Di-μ(2)-chlorido-bis-[aqua-(2,2'-bipyridine-4,4'-dicarboxylic acid-κN,N')(nitrato-κO)copper(II)].

In the title compound, [Cu(2)Cl(2)(NO(3))(2)(C(12)H(8)N(2)O(4))(2)(H(2)O)(2)], which consists of a chloride-bridged Cu(II) dimer, the Cu atom is in a distorted octa-hedral environment defined by two N atoms from the 2,2'-bipyridine-4,4'-dicarboxylic acid ligand (H(2)bpdca), two bridging chlorido ligands, and two O atoms from an equatorial water mol-ecule and an axial nitrate anion, respectively. The two halves of the dimeric unit are related by an inversion centre at the midpoint between the two Cu atoms. Both carboxylic acid groups in the H(2)bpdca ligand remain protonated, as confirmed by the two sets of C-O bond lengths. The dinuclear mol-ecules are linked into a three-dimensional network via inter-molecular hydrogen bonds.

Related literature

For related literature, see: Aitipamula et al. (2002 ▶); Batten & Robson (1998 ▶); Desiraju (2002 ▶); Etter (1990 ▶); Han et al. (2007 ▶); Holliday & Mirkin (2001 ▶); Kitagawa et al. (2004 ▶); Kumar et al. (2006 ▶); Liu et al. (2002 ▶); Moulton & Zaworotko (2001 ▶); Ockwig et al. (2005 ▶); Schareina et al. (2001a ▶,b ▶); Tynan et al. (2004 ▶, 2005 ▶); Wu (2006 ▶); Wu et al. (2006 ▶).

Experimental

Crystal data

[Cu2Cl2(NO3)2(C12H8N2O4)2(H2O)2]

M = 846.46

Triclinic,

a = 6.9500 (7) Å

b = 8.1490 (7) Å

c = 13.5480 (10) Å

α = 92.315 (2)°

β = 103.384 (4)°

γ = 98.556 (3)°

V = 735.91 (11) Å3

Z = 1

Mo Kα radiation

μ = 1.72 mm−1

T = 295 (2) K

0.30 × 0.24 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.627, T max = 0.725

5180 measured reflections

3301 independent reflections

3116 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.106

S = 1.11

3301 reflections

238 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.67 e Å−3

Δρmin = −0.72 e Å−3

Data collection: RAPID-AUTO (Rigaku 2001 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028511/rt2020sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028511/rt2020Isup2.hkl

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

[Cu2Cl2(NO3)2(C12H8N2O4)2(H2O)2]	Z = 1
Mr = 846.46	F000 = 426
Triclinic, P1	Dx = 1.91 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 6.9500 (7) Å	Cell parameters from 6664 reflections
b = 8.1490 (7) Å	θ = 1.6–27.5º
c = 13.5480 (10) Å	µ = 1.72 mm−1
α = 92.315 (2)º	T = 295 (2) K
β = 103.384 (4)º	Block, blue
γ = 98.556 (3)º	0.30 × 0.24 × 0.20 mm
V = 735.91 (11) Å3

Rigaku R-AXIS RAPID IP area-detector diffractometer	Rint = 0.021
ω oscillation scans	θmax = 27.5º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)	θmin = 1.6º
Tmin = 0.627, Tmax = 0.725	h = −9→9
5180 measured reflections	k = −10→10
3301 independent reflections	l = −17→17
3116 reflections with I > 2σ(I)

Refinement on F2	3 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.035	w = 1/[σ2(Fo2) + (0.0591P)2 + 0.6991P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.106	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.67 e Å−3
3301 reflections	Δρmin = −0.72 e Å−3
238 parameters	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
O6	0.1325 (5)	0.1681 (3)	0.1741 (2)	0.0691 (8)
Cu1	0.37742 (4)	0.02464 (4)	0.10473 (2)	0.02764 (12)
Cl1	0.30801 (9)	0.10642 (8)	−0.05463 (4)	0.03186 (15)
N1	0.4725 (3)	−0.0507 (2)	0.24369 (15)	0.0250 (4)
N2	0.5689 (3)	0.2299 (3)	0.16874 (16)	0.0274 (4)
N3	0.1423 (4)	0.3230 (4)	0.1725 (2)	0.0465 (6)
O1	0.1477 (3)	−0.1609 (3)	0.07198 (16)	0.0380 (4)
O2	0.9538 (3)	0.7885 (2)	0.28428 (16)	0.0396 (5)
O3	1.0190 (4)	0.6606 (3)	0.42733 (17)	0.0536 (6)
O4	0.8547 (3)	−0.0671 (3)	0.60227 (16)	0.0454 (5)
O5	0.6480 (3)	−0.3083 (2)	0.57019 (15)	0.0395 (5)
O7	0.2266 (4)	0.4133 (3)	0.25273 (16)	0.0443 (5)
O8	0.0715 (7)	0.3831 (6)	0.0958 (2)	0.1053 (15)
C1	0.6048 (5)	0.3690 (3)	0.1234 (2)	0.0368 (6)
H1	0.546	0.371	0.0545	0.044*
C2	0.7267 (5)	0.5113 (3)	0.1753 (2)	0.0369 (6)
H2	0.7505	0.607	0.1419	0.044*
C3	0.8119 (4)	0.5075 (3)	0.27753 (19)	0.0269 (5)
C4	0.7771 (4)	0.3630 (3)	0.32546 (18)	0.0264 (5)
H4	0.8347	0.3585	0.3943	0.032*
C5	0.6542 (3)	0.2250 (3)	0.26844 (17)	0.0238 (4)
C6	0.6057 (3)	0.0642 (3)	0.31031 (18)	0.0241 (4)
C7	0.6879 (4)	0.0294 (3)	0.40842 (18)	0.0256 (5)
H7	0.7793	0.1096	0.4532	0.031*
C8	0.6319 (4)	−0.1272 (3)	0.43924 (18)	0.0247 (4)
C9	0.4958 (4)	−0.2451 (3)	0.37088 (19)	0.0289 (5)
H9	0.4564	−0.3507	0.3903	0.035*
C10	0.4201 (4)	−0.2024 (3)	0.27330 (19)	0.0287 (5)
H10	0.3303	−0.2814	0.2269	0.034*
C11	0.9409 (4)	0.6586 (3)	0.3387 (2)	0.0298 (5)
C12	0.7236 (4)	−0.1641 (3)	0.54572 (19)	0.0276 (5)
H1WA	0.050 (4)	−0.139 (5)	0.090 (3)	0.041*
H1WB	0.113 (5)	−0.204 (4)	0.0152 (17)	0.041*
H2A	1.017 (5)	0.861 (5)	0.322 (3)	0.041*
H5A	0.694 (5)	−0.333 (4)	0.6256 (17)	0.041*

	U11	U22	U33	U12	U13	U23
O6	0.0764 (18)	0.0465 (14)	0.083 (2)	−0.0156 (12)	0.0381 (16)	−0.0248 (14)
Cu1	0.03280 (18)	0.02355 (17)	0.02061 (17)	−0.00261 (12)	−0.00096 (12)	0.00132 (11)
Cl1	0.0367 (3)	0.0334 (3)	0.0226 (3)	0.0066 (2)	0.0004 (2)	0.0039 (2)
N1	0.0277 (9)	0.0206 (9)	0.0236 (9)	−0.0004 (7)	0.0029 (7)	0.0005 (7)
N2	0.0319 (10)	0.0229 (9)	0.0229 (10)	−0.0007 (8)	0.0013 (8)	0.0011 (8)
N3	0.0386 (13)	0.0620 (18)	0.0352 (13)	0.0166 (12)	−0.0014 (10)	−0.0100 (12)
O1	0.0364 (10)	0.0346 (10)	0.0334 (10)	−0.0049 (8)	−0.0035 (8)	−0.0017 (8)
O2	0.0515 (12)	0.0230 (9)	0.0329 (10)	−0.0102 (8)	−0.0024 (9)	0.0017 (8)
O3	0.0758 (16)	0.0345 (11)	0.0312 (11)	−0.0132 (10)	−0.0119 (10)	0.0039 (9)
O4	0.0549 (13)	0.0326 (10)	0.0323 (10)	−0.0135 (9)	−0.0098 (9)	0.0055 (8)
O5	0.0518 (12)	0.0285 (9)	0.0276 (10)	−0.0093 (8)	−0.0032 (8)	0.0098 (8)
O7	0.0621 (13)	0.0303 (10)	0.0298 (10)	0.0002 (9)	−0.0052 (9)	−0.0007 (8)
O8	0.145 (3)	0.132 (3)	0.0376 (15)	0.086 (3)	−0.0179 (18)	−0.0050 (18)
C1	0.0498 (15)	0.0273 (12)	0.0242 (12)	−0.0046 (11)	−0.0033 (11)	0.0058 (10)
C2	0.0501 (16)	0.0250 (12)	0.0279 (13)	−0.0043 (11)	−0.0001 (11)	0.0078 (10)
C3	0.0278 (11)	0.0219 (11)	0.0267 (12)	−0.0015 (9)	0.0018 (9)	0.0004 (9)
C4	0.0298 (11)	0.0229 (11)	0.0219 (11)	−0.0017 (9)	0.0002 (9)	0.0032 (9)
C5	0.0269 (10)	0.0211 (10)	0.0216 (11)	0.0005 (8)	0.0042 (8)	0.0031 (8)
C6	0.0254 (10)	0.0204 (10)	0.0245 (11)	−0.0006 (8)	0.0049 (9)	0.0002 (8)
C7	0.0290 (11)	0.0202 (10)	0.0238 (11)	−0.0020 (8)	0.0023 (9)	0.0008 (8)
C8	0.0286 (11)	0.0207 (10)	0.0225 (11)	−0.0001 (8)	0.0038 (9)	0.0014 (8)
C9	0.0327 (12)	0.0205 (11)	0.0293 (12)	−0.0031 (9)	0.0036 (9)	0.0030 (9)
C10	0.0316 (12)	0.0213 (11)	0.0278 (12)	−0.0038 (9)	0.0020 (9)	0.0000 (9)
C11	0.0319 (12)	0.0235 (11)	0.0294 (12)	−0.0027 (9)	0.0027 (10)	0.0005 (9)
C12	0.0327 (12)	0.0216 (11)	0.0256 (11)	0.0002 (9)	0.0034 (9)	0.0034 (9)

O6—N3	1.255 (4)	O5—C12	1.302 (3)
O6—Cu1	2.528 (3)	O5—H5A	0.790 (18)
Cu1—O1	1.982 (2)	C1—C2	1.387 (4)
Cu1—N1	1.999 (2)	C1—H1	0.93
Cu1—N2	2.002 (2)	C2—C3	1.378 (4)
Cu1—Cl1	2.2511 (7)	C2—H2	0.93
Cu1—Cl1i	2.7757 (8)	C3—C4	1.384 (3)
N1—C10	1.340 (3)	C3—C11	1.501 (3)
N1—C6	1.355 (3)	C4—C5	1.389 (3)
N2—C1	1.330 (3)	C4—H4	0.93
N2—C5	1.348 (3)	C5—C6	1.473 (3)
N3—O8	1.199 (4)	C6—C7	1.379 (3)
N3—O7	1.256 (3)	C7—C8	1.387 (3)
O1—H1WA	0.819 (18)	C7—H7	0.93
O1—H1WB	0.802 (18)	C8—C9	1.389 (3)
O2—C11	1.318 (3)	C8—C12	1.498 (3)
O2—H2A	0.77 (4)	C9—C10	1.384 (4)
O3—C11	1.196 (3)	C9—H9	0.93
O4—C12	1.207 (3)	C10—H10	0.93
N3—O6—Cu1	119.8 (2)	C2—C3—C4	119.9 (2)
O1—Cu1—N1	91.33 (8)	C2—C3—C11	121.1 (2)
O1—Cu1—N2	163.29 (9)	C4—C3—C11	119.0 (2)
N1—Cu1—N2	81.03 (8)	C3—C4—C5	118.5 (2)
O1—Cu1—Cl1	92.53 (6)	C3—C4—H4	120.8
N1—Cu1—Cl1	172.93 (6)	C5—C4—H4	120.8
N2—Cu1—Cl1	96.72 (6)	N2—C5—C4	121.5 (2)
O1—Cu1—O6	82.22 (9)	N2—C5—C6	114.76 (19)
N1—Cu1—O6	87.84 (10)	C4—C5—C6	123.8 (2)
N2—Cu1—O6	82.67 (9)	N1—C6—C7	121.6 (2)
Cl1—Cu1—O6	98.54 (8)	N1—C6—C5	114.4 (2)
C10—N1—C6	119.4 (2)	C7—C6—C5	124.0 (2)
C10—N1—Cu1	125.70 (16)	C6—C7—C8	118.9 (2)
C6—N1—Cu1	114.87 (16)	C6—C7—H7	120.5
C1—N2—C5	119.5 (2)	C8—C7—H7	120.5
C1—N2—Cu1	125.61 (17)	C7—C8—C9	119.5 (2)
C5—N2—Cu1	114.73 (16)	C7—C8—C12	118.5 (2)
O8—N3—O6	120.4 (3)	C9—C8—C12	122.0 (2)
O8—N3—O7	120.8 (3)	C10—C9—C8	118.6 (2)
O6—N3—O7	118.8 (3)	C10—C9—H9	120.7
Cu1—O1—H1WA	113 (3)	C8—C9—H9	120.7
Cu1—O1—H1WB	118 (3)	N1—C10—C9	121.9 (2)
H1WA—O1—H1WB	110 (4)	N1—C10—H10	119
C11—O2—H2A	106 (3)	C9—C10—H10	119
C12—O5—H5A	116 (3)	O3—C11—O2	124.3 (2)
N2—C1—C2	122.3 (2)	O3—C11—C3	123.3 (2)
N2—C1—H1	118.9	O2—C11—C3	112.3 (2)
C2—C1—H1	118.9	O4—C12—O5	124.2 (2)
C3—C2—C1	118.4 (2)	O4—C12—C8	122.1 (2)
C3—C2—H2	120.8	O5—C12—C8	113.7 (2)
C1—C2—H2	120.8
N3—O6—Cu1—O1	−149.3 (3)	Cu1—N2—C5—C4	−174.51 (18)
N3—O6—Cu1—N1	119.1 (3)	C1—N2—C5—C6	−179.3 (2)
N3—O6—Cu1—N2	37.8 (3)	Cu1—N2—C5—C6	5.3 (3)
N3—O6—Cu1—Cl1	−57.9 (3)	C3—C4—C5—N2	−0.3 (4)
O1—Cu1—N1—C10	18.5 (2)	C3—C4—C5—C6	179.9 (2)
N2—Cu1—N1—C10	−176.4 (2)	C10—N1—C6—C7	−0.6 (3)
Cl1—Cu1—N1—C10	−104.5 (5)	Cu1—N1—C6—C7	−178.66 (18)
O6—Cu1—N1—C10	100.7 (2)	C10—N1—C6—C5	178.9 (2)
O1—Cu1—N1—C6	−163.57 (17)	Cu1—N1—C6—C5	0.9 (3)
N2—Cu1—N1—C6	1.50 (16)	N2—C5—C6—N1	−4.1 (3)
Cl1—Cu1—N1—C6	73.4 (5)	C4—C5—C6—N1	175.7 (2)
O6—Cu1—N1—C6	−81.41 (17)	N2—C5—C6—C7	175.4 (2)
O1—Cu1—N2—C1	−115.2 (3)	C4—C5—C6—C7	−4.7 (4)
N1—Cu1—N2—C1	−178.8 (2)	N1—C6—C7—C8	−0.1 (4)
Cl1—Cu1—N2—C1	7.9 (2)	C5—C6—C7—C8	−179.5 (2)
O6—Cu1—N2—C1	−89.9 (2)	C6—C7—C8—C9	0.3 (4)
O1—Cu1—N2—C5	59.8 (4)	C6—C7—C8—C12	179.4 (2)
N1—Cu1—N2—C5	−3.82 (17)	C7—C8—C9—C10	0.2 (4)
Cl1—Cu1—N2—C5	−177.06 (16)	C12—C8—C9—C10	−179.0 (2)
O6—Cu1—N2—C5	85.14 (19)	C6—N1—C10—C9	1.1 (4)
Cu1—O6—N3—O8	80.0 (4)	Cu1—N1—C10—C9	178.90 (19)
Cu1—O6—N3—O7	−100.2 (3)	C8—C9—C10—N1	−0.8 (4)
C5—N2—C1—C2	−0.5 (4)	C2—C3—C11—O3	−179.4 (3)
Cu1—N2—C1—C2	174.3 (2)	C4—C3—C11—O3	1.3 (4)
N2—C1—C2—C3	−0.4 (5)	C2—C3—C11—O2	2.1 (4)
C1—C2—C3—C4	1.0 (4)	C4—C3—C11—O2	−177.3 (2)
C1—C2—C3—C11	−178.3 (3)	C7—C8—C12—O4	−5.8 (4)
C2—C3—C4—C5	−0.6 (4)	C9—C8—C12—O4	173.4 (3)
C11—C3—C4—C5	178.7 (2)	C7—C8—C12—O5	174.0 (2)
C1—N2—C5—C4	0.8 (4)	C9—C8—C12—O5	−6.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ii	0.93	2.45	3.376 (3)	172
C4—H4···O3ii	0.93	2.42	3.346 (3)	179
C2—H2···Cl1iii	0.93	2.7	3.590 (3)	160
C1—H1···Cl1	0.93	2.67	3.258 (3)	122
O5—H5A···O7iv	0.790 (18)	1.798 (19)	2.582 (3)	172 (4)
O2—H2A···O4ii	0.77 (4)	1.92 (4)	2.676 (3)	169 (4)
O1—H1WB···O8v	0.802 (18)	2.10 (2)	2.830 (4)	152 (4)
O1—H1WA···Cl1v	0.819 (18)	2.48 (2)	3.220 (2)	152 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3i	0.93	2.45	3.376 (3)	172
C4—H4⋯O3i	0.93	2.42	3.346 (3)	179
C2—H2⋯Cl1ii	0.93	2.7	3.590 (3)	160
C1—H1⋯Cl1	0.93	2.67	3.258 (3)	122
O5—H5A⋯O7iii	0.790 (18)	1.798 (19)	2.582 (3)	172 (4)
O2—H2A⋯O4i	0.77 (4)	1.92 (4)	2.676 (3)	169 (4)
O1—H1WB⋯O8iv	0.802 (18)	2.10 (2)	2.830 (4)	152 (4)
O1—H1WA⋯Cl1iv	0.819 (18)	2.48 (2)	3.220 (2)	152 (3)

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