μ-4,4'-Bipyridine-bis-[aqua-(4-hy-droxy-pyridine-2,6-dicarboxyl-ato)copper(II)].

The title compound, [Cu(2)(C(7)H(3)NO(5))(2)(C(10)H(8)N(2))(H(2)O)(2)], exhibits a centrosymmetric binuclear molecule. Each completely deprotonated 4-hy-droxy-pyridine-2,6-dicarb-oxy-lic acid mol-ecule assumes a tridentate chelating coordination mode. The square-pyramidal coordination geometry around the Cu(II) ion is completed by the bridging bipyridine ligand and an apical water molecule. Adjacent complexes are connected via O-H⋯O and C-H⋯O hydrogen bonds to generate a three-dimensional supra-molecular structure.

Related literature

For related literature on the construction of supra­molecular structures, see: Robin & Fromm (2006 ▶); Desiraju (1989 ▶). For compounds using heterocyclic carb­oxy­lic acids such as pyridine-, pyrazole- and imidazole­carb­oxy­lic acids as building blocks, see: Lin et al. (1998 ▶); Zhao et al. (2003 ▶); Pan et al. (2000 ▶); Liu et al. (2004 ▶); Mahata & Natarajan (2005 ▶); Panagiotis et al. (2005 ▶).

Experimental

Crystal data

[Cu2(C7H3NO5)2(C10H8N2)(H2O)2]

M = 681.50

Monoclinic,

a = 8.3945 (9) Å

b = 18.433 (2) Å

c = 7.8686 (10) Å

β = 100.044 (2)°

V = 1198.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.85 mm−1

T = 296 K

0.30 × 0.25 × 0.25 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.579, T max = 0.629

6528 measured reflections

2433 independent reflections

1972 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.103

S = 1.09

2433 reflections

197 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004758/ff2054sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004758/ff2054Isup2.hkl

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

[Cu2(C7H3NO5)2(C10H8N2)(H2O)2]	F(000) = 688
Mr = 681.50	Dx = 1.888 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2433 reflections
a = 8.3945 (9) Å	θ = 2.2–26.4°
b = 18.433 (2) Å	µ = 1.85 mm−1
c = 7.8686 (10) Å	T = 296 K
β = 100.044 (2)°	Prism, blue
V = 1198.9 (2) Å3	0.30 × 0.25 × 0.25 mm
Z = 2

Bruker SMART 1000 diffractometer	2433 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.579, Tmax = 0.629	k = −20→23
6528 measured reflections	l = −8→9

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0447P)2] where P = (Fo2 + 2Fc2)/3
2433 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.44 e Å−3
2 restraints	Δρmin = −0.60 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	0.47889 (5)	0.38222 (2)	0.23311 (6)	0.03017 (17)
N1	0.2865 (3)	0.34582 (14)	0.2945 (4)	0.0261 (6)
N2	0.6518 (3)	0.42601 (15)	0.1330 (4)	0.0300 (7)
O1	0.3886 (3)	0.47502 (11)	0.3063 (3)	0.0332 (6)
O2	0.1826 (3)	0.51815 (12)	0.4202 (4)	0.0377 (7)
O3	−0.1274 (3)	0.26614 (12)	0.4182 (4)	0.0463 (8)
H3	−0.1858	0.2984	0.4443	0.069*
O4	0.4981 (3)	0.27793 (12)	0.1646 (4)	0.0386 (7)
O5	0.3903 (3)	0.16954 (12)	0.1994 (4)	0.0428 (7)
C1	0.2557 (4)	0.46880 (17)	0.3631 (5)	0.0280 (8)
C2	0.1880 (4)	0.39256 (16)	0.3559 (4)	0.0245 (7)
C3	0.0461 (4)	0.36900 (17)	0.4026 (5)	0.0292 (8)
H3A	−0.0223	0.4010	0.4462	0.035*
C4	0.0081 (4)	0.29506 (17)	0.3821 (5)	0.0305 (8)
C5	0.1158 (4)	0.24840 (18)	0.3192 (5)	0.0318 (8)
H5	0.0925	0.1992	0.3060	0.038*
C6	0.2553 (4)	0.27552 (17)	0.2772 (5)	0.0266 (8)
C7	0.3911 (4)	0.23570 (19)	0.2084 (5)	0.0316 (8)
C8	0.6991 (4)	0.49448 (19)	0.1714 (5)	0.0369 (9)
H8	0.6384	0.5229	0.2341	0.044*
C9	0.8328 (4)	0.52411 (18)	0.1222 (5)	0.0363 (9)
H9	0.8621	0.5715	0.1542	0.044*
C10	0.9259 (4)	0.48484 (17)	0.0252 (4)	0.0276 (8)
C11	0.8717 (4)	0.41528 (19)	−0.0187 (5)	0.0377 (10)
H11	0.9275	0.3867	−0.0861	0.045*
C12	0.7374 (5)	0.38763 (18)	0.0353 (5)	0.0399 (10)
H12	0.7044	0.3407	0.0030	0.048*
O6	0.6528 (3)	0.35779 (13)	0.5027 (4)	0.0359 (6)
H6A	0.689 (4)	0.3975 (13)	0.543 (5)	0.043*
H6B	0.593 (4)	0.3429 (19)	0.564 (4)	0.043*

	U11	U22	U33	U12	U13	U23
Cu1	0.0234 (3)	0.0274 (3)	0.0441 (3)	−0.00220 (18)	0.0182 (2)	−0.00282 (19)
N1	0.0228 (15)	0.0241 (14)	0.0344 (17)	0.0011 (12)	0.0136 (13)	−0.0017 (13)
N2	0.0243 (15)	0.0311 (16)	0.0384 (18)	0.0006 (12)	0.0161 (14)	0.0009 (13)
O1	0.0278 (13)	0.0223 (12)	0.0547 (17)	−0.0030 (10)	0.0215 (12)	−0.0014 (11)
O2	0.0336 (14)	0.0254 (13)	0.0598 (19)	−0.0023 (11)	0.0238 (13)	−0.0090 (12)
O3	0.0297 (14)	0.0281 (13)	0.088 (2)	−0.0026 (11)	0.0305 (15)	0.0064 (15)
O4	0.0310 (14)	0.0336 (14)	0.0572 (18)	−0.0015 (11)	0.0239 (13)	−0.0100 (13)
O5	0.0412 (16)	0.0261 (14)	0.0638 (19)	0.0039 (12)	0.0165 (14)	−0.0095 (13)
C1	0.0260 (18)	0.0241 (17)	0.035 (2)	−0.0014 (14)	0.0094 (16)	−0.0017 (15)
C2	0.0203 (17)	0.0250 (17)	0.0291 (19)	0.0006 (13)	0.0071 (14)	−0.0002 (14)
C3	0.0216 (18)	0.0296 (18)	0.038 (2)	0.0019 (14)	0.0108 (16)	0.0018 (16)
C4	0.0226 (18)	0.0265 (18)	0.044 (2)	−0.0029 (14)	0.0109 (16)	0.0042 (16)
C5	0.0311 (19)	0.0220 (17)	0.045 (2)	−0.0010 (15)	0.0144 (17)	0.0022 (16)
C6	0.0243 (18)	0.0223 (17)	0.035 (2)	0.0001 (14)	0.0091 (15)	−0.0002 (15)
C7	0.029 (2)	0.034 (2)	0.033 (2)	0.0039 (16)	0.0077 (16)	−0.0084 (16)
C8	0.037 (2)	0.0298 (19)	0.050 (3)	0.0017 (16)	0.0242 (19)	−0.0058 (18)
C9	0.037 (2)	0.0253 (18)	0.051 (2)	−0.0088 (16)	0.0220 (19)	−0.0089 (17)
C10	0.0269 (19)	0.0270 (18)	0.032 (2)	−0.0004 (15)	0.0120 (16)	0.0057 (15)
C11	0.034 (2)	0.0312 (19)	0.055 (3)	−0.0020 (16)	0.0280 (19)	−0.0057 (18)
C12	0.040 (2)	0.0288 (19)	0.057 (3)	−0.0072 (17)	0.027 (2)	−0.0071 (18)
O6	0.0350 (16)	0.0296 (13)	0.0482 (18)	−0.0092 (11)	0.0211 (13)	−0.0041 (12)

Cu1—N1	1.888 (3)	C3—C4	1.403 (4)
Cu1—N2	1.944 (3)	C3—H3A	0.9300
Cu1—O1	1.996 (2)	C4—C5	1.400 (4)
Cu1—O4	2.011 (2)	C5—C6	1.365 (4)
Cu1—O6	2.399 (3)	C5—H5	0.9300
N1—C6	1.324 (4)	C6—C7	1.532 (4)
N1—C2	1.341 (4)	C8—C9	1.363 (4)
N2—C12	1.342 (4)	C8—H8	0.9300
N2—C8	1.342 (4)	C9—C10	1.388 (4)
O1—C1	1.277 (4)	C9—H9	0.9300
O2—C1	1.226 (4)	C10—C11	1.384 (5)
O3—C4	1.330 (4)	C10—C10i	1.480 (6)
O3—H3	0.8200	C11—C12	1.370 (5)
O4—C7	1.280 (4)	C11—H11	0.9300
O5—C7	1.222 (4)	C12—H12	0.9300
C1—C2	1.513 (4)	O6—H6A	0.834 (18)
C2—C3	1.377 (4)	O6—H6B	0.804 (18)
N1—Cu1—N2	169.74 (13)	O3—C4—C3	123.4 (3)
N1—Cu1—O1	81.12 (10)	C5—C4—C3	119.3 (3)
N2—Cu1—O1	96.27 (10)	C6—C5—C4	119.7 (3)
N1—Cu1—O4	80.85 (10)	C6—C5—H5	120.2
N2—Cu1—O4	100.83 (10)	C4—C5—H5	120.2
O1—Cu1—O4	161.60 (9)	N1—C6—C5	119.7 (3)
N1—Cu1—O6	97.05 (10)	N1—C6—C7	111.0 (3)
N2—Cu1—O6	93.09 (10)	C5—C6—C7	129.2 (3)
O1—Cu1—O6	96.24 (10)	O5—C7—O4	126.0 (3)
O4—Cu1—O6	89.58 (10)	O5—C7—C6	120.1 (3)
C6—N1—C2	122.8 (3)	O4—C7—C6	113.8 (3)
C6—N1—Cu1	119.0 (2)	N2—C8—C9	122.6 (3)
C2—N1—Cu1	118.2 (2)	N2—C8—H8	118.7
C12—N2—C8	117.3 (3)	C9—C8—H8	118.7
C12—N2—Cu1	121.7 (2)	C8—C9—C10	121.2 (3)
C8—N2—Cu1	120.8 (2)	C8—C9—H9	119.4
C1—O1—Cu1	115.01 (19)	C10—C9—H9	119.4
C4—O3—H3	109.5	C11—C10—C9	115.4 (3)
C7—O4—Cu1	114.6 (2)	C11—C10—C10i	122.6 (4)
O2—C1—O1	125.8 (3)	C9—C10—C10i	122.1 (4)
O2—C1—C2	119.6 (3)	C12—C11—C10	121.3 (3)
O1—C1—C2	114.6 (3)	C12—C11—H11	119.3
N1—C2—C3	120.7 (3)	C10—C11—H11	119.3
N1—C2—C1	111.0 (3)	N2—C12—C11	122.2 (3)
C3—C2—C1	128.3 (3)	N2—C12—H12	118.9
C2—C3—C4	117.8 (3)	C11—C12—H12	118.9
C2—C3—H3A	121.1	Cu1—O6—H6A	107 (3)
C4—C3—H3A	121.1	Cu1—O6—H6B	104 (3)
O3—C4—C5	117.3 (3)	H6A—O6—H6B	107 (4)
N2—Cu1—N1—C6	103.6 (6)	O1—C1—C2—N1	1.8 (5)
O1—Cu1—N1—C6	179.6 (3)	O2—C1—C2—C3	1.9 (6)
O4—Cu1—N1—C6	3.3 (3)	O1—C1—C2—C3	−178.0 (3)
O6—Cu1—N1—C6	−85.2 (3)	N1—C2—C3—C4	−0.5 (5)
N2—Cu1—N1—C2	−77.2 (7)	C1—C2—C3—C4	179.2 (3)
O1—Cu1—N1—C2	−1.2 (3)	C2—C3—C4—O3	−178.2 (3)
O4—Cu1—N1—C2	−177.5 (3)	C2—C3—C4—C5	1.2 (5)
O6—Cu1—N1—C2	94.1 (3)	O3—C4—C5—C6	178.9 (3)
N1—Cu1—N2—C12	−93.6 (7)	C3—C4—C5—C6	−0.6 (6)
O1—Cu1—N2—C12	−168.3 (3)	C2—N1—C6—C5	1.6 (5)
O4—Cu1—N2—C12	4.9 (3)	Cu1—N1—C6—C5	−179.3 (3)
O6—Cu1—N2—C12	95.1 (3)	C2—N1—C6—C7	−178.6 (3)
N1—Cu1—N2—C8	92.1 (7)	Cu1—N1—C6—C7	0.6 (4)
O1—Cu1—N2—C8	17.4 (3)	C4—C5—C6—N1	−0.8 (5)
O4—Cu1—N2—C8	−169.4 (3)	C4—C5—C6—C7	179.4 (4)
O6—Cu1—N2—C8	−79.2 (3)	Cu1—O4—C7—O5	−170.6 (3)
N1—Cu1—O1—C1	2.3 (3)	Cu1—O4—C7—C6	9.4 (4)
N2—Cu1—O1—C1	172.2 (3)	N1—C6—C7—O5	173.3 (3)
O4—Cu1—O1—C1	13.9 (5)	C5—C6—C7—O5	−6.9 (6)
O6—Cu1—O1—C1	−93.9 (3)	N1—C6—C7—O4	−6.8 (5)
N1—Cu1—O4—C7	−7.3 (3)	C5—C6—C7—O4	173.1 (4)
N2—Cu1—O4—C7	−177.1 (3)	C12—N2—C8—C9	−3.2 (6)
O1—Cu1—O4—C7	−19.0 (5)	Cu1—N2—C8—C9	171.4 (3)
O6—Cu1—O4—C7	89.9 (3)	N2—C8—C9—C10	1.5 (6)
Cu1—O1—C1—O2	177.3 (3)	C8—C9—C10—C11	1.0 (6)
Cu1—O1—C1—C2	−2.8 (4)	C8—C9—C10—C10i	−178.2 (4)
C6—N1—C2—C3	−0.9 (5)	C9—C10—C11—C12	−1.6 (6)
Cu1—N1—C2—C3	179.9 (3)	C10i—C10—C11—C12	177.5 (4)
C6—N1—C2—C1	179.3 (3)	C8—N2—C12—C11	2.5 (6)
Cu1—N1—C2—C1	0.1 (4)	Cu1—N2—C12—C11	−172.0 (3)
O2—C1—C2—N1	−178.2 (3)	C10—C11—C12—N2	−0.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6ii	0.82	1.86	2.670 (3)	169
O6—H6B···O4iii	0.80 (2)	2.54 (3)	3.185 (3)	139 (3)
O6—H6B···O5iii	0.80 (2)	2.17 (2)	2.948 (3)	163 (4)
C12—H12···O3iv	0.93	2.58	3.246 (4)	129
C8—H8···O1	0.93	2.43	3.003 (4)	120
C12—H12···O4	0.93	2.59	3.142 (4)	118

Table 1

Selected bond lengths (Å)

Cu1—N1	1.888 (3)
Cu1—N2	1.944 (3)
Cu1—O1	1.996 (2)
Cu1—O4	2.011 (2)
Cu1—O6	2.399 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O6i	0.82	1.86	2.670 (3)	169
O6—H6B⋯O4ii	0.80 (2)	2.54 (3)	3.185 (3)	139 (3)
O6—H6B⋯O5ii	0.80 (2)	2.17 (2)	2.948 (3)	163 (4)
C12—H12⋯O3iii	0.93	2.58	3.246 (4)	129
C8—H8⋯O1	0.93	2.43	3.003 (4)	120
C12—H12⋯O4	0.93	2.59	3.142 (4)	118

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