinated water molecules (Fig.1). The CdII atom exists in a pentagonal bipyramidal configuration, with the equatorial plane being defined by the atoms O3, O4, O7, O8 and O10. Atoms O9 and O11 occupy the axial sites.

The structure is stabilized by hydrogen bonding interactions (Table 1) that link the individual components into a two-dimensional layer structure (Fig. 2).

Related literature

For related literature, see: Gao et al. (2006); Shi et al., 2007; Nobles & Thompson (1965).

S2. Experimental

2-Nitrophenylsulfanylacetic acid was prepared by nucleophilic reaction of chloroacetic acid and 2-nitrothiophenol under basic conditions. (Nobles et al., 1965). Cadmium(II) nitrate tetrhydrate (0.617 g, 2 mmol) and 2-nitrophenylsulfanylacetic acid (0.394 g, 2 mmol) were dissolved in water and the pH was adjusted to 6 with 0.01M sodium hydroxide; yellow crystals separated from the filtered solution after several days.

S3. Refinement

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 U_iso(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 U_iso(H) = 1.5Ueq(O).

Computing details

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

	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.
	Fig. 2. A partial packing view, showing the two-dimensional hydrogen-bonding plan. Dashed lines indicate the hydrogen-bonding interactions.

Triaquabis[(2-nitrophenylsulfanyl)acetato-κ²O,O']cadmium(II) dihydrate

Crystal data

[Cd(C8H6NO4S)2(H2O)3]·2H2O	F(000) = 1264
Mr = 626.91	Dx = 1.778 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16259 reflections
a = 19.550 (7) Å	θ = 6.2–55.0°
b = 8.216 (3) Å	µ = 1.18 mm^−1
c = 14.703 (7) Å	T = 293 K
β = 97.350 (18)°	Block, colorless
V = 2342.3 (17) Å^3	0.24 × 0.21 × 0.15 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	5356 independent reflections
Radiation source: fine-focus sealed tube	3874 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scan	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −25→25
Tmin = 0.768, Tmax = 0.841	k = −9→10
21719 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0397P)^2] where P = (Fo^2 + 2Fc^2)/3
5356 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.30664 (11)	0.4539 (3)	−0.04068 (16)	0.0378 (5)
C2	0.36823 (13)	0.3932 (4)	−0.06608 (19)	0.0489 (7)
C3	0.42292 (14)	0.4928 (5)	−0.0796 (2)	0.0663 (9)
H1	0.4634	0.4478	−0.0957	0.080*
C4	0.41770 (15)	0.6556 (5)	−0.0695 (2)	0.0736 (10)
H2	0.4546	0.7227	−0.0784	0.088*
C5	0.35827 (16)	0.7214 (4)	−0.0462 (2)	0.0620 (8)
H3	0.3547	0.8337	−0.0403	0.074*
C6	0.30320 (13)	0.6233 (3)	−0.03103 (18)	0.0474 (6)
H4	0.2634	0.6704	−0.0142	0.057*
C7	0.18219 (11)	0.4613 (3)	0.02960 (17)	0.0372 (5)
H5A	0.2078	0.5156	0.0819	0.045*
H6B	0.1652	0.5437	−0.0149	0.045*
C8	0.12181 (11)	0.3701 (3)	0.06027 (16)	0.0353 (5)
C9	−0.30084 (11)	0.3969 (3)	0.29923 (16)	0.0351 (5)
C10	−0.36354 (12)	0.3215 (3)	0.30859 (18)	0.0423 (6)
C11	−0.42148 (13)	0.4089 (4)	0.3233 (2)	0.0598 (8)
H7	−0.4626	0.3552	0.3287	0.072*
C12	−0.41807 (15)	0.5750 (4)	0.3297 (2)	0.0649 (9)
H8	−0.4570	0.6346	0.3392	0.078*
C13	−0.35742 (14)	0.6531 (4)	0.3222 (2)	0.0570 (7)
H9	−0.3553	0.7659	0.3269	0.068*
C14	−0.29904 (13)	0.5667 (3)	0.30782 (18)	0.0457 (6)
H10	−0.2580	0.6221	0.3038	0.055*
C15	−0.17024 (11)	0.4421 (3)	0.24590 (17)	0.0360 (5)
H11A	−0.1951	0.5165	0.2023	0.043*
H12B	−0.1521	0.5036	0.2999	0.043*
C16	−0.11144 (11)	0.3636 (3)	0.20362 (16)	0.0356 (5)
Cd4	0.003378 (7)	0.259713 (19)	0.126486 (11)	0.03280 (7)
N1	0.37706 (13)	0.2193 (4)	−0.0799 (2)	0.0645 (7)
N2	−0.37058 (12)	0.1454 (3)	0.30343 (17)	0.0561 (6)
O1	0.43488 (12)	0.1638 (4)	−0.0765 (2)	0.1115 (10)
O2	0.32566 (12)	0.1340 (3)	−0.09545 (19)	0.0847 (8)
O3	0.07383 (8)	0.4577 (2)	0.08316 (12)	0.0436 (4)
O4	0.12048 (9)	0.2188 (2)	0.06435 (14)	0.0498 (5)
O5	−0.42770 (11)	0.0854 (3)	0.3025 (2)	0.1051 (10)
O6	−0.31884 (10)	0.0624 (2)	0.30212 (16)	0.0672 (6)
O7	−0.10346 (9)	0.2133 (2)	0.20501 (14)	0.0531 (5)
O8	−0.07214 (8)	0.4579 (2)	0.16682 (12)	0.0419 (4)
O9	−0.05832 (9)	0.23693 (18)	−0.01830 (12)	0.0393 (4)
H13	−0.0962	0.1894	−0.0130	0.059*
H14	−0.0663	0.3271	−0.0460	0.059*
O10	0.00194 (8)	−0.0128 (2)	0.12473 (11)	0.0482 (5)
H15	−0.0216	−0.0704	0.1574	0.072*
H16	0.0210	−0.0737	0.0886	0.072*
O11	0.06326 (8)	0.26541 (18)	0.27275 (12)	0.0391 (4)
H17	0.0687	0.1752	0.3011	0.059*
H18	0.1021	0.3097	0.2692	0.059*
O12	0.18552 (11)	0.4145 (3)	0.28311 (18)	0.0932 (9)
H19	0.1778	0.5146	0.2712	0.140*
H20	0.2280	0.3976	0.3013	0.140*
O13	0.17204 (9)	0.5729 (2)	0.48872 (14)	0.0618 (5)
H21	0.1670	0.5556	0.4312	0.093*
H22	0.1674	0.4839	0.5167	0.093*
S1	0.23822 (3)	0.32432 (8)	−0.02060 (5)	0.04267 (16)
S7	−0.22770 (3)	0.28581 (7)	0.27683 (5)	0.04085 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0292 (11)	0.0449 (14)	0.0400 (14)	−0.0044 (11)	0.0076 (10)	0.0032 (11)
C2	0.0357 (13)	0.0665 (19)	0.0459 (16)	0.0000 (13)	0.0102 (11)	0.0022 (13)
C3	0.0369 (14)	0.100 (3)	0.064 (2)	−0.0121 (17)	0.0161 (13)	0.0071 (19)
C4	0.0475 (17)	0.099 (3)	0.076 (2)	−0.0333 (19)	0.0151 (15)	0.013 (2)
C5	0.0679 (19)	0.0563 (18)	0.062 (2)	−0.0250 (16)	0.0098 (15)	0.0089 (15)
C6	0.0418 (13)	0.0467 (15)	0.0558 (17)	−0.0100 (12)	0.0140 (12)	0.0055 (12)
C7	0.0323 (12)	0.0354 (12)	0.0463 (14)	−0.0037 (10)	0.0145 (10)	−0.0009 (10)
C8	0.0317 (11)	0.0394 (13)	0.0359 (13)	−0.0035 (10)	0.0089 (10)	0.0036 (10)
C9	0.0299 (11)	0.0399 (13)	0.0368 (13)	0.0039 (10)	0.0093 (9)	0.0012 (10)
C10	0.0341 (12)	0.0477 (14)	0.0467 (16)	−0.0032 (12)	0.0107 (10)	0.0005 (12)
C11	0.0311 (13)	0.083 (2)	0.068 (2)	−0.0007 (15)	0.0155 (13)	−0.0002 (17)
C12	0.0463 (16)	0.069 (2)	0.082 (2)	0.0195 (16)	0.0214 (15)	−0.0056 (17)
C13	0.0546 (17)	0.0488 (16)	0.070 (2)	0.0160 (14)	0.0189 (14)	−0.0064 (15)
C14	0.0386 (13)	0.0402 (14)	0.0606 (17)	0.0036 (11)	0.0145 (12)	−0.0041 (12)
C15	0.0303 (11)	0.0355 (12)	0.0444 (14)	0.0030 (10)	0.0131 (10)	−0.0023 (10)
C16	0.0279 (11)	0.0428 (13)	0.0367 (14)	0.0052 (11)	0.0066 (10)	−0.0057 (11)
Cd4	0.03174 (10)	0.02779 (10)	0.04123 (11)	0.00020 (7)	0.01369 (7)	−0.00157 (7)
N1	0.0470 (14)	0.0758 (19)	0.0743 (19)	0.0177 (14)	0.0217 (12)	−0.0025 (14)
N2	0.0441 (13)	0.0549 (15)	0.0705 (18)	−0.0129 (12)	0.0116 (11)	0.0017 (12)
O1	0.0553 (14)	0.113 (2)	0.172 (3)	0.0363 (15)	0.0375 (16)	−0.003 (2)
O2	0.0604 (14)	0.0629 (15)	0.134 (2)	0.0074 (12)	0.0241 (14)	−0.0206 (14)
O3	0.0363 (9)	0.0424 (10)	0.0559 (11)	0.0021 (8)	0.0209 (8)	0.0063 (8)
O4	0.0513 (11)	0.0340 (10)	0.0687 (13)	−0.0051 (8)	0.0252 (9)	0.0025 (9)
O5	0.0455 (12)	0.0763 (17)	0.196 (3)	−0.0287 (13)	0.0247 (15)	−0.0053 (18)
O6	0.0552 (12)	0.0437 (11)	0.1051 (18)	−0.0057 (10)	0.0193 (12)	0.0036 (11)
O7	0.0490 (10)	0.0401 (10)	0.0753 (14)	0.0072 (8)	0.0272 (9)	−0.0033 (9)
O8	0.0340 (8)	0.0452 (10)	0.0501 (11)	0.0005 (8)	0.0190 (7)	−0.0040 (8)
O9	0.0437 (9)	0.0312 (8)	0.0447 (10)	0.0014 (7)	0.0118 (7)	−0.0014 (7)
O10	0.0691 (13)	0.0251 (8)	0.0578 (12)	0.0010 (7)	0.0365 (10)	−0.0005 (7)
O11	0.0388 (8)	0.0347 (9)	0.0451 (10)	0.0015 (7)	0.0100 (7)	0.0019 (7)
O12	0.0616 (14)	0.0817 (16)	0.132 (2)	−0.0254 (13)	−0.0041 (14)	0.0425 (15)
O13	0.0671 (12)	0.0495 (11)	0.0703 (14)	0.0076 (10)	0.0146 (10)	−0.0037 (10)
S1	0.0346 (3)	0.0338 (3)	0.0629 (4)	−0.0024 (3)	0.0192 (3)	−0.0011 (3)
S7	0.0341 (3)	0.0326 (3)	0.0588 (4)	0.0031 (3)	0.0174 (3)	0.0013 (3)

Geometric parameters (Å, º)

C1—C2	1.398 (3)	C14—H10	0.9300
C1—C6	1.401 (3)	C15—C16	1.519 (3)
C1—S1	1.764 (2)	C15—S7	1.802 (2)
C2—C3	1.381 (4)	C15—H11A	0.9700
C2—N1	1.456 (4)	C15—H12B	0.9700
C3—C4	1.352 (5)	C16—O7	1.244 (3)
C3—H1	0.9300	C16—O8	1.261 (3)
C4—C5	1.364 (4)	Cd4—O10	2.2392 (18)
C4—H2	0.9300	Cd4—O3	2.2743 (17)
C5—C6	1.386 (3)	Cd4—O11	2.314 (2)
C5—H3	0.9300	Cd4—O9	2.316 (2)
C6—H4	0.9300	Cd4—O8	2.3251 (17)
C7—C8	1.515 (3)	Cd4—O7	2.541 (2)
C7—S1	1.794 (2)	Cd4—O4	2.593 (2)
C7—H5A	0.9700	N1—O1	1.214 (3)
C7—H6B	0.9700	N1—O2	1.223 (3)
C8—O4	1.244 (3)	N2—O5	1.219 (3)
C8—O3	1.262 (3)	N2—O6	1.222 (3)
C9—C10	1.396 (3)	O9—H13	0.8501
C9—C14	1.401 (3)	O9—H14	0.8500
C9—S7	1.763 (2)	O10—H15	0.8501
C10—C11	1.381 (4)	O10—H16	0.8499
C10—N2	1.454 (4)	O11—H17	0.8500
C11—C12	1.369 (4)	O11—H18	0.8500
C11—H7	0.9300	O12—H19	0.8500
C12—C13	1.365 (4)	O12—H20	0.8500
C12—H8	0.9300	O13—H21	0.8500
C13—C14	1.383 (3)	O13—H22	0.8500
C13—H9	0.9300
C2—C1—C6	115.8 (2)	S7—C15—H12B	109.8
C2—C1—S1	121.8 (2)	H11A—C15—H12B	108.3
C6—C1—S1	122.37 (19)	O7—C16—O8	122.3 (2)
C3—C2—C1	122.5 (3)	O7—C16—C15	121.0 (2)
C3—C2—N1	116.9 (3)	O8—C16—C15	116.7 (2)
C1—C2—N1	120.6 (2)	O10—Cd4—O3	135.97 (6)
C4—C3—C2	120.0 (3)	O10—Cd4—O11	92.01 (5)
C4—C3—H1	120.0	O3—Cd4—O11	89.62 (6)
C2—C3—H1	120.0	O10—Cd4—O9	84.51 (6)
C3—C4—C5	119.9 (3)	O3—Cd4—O9	93.62 (6)
C3—C4—H2	120.0	O11—Cd4—O9	176.36 (5)
C5—C4—H2	120.0	O10—Cd4—O8	134.08 (6)
C4—C5—C6	120.9 (3)	O3—Cd4—O8	89.87 (7)
C4—C5—H3	119.5	O11—Cd4—O8	90.64 (6)
C6—C5—H3	119.5	O9—Cd4—O8	91.03 (6)
C5—C6—C1	120.9 (3)	O10—Cd4—O7	81.10 (6)
C5—C6—H4	119.6	O3—Cd4—O7	142.85 (6)
C1—C6—H4	119.6	O11—Cd4—O7	85.89 (7)
C8—C7—S1	110.62 (16)	O9—Cd4—O7	92.51 (7)
C8—C7—H5A	109.5	O8—Cd4—O7	53.39 (6)
S1—C7—H5A	109.5	O10—Cd4—O4	82.92 (5)
C8—C7—H6B	109.5	O3—Cd4—O4	53.15 (6)
S1—C7—H6B	109.5	O11—Cd4—O4	88.02 (7)
H5A—C7—H6B	108.1	O9—Cd4—O4	92.59 (7)
O4—C8—O3	122.4 (2)	O8—Cd4—O4	142.99 (6)
O4—C8—C7	122.0 (2)	O7—Cd4—O4	162.68 (6)
O3—C8—C7	115.6 (2)	O1—N1—O2	122.1 (3)
C10—C9—C14	116.5 (2)	O1—N1—C2	119.3 (3)
C10—C9—S7	122.14 (19)	O2—N1—C2	118.6 (2)
C14—C9—S7	121.40 (18)	O5—N2—O6	122.2 (3)
C11—C10—C9	122.2 (3)	O5—N2—C10	118.9 (2)
C11—C10—N2	116.8 (2)	O6—N2—C10	118.9 (2)
C9—C10—N2	121.0 (2)	C8—O3—Cd4	99.46 (14)
C12—C11—C10	119.7 (3)	C8—O4—Cd4	84.99 (14)
C12—C11—H7	120.2	C16—O7—Cd4	87.26 (14)
C10—C11—H7	120.2	C16—O8—Cd4	96.93 (14)
C13—C12—C11	119.9 (3)	Cd4—O9—H13	108.1
C13—C12—H8	120.1	Cd4—O9—H14	114.3
C11—C12—H8	120.1	H13—O9—H14	109.6
C12—C13—C14	120.9 (3)	Cd4—O10—H15	123.8
C12—C13—H9	119.5	Cd4—O10—H16	126.1
C14—C13—H9	119.5	H15—O10—H16	109.8
C13—C14—C9	120.9 (2)	Cd4—O11—H17	117.1
C13—C14—H10	119.6	Cd4—O11—H18	107.6
C9—C14—H10	119.6	H17—O11—H18	110.2
C16—C15—S7	109.21 (16)	H19—O12—H20	111.3
C16—C15—H11A	109.8	H21—O13—H22	109.4
S7—C15—H11A	109.8	C1—S1—C7	101.89 (11)
C16—C15—H12B	109.8	C9—S7—C15	102.98 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H13···O13^i	0.85	1.84	2.682 (3)	173
O11—H18···O12	0.85	1.83	2.673 (3)	170
O9—H14···O3^ii	0.85	1.85	2.688 (2)	168
O10—H15···O11^i	0.85	1.94	2.777 (2)	169
O10—H16···O9^iii	0.85	1.90	2.738 (2)	171
O11—H17···O8^i	0.85	1.85	2.677 (2)	165
O13—H21···O12	0.85	2.53	3.332 (4)	157
O13—H21···O7^iv	0.85	2.57	3.204 (3)	132
O12—H19···O7^iv	0.85	2.24	2.950 (3)	141
O12—H19···S7^iv	0.85	2.57	3.309 (2)	146
O12—H20···O2^v	0.85	2.30	3.099 (3)	157
O13—H22···O4^v	0.85	2.07	2.879 (3)	160
O13—H22···S1^v	0.85	2.97	3.520 (2)	124

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x, −y, −z; (iv) −x, y+1/2, −z+1/2; (v) x, −y+1/2, z+1/2.