Poly[[aqua-(μ-4,4'-bipyridine-κN:N')(μ(3)-2-nitro-5-sulfonatobenzoato-κO:O:O)copper(II)] 4,4'-bipyridine hemisolvate].

In the title compound, [Cu(C(7)H(3)NO(7)S)(C(10)H(8)N(2))(H(2)O)]·0.5C(10)H(8)N(2), the Cu(II) atom is six-coordinated by two N atoms from two different bipyridine (bipy) ligands, one sulfonate O atom and two carboxyl-ate O atoms from three 2-nitro-5-sulfonatobenzoate ligands and one water O atom in a distorted octa-hedral geometry. The bipy solvent mol-ecule lies on an inversion center. The Cu(II) atoms are linked by the bipy ligands, forming one-dimensional chains, which are connected by the 2-nitro-5-sulfonatobenzoate ligands into a two-dimensional layer-like network. The two-dimensional structure is extended by O-H⋯O and O-H⋯N hydrogen bonds into a three-dimensional supra-molecular network.

Related literature

For general background to copper(II) sulfonate complexes, see: Du et al. (2009 ▶); Li et al. (2009 ▶); Liu et al. (2009 ▶); Sonnauer & Stock (2008 ▶); Sonnauer et al. (2009 ▶). For related structures, see: Dong et al. (2009 ▶).

Experimental

Crystal data

[Cu(C7H3NO7S)(C10H8N2)(H2O)]·0.5C10H8N2

M = 561.00

Monoclinic,

a = 11.4549 (17) Å

b = 11.0447 (16) Å

c = 17.089 (3) Å

β = 92.738 (3)°

V = 2159.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.17 mm−1

T = 293 K

0.23 × 0.17 × 0.14 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.767, T max = 0.850

11892 measured reflections

4260 independent reflections

2560 reflections with I > 2σ(I)

R int = 0.088

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.135

S = 1.00

4260 reflections

331 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.86 e Å−3

Δρmin = −0.46 e Å−3

Data collection: SMART (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 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039294/hy2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039294/hy2230Isup2.hkl

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

[Cu(C7H3NO7S)(C10H8N2)(H2O)]·0.5C10H8N2	F(000) = 1144
Mr = 561.00	Dx = 1.725 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4260 reflections
a = 11.4549 (17) Å	θ = 1.8–26.0°
b = 11.0447 (16) Å	µ = 1.17 mm−1
c = 17.089 (3) Å	T = 293 K
β = 92.738 (3)°	Block, blue
V = 2159.5 (5) Å3	0.23 × 0.17 × 0.14 mm
Z = 4

Bruker SMART APEX CCD diffractometer	4260 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
graphite	Rint = 0.088
φ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
Tmin = 0.767, Tmax = 0.850	k = −13→13
11892 measured reflections	l = −21→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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0455P)2] where P = (Fo2 + 2Fc2)/3
4260 reflections	(Δ/σ)max = 0.001
331 parameters	Δρmax = 0.86 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

	x	y	z	Uiso*/Ueq
C1	0.2223 (4)	0.7923 (4)	0.6944 (3)	0.0215 (13)
C2	0.2994 (4)	0.7254 (4)	0.6511 (3)	0.0198 (12)
H2	0.3565	0.7656	0.6243	0.024*
C3	0.2929 (4)	0.5989 (5)	0.6472 (3)	0.0195 (12)
C4	0.2051 (5)	0.5449 (4)	0.6866 (3)	0.0224 (13)
C5	0.1244 (5)	0.6090 (5)	0.7293 (4)	0.0321 (15)
H5	0.0649	0.5692	0.7542	0.039*
C6	0.1356 (5)	0.7338 (5)	0.7335 (4)	0.0313 (15)
H6	0.0846	0.7786	0.7627	0.038*
C7	0.3842 (5)	0.5338 (4)	0.6006 (3)	0.0177 (12)
C8	0.5609 (4)	0.2511 (4)	0.6504 (3)	0.0229 (13)
H8	0.5129	0.2936	0.6831	0.027*
C9	0.5560 (4)	0.1262 (4)	0.6501 (3)	0.0237 (13)
H9	0.5067	0.0860	0.6831	0.028*
C10	0.6248 (5)	0.0607 (4)	0.6005 (3)	0.0183 (13)
C11	0.6982 (4)	0.1266 (4)	0.5532 (3)	0.0205 (13)
H11	0.7454	0.0869	0.5186	0.025*
C12	0.6997 (4)	0.2501 (4)	0.5582 (3)	0.0208 (13)
H12	0.7504	0.2924	0.5273	0.025*
C13	0.6233 (4)	−0.0732 (4)	0.5994 (3)	0.0191 (13)
C14	0.6096 (4)	−0.1390 (4)	0.6673 (3)	0.0207 (13)
H14	0.5960	−0.0992	0.7140	0.025*
C15	0.6162 (5)	−0.2632 (4)	0.6656 (3)	0.0241 (13)
H15	0.6098	−0.3057	0.7122	0.029*
C16	0.6431 (5)	−0.2628 (4)	0.5338 (3)	0.0248 (13)
H16	0.6541	−0.3054	0.4878	0.030*
C17	0.6397 (5)	−0.1375 (4)	0.5304 (3)	0.0236 (13)
H17	0.6482	−0.0971	0.4833	0.028*
C18	0.0395 (6)	0.2255 (6)	1.0226 (4)	0.052 (2)
H18	0.0316	0.1641	1.0593	0.063*
C19	0.0134 (6)	0.3431 (6)	1.0445 (4)	0.0483 (19)
H19	−0.0057	0.3597	1.0957	0.058*
C20	0.0160 (5)	0.4360 (5)	0.9900 (4)	0.0353 (16)
C21	0.0488 (5)	0.4042 (6)	0.9165 (4)	0.0408 (17)
H21	0.0509	0.4629	0.8776	0.049*
C22	0.0790 (5)	0.2855 (6)	0.8995 (4)	0.0421 (17)
H22	0.1028	0.2677	0.8495	0.051*
N1	0.1916 (4)	0.4121 (4)	0.6833 (3)	0.0327 (13)
N2	0.6323 (4)	0.3136 (3)	0.6052 (3)	0.0212 (11)
N3	0.6313 (4)	−0.3253 (4)	0.5997 (3)	0.0194 (10)
N4	0.0754 (4)	0.1954 (5)	0.9520 (3)	0.0406 (14)
O1	0.1331 (3)	0.9957 (3)	0.7351 (2)	0.0321 (9)
O2	0.3416 (3)	0.9755 (3)	0.7461 (2)	0.0283 (10)
O3	0.2451 (4)	0.9910 (3)	0.6178 (2)	0.0373 (10)
O4	0.4740 (3)	0.5046 (3)	0.6409 (2)	0.0223 (8)
O5	0.3643 (3)	0.5231 (3)	0.5297 (2)	0.0277 (9)
O6	0.8116 (3)	0.4917 (4)	0.6061 (2)	0.0259 (9)
O7	0.2618 (3)	0.3519 (3)	0.6486 (3)	0.0376 (11)
O8	0.1112 (4)	0.3662 (4)	0.7165 (3)	0.0676 (17)
S1	0.23675 (13)	0.95326 (12)	0.69752 (9)	0.0243 (4)
Cu1	0.63413 (5)	0.49342 (5)	0.60435 (4)	0.0195 (2)
H1A	0.833 (5)	0.486 (5)	0.653 (3)	0.029*
H1B	0.843 (5)	0.543 (5)	0.576 (3)	0.029*

	U11	U22	U33	U12	U13	U23
C1	0.025 (3)	0.019 (3)	0.021 (3)	0.002 (2)	−0.001 (3)	−0.003 (3)
C2	0.024 (3)	0.018 (3)	0.019 (3)	−0.002 (2)	0.004 (2)	0.001 (2)
C3	0.020 (3)	0.018 (3)	0.021 (3)	0.003 (2)	0.001 (3)	−0.002 (3)
C4	0.027 (3)	0.013 (3)	0.027 (4)	0.001 (2)	0.005 (3)	0.005 (2)
C5	0.027 (3)	0.029 (3)	0.042 (4)	−0.001 (3)	0.018 (3)	0.007 (3)
C6	0.032 (3)	0.026 (3)	0.037 (4)	0.009 (3)	0.013 (3)	0.001 (3)
C7	0.030 (3)	0.007 (3)	0.016 (3)	−0.005 (2)	0.006 (3)	0.001 (2)
C8	0.029 (3)	0.015 (3)	0.027 (3)	0.000 (2)	0.014 (3)	0.001 (3)
C9	0.030 (3)	0.014 (3)	0.028 (4)	−0.004 (2)	0.007 (3)	0.002 (3)
C10	0.029 (3)	0.005 (2)	0.020 (3)	0.002 (2)	−0.007 (3)	0.001 (2)
C11	0.028 (3)	0.011 (3)	0.024 (3)	−0.001 (2)	0.010 (3)	−0.004 (2)
C12	0.026 (3)	0.011 (3)	0.027 (3)	−0.001 (2)	0.007 (3)	0.004 (2)
C13	0.024 (3)	0.009 (3)	0.025 (4)	0.000 (2)	0.005 (3)	−0.002 (3)
C14	0.030 (3)	0.013 (3)	0.021 (3)	0.002 (2)	0.010 (3)	0.000 (2)
C15	0.032 (3)	0.016 (3)	0.025 (4)	−0.001 (2)	0.008 (3)	0.005 (3)
C16	0.040 (3)	0.014 (3)	0.022 (3)	0.003 (3)	0.011 (3)	−0.006 (3)
C17	0.035 (3)	0.015 (3)	0.021 (3)	−0.001 (3)	0.006 (3)	0.006 (3)
C18	0.068 (5)	0.043 (4)	0.048 (5)	0.014 (4)	0.020 (4)	0.011 (4)
C19	0.066 (5)	0.034 (4)	0.045 (5)	0.019 (4)	0.013 (4)	−0.004 (4)
C20	0.030 (4)	0.039 (4)	0.038 (4)	0.007 (3)	0.004 (3)	−0.004 (3)
C21	0.049 (4)	0.037 (4)	0.037 (4)	0.010 (3)	0.003 (4)	0.000 (3)
C22	0.047 (4)	0.043 (4)	0.037 (4)	0.007 (3)	0.004 (3)	−0.013 (4)
N1	0.033 (3)	0.025 (3)	0.041 (4)	−0.006 (2)	0.006 (3)	0.001 (3)
N2	0.029 (3)	0.011 (2)	0.024 (3)	0.002 (2)	0.005 (2)	−0.003 (2)
N3	0.022 (2)	0.011 (2)	0.026 (3)	−0.0013 (19)	0.005 (2)	0.001 (2)
N4	0.038 (3)	0.036 (3)	0.048 (4)	0.002 (2)	0.000 (3)	−0.003 (3)
O1	0.031 (2)	0.026 (2)	0.039 (2)	0.0052 (19)	0.0013 (19)	−0.006 (2)
O2	0.029 (2)	0.020 (2)	0.036 (3)	−0.0042 (16)	0.0006 (19)	−0.0048 (19)
O3	0.065 (3)	0.023 (2)	0.025 (2)	0.002 (2)	0.002 (2)	0.001 (2)
O4	0.0249 (19)	0.0142 (18)	0.028 (2)	0.0021 (17)	0.0053 (17)	0.0024 (19)
O5	0.045 (2)	0.017 (2)	0.021 (2)	0.0056 (17)	0.0079 (19)	−0.0030 (18)
O6	0.030 (2)	0.021 (2)	0.027 (2)	−0.0013 (18)	0.0064 (19)	0.006 (2)
O7	0.046 (3)	0.019 (2)	0.049 (3)	−0.005 (2)	0.019 (2)	−0.007 (2)
O8	0.066 (3)	0.035 (3)	0.106 (5)	−0.012 (2)	0.056 (3)	0.005 (3)
S1	0.0298 (8)	0.0166 (7)	0.0269 (9)	0.0041 (6)	0.0063 (7)	−0.0020 (6)
Cu1	0.0252 (3)	0.0066 (3)	0.0273 (4)	0.0008 (3)	0.0082 (3)	−0.0005 (3)

C1—C6	1.382 (7)	C15—H15	0.9300
C1—C2	1.391 (7)	C16—N3	1.334 (6)
C1—S1	1.787 (5)	C16—C17	1.385 (7)
C2—C3	1.401 (6)	C16—H16	0.9300
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.373 (7)	C18—N4	1.335 (8)
C3—C7	1.525 (7)	C18—C19	1.389 (9)
C4—C5	1.398 (7)	C18—H18	0.9300
C4—N1	1.475 (7)	C19—C20	1.386 (9)
C5—C6	1.386 (7)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.375 (8)
C6—H6	0.9300	C20—C20i	1.505 (11)
C7—O5	1.227 (6)	C21—C22	1.390 (8)
C7—O4	1.254 (6)	C21—H21	0.9300
C8—N2	1.341 (6)	C22—N4	1.342 (8)
C8—C9	1.381 (7)	C22—H22	0.9300
C8—H8	0.9300	N1—O8	1.216 (6)
C9—C10	1.388 (7)	N1—O7	1.219 (6)
C9—H9	0.9300	O1—S1	1.454 (4)
C10—C11	1.398 (7)	O2—S1	1.448 (4)
C10—C13	1.479 (6)	O3—S1	1.432 (4)
C11—C12	1.366 (6)	O6—H1A	0.83 (5)
C11—H11	0.9300	O6—H1B	0.86 (5)
C12—N2	1.339 (6)	Cu1—N2	1.986 (4)
C12—H12	0.9300	Cu1—N3ii	2.004 (4)
C13—C14	1.384 (7)	Cu1—O2iii	2.565 (4)
C13—C17	1.397 (7)	Cu1—O4	1.969 (3)
C14—C15	1.374 (6)	Cu1—O5iv	2.299 (4)
C14—H14	0.9300	Cu1—O6	2.032 (4)
C15—N3	1.337 (6)
C6—C1—C2	119.9 (5)	N4—C18—C19	123.8 (7)
C6—C1—S1	121.2 (4)	N4—C18—H18	118.1
C2—C1—S1	118.9 (4)	C19—C18—H18	118.1
C1—C2—C3	121.4 (5)	C20—C19—C18	119.9 (7)
C1—C2—H2	119.3	C20—C19—H19	120.0
C3—C2—H2	119.3	C18—C19—H19	120.0
C4—C3—C2	116.7 (5)	C21—C20—C19	116.2 (6)
C4—C3—C7	126.0 (5)	C21—C20—C20i	121.8 (8)
C2—C3—C7	117.3 (5)	C19—C20—C20i	122.0 (8)
C3—C4—C5	123.6 (5)	C20—C21—C22	120.9 (6)
C3—C4—N1	119.4 (5)	C20—C21—H21	119.5
C5—C4—N1	116.9 (5)	C22—C21—H21	119.5
C6—C5—C4	117.9 (5)	N4—C22—C21	122.9 (6)
C6—C5—H5	121.0	N4—C22—H22	118.6
C4—C5—H5	121.0	C21—C22—H22	118.6
C1—C6—C5	120.5 (5)	O8—N1—O7	122.2 (5)
C1—C6—H6	119.8	O8—N1—C4	118.4 (5)
C5—C6—H6	119.8	O7—N1—C4	119.4 (5)
O5—C7—O4	128.8 (5)	C12—N2—C8	117.4 (4)
O5—C7—C3	117.5 (5)	C12—N2—Cu1	120.8 (4)
O4—C7—C3	113.6 (5)	C8—N2—Cu1	121.7 (4)
N2—C8—C9	122.5 (5)	C16—N3—C15	117.9 (4)
N2—C8—H8	118.7	C16—N3—Cu1v	123.2 (4)
C9—C8—H8	118.7	C15—N3—Cu1v	118.8 (4)
C8—C9—C10	119.9 (5)	C18—N4—C22	116.2 (6)
C8—C9—H9	120.0	C7—O4—Cu1	126.4 (3)
C10—C9—H9	120.0	C7—O5—Cu1iv	168.9 (4)
C9—C10—C11	117.2 (4)	Cu1—O6—H1A	105 (4)
C9—C10—C13	121.5 (5)	Cu1—O6—H1B	115 (4)
C11—C10—C13	121.4 (5)	H1A—O6—H1B	122 (5)
C12—C11—C10	119.3 (5)	O3—S1—O2	113.9 (2)
C12—C11—H11	120.4	O3—S1—O1	114.8 (2)
C10—C11—H11	120.4	O2—S1—O1	111.4 (2)
N2—C12—C11	123.7 (5)	O3—S1—C1	105.8 (3)
N2—C12—H12	118.1	O2—S1—C1	105.0 (2)
C11—C12—H12	118.1	O1—S1—C1	104.9 (2)
C14—C13—C17	117.7 (5)	O4—Cu1—N2	92.84 (16)
C14—C13—C10	121.1 (5)	O4—Cu1—N3ii	86.36 (16)
C17—C13—C10	121.1 (5)	N2—Cu1—N3ii	177.66 (18)
C15—C14—C13	119.9 (5)	O4—Cu1—O6	160.42 (16)
C15—C14—H14	120.1	N2—Cu1—O6	90.09 (17)
C13—C14—H14	120.1	N3ii—Cu1—O6	91.39 (17)
N3—C15—C14	122.6 (5)	O4—Cu1—O5iv	111.89 (14)
N3—C15—H15	118.7	N2—Cu1—O5iv	85.92 (16)
C14—C15—H15	118.7	N3ii—Cu1—O5iv	92.34 (16)
N3—C16—C17	123.2 (5)	O6—Cu1—O5iv	87.62 (15)
N3—C16—H16	118.4	O2iii—Cu1—N2	85.20 (17)
C17—C16—H16	118.4	O2iii—Cu1—N3ii	96.74 (17)
C16—C17—C13	118.5 (5)	O2iii—Cu1—O4	75.35 (13)
C16—C17—H17	120.7	O2iii—Cu1—O5iv	168.81 (12)
C13—C17—H17	120.7	O2iii—Cu1—O6	85.63 (13)
C6—C1—C2—C3	−1.2 (8)	C20i—C20—C21—C22	179.5 (7)
S1—C1—C2—C3	179.4 (4)	C20—C21—C22—N4	1.7 (10)
C1—C2—C3—C4	1.4 (8)	C3—C4—N1—O8	−177.7 (6)
C1—C2—C3—C7	−177.9 (5)	C5—C4—N1—O8	0.9 (8)
C2—C3—C4—C5	0.1 (9)	C3—C4—N1—O7	3.5 (8)
C7—C3—C4—C5	179.2 (5)	C5—C4—N1—O7	−178.0 (5)
C2—C3—C4—N1	178.5 (5)	C11—C12—N2—C8	1.0 (8)
C7—C3—C4—N1	−2.3 (9)	C11—C12—N2—Cu1	−176.6 (4)
C3—C4—C5—C6	−1.7 (9)	C9—C8—N2—C12	0.5 (8)
N1—C4—C5—C6	179.8 (5)	C9—C8—N2—Cu1	178.1 (4)
C2—C1—C6—C5	−0.5 (9)	C17—C16—N3—C15	−0.4 (8)
S1—C1—C6—C5	178.9 (5)	C17—C16—N3—Cu1v	179.2 (4)
C4—C5—C6—C1	1.9 (9)	C14—C15—N3—C16	1.6 (8)
C4—C3—C7—O5	95.3 (7)	C14—C15—N3—Cu1v	−178.0 (4)
C2—C3—C7—O5	−85.6 (6)	C19—C18—N4—C22	−3.8 (10)
C4—C3—C7—O4	−88.7 (7)	C21—C22—N4—C18	0.7 (9)
C2—C3—C7—O4	90.4 (6)	O5—C7—O4—Cu1	26.7 (7)
N2—C8—C9—C10	−1.5 (9)	C3—C7—O4—Cu1	−148.7 (3)
C8—C9—C10—C11	0.9 (8)	O4—C7—O5—Cu1iv	−29 (2)
C8—C9—C10—C13	179.0 (5)	C3—C7—O5—Cu1iv	146.5 (15)
C9—C10—C11—C12	0.6 (8)	C6—C1—S1—O3	−130.7 (5)
C13—C10—C11—C12	−177.6 (5)	C2—C1—S1—O3	48.7 (5)
C10—C11—C12—N2	−1.6 (8)	C6—C1—S1—O2	108.6 (5)
C9—C10—C13—C14	−35.0 (8)	C2—C1—S1—O2	−72.0 (5)
C11—C10—C13—C14	143.0 (5)	C6—C1—S1—O1	−9.0 (5)
C9—C10—C13—C17	147.2 (5)	C2—C1—S1—O1	170.5 (4)
C11—C10—C13—C17	−34.7 (8)	C7—O4—Cu1—N2	−106.1 (4)
C17—C13—C14—C15	2.0 (8)	C7—O4—Cu1—N3ii	71.7 (4)
C10—C13—C14—C15	−175.8 (5)	C7—O4—Cu1—O6	155.6 (5)
C13—C14—C15—N3	−2.5 (8)	C7—O4—Cu1—O5iv	−19.4 (4)
N3—C16—C17—C13	0.1 (8)	C12—N2—Cu1—O4	153.9 (4)
C14—C13—C17—C16	−0.9 (8)	C8—N2—Cu1—O4	−23.6 (4)
C10—C13—C17—C16	176.9 (5)	C12—N2—Cu1—O6	−45.4 (4)
N4—C18—C19—C20	4.6 (11)	C8—N2—Cu1—O6	137.1 (4)
C18—C19—C20—C21	−2.0 (10)	C12—N2—Cu1—O5iv	42.2 (4)
C18—C19—C20—C20i	177.6 (7)	C8—N2—Cu1—O5iv	−135.3 (4)
C19—C20—C21—C22	−0.9 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1A···O1iii	0.83 (5)	1.94 (5)	2.758 (5)	171 (6)
O6—H1B···N4vi	0.86 (5)	2.00 (5)	2.801 (6)	156 (5)

Table 1

Selected bond lengths (Å)

Cu1—N2	1.986 (4)
Cu1—N3i	2.004 (4)
Cu1—O2ii	2.565 (4)
Cu1—O4	1.969 (3)
Cu1—O5iii	2.299 (4)
Cu1—O6	2.032 (4)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1A⋯O1ii	0.83 (5)	1.94 (5)	2.758 (5)	171 (6)
O6—H1B⋯N4iv	0.86 (5)	2.00 (5)	2.801 (6)	156 (5)

Symmetry codes: (ii) ; (iv) .