Tetra­kis(2,2′-bipyrid­yl)dichlorido­di-μ3-hydroxido-di-μ2-hydroxido-tetra­copper(II) dinitrate hexa­hydrate

Fan, Y.; Cui, Y.-T.; Qian, H.-F.; Liu, J.-L.; Huang, W.

doi:10.1107/S160053680804381X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m131-m132

doi:10.1107/S160053680804381X

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Tetrakis(2,2′-bipyridyl)dichloridodi-μ₃-hydroxido-di-μ₂-hydroxido-tetracopper(II) dinitrate hexahydrate

Ying Fan,^a Yong-Tao Cui,^a Hui-Fen Qian,^a ^* Jian-Lan Liu ^a and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing, 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn,

(Received 11 December 2008; accepted 24 December 2008; online 8 January 2009)

The tetranuclear copper(II) title complex, [Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O, has a crystallographically imposed centre of symmetry. The metal atoms display a distorted tetragonal-pyramidal coordination geometry, and are linked by two μ₂- and two μ₃-hydroxo groups, assuming a chair-like conformation for the Cu₄O₂ core. In the crystal, the complex molecules are linked into a three-dimensional network by intermolecular O—H⋯O, O—H⋯Cl, C—H⋯O and C—H⋯Cl hydrogen bonds and π–π stacking interactions with centroid–centroid separations of 3.724 (2) and 3.767 (3) Å.

Related literature

For the structures of related complexes, see: Albada et al. (2002 ); Chandrasekhar et al. (2000 ); Lu et al. (2007 ); Sletten et al. (1990 ); Zheng & Lin (2002 ).

Experimental

Crystal data

[Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O
M_r = 1249.94
Triclinic, $[P \overline 1]$
a = 9.389 (3) Å
b = 10.622 (3) Å
c = 12.950 (4) Å
α = 86.909 (4)°
β = 77.263 (3)°
γ = 72.512 (4)°
V = 1201.4 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.94 mm⁻¹
T = 291 (2) K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.747, T_max = 0.830
6088 measured reflections
4181 independent reflections
3156 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.153
S = 1.08
4181 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O2	1.927 (3)
Cu1—O1	1.980 (3)
Cu1—N1	2.016 (4)
Cu1—N2	2.029 (4)
Cu1—Cl1	2.5942 (17)
Cu2—O2	1.924 (3)
Cu2—O1	1.959 (3)
Cu2—N4	1.989 (4)
Cu2—N3	2.012 (4)
Cu2—O1ⁱ	2.323 (3)
Symmetry code: (i) -x+1, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4	0.85	2.02	2.835 (7)	160
O2—H2A⋯O6	0.85	2.28	2.874 (6)	127
O7—H7A⋯O8ⁱⁱ	0.85	2.17	2.714 (9)	121
O8—H8A⋯Cl1	0.85	2.39	3.187 (7)	157
C2—H2⋯Cl1ⁱⁱⁱ	0.93	2.82	3.692 (5)	156
C5—H5⋯O4	0.93	2.55	3.394 (7)	152
C10—H10⋯O6	0.93	2.46	3.318 (7)	154
C12—H12⋯Cl1^iv	0.93	2.78	3.679 (5)	162
C15—H15⋯O4	0.93	2.58	3.185 (8)	123
Symmetry codes: (ii) x+1, y, z; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680804381X/rz2280sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680804381X/rz2280Isup2.hkl

checkCIF report

Comment top

Recently, some tetranuclear hydroxo-bridged copper(II) complexes with cubane and the chair-like structure have been reported (Zheng & Lin, 2002; Sletten et al., 1990; Albada et al., 2002; Lu et al., 2007; Chandrasekhar et al., 2000). In this paper, the crystal structure of a new copper(II) complex exhibiting a chair-like tetranuclear motif is presented.

The atom-numbering scheme of the title compound is shown in Fig. 1, while selected bond distances are given in Table 1. The title complex has a crystallographically imposed centre of symmetry, and consists of a chair-like [Cu₄(bpy)₄(µ₂-OH)₂(µ₃-OH)₂Cl₂]²⁺ dication (bpy = 2,2'-bipyridine), two nitrate anions, and six lattice water molecules. The coordination geometry around each copper(II) ion can be described as a five-coordinate distorted pyramid. The basal sites are occupied by two N atoms from a bpy ligand and two O atoms from two µ₂-bridging hydroxo groups, with mean Cu–N and Cu–O bond distances of 2.011 (4) 1.948 (3) Å, respectively; the apical position is occupied by a chloride anion for atom Cu1 (Cu1–Cl1 = 2.594 (2) Å) and a µ₃-bridged OH anion for Cu2 (Cu2–O1ⁱ = 2.323 (3) Å; symmetry code: (i) = 1-x, 1-y, -z).

In the crystal packing, the complex molecules are linked into a three-dimensional network by intra- and intermolecular O—H···O, O—H···Cl, C—H···O and C—H···Cl hydrogen bonding interactions involving the solvent water molecules, the hydroxo groups and the chloride and nitrate anions (Table 2). The structure is further stabilized by π–π stacking interactions between adjacent bpy molecules with centroid-to-centroid separations of 3.724 (2) and 3.767 (3) Å (Fig. 2).

Related literature top

For the structures of related complexes, see: Albada et al. (2002); Chandrasekhar et al. (2000); Lu et al. (2007); Sletten et al. (1990); Zheng et al. (2002).

Experimental top

The title compound was obtained as a by-product from the reaction between [Cu(bpy)](NO₃)₂ (0.398 g, 1 mmol) and D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine dihydrogenchloride salt (0.284 g, 2 mmol) in the presence of NaOH (0.080 g, 2 mmol). Yield: 35 % based on the copper(II) amount. Single crystals suitable for X-ray diffraction were grown from a mixture of methanol/water (1:1 v/v) by slow evaporation in air at room temperature. Elemental Analysis: Calcd. for C₄₀H₄₈Cl₂Cu₄N₁₀O₁₆: C, 38.44; H, 3.87; N, 11.21 %; found: C,38.66; H,3.67; N, 11.03 %. Main FT-IR absorptions (KBr pellets, cm^-1): 3427 (vs), 2372 (m), 2341 (m), 1634 (s), 1383 (m), 1080 (s), 991 (m), 773 (m), and 549 (m).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabeled atoms are related to the labeled atoms by (1-x, 1-y, -z).
	Fig. 2. Perspective view of the crystal packing the title compound showing the the hydrogen bonds and π–π stacking interactions as dashed lines.

Tetrakis(2,2'-bipyridyl)dichloridodi-µ₃-hydroxido-di-µ₂-hydroxido- tetracopper(II) dinitrate hexahydrate top

Crystal data top

[Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O	Z = 1
M_r = 1249.94	F(000) = 636
Triclinic, P1	D_x = 1.728 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.389 (3) Å	Cell parameters from 2700 reflections
b = 10.622 (3) Å	θ = 2.3–27.2°
c = 12.950 (4) Å	µ = 1.94 mm⁻¹
α = 86.909 (4)°	T = 291 K
β = 77.263 (3)°	Block, blue
γ = 72.512 (4)°	0.16 × 0.12 × 0.10 mm
V = 1201.4 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4181 independent reflections
Radiation source: fine-focus sealed tube	3156 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→11
T_min = 0.747, T_max = 0.830	k = −12→12
6088 measured reflections	l = −15→13

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0958P)²] where P = (F_o² + 2F_c²)/3
4181 reflections	(Δ/σ)_max < 0.001
319 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

[Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O	γ = 72.512 (4)°
M_r = 1249.94	V = 1201.4 (6) Å³
Triclinic, P1	Z = 1
a = 9.389 (3) Å	Mo Kα radiation
b = 10.622 (3) Å	µ = 1.94 mm⁻¹
c = 12.950 (4) Å	T = 291 K
α = 86.909 (4)°	0.16 × 0.12 × 0.10 mm
β = 77.263 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4181 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3156 reflections with I > 2σ(I)
T_min = 0.747, T_max = 0.830	R_int = 0.025
6088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.08	Δρ_max = 0.94 e Å⁻³
4181 reflections	Δρ_min = −1.04 e Å⁻³
319 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.46249 (6)	0.44695 (6)	0.22215 (4)	0.03567 (19)
Cu2	0.36457 (6)	0.43378 (5)	0.02528 (4)	0.03328 (18)
C1	0.6144 (5)	0.5218 (5)	0.3666 (3)	0.0348 (10)
C2	0.6642 (6)	0.5990 (6)	0.4245 (4)	0.0490 (13)
H2	0.7294	0.5603	0.4696	0.059*
C3	0.6160 (7)	0.7337 (6)	0.4146 (4)	0.0528 (14)
H3	0.6491	0.7872	0.4526	0.063*
C4	0.5183 (6)	0.7893 (6)	0.3479 (4)	0.0509 (13)
H4	0.4827	0.8804	0.3414	0.061*
C5	0.4755 (6)	0.7075 (5)	0.2917 (4)	0.0453 (12)
H5	0.4116	0.7447	0.2455	0.054*
C6	0.6549 (5)	0.3764 (5)	0.3726 (3)	0.0366 (11)
C7	0.7526 (6)	0.3022 (6)	0.4334 (4)	0.0507 (13)
H7	0.7974	0.3424	0.4740	0.061*
C8	0.7825 (7)	0.1664 (6)	0.4324 (5)	0.0602 (15)
H8	0.8485	0.1143	0.4725	0.072*
C9	0.7158 (7)	0.1094 (6)	0.3732 (4)	0.0547 (14)
H9	0.7348	0.0183	0.3724	0.066*
C10	0.6195 (6)	0.1888 (5)	0.3144 (4)	0.0458 (12)
H10	0.5734	0.1500	0.2737	0.055*
C11	0.1473 (5)	0.5060 (5)	−0.1073 (4)	0.0372 (11)
C12	0.0421 (6)	0.5816 (6)	−0.1627 (4)	0.0481 (13)
H12	−0.0076	0.5418	−0.1997	0.058*
C13	0.0117 (6)	0.7171 (6)	−0.1622 (4)	0.0537 (14)
H13	−0.0596	0.7695	−0.1985	0.064*
C14	0.0865 (6)	0.7741 (6)	−0.1082 (4)	0.0499 (13)
H14	0.0670	0.8653	−0.1072	0.060*
C15	0.1916 (6)	0.6937 (5)	−0.0553 (4)	0.0432 (12)
H15	0.2442	0.7321	−0.0198	0.052*
C16	0.1902 (5)	0.3603 (5)	−0.1028 (3)	0.0350 (10)
C17	0.1309 (6)	0.2829 (6)	−0.1531 (4)	0.0474 (13)
H17	0.0568	0.3218	−0.1918	0.057*
C18	0.1819 (6)	0.1486 (6)	−0.1455 (4)	0.0518 (14)
H18	0.1422	0.0953	−0.1785	0.062*
C19	0.2941 (6)	0.0924 (5)	−0.0878 (4)	0.0507 (13)
H19	0.3314	0.0012	−0.0824	0.061*
C20	0.3483 (6)	0.1740 (5)	−0.0393 (4)	0.0448 (12)
H20	0.4228	0.1365	−0.0007	0.054*
Cl1	0.18510 (17)	0.49867 (15)	0.33336 (11)	0.059
N1	0.5207 (4)	0.5767 (4)	0.3000 (3)	0.0360 (9)
N2	0.5897 (4)	0.3206 (4)	0.3135 (3)	0.0372 (9)
N3	0.2209 (4)	0.5615 (4)	−0.0532 (3)	0.0351 (9)
N4	0.2985 (4)	0.3057 (4)	−0.0451 (3)	0.0362 (9)
N5	0.1809 (5)	0.8933 (4)	0.1658 (4)	0.0347 (10)
O1	0.4182 (4)	0.5621 (3)	0.1006 (2)	0.0344 (7)
H1A	0.3305	0.6140	0.1271	0.052*
O2	0.4539 (4)	0.3165 (3)	0.1278 (2)	0.0408 (8)
H2A	0.4821	0.2327	0.1302	0.061*
O3	0.0821 (8)	0.9740 (6)	0.2427 (6)	0.130 (2)
O4	0.1649 (6)	0.7823 (6)	0.1809 (5)	0.1076 (18)
O5	0.2665 (11)	0.9185 (7)	0.1204 (6)	0.140 (3)
O6	0.3529 (6)	0.1021 (5)	0.2300 (4)	0.0985 (17)
H6A	0.3847	0.0186	0.2223	0.148*
H6B	0.2923	0.1204	0.1876	0.148*
O7	0.8224 (8)	0.7897 (8)	0.5938 (5)	0.156 (3)
H7A	0.8445	0.7449	0.5370	0.235*
H7B	0.7521	0.7659	0.6357	0.235*
O8	−0.0164 (7)	0.7957 (7)	0.3929 (5)	0.124 (2)
H8A	0.0125	0.7120	0.3871	0.185*
H8B	0.0606	0.8244	0.3741	0.185*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0413 (4)	0.0418 (4)	0.0281 (3)	−0.0113 (3)	−0.0174 (2)	0.0003 (2)
Cu2	0.0359 (3)	0.0396 (3)	0.0297 (3)	−0.0123 (3)	−0.0165 (2)	0.0008 (2)
C1	0.033 (2)	0.051 (3)	0.026 (2)	−0.017 (2)	−0.0108 (18)	0.001 (2)
C2	0.053 (3)	0.068 (4)	0.036 (3)	−0.023 (3)	−0.023 (2)	0.002 (2)
C3	0.066 (4)	0.063 (4)	0.044 (3)	−0.032 (3)	−0.022 (3)	−0.002 (3)
C4	0.060 (3)	0.049 (3)	0.048 (3)	−0.019 (3)	−0.015 (3)	0.000 (2)
C5	0.045 (3)	0.050 (3)	0.043 (3)	−0.009 (2)	−0.020 (2)	−0.002 (2)
C6	0.032 (2)	0.048 (3)	0.028 (2)	−0.006 (2)	−0.0087 (19)	0.000 (2)
C7	0.051 (3)	0.061 (4)	0.046 (3)	−0.014 (3)	−0.028 (3)	0.004 (3)
C8	0.054 (4)	0.067 (4)	0.056 (4)	−0.003 (3)	−0.030 (3)	0.014 (3)
C9	0.062 (4)	0.047 (3)	0.053 (3)	−0.007 (3)	−0.022 (3)	0.007 (3)
C10	0.051 (3)	0.044 (3)	0.040 (3)	−0.006 (2)	−0.015 (2)	−0.007 (2)
C11	0.028 (2)	0.051 (3)	0.031 (2)	−0.009 (2)	−0.0067 (19)	0.000 (2)
C12	0.036 (3)	0.071 (4)	0.041 (3)	−0.016 (3)	−0.019 (2)	0.005 (3)
C13	0.040 (3)	0.062 (4)	0.053 (3)	0.000 (3)	−0.020 (2)	0.014 (3)
C14	0.049 (3)	0.047 (3)	0.052 (3)	−0.008 (3)	−0.017 (2)	0.009 (2)
C15	0.046 (3)	0.045 (3)	0.036 (3)	−0.009 (2)	−0.011 (2)	0.002 (2)
C16	0.029 (2)	0.049 (3)	0.029 (2)	−0.015 (2)	−0.0062 (18)	0.000 (2)
C17	0.044 (3)	0.065 (4)	0.042 (3)	−0.023 (3)	−0.015 (2)	−0.006 (3)
C18	0.053 (3)	0.061 (4)	0.053 (3)	−0.028 (3)	−0.016 (3)	−0.010 (3)
C19	0.062 (4)	0.043 (3)	0.052 (3)	−0.019 (3)	−0.016 (3)	−0.003 (2)
C20	0.044 (3)	0.046 (3)	0.044 (3)	−0.008 (2)	−0.015 (2)	−0.001 (2)
Cl1	0.059	0.067	0.055	−0.021	−0.019	−0.008
N1	0.039 (2)	0.041 (2)	0.031 (2)	−0.0119 (18)	−0.0130 (16)	0.0004 (17)
N2	0.036 (2)	0.046 (2)	0.029 (2)	−0.0080 (18)	−0.0118 (16)	−0.0009 (17)
N3	0.030 (2)	0.045 (2)	0.032 (2)	−0.0100 (18)	−0.0110 (16)	−0.0012 (17)
N4	0.037 (2)	0.042 (2)	0.033 (2)	−0.0127 (18)	−0.0127 (17)	0.0019 (17)
N5	0.029 (2)	0.0156 (19)	0.066 (3)	−0.0057 (17)	−0.026 (2)	0.0040 (19)
O1	0.0386 (18)	0.0388 (18)	0.0292 (16)	−0.0108 (14)	−0.0145 (13)	−0.0016 (13)
O2	0.053 (2)	0.0387 (19)	0.0348 (18)	−0.0112 (16)	−0.0226 (15)	0.0014 (14)
O3	0.139 (6)	0.086 (4)	0.152 (6)	−0.031 (4)	−0.007 (5)	−0.010 (4)
O4	0.085 (4)	0.118 (5)	0.110 (5)	−0.015 (3)	−0.019 (3)	−0.019 (4)
O5	0.184 (8)	0.117 (6)	0.110 (6)	−0.033 (6)	−0.031 (5)	0.004 (4)
O6	0.088 (4)	0.093 (4)	0.132 (5)	−0.043 (3)	−0.046 (3)	0.039 (3)
O7	0.159 (6)	0.232 (9)	0.119 (5)	−0.129 (6)	−0.004 (5)	−0.040 (5)
O8	0.112 (5)	0.149 (6)	0.101 (5)	−0.018 (4)	−0.031 (4)	−0.008 (4)

Geometric parameters (Å, º) top

Cu1—O2	1.927 (3)	C11—C12	1.382 (7)
Cu1—O1	1.980 (3)	C11—C16	1.479 (7)
Cu1—N1	2.016 (4)	C12—C13	1.381 (8)
Cu1—N2	2.029 (4)	C12—H12	0.9300
Cu1—Cl1	2.5942 (17)	C13—C14	1.366 (8)
Cu2—O2	1.924 (3)	C13—H13	0.9300
Cu2—O1	1.959 (3)	C14—C15	1.379 (7)
Cu2—N4	1.989 (4)	C14—H14	0.9300
Cu2—N3	2.012 (4)	C15—N3	1.347 (6)
Cu2—O1ⁱ	2.323 (3)	C15—H15	0.9300
C1—N1	1.352 (5)	C16—N4	1.364 (6)
C1—C2	1.380 (6)	C16—C17	1.380 (6)
C1—C6	1.478 (7)	C17—C18	1.367 (8)
C2—C3	1.373 (8)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.396 (7)
C3—C4	1.381 (7)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.367 (7)
C4—C5	1.361 (7)	C19—H19	0.9300
C4—H4	0.9300	C20—N4	1.338 (6)
C5—N1	1.331 (6)	C20—H20	0.9300
C5—H5	0.9300	N5—O5	0.983 (8)
C6—N2	1.336 (6)	N5—O4	1.233 (7)
C6—C7	1.378 (7)	N5—O3	1.339 (7)
C7—C8	1.384 (8)	O1—Cu2ⁱ	2.323 (3)
C7—H7	0.9300	O1—H1A	0.8500
C8—C9	1.357 (8)	O2—H2A	0.8501
C8—H8	0.9300	O6—H6A	0.8501
C9—C10	1.373 (7)	O6—H6B	0.8498
C9—H9	0.9300	O7—H7A	0.8499
C10—N2	1.342 (6)	O7—H7B	0.8501
C10—H10	0.9300	O8—H8A	0.8499
C11—N3	1.349 (6)	O8—H8B	0.8500

O2—Cu1—O1	81.23 (13)	C13—C12—H12	120.5
O2—Cu1—N1	166.66 (15)	C11—C12—H12	120.5
O1—Cu1—N1	96.22 (14)	C14—C13—C12	119.9 (5)
O2—Cu1—N2	97.19 (15)	C14—C13—H13	120.1
O1—Cu1—N2	157.97 (15)	C12—C13—H13	120.1
N1—Cu1—N2	80.23 (15)	C13—C14—C15	118.6 (5)
O2—Cu1—Cl1	98.14 (11)	C13—C14—H14	120.7
O1—Cu1—Cl1	98.03 (10)	C15—C14—H14	120.7
N1—Cu1—Cl1	95.17 (12)	N3—C15—C14	122.5 (5)
N2—Cu1—Cl1	103.92 (11)	N3—C15—H15	118.8
O2—Cu2—O1	81.86 (13)	C14—C15—H15	118.8
O2—Cu2—N4	97.99 (15)	N4—C16—C17	121.4 (5)
O1—Cu2—N4	176.65 (14)	N4—C16—C11	114.1 (4)
O2—Cu2—N3	165.08 (15)	C17—C16—C11	124.5 (4)
O1—Cu2—N3	98.37 (14)	C18—C17—C16	119.4 (5)
N4—Cu2—N3	80.91 (15)	C18—C17—H17	120.3
O2—Cu2—O1ⁱ	100.99 (13)	C16—C17—H17	120.3
O1—Cu2—O1ⁱ	83.97 (12)	C17—C18—C19	119.3 (5)
N4—Cu2—O1ⁱ	99.33 (13)	C17—C18—H18	120.3
N3—Cu2—O1ⁱ	93.86 (13)	C19—C18—H18	120.3
N1—C1—C2	121.1 (5)	C20—C19—C18	118.6 (5)
N1—C1—C6	114.9 (4)	C20—C19—H19	120.7
C2—C1—C6	124.0 (4)	C18—C19—H19	120.7
C3—C2—C1	119.0 (5)	N4—C20—C19	122.8 (5)
C3—C2—H2	120.5	N4—C20—H20	118.6
C1—C2—H2	120.5	C19—C20—H20	118.6
C2—C3—C4	119.6 (5)	C5—N1—C1	118.9 (4)
C2—C3—H3	120.2	C5—N1—Cu1	126.2 (3)
C4—C3—H3	120.2	C1—N1—Cu1	114.9 (3)
C5—C4—C3	118.4 (5)	C6—N2—C10	118.9 (4)
C5—C4—H4	120.8	C6—N2—Cu1	115.1 (3)
C3—C4—H4	120.8	C10—N2—Cu1	125.9 (3)
N1—C5—C4	123.0 (5)	C15—N3—C11	118.5 (4)
N1—C5—H5	118.5	C15—N3—Cu2	126.6 (3)
C4—C5—H5	118.5	C11—N3—Cu2	114.9 (3)
N2—C6—C7	121.8 (5)	C20—N4—C16	118.4 (4)
N2—C6—C1	114.7 (4)	C20—N4—Cu2	126.2 (3)
C7—C6—C1	123.5 (4)	C16—N4—Cu2	115.4 (3)
C6—C7—C8	118.4 (5)	O5—N5—O4	128.5 (7)
C6—C7—H7	120.8	O5—N5—O3	121.4 (6)
C8—C7—H7	120.8	O4—N5—O3	108.1 (5)
C9—C8—C7	120.1 (5)	Cu2—O1—Cu1	95.59 (13)
C9—C8—H8	119.9	Cu2—O1—Cu2ⁱ	96.03 (12)
C7—C8—H8	119.9	Cu1—O1—Cu2ⁱ	113.66 (14)
C8—C9—C10	118.7 (5)	Cu2—O1—H1A	101.5
C8—C9—H9	120.7	Cu1—O1—H1A	101.5
C10—C9—H9	120.7	Cu2ⁱ—O1—H1A	138.7
N2—C10—C9	122.2 (5)	Cu2—O2—Cu1	98.51 (15)
N2—C10—H10	118.9	Cu2—O2—H2A	130.7
C9—C10—H10	118.9	Cu1—O2—H2A	130.8
N3—C11—C12	121.5 (5)	H6A—O6—H6B	99.3
N3—C11—C16	114.6 (4)	H7A—O7—H7B	106.7
C12—C11—C16	123.9 (4)	H8A—O8—H8B	109.5
C13—C12—C11	119.0 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.85	2.02	2.835 (7)	160
O2—H2A···O6	0.85	2.28	2.874 (6)	127
O7—H7A···O8ⁱⁱ	0.85	2.17	2.714 (9)	121
O8—H8A···Cl1	0.85	2.39	3.187 (7)	157
C2—H2···Cl1ⁱⁱⁱ	0.93	2.82	3.692 (5)	156
C5—H5···O4	0.93	2.55	3.394 (7)	152
C10—H10···O6	0.93	2.46	3.318 (7)	154
C12—H12···Cl1^iv	0.93	2.78	3.679 (5)	162
C15—H15···O4	0.93	2.58	3.185 (8)	123

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

Experimental details

Crystal data
Chemical formula	[Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O
M_r	1249.94
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.389 (3), 10.622 (3), 12.950 (4)
α, β, γ (°)	86.909 (4), 77.263 (3), 72.512 (4)
V (Å³)	1201.4 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.94
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.747, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	6088, 4181, 3156
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.153, 1.08
No. of reflections	4181
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −1.04

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O2	1.927 (3)	Cu2—O2	1.924 (3)
Cu1—O1	1.980 (3)	Cu2—O1	1.959 (3)
Cu1—N1	2.016 (4)	Cu2—N4	1.989 (4)
Cu1—N2	2.029 (4)	Cu2—N3	2.012 (4)
Cu1—Cl1	2.5942 (17)	Cu2—O1ⁱ	2.323 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.85	2.02	2.835 (7)	160.0
O2—H2A···O6	0.85	2.28	2.874 (6)	127.2
O7—H7A···O8ⁱⁱ	0.85	2.17	2.714 (9)	121.4
O8—H8A···Cl1	0.85	2.39	3.187 (7)	156.5
C2—H2···Cl1ⁱⁱⁱ	0.93	2.82	3.692 (5)	155.8
C5—H5···O4	0.93	2.55	3.394 (7)	151.7
C10—H10···O6	0.93	2.46	3.318 (7)	153.6
C12—H12···Cl1^iv	0.93	2.78	3.679 (5)	162.3
C15—H15···O4	0.93	2.58	3.185 (8)	123.2

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

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20871065) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for financial aid.

References

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