catena-Poly[[(2,2′-bipyrimidine-κ2N1,N1′)diperchloratocopper(II)]-μ-4,4′-bipyridine-κ2N:N′]

Xu, W.; Lin, J.-L.; Xie, H.-Z.

doi:10.1107/S1600536808021296

metal-organic compounds

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Volume 64| Part 8| August 2008| Page m1031

doi:10.1107/S1600536808021296

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catena-Poly[[(2,2′-bipyrimidine-κ²N¹,N^1′)diperchloratocopper(II)]-μ-4,4′-bipyridine-κ²N:N′]

Wei Xu,^a ^* Jian-Li Lin ^a and Hong-Zhen Xie ^a

^aState Key Laboratory Base of Novel Functional Materials & Prepation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 19 June 2008; accepted 9 July 2008; online 16 July 2008)

The central CuN₄O₂ motif of the title compound, [Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]_n, exhibits a Jahn–Teller-distorted octahedral geometry around the metal centre, showing a considerably long Cu—O bond distance of 2.634 (4) Å towards the second perchlorate group occupying the sixth coordination site, giving a (4+1+1)-type coordination mode. The 4,4′-bipyridine (bipy) ligands are highly twisted with respect to each other, the dihedral angle between the two pyridyl ring planes being 38.9 (2)°. The bipy ligands act as bridging ligands between [Cu(ClO₄)₂(2,2′-bpym)] (2,2′-bpym is 2,2′-bipyrimidine) units, generating an infinite one-dimensional zigzag chain along [010]. Intra- and intermolecular C—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For related literature, see: Biradha & Fujita (2000 ); Eddaoudi et al. (2001 ); Hathaway (1973 ); Kaye & Long (2008 ); Kitagawa et al. (2006 ); Subramanian & Zaworotko (1995 ).

Experimental

Crystal data

[Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]
M_r = 576.75
Monoclinic, P 2₁ /n
a = 11.334 (2) Å
b = 14.266 (3) Å
c = 13.299 (3) Å
β = 96.55 (3)°
V = 2136.3 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 295 (2) K
0.32 × 0.26 × 0.15 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.664, T_max = 0.815
4265 measured reflections
3686 independent reflections
2896 reflections with I > 2σ(I)
R_int = 0.045
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.160
S = 1.06
3686 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O6ⁱ	0.93	2.59	3.415 (9)	147
C6—H6⋯O2ⁱⁱ	0.93	2.58	3.425 (7)	151
C7—H7⋯O3ⁱⁱⁱ	0.93	2.58	3.189 (7)	124
C9—H9⋯O3	0.93	2.56	3.480 (7)	171
C9—H9⋯O4	0.93	2.49	3.185 (6)	132
C11—H11⋯O2^iv	0.93	2.46	3.342 (6)	159
C16—H16⋯O4^v	0.93	2.57	3.299 (6)	135
C17—H17⋯O8^v	0.93	2.47	3.082 (6)	124
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021296/im2074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021296/im2074Isup2.hkl

checkCIF report

Comment top

A great deal of interest in self-assembly of coordination complexes with specific frameworks is expanding rapidly in view of their potentially useful magnetic, catalytic and nonlinear optical properties (Eddaoudi, et al., 2001; Kitagawa, et al., 2006; Kaye & Long, 2008). The ligand 4,4'-bipyridine is an ideal bridging ligand between transition metal atoms to establish coordination networks due to itss two potential binding sites that are arranged in a divergent (exo) fashion and its a rigid structure helping to predict network geometries (Subramanian & Zaworotko, 1995; Biradha & Fujita, 2000). 2,2'-bipyrimidine also is a versatile blocking and bridging ligand due to its N₂ chelating sites on both sides of the ligand. Herein, we report a new complex with one-dimensional zigzag chains, (I), obtained by self-assembly from Cu(ClO₄)₂, 4,4'-bpy and 2,2'-bpym in DMF solution. 2,2'-bpym acts as a bidentate ligand with the second chelating site not coodinating the metal atom.

In the title compound, the Cu atom is located in a Jahn-Teller distorted octahedral coordination environment with four N atoms from one 2,2'-bpym ligand (N1, N2) and two 4,4'-bpy ligands [N5, N6^#1 (#1 = 1/2 - x, 1/2 + y, 1/2 - z)] adopting a planar arrangement (d(Cu—N) = 1.998 (4)–2.008 (4) Å). The Cu(II) centre is displaced out of the N₄ plane by 0.062 (2) Å in the direction of one of perchlorate ligand with d(Cu—O8) = 2.421 (4) Å. The O atom of the second perchlorate group occupies a sixth coordination site at a longer distance of 2.634 (4) Å, completing the overall (4 + 1 + 1) type coordination. O4 is situated slightly off the axial direct of the square pyramid, nevertheless it is close enough to the Cu atom (Hathaway, 1973). The complex can thus be interpreted of consisting of [(2,2'-bpym)Cu(ClO₄)₂] units attached to each other via 4,4'-bpy to give a zigzag one-dimensional chain along [010] with the chelating 2,2'-bpym ligands extending outwards. The pyrimidine rings of the 2,2'-bpym ligand are twisted relative to each other at 8.7 (1)°, while the dihedral angel of the pyridine rings of the 4,4'-bpy ligand is 38.9 (2)°. Another interesting feature of the structure is that the backbone of the 2,2'-bpym ligand extends sideways from either face of the 4,4'-bpy ribbon and intimately interlocks the interchain region that separates adjacent 4,4'-bpy ribbons (Fig. 2). The perchlorate groups exhibit weak intramolecular hydrogen bonds between the O atoms and the C atoms of the 4,4'-bpy ligands with d(C···O) = 3.082 (6)–3.480 (7) Å and <(C—H···O) = 124–171° (Table 1.). In addition, intermolecular C—H···O hydrogen bonds between the C atoms of the 2,2'-bpym and 4,4'-bpy ligands and the O atoms of the perchlorate groups (d(C···O) = 3.189 (7)–3.425 (7) Å and <(C—H···O) = 124–159°) are observed that are responsible for the three-dimensional supramolecular assembly.

Related literature top

For related literature, see: Biradha & Fujita (2000); Eddaoudi et al. (2001); Hathaway (1973); Kaye & Long (2008); Kitagawa et al. (2006); Subramanian & Zaworotko (1995).

Experimental top

Addition of 0.372 g (1.0 mmol) Cu(ClO₄)₂, 0.158 g (1.0 mmol) 4,4'-bipyridine and 0.158 g (1.0 mmol) 2,2'-bipyrimidine to a stirred DMF solution (30 ml) yielde a purple precipitate, which was refluxed for 2 h at 403 K followed by filtration after cooling. The resulting light-green filtrate was maintained at room temperature, slow evaporation afforded a small amount of purple block crystals two weeks later.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound. The displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Schematic representation showing the interlocking of 2,2'-bpym rings of two strands resulting in an infinite one-dimensional sheet (perchlorates are omitted for clarity).

catena-Poly[[(2,2'-bipyrimidine- κ²N¹,N^1')diperchloratocopper(II)]- µ-4,4'-bipyridine-κ²N:N'] top

Crystal data top

[Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]	F(000) = 1164
M_r = 576.75	D_x = 1.793 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 11.334 (2) Å	θ = 5.0–12.5°
b = 14.266 (3) Å	µ = 1.34 mm⁻¹
c = 13.299 (3) Å	T = 295 K
β = 96.55 (3)°	Block, purple
V = 2136.3 (8) Å³	0.32 × 0.26 × 0.15 mm
Z = 4

Data collection top

Bruker P4 diffractometer	2896 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
θ/2θ scans	h = −13→1
Absorption correction: multi-scan (XSCANS; Siemens, 1996)	k = −1→16
T_min = 0.664, T_max = 0.815	l = −15→15
4265 measured reflections	3 standard reflections every 97 reflections
3686 independent reflections	intensity decay: none

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0889P)² + 4.3786P] where P = (F_o² + 2F_c²)/3
3686 reflections	(Δ/σ)_max = 0.001
317 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]	V = 2136.3 (8) Å³
M_r = 576.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.334 (2) Å	µ = 1.34 mm⁻¹
b = 14.266 (3) Å	T = 295 K
c = 13.299 (3) Å	0.32 × 0.26 × 0.15 mm
β = 96.55 (3)°

Data collection top

Bruker P4 diffractometer	2896 reflections with I > 2σ(I)
Absorption correction: multi-scan (XSCANS; Siemens, 1996)	R_int = 0.045
T_min = 0.664, T_max = 0.815	3 standard reflections every 97 reflections
4265 measured reflections	intensity decay: none
3686 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.06	Δρ_max = 0.93 e Å⁻³
3686 reflections	Δρ_min = −0.61 e Å⁻³
317 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.

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
Cu	0.59615 (4)	0.21166 (4)	0.34471 (4)	0.0296 (2)
Cl1	0.73943 (10)	0.14413 (9)	0.10813 (9)	0.0398 (3)
Cl2	0.62782 (13)	0.18070 (11)	0.60732 (10)	0.0534 (4)
N1	0.6774 (3)	0.0876 (3)	0.3709 (3)	0.0331 (8)
N2	0.7638 (3)	0.2575 (3)	0.3759 (3)	0.0299 (8)
N3	0.8653 (4)	0.0233 (3)	0.4312 (3)	0.0459 (11)
N4	0.9612 (3)	0.2015 (3)	0.4100 (4)	0.0460 (11)
N5	0.4387 (3)	0.1567 (3)	0.2901 (3)	0.0309 (8)
N6	−0.0235 (3)	−0.1609 (3)	0.1722 (3)	0.0307 (8)
C1	0.6283 (5)	0.0024 (3)	0.3741 (4)	0.0429 (12)
H1	0.5471	−0.0046	0.3557	0.051*
C2	0.6961 (6)	−0.0750 (4)	0.4043 (5)	0.0548 (15)
H2	0.6629	−0.1346	0.4050	0.066*
C3	0.8144 (5)	−0.0602 (4)	0.4332 (4)	0.0518 (14)
H3	0.8614	−0.1113	0.4553	0.062*
C4	0.7946 (4)	0.0938 (3)	0.3996 (3)	0.0328 (10)
C5	0.8442 (4)	0.1889 (3)	0.3958 (3)	0.0335 (10)
C6	0.9985 (4)	0.2895 (4)	0.4055 (5)	0.0528 (15)
H6	1.0798	0.3009	0.4147	0.063*
C7	0.9233 (5)	0.3644 (4)	0.3880 (5)	0.0562 (15)
H7	0.9516	0.4255	0.3858	0.067*
C8	0.8037 (4)	0.3446 (4)	0.3737 (4)	0.0399 (11)
H8	0.7496	0.3935	0.3623	0.048*
C9	0.4280 (4)	0.1042 (4)	0.2051 (4)	0.0386 (11)
H9	0.4910	0.1029	0.1661	0.046*
C10	0.3281 (4)	0.0526 (3)	0.1737 (4)	0.0378 (11)
H10	0.3243	0.0166	0.1151	0.045*
C11	0.3444 (4)	0.1639 (3)	0.3396 (4)	0.0336 (10)
H11	0.3486	0.2039	0.3951	0.040*
C12	0.2399 (4)	0.1153 (3)	0.3132 (4)	0.0326 (10)
H12	0.1756	0.1228	0.3501	0.039*
C13	0.2324 (4)	0.0551 (3)	0.2310 (3)	0.0295 (9)
C14	0.1326 (4)	−0.0117 (3)	0.2077 (4)	0.0316 (10)
C15	0.0802 (4)	−0.0526 (4)	0.2857 (4)	0.0383 (11)
H15	0.0956	−0.0296	0.3514	0.046*
C16	0.0050 (4)	−0.1276 (3)	0.2654 (4)	0.0378 (11)
H16	−0.0273	−0.1562	0.3188	0.045*
C17	0.0193 (4)	−0.1170 (3)	0.0946 (4)	0.0348 (10)
H17	−0.0041	−0.1368	0.0287	0.042*
C18	0.0976 (4)	−0.0428 (3)	0.1113 (3)	0.0335 (10)
H18	0.1269	−0.0137	0.0567	0.040*
O1	0.8332 (5)	0.1061 (6)	0.1735 (4)	0.114 (2)
O2	0.7807 (4)	0.1965 (3)	0.0279 (3)	0.0648 (12)
O3	0.6646 (5)	0.0702 (3)	0.0637 (4)	0.0770 (14)
O4	0.6684 (3)	0.2050 (3)	0.1635 (3)	0.0522 (10)
O5	0.5763 (7)	0.1934 (7)	0.6933 (5)	0.140 (3)
O6	0.6507 (6)	0.0798 (4)	0.6044 (5)	0.111 (2)
O7	0.7399 (5)	0.2209 (5)	0.6042 (5)	0.100 (2)
O8	0.5503 (4)	0.1986 (3)	0.5175 (3)	0.0596 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0195 (3)	0.0221 (3)	0.0458 (4)	0.00049 (19)	−0.0030 (2)	0.0002 (2)
Cl1	0.0354 (6)	0.0419 (7)	0.0432 (7)	0.0003 (5)	0.0089 (5)	0.0013 (5)
Cl2	0.0532 (8)	0.0679 (9)	0.0384 (7)	−0.0110 (7)	0.0023 (6)	0.0033 (6)
N1	0.034 (2)	0.0248 (19)	0.040 (2)	0.0037 (15)	0.0016 (16)	0.0017 (16)
N2	0.0261 (18)	0.0251 (19)	0.036 (2)	0.0020 (15)	−0.0055 (15)	0.0004 (15)
N3	0.044 (2)	0.043 (2)	0.051 (3)	0.020 (2)	0.007 (2)	0.011 (2)
N4	0.0232 (19)	0.051 (3)	0.061 (3)	0.0069 (18)	−0.0050 (18)	0.000 (2)
N5	0.0236 (17)	0.0280 (19)	0.041 (2)	−0.0027 (15)	0.0019 (15)	−0.0057 (16)
N6	0.0202 (16)	0.0299 (19)	0.041 (2)	−0.0021 (14)	−0.0016 (15)	−0.0023 (16)
C1	0.048 (3)	0.029 (2)	0.051 (3)	−0.003 (2)	0.006 (2)	0.001 (2)
C2	0.077 (4)	0.030 (3)	0.059 (4)	0.007 (3)	0.019 (3)	0.006 (2)
C3	0.069 (4)	0.035 (3)	0.055 (3)	0.023 (3)	0.022 (3)	0.012 (2)
C4	0.035 (2)	0.033 (2)	0.031 (2)	0.0108 (19)	0.0043 (18)	0.0046 (18)
C5	0.028 (2)	0.038 (3)	0.033 (2)	0.0066 (19)	−0.0029 (18)	−0.0033 (19)
C6	0.024 (2)	0.058 (4)	0.073 (4)	−0.005 (2)	−0.003 (2)	−0.008 (3)
C7	0.035 (3)	0.043 (3)	0.088 (5)	−0.008 (2)	−0.004 (3)	−0.004 (3)
C8	0.028 (2)	0.037 (3)	0.053 (3)	−0.001 (2)	−0.002 (2)	−0.003 (2)
C9	0.027 (2)	0.045 (3)	0.046 (3)	−0.008 (2)	0.011 (2)	−0.011 (2)
C10	0.030 (2)	0.039 (3)	0.045 (3)	−0.007 (2)	0.005 (2)	−0.007 (2)
C11	0.031 (2)	0.026 (2)	0.043 (3)	−0.0042 (18)	0.0029 (19)	−0.0080 (19)
C12	0.027 (2)	0.032 (2)	0.039 (2)	−0.0031 (18)	0.0076 (18)	−0.0071 (19)
C13	0.024 (2)	0.027 (2)	0.037 (2)	−0.0026 (17)	0.0000 (17)	−0.0003 (18)
C14	0.0207 (19)	0.029 (2)	0.045 (3)	−0.0007 (17)	0.0016 (18)	−0.0006 (19)
C15	0.031 (2)	0.042 (3)	0.042 (3)	−0.010 (2)	0.0049 (19)	−0.005 (2)
C16	0.033 (2)	0.041 (3)	0.040 (3)	−0.011 (2)	0.011 (2)	−0.002 (2)
C17	0.032 (2)	0.032 (2)	0.038 (3)	−0.0027 (19)	−0.0050 (19)	0.000 (2)
C18	0.034 (2)	0.033 (2)	0.032 (2)	−0.0057 (19)	−0.0001 (18)	0.0025 (19)
O1	0.077 (3)	0.183 (7)	0.078 (4)	0.063 (4)	−0.006 (3)	0.023 (4)
O2	0.071 (3)	0.064 (3)	0.065 (3)	−0.014 (2)	0.036 (2)	0.002 (2)
O3	0.089 (3)	0.047 (2)	0.099 (4)	−0.023 (2)	0.028 (3)	−0.021 (2)
O4	0.052 (2)	0.053 (2)	0.055 (2)	−0.0009 (18)	0.0210 (18)	−0.0097 (18)
O5	0.116 (5)	0.254 (10)	0.054 (3)	0.016 (6)	0.026 (3)	−0.011 (5)
O6	0.126 (5)	0.068 (4)	0.131 (5)	0.011 (3)	−0.023 (4)	0.034 (4)
O7	0.083 (4)	0.130 (5)	0.083 (4)	−0.041 (3)	−0.004 (3)	0.015 (3)
O8	0.056 (2)	0.078 (3)	0.044 (2)	0.021 (2)	0.0044 (18)	0.012 (2)

Geometric parameters (Å, º) top

Cu—N6ⁱ	1.998 (4)	C1—H1	0.9300
Cu—N1	2.007 (4)	C2—C3	1.369 (9)
Cu—N2	2.008 (4)	C2—H2	0.9300
Cu—N5	2.008 (4)	C3—H3	0.9300
Cu—O8	2.421 (4)	C4—C5	1.471 (7)
Cu—O4	2.634 (4)	C6—C7	1.370 (8)
Cl1—O1	1.403 (5)	C6—H6	0.9300
Cl1—O2	1.424 (4)	C7—C8	1.377 (7)
Cl1—O3	1.438 (4)	C7—H7	0.9300
Cl1—O4	1.442 (4)	C8—H8	0.9300
Cl2—O5	1.354 (6)	C9—C10	1.376 (6)
Cl2—O7	1.399 (6)	C9—H9	0.9300
Cl2—O8	1.422 (4)	C10—C13	1.395 (6)
Cl2—O6	1.464 (6)	C10—H10	0.9300
N1—C1	1.339 (6)	C11—C12	1.383 (6)
N1—C4	1.343 (6)	C11—H11	0.9300
N2—C8	1.323 (6)	C12—C13	1.385 (6)
N2—C5	1.343 (6)	C12—H12	0.9300
N3—C4	1.325 (6)	C13—C14	1.484 (6)
N3—C3	1.325 (7)	C14—C18	1.372 (6)
N4—C6	1.329 (7)	C14—C15	1.382 (7)
N4—C5	1.331 (6)	C15—C16	1.376 (7)
N5—C11	1.321 (6)	C15—H15	0.9300
N5—C9	1.350 (6)	C16—H16	0.9300
N6—C16	1.332 (6)	C17—C18	1.383 (6)
N6—C17	1.344 (6)	C17—H17	0.9300
N6—Cuⁱⁱ	1.998 (4)	C18—H18	0.9300
C1—C2	1.379 (7)

N6ⁱ—Cu—N1	175.53 (15)	C2—C3—H3	118.4
N6ⁱ—Cu—N2	95.45 (14)	N3—C4—N1	125.7 (4)
N1—Cu—N2	81.19 (15)	N3—C4—C5	119.4 (4)
N6ⁱ—Cu—N5	88.66 (15)	N1—C4—C5	114.9 (4)
N1—Cu—N5	95.15 (15)	N4—C5—N2	124.9 (5)
N2—Cu—N5	169.48 (15)	N4—C5—C4	119.9 (4)
N6ⁱ—Cu—O8	92.65 (15)	N2—C5—C4	115.2 (4)
N1—Cu—O8	84.89 (15)	N4—C6—C7	123.4 (5)
N2—Cu—O8	97.45 (15)	N4—C6—H6	118.3
N5—Cu—O8	92.00 (15)	C7—C6—H6	118.3
N6ⁱ—Cu—O4	95.57 (14)	C6—C7—C8	116.6 (5)
N1—Cu—O4	86.74 (14)	C6—C7—H7	121.7
N2—Cu—O4	79.35 (14)	C8—C7—H7	121.7
N5—Cu—O4	90.64 (14)	N2—C8—C7	121.5 (5)
O8—Cu—O4	171.41 (13)	N2—C8—H8	119.2
O1—Cl1—O2	112.1 (4)	C7—C8—H8	119.2
O1—Cl1—O3	109.9 (4)	N5—C9—C10	122.9 (4)
O2—Cl1—O3	107.8 (3)	N5—C9—H9	118.5
O1—Cl1—O4	110.2 (3)	C10—C9—H9	118.5
O2—Cl1—O4	108.5 (3)	C9—C10—C13	119.0 (4)
O3—Cl1—O4	108.3 (3)	C9—C10—H10	120.5
O5—Cl2—O7	116.8 (5)	C13—C10—H10	120.5
O5—Cl2—O8	113.6 (4)	N5—C11—C12	123.5 (4)
O7—Cl2—O8	112.2 (3)	N5—C11—H11	118.2
O5—Cl2—O6	104.4 (5)	C12—C11—H11	118.2
O7—Cl2—O6	103.8 (4)	C11—C12—C13	119.0 (4)
O8—Cl2—O6	104.4 (3)	C11—C12—H12	120.5
C1—N1—C4	116.9 (4)	C13—C12—H12	120.5
C1—N1—Cu	128.4 (3)	C12—C13—C10	117.7 (4)
C4—N1—Cu	114.2 (3)	C12—C13—C14	122.6 (4)
C8—N2—C5	117.6 (4)	C10—C13—C14	119.4 (4)
C8—N2—Cu	128.2 (3)	C18—C14—C15	117.5 (4)
C5—N2—Cu	114.1 (3)	C18—C14—C13	122.3 (4)
C4—N3—C3	116.1 (5)	C15—C14—C13	119.8 (4)
C6—N4—C5	116.0 (4)	C16—C15—C14	119.3 (5)
C11—N5—C9	117.4 (4)	C16—C15—H15	120.3
C11—N5—Cu	121.7 (3)	C14—C15—H15	120.3
C9—N5—Cu	120.7 (3)	N6—C16—C15	122.6 (4)
C16—N6—C17	118.6 (4)	N6—C16—H16	118.7
C16—N6—Cuⁱⁱ	118.8 (3)	C15—C16—H16	118.7
C17—N6—Cuⁱⁱ	121.2 (3)	N6—C17—C18	121.0 (4)
N1—C1—C2	121.1 (5)	N6—C17—H17	119.5
N1—C1—H1	119.5	C18—C17—H17	119.5
C2—C1—H1	119.5	C14—C18—C17	120.6 (4)
C3—C2—C1	117.0 (5)	C14—C18—H18	119.7
C3—C2—H2	121.5	C17—C18—H18	119.7
C1—C2—H2	121.5	Cl1—O4—Cu	137.6 (2)
N3—C3—C2	123.2 (5)	Cl2—O8—Cu	129.2 (2)
N3—C3—H3	118.4

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O6ⁱⁱⁱ	0.93	2.59	3.415 (9)	147
C6—H6···O2^iv	0.93	2.58	3.425 (7)	151
C7—H7···O3^v	0.93	2.58	3.189 (7)	124
C9—H9···O3	0.93	2.56	3.480 (7)	171
C9—H9···O4	0.93	2.49	3.185 (6)	132
C11—H11···O2^vi	0.93	2.46	3.342 (6)	159
C16—H16···O4ⁱⁱ	0.93	2.57	3.299 (6)	135
C17—H17···O8ⁱⁱ	0.93	2.47	3.082 (6)	124

Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]
M_r	576.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	11.334 (2), 14.266 (3), 13.299 (3)
β (°)	96.55 (3)
V (Å³)	2136.3 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.32 × 0.26 × 0.15

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (XSCANS; Siemens, 1996)
T_min, T_max	0.664, 0.815
No. of measured, independent and observed [I > 2σ(I)] reflections	4265, 3686, 2896
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.160, 1.06
No. of reflections	3686
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.61

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O6ⁱ	0.93	2.59	3.415 (9)	147
C6—H6···O2ⁱⁱ	0.93	2.58	3.425 (7)	151
C7—H7···O3ⁱⁱⁱ	0.93	2.58	3.189 (7)	124
C9—H9···O3	0.93	2.56	3.480 (7)	171
C9—H9···O4	0.93	2.49	3.185 (6)	132
C11—H11···O2^iv	0.93	2.46	3.342 (6)	159
C16—H16···O4^v	0.93	2.57	3.299 (6)	135
C17—H17···O8^v	0.93	2.47	3.082 (6)	124

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University, the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061) and the Newer Training Program Foundation for Talents of the Science and Technology Department of Zhejiang Province (grant No. 2007R40G2070020).

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