Di-μ2-chlorido-bis­[aqua­(2,2′-bipyridine-4,4′-dicarboxylic acid-κ2N,N′)(nitrato-κO)copper(II)]

Han, K.-F.; Wu, H.-Y.; Wang, Z.-M.; Guo, H.-Y.

doi:10.1107/S1600536808028511

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Pages m1607-m1608

doi:10.1107/S1600536808028511

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Di-μ₂-chlorido-bis[aqua(2,2′-bipyridine-4,4′-dicarboxylic acid-κ²N,N′)(nitrato-κO)copper(II)]

Ke-Fei Han,^a Hui-Yong Wu,^a Zhong-Ming Wang ^a ^* and Hong-You Guo ^a

^aDepartment of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China
^*Correspondence e-mail: wangzm@mail.buct.edu.cn

(Received 2 April 2008; accepted 5 September 2008; online 22 November 2008)

In the title compound, [Cu₂Cl₂(NO₃)₂(C₁₂H₈N₂O₄)₂(H₂O)₂], which consists of a chloride-bridged Cu^II dimer, the Cu atom is in a distorted octahedral environment defined by two N atoms from the 2,2′-bipyridine-4,4′-dicarboxylic acid ligand (H₂bpdca), two bridging chlorido ligands, and two O atoms from an equatorial water molecule 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 H₂bpdca ligand remain protonated, as confirmed by the two sets of C—O bond lengths. The dinuclear molecules are linked into a three-dimensional network via intermolecular 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_r = 846.46
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.106
S = 1.11
3301 reflections
238 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.72 e Å⁻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⋯O8^iv	0.802 (18)	2.10 (2)	2.830 (4)	152 (4)
O1—H1WA⋯Cl1^iv	0.819 (18)	2.48 (2)	3.220 (2)	152 (3)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) -x+1, -y, -z+1; (iv) -x, -y, -z.

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 ).

Supporting information

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

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

checkCIF report

Comment top

In the field of crystal engineering, based on the metal–ligand coordination interactions, a large number of coordination polymers have been designed and prepared to develop novel functional materials. (For example, Batten & Robson, 1998; Kitagawa et al., 2004; Ockwig et al., 2005). Hydrogen bonding interactions, because of its unique strength and direction, have been widely explored as one of the principal means to control organic molecular assemblies (Desiraju, 2002; Moulton & Zaworotko 2001). As an important synthetic strategy, the combination of both metal–ligand coordination and hydrogen bonding in designing various supramolecular architectures has been extensively used over the past few years (Aitipamula et al., 2002; Holliday & Mirkin, 2001; Kumar et al., 2006; Han et al., 2007). For example, 2,2'-bipyridine-4,4'-dicarboxylic acid (H₂bpdca), which possesses two N atoms and carboxylic acid groups, has been employed as ligand with the N atoms chelating a metal ion and the carboxylic acid forming either self-complementary hydrogen bonds to neighboring ligands, or coordinating directly to adjacent metal ions following deprotonation (Tynan et al., 2005; Tynan et al., 2004; Liu et al., 2002; Schareina et al., 2001a; Schareina et al., 2001b; Wu, 2006; Wu et al., 2006). Here we report a copper(II)–H₂bpdca complex, [Cu₂(C₁₂H₈N₂O₄)₂Cl₂(NO₃)₂(H₂O)₂], (I), with a three-dimensional H-bonding network structure induced by the carboxylic acid groups and water molecules acting as hydrogen-bond donors.

As shown in Fig. 1, the structure of (I) consists of a chloride-bridged Cu(II) dimer, in which the H₂bpdca ligand remains protonated. The two halves of the dimer unit are related by an inversion centre at the midpoint between the two Cu atoms. Each copper atom has a distorted octahedral geometry, with the equatorial positions utilised by two chelating nitrogen atoms from the H₂bpdca ligand (average of Cu—N bond length, 2.001 (2) Å), one bridging chlorido ligand (Cu1—Cl1 = 2.2513 (6) Å) and one coordinated water molecule (Cu1—O1 = 1.9828 (21) Å). In the elongated axial direction, one site is occupied by another bridging chloride atom (Cu1—Cl1ⁱ = 2.7757 (8) Å, symmetry code: (i), 1 - x, -y, -z), and the other site by an O atom from a nitrate anion (Cu1—O6 = 2.5280 (4) Å). Both bond lengths are longer than those corresponding to usual coordination bonds, indicating a weak coordination. The two pyridyl rings of the H₂bpdca ligand are slightly twisted, as indicated by its dihedral angle (4.46 (12)°), while the copper-to-copper separation in the dimeric unit is 3.6698 (5) Å. The copper atoms and the bridging chloride atoms occupy the same plane as required by the symmetry, and results in a chloride–chloride separation of 3.4755 (9) Å. The carboxylic group at C11 is almost coplanar with the attached pyridyl ring (dihedral angle ca 3.19°), whereas the carboxylic group at C12 is slightly twisted by ca 12.31° toward the corresponding pyridyl ring. As expected for protonated carboxylic acids, there are two sets of C—O bond lengths: the carbon to hydroxyl oxygen single bond, which average 1.3095 Å, and the carbon to carbonyl oxygen double bond, which average 1.2013 Å. The coordinated nitrato and chlorido ligands provide the charge balance for the title complex.

The dimeric unit is extended into a three-dimensional network through hydrogen bond interactions (Table 1). Double intermolecular hydrogen bonds (O2—H2A···O4) are formed by means of the double carboxylic acid self-complementary interaction of an adjacent complex, resulting in a centrosymmetric R²₂(22) motif (Etter 1990), with the two O3 carbonyl oxygen atoms pointing toward the middle of the ring. Due to its position, the O3 atom can act as a hydrogen bond acceptor from two pyridyl C—H groups (C4—H4···O3 and C7—H7···O3) which further supports the R²₂(22) motif. In addition, the coordinated water molecule, O1, is a hydrogen bond donor to the Cl1 atom on adjacent complexes (O1—H1WA···Cl1). These intermolecular hydrogen bonds result in a two-dimensional structure (Fig. 2). Further hydrogen bonding between the non-coordinated O7 atom of nitrate anion and a carboxylic acid group (O5—H5A···O7), and between the O8 atom of same nitrate anion and water molecule of an adjacent complex (O1—H1WB···O8), links the two-dimensional frame into a three-dimensional network (Fig. 3).

Related literature top

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 top

A mixture of CuCl₂.2H₂O (0.0170 g, 0.1 mmol), H₂bpdca (0.0244 g, 0.1 mmol) in the molar ratio 1:1, was placed in a 25 ml Teflon-lined digestion bomb with 4 ml distilled water and 1 ml concentrated HNO₃. The sealed vessel was heated to 473 K for 10 h and then slowly cooled to room temperature (3 K h^-1). The resulting blue solution was allowed to stand in air at room temperature for one month, yielding blue crystals in 46% yield based on H₂bpdca. IR spectroscopic analysis (solid KBr disc, ν, cm^-1): 3410.3(s), 3179.0(m) 1731.2 (vs), 1694.4(m), 1625.5 (m), 1560.5(m), 1403.8 (vs), 1382.1 (vs), 1235.3 (m), 1209.8 (s), 1036.3 (w), 824.0 (w), 660.6 (s).

Computing details top

Data collection: RAPID-AUTO (Rigaku 2001); cell refinement: RAPID-AUTO (Rigaku 2001); data reduction: RAPID-AUTO (Rigaku 2001); 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 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of a fragment of the title compound, showing 50% probability displacement ellipsoids for non-H atoms. H atoms are shown as small spheres of arbitrary size.
	Fig. 2. The two-dimensional network formed by hydrogen-bonding interactions (blue dotted lines). For clarity, H atoms attached to C atoms have been omitted.
	Fig. 3. The three-dimensional packing of (I), viewed down the b axis, showing a network structure connected by hydrogen bonds (blue dotted lines). All H atoms have been omitted for clarity.

Di-µ₂-chlorido-bis[aqua(2,2'-bipyridine-4,4'-dicarboxylic acid-κ²N,N')(nitrato-κO)copper(II)] top

Crystal data top

[Cu₂Cl₂(NO₃)₂(C₁₂H₈N₂O₄)₂(H₂O)₂]	Z = 1
M_r = 846.46	F(000) = 426
Triclinic, P1	D_x = 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 = 1.6–27.5°
c = 13.548 (1) Å	µ = 1.72 mm⁻¹
α = 92.315 (2)°	T = 295 K
β = 103.384 (4)°	Block, blue
γ = 98.556 (3)°	0.30 × 0.24 × 0.20 mm
V = 735.91 (11) Å³

Data collection top

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

Refinement top

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(F_o²) + (0.0591P)² + 0.6991P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.106	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.67 e Å⁻³
3301 reflections	Δρ_min = −0.72 e Å⁻³
238 parameters

Crystal data top

[Cu₂Cl₂(NO₃)₂(C₁₂H₈N₂O₄)₂(H₂O)₂]	γ = 98.556 (3)°
M_r = 846.46	V = 735.91 (11) Å³
Triclinic, P1	Z = 1
a = 6.9500 (7) Å	Mo Kα radiation
b = 8.1490 (7) Å	µ = 1.72 mm⁻¹
c = 13.548 (1) Å	T = 295 K
α = 92.315 (2)°	0.30 × 0.24 × 0.20 mm
β = 103.384 (4)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	3301 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3116 reflections with I > 2σ(I)
T_min = 0.627, T_max = 0.725	R_int = 0.021
5180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.67 e Å⁻³
3301 reflections	Δρ_min = −0.72 e Å⁻³
238 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

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···O7^iv	0.79 (2)	1.80 (2)	2.582 (3)	172 (4)
O2—H2A···O4ⁱⁱ	0.77 (4)	1.92 (4)	2.676 (3)	169 (4)
O1—H1WB···O8^v	0.80 (2)	2.10 (2)	2.830 (4)	152 (4)
O1—H1WA···Cl1^v	0.82 (2)	2.48 (2)	3.220 (2)	152 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu₂Cl₂(NO₃)₂(C₁₂H₈N₂O₄)₂(H₂O)₂]
M_r	846.46
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.9500 (7), 8.1490 (7), 13.548 (1)
α, β, γ (°)	92.315 (2), 103.384 (4), 98.556 (3)
V (Å³)	735.91 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.627, 0.725
No. of measured, independent and observed [I > 2σ(I)] reflections	5180, 3301, 3116
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.106, 1.11
No. of reflections	3301
No. of parameters	238
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.72

Computer programs: RAPID-AUTO (Rigaku 2001), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.93	2.45	3.376 (3)	172.2
C4—H4···O3ⁱ	0.93	2.42	3.346 (3)	178.6
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···O8^iv	0.802 (18)	2.10 (2)	2.830 (4)	152 (4)
O1—H1WA···Cl1^iv	0.819 (18)	2.48 (2)	3.220 (2)	152 (3)

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

Acknowledgements

This work was supported financially by Beijing University of Chemical Technology.

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