Poly[[aqua-{μ4-2-[(carb-oxy-meth-yl)sulfan-yl]nicotinato-κ(4) O:O':O'':O'''}copper(II)] trihydrate].

In the polymeric title complex, {[Cu(C8H5NO4S)(H2O)]·3H2O} n , the Cu(II) cation is coordinated by one water mol-ecule and four carboxyl-ate O atoms from four 2-[(carb-oxy-meth-yl)sulfan-yl]nicotinate anions in a distorted square-pyramidal geometry. The 2-[(carb-oxy-meth-yl)sulfan-yl]nicotinate anion bridges four Cu(II) cations, forming a two-dimensional polymeric complex parallel to the bc plane. In the crystal, O-H⋯O, O-H⋯N and O-H⋯S hydrogen bonds link the complex mol-ecules and lattice water mol-ecules into a three-dimensional supra-molecular architecture.

Related literature

For background to the 2-[(carb­oxy­meth­yl)sulfan­yl]nicotinato ligand, see: Wang & Feng (2010 ▶). For related compounds, see: Jiang et al. (2012 ▶). For metal complexes with 2-mercaptonanicotinate ligands, see: Humphrey et al. (2006 ▶); Sun et al. (2011 ▶).

Experimental

Crystal data

[Cu(C8H5NO4S)(H2O)]·3H2O

M = 346.82

Monoclinic,

a = 9.940 (7) Å

b = 16.639 (9) Å

c = 7.876 (4) Å

β = 96.28 (5)°

V = 1294.8 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.88 mm−1

T = 296 K

0.25 × 0.09 × 0.06 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.812, T max = 0.892

20324 measured reflections

2973 independent reflections

2331 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.085

S = 1.04

2973 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009604/xu5692sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009604/xu5692Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009604/xu5692Isup3.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C8H5NO4S)(H2O)]·3H2O	F(000) = 708
Mr = 346.82	Dx = 1.779 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3501 reflections
a = 9.940 (7) Å	θ = 2.1–27.6°
b = 16.639 (9) Å	µ = 1.88 mm−1
c = 7.876 (4) Å	T = 296 K
β = 96.28 (5)°	Plate, blue
V = 1294.8 (13) Å3	0.25 × 0.09 × 0.06 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	2973 independent reflections
Radiation source: fine-focus sealed tube	2331 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→12
Tmin = 0.812, Tmax = 0.892	k = −21→21
20324 measured reflections	l = −10→10

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0455P)2 + 0.2317P] where P = (Fo2 + 2Fc2)/3
2973 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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
Cu1	1.10928 (3)	0.455426 (15)	0.48878 (4)	0.02469 (11)
S1	0.96122 (7)	0.21713 (3)	0.44052 (8)	0.03032 (16)
O1	0.97500 (18)	0.37850 (10)	0.3866 (2)	0.0338 (4)
O1W	1.2932 (2)	0.39085 (12)	0.4498 (3)	0.0473 (5)
H1WA	1.2787	0.3469	0.4037	0.057*
H1WB	1.3419	0.4141	0.3845	0.057*
O2	0.7893 (2)	0.45444 (10)	0.3972 (3)	0.0369 (4)
O3	1.0779 (2)	0.08898 (11)	0.2128 (2)	0.0374 (4)
O4	0.89346 (19)	0.01319 (10)	0.2319 (2)	0.0328 (4)
N1	0.7301 (2)	0.17934 (12)	0.2526 (3)	0.0341 (5)
C1	0.5606 (3)	0.27286 (16)	0.1366 (4)	0.0398 (7)
H1A	0.4768	0.2817	0.0745	0.048*
C2	0.7636 (3)	0.32137 (14)	0.2965 (3)	0.0267 (5)
C3	0.6384 (3)	0.33602 (16)	0.2060 (4)	0.0348 (6)
H3A	0.6068	0.3885	0.1919	0.042*
C4	0.6114 (3)	0.19624 (16)	0.1627 (4)	0.0393 (7)
H4A	0.5600	0.1536	0.1147	0.047*
C5	0.8059 (3)	0.24081 (14)	0.3179 (3)	0.0260 (5)
C6	0.8489 (3)	0.38985 (13)	0.3664 (3)	0.0268 (5)
C7	0.9514 (3)	0.10887 (14)	0.4500 (3)	0.0319 (6)
H7A	1.0178	0.0897	0.5403	0.038*
H7B	0.8626	0.0938	0.4794	0.038*
C8	0.9757 (3)	0.06765 (14)	0.2838 (3)	0.0286 (5)
O2W	0.6123 (3)	−0.00071 (16)	0.2997 (4)	0.0759 (8)
H2WA	0.6385	−0.0244	0.3907	0.091*
H2WB	0.6774	0.0299	0.2886	0.091*
O3W	0.3765 (3)	0.07734 (18)	0.3764 (4)	0.0831 (9)
H3WA	0.3048	0.0589	0.3329	0.100*
H3WB	0.4364	0.0491	0.3424	0.100*
O4W	0.2538 (3)	0.24845 (18)	0.2749 (5)	0.1001 (11)
H4WA	0.2766	0.2280	0.1881	0.120*
H4WB	0.1699	0.2362	0.2691	0.120*

	U11	U22	U33	U12	U13	U23
Cu1	0.02945 (19)	0.01710 (15)	0.02766 (18)	0.00031 (11)	0.00377 (12)	0.00057 (11)
S1	0.0364 (4)	0.0231 (3)	0.0307 (4)	0.0012 (3)	0.0001 (3)	−0.0052 (2)
O1	0.0335 (11)	0.0208 (8)	0.0472 (12)	−0.0032 (7)	0.0043 (9)	−0.0036 (7)
O1W	0.0429 (12)	0.0403 (11)	0.0603 (14)	0.0085 (9)	0.0123 (10)	−0.0024 (9)
O2	0.0382 (11)	0.0238 (9)	0.0469 (12)	0.0011 (8)	−0.0026 (9)	−0.0080 (8)
O3	0.0434 (12)	0.0363 (10)	0.0337 (10)	−0.0079 (9)	0.0093 (9)	−0.0118 (8)
O4	0.0412 (11)	0.0248 (8)	0.0330 (10)	−0.0010 (8)	0.0066 (8)	−0.0051 (7)
N1	0.0417 (14)	0.0242 (10)	0.0357 (13)	−0.0065 (9)	0.0016 (10)	−0.0041 (9)
C1	0.0335 (16)	0.0393 (15)	0.0444 (17)	−0.0048 (12)	−0.0052 (13)	−0.0017 (12)
C2	0.0320 (14)	0.0234 (12)	0.0254 (13)	−0.0021 (10)	0.0056 (10)	−0.0014 (9)
C3	0.0357 (16)	0.0275 (13)	0.0410 (16)	−0.0008 (11)	0.0027 (12)	0.0011 (11)
C4	0.0424 (17)	0.0338 (14)	0.0403 (16)	−0.0121 (12)	−0.0012 (13)	−0.0045 (12)
C5	0.0308 (14)	0.0242 (11)	0.0238 (12)	−0.0016 (10)	0.0066 (10)	−0.0016 (9)
C6	0.0398 (16)	0.0188 (11)	0.0221 (12)	−0.0042 (10)	0.0039 (11)	0.0023 (9)
C7	0.0499 (17)	0.0225 (12)	0.0234 (13)	0.0016 (11)	0.0039 (12)	−0.0010 (9)
C8	0.0388 (15)	0.0202 (11)	0.0263 (13)	0.0065 (10)	0.0015 (11)	−0.0008 (9)
O2W	0.0679 (18)	0.0680 (17)	0.097 (2)	−0.0153 (14)	0.0337 (15)	−0.0023 (15)
O3W	0.0590 (18)	0.0867 (19)	0.098 (2)	−0.0033 (15)	−0.0178 (15)	−0.0172 (17)
O4W	0.069 (2)	0.090 (2)	0.150 (3)	−0.0265 (17)	0.048 (2)	−0.055 (2)

Cu1—O1	1.958 (2)	N1—C5	1.340 (3)
Cu1—O2i	1.9682 (19)	C1—C4	1.379 (4)
Cu1—O3ii	1.9687 (19)	C1—C3	1.382 (4)
Cu1—O4iii	1.9836 (19)	C1—H1A	0.9300
Cu1—O1W	2.171 (2)	C2—C3	1.386 (4)
Cu1—Cu1i	2.6524 (15)	C2—C5	1.410 (3)
S1—C5	1.773 (3)	C2—C6	1.489 (3)
S1—C7	1.806 (3)	C3—H3A	0.9300
O1—C6	1.261 (3)	C4—H4A	0.9300
O1W—H1WA	0.8228	C7—C8	1.521 (3)
O1W—H1WB	0.8384	C7—H7A	0.9700
O2—C6	1.263 (3)	C7—H7B	0.9700
O2—Cu1i	1.9682 (19)	O2W—H2WA	0.8345
O3—C8	1.263 (3)	O2W—H2WB	0.8359
O3—Cu1iv	1.9687 (19)	O3W—H3WA	0.8165
O4—C8	1.258 (3)	O3W—H3WB	0.8253
O4—Cu1v	1.9836 (19)	O4W—H4WA	0.8176
N1—C4	1.337 (4)	O4W—H4WB	0.8547
O1—Cu1—O2i	167.93 (8)	C3—C2—C5	117.9 (2)
O1—Cu1—O3ii	87.44 (9)	C3—C2—C6	119.9 (2)
O2i—Cu1—O3ii	90.03 (9)	C5—C2—C6	122.2 (2)
O1—Cu1—O4iii	90.75 (9)	C1—C3—C2	120.1 (2)
O2i—Cu1—O4iii	89.31 (9)	C1—C3—H3A	119.9
O3ii—Cu1—O4iii	168.14 (8)	C2—C3—H3A	119.9
O1—Cu1—O1W	99.49 (9)	N1—C4—C1	124.1 (3)
O2i—Cu1—O1W	92.56 (9)	N1—C4—H4A	117.9
O3ii—Cu1—O1W	99.18 (9)	C1—C4—H4A	117.9
O4iii—Cu1—O1W	92.69 (9)	N1—C5—C2	122.1 (2)
O1—Cu1—Cu1i	82.33 (7)	N1—C5—S1	117.35 (19)
O2i—Cu1—Cu1i	85.74 (7)	C2—C5—S1	120.48 (19)
O3ii—Cu1—Cu1i	86.50 (7)	O1—C6—O2	125.7 (2)
O4iii—Cu1—Cu1i	81.64 (7)	O1—C6—C2	116.7 (2)
O1W—Cu1—Cu1i	174.09 (6)	O2—C6—C2	117.5 (2)
C5—S1—C7	101.32 (12)	C8—C7—S1	113.56 (17)
C6—O1—Cu1	125.29 (16)	C8—C7—H7A	108.9
Cu1—O1W—H1WA	113.2	S1—C7—H7A	108.9
Cu1—O1W—H1WB	114.3	C8—C7—H7B	108.9
H1WA—O1W—H1WB	103.0	S1—C7—H7B	108.9
C6—O2—Cu1i	120.56 (18)	H7A—C7—H7B	107.7
C8—O3—Cu1iv	120.36 (16)	O4—C8—O3	125.7 (2)
C8—O4—Cu1v	125.43 (17)	O4—C8—C7	116.5 (2)
C4—N1—C5	118.0 (2)	O3—C8—C7	117.8 (2)
C4—C1—C3	117.6 (3)	H2WA—O2W—H2WB	101.8
C4—C1—H1A	121.2	H3WA—O3W—H3WB	106.2
C3—C1—H1A	121.2	H4WA—O4W—H4WB	102.4

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4Wvi	0.82	1.93	2.747 (4)	174
O1W—H1WB···O2Wiii	0.84	2.11	2.899 (4)	156
O2W—H2WA···O3Wvii	0.83	2.05	2.843 (5)	157
O2W—H2WB···O4	0.84	2.26	2.911 (4)	135
O2W—H2WB···N1	0.84	2.56	3.253 (4)	141
O3W—H3WA···O3viii	0.82	2.40	3.110 (4)	146
O3W—H3WB···O2W	0.83	2.00	2.803 (5)	165
O4W—H4WB···S1viii	0.85	2.62	3.356 (4)	146

Table 1

Selected bond lengths (Å)

Cu1—O1	1.958 (2)
Cu1—O2i	1.9682 (19)
Cu1—O3ii	1.9687 (19)
Cu1—O4iii	1.9836 (19)
Cu1—O1W	2.171 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4W iv	0.82	1.93	2.747 (4)	174
O1W—H1WB⋯O2W iii	0.84	2.11	2.899 (4)	156
O2W—H2WA⋯O3W v	0.83	2.05	2.843 (5)	157
O2W—H2WB⋯O4	0.84	2.26	2.911 (4)	135
O2W—H2WB⋯N1	0.84	2.56	3.253 (4)	141
O3W—H3WA⋯O3vi	0.82	2.40	3.110 (4)	146
O3W—H3WB⋯O2W	0.83	2.00	2.803 (5)	165
O4W—H4WB⋯S1vi	0.85	2.62	3.356 (4)	146

Symmetry codes: (iii) ; (iv) ; (v) ; (vi) .