catena-Poly[[(2,2′-bipyidine-2κ2N,N′)-μ-cyanido-1:2κ2N:C-dicopper(I)]-μ-bromido-[(2,2′-bipyidine-2κ2N,N′)-μ-cyanido-1:2κ2N:C-dicopper(I)]-μ-cyanido-κ2N:C]

Gu, J.; Jiang, X.; Su, Z.; Zhou, B.

doi:10.1107/S1600536812018120

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m693

doi:10.1107/S1600536812018120

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catena-Poly[[(2,2′-bipyidine-2κ²N,N′)-μ-cyanido-1:2κ²N:C-dicopper(I)]-μ-bromido-[(2,2′-bipyidine-2κ²N,N′)-μ-cyanido-1:2κ²N:C-dicopper(I)]-μ-cyanido-κ²N:C]

Jia Gu,^a Xuee Jiang,^a ^* Zhanhua Su ^a and Baibin Zhou ^a

^aColleges of Chemistry & Chemical Engineering, Harbin Normal University, Harbin 150025, People's Republic of China
^*Correspondence e-mail: jxuee@yahoo.com

(Received 3 April 2012; accepted 23 April 2012; online 28 April 2012)

In the title complex, [Cu₄Br(CN)₃(C₁₀H₈N₂)₂]_n, the four independent Cu^I atoms are all in distorted trigonal-planar geometries. One is formed by one N atom and one C atom from two cyanide groups and one Br atom, one is formed by two N atoms from two cyanide groups and one Br atom, and the other two are formed by two N atoms from a chelating 2,2′-bipyridine (bpy) ligand and one C atom from a cyanide group. The structure exhibits a zigzag chain backbone along [101] constructed by bromide and cyanide anions bridging the Cu^I atoms, with the [Cu(bpy)(CN)] units pointing laterally.

Related literature

For copper cyanide coordination polymers, see: Korzeniak et al. (2005 ); Yi et al. (2004 ). For structures containing cyanide groups, see: Zhang et al. (2000 ). For related copper complexes, see: He et al. (2006 ).

Experimental

Crystal data

[Cu₄Br(CN)₃(C₁₀H₈N₂)₂]
M_r = 724.53
Monoclinic, P 2₁ /n
a = 10.0074 (10) Å
b = 17.7556 (17) Å
c = 14.5125 (14) Å
β = 102.924 (1)°
V = 2513.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.96 mm⁻¹
T = 273 K
0.24 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.383, T_max = 0.409
23142 measured reflections
6171 independent reflections
3491 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.084
S = 1.00
6171 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.025 (3)
Cu1—N2	2.029 (3)
Cu1—C21	1.836 (4)
Cu2—N3	2.055 (3)
Cu2—N4	2.010 (3)
Cu2—C23	1.836 (3)
Cu3—N5	1.876 (3)
Cu3—Br1	2.5163 (6)
Cu3—C22	1.842 (3)
Cu4—N6ⁱ	1.906 (3)
Cu4—N7	1.878 (3)
Cu4—Br1	2.4650 (6)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018120/hy2536sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018120/hy2536Isup2.hkl

checkCIF report

Comment top

Considerable attention has been paid to the study of copper cyanide coordination polymers due to their fascinating structural frameworks, physical and chemical properties, and potential applications in many fields (Korzeniak et al., 2005; Yi et al., 2004). Cyanide group is a versatile ligand that can act as a monodentate ligand as well as a µ₂-, µ₃- or µ₄-bridging ligand, exhibiting intriguing topological architectures (Zhang et al., 2000). Copper atom has versatile coordination properties and normally adopts two-, three-, four-, five-, or six-coordination, forming diverse geometries (He et al., 2006). Herein, we report a copper cyanide coordination polymers derived from 2,2'-bipyidine ligand. The title complex contains four unique Cu^I ions, which are all in distorted trigonal-planar geometries. However, the detailed coordination environments of these Cu^I atoms are different, as Cu1 and Cu2 are each coordinated by two N atoms of a 2,2'-bipyidine ligand and one µ₂-cyanide group. Cu3 and Cu4 are each coordinated by two µ₂-cyanide groups and one bromide ion (Fig. 1, Table 1). The structure exhibits by a zigzag chain backbone, [Cu₂Br(CN)]_n, along [1 0 1] (Fig. 2). The [Cu(bpy)(CN)] units point lateral of the chain.

Related literature top

For copper cyanide coordination polymers, see: Korzeniak et al. (2005); Yi et al. (2004). For structures containing cyanide groups, see: Zhang et al. (2000). For related copper complexes, see: He et al. (2006).

Experimental top

A mixture of CuBr₂ (0.33 g, 1.48 mmol), K₄Fe(CN)₆.3H₂O (0.42 g, 0.99 mmol), 2,2'-bipyridine (0.156 g, 1.00 mmol) and 24 ml H₂O was stirred for 30 min in air. The resulting gel was then transferred to a 30 ml Teflon-lined autoclave and kept at 160°C for 5 days. After the mixture was slowly cooled to room temperature, yellow block crystals of the title complex were filtered, washed with water and dried at room temperature (yield: 0.17 g, 66%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title complex, showing the coordination environments around the Cu^I atoms. Displacement ellipsoids are drawn at 50% probability level. [Symmetry code: (i) x+1/2, -y+1/2, z+1/2.]
	Fig. 2. The zigzag chain in the title complex.

catena-Poly[[(2,2'-bipyidine-2κ²N,N')-µ-cyanido- 1:2κ²N:C-dicopper(I)]-µ-bromido-[(2,2'-bipyidine- 2κ²N,N')-µ-cyanido-1:2κ²N:C-dicopper(I)]- µ-cyanido-κ²N:C] top

Crystal data top

[Cu₄Br(CN)₃(C₁₀H₈N₂)₂]	F(000) = 1416
M_r = 724.53	D_x = 1.915 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4357 reflections
a = 10.0074 (10) Å	θ = 2.3–22.8°
b = 17.7556 (17) Å	µ = 4.96 mm⁻¹
c = 14.5125 (14) Å	T = 273 K
β = 102.924 (1)°	Block, yellow
V = 2513.4 (4) Å³	0.24 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	6171 independent reflections
Radiation source: fine-focus sealed tube	3491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.383, T_max = 0.409	k = −21→23
23142 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0336P)² + 0.2889P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
6171 reflections	Δρ_max = 0.37 e Å⁻³
317 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00042 (11)

Crystal data top

[Cu₄Br(CN)₃(C₁₀H₈N₂)₂]	V = 2513.4 (4) Å³
M_r = 724.53	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0074 (10) Å	µ = 4.96 mm⁻¹
b = 17.7556 (17) Å	T = 273 K
c = 14.5125 (14) Å	0.24 × 0.24 × 0.22 mm
β = 102.924 (1)°

Data collection top

Bruker APEXII CCD diffractometer	6171 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3491 reflections with I > 2σ(I)
T_min = 0.383, T_max = 0.409	R_int = 0.035
23142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.00	Δρ_max = 0.37 e Å⁻³
6171 reflections	Δρ_min = −0.41 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
Cu1	0.35793 (5)	0.01457 (3)	0.84772 (3)	0.08134 (17)
Cu2	1.10313 (5)	0.03539 (3)	0.62780 (4)	0.1015 (2)
Cu3	0.46792 (5)	0.19932 (3)	0.63059 (3)	0.07283 (15)
Cu4	0.87398 (4)	0.19909 (2)	0.81033 (3)	0.06160 (13)
Br1	0.66910 (4)	0.26922 (3)	0.72846 (3)	0.08278 (14)
N1	0.2531 (3)	0.01213 (16)	0.95197 (18)	0.0624 (7)
N2	0.4332 (3)	−0.08313 (16)	0.91135 (18)	0.0633 (7)
N3	1.1656 (3)	−0.07460 (17)	0.6509 (2)	0.0754 (8)
N4	1.2024 (3)	0.02421 (17)	0.5226 (2)	0.0719 (8)
N5	0.4205 (3)	0.12318 (17)	0.70702 (19)	0.0722 (8)
N6	0.4104 (3)	0.26904 (16)	0.4389 (2)	0.0695 (8)
N7	0.9502 (3)	0.13623 (16)	0.73146 (19)	0.0681 (7)
C1	0.1708 (4)	0.0657 (2)	0.9725 (3)	0.0736 (10)
H1	0.1423	0.1037	0.9284	0.088*
C2	0.1261 (4)	0.0676 (2)	1.0554 (3)	0.0766 (10)
H2	0.0695	0.1061	1.0674	0.092*
C3	0.1669 (4)	0.0114 (2)	1.1194 (3)	0.0718 (10)
H3	0.1379	0.0109	1.1760	0.086*
C4	0.2521 (3)	−0.04517 (19)	1.0997 (2)	0.0605 (8)
H4	0.2813	−0.0836	1.1431	0.073*
C5	0.2931 (3)	−0.04371 (18)	1.0149 (2)	0.0535 (8)
C6	0.3839 (3)	−0.10117 (18)	0.9871 (2)	0.0550 (8)
C7	0.4153 (3)	−0.1688 (2)	1.0339 (2)	0.0668 (9)
H7	0.3800	−0.1803	1.0863	0.080*
C8	0.4990 (4)	−0.2189 (2)	1.0022 (3)	0.0851 (12)
H8	0.5201	−0.2650	1.0324	0.102*
C9	0.5519 (4)	−0.2003 (3)	0.9248 (3)	0.0854 (12)
H9	0.6096	−0.2331	0.9022	0.102*
C10	0.5169 (4)	−0.1325 (3)	0.8830 (3)	0.0805 (11)
H10	0.5533	−0.1196	0.8315	0.097*
C11	1.1467 (4)	−0.1211 (3)	0.7194 (3)	0.0967 (14)
H11	1.0891	−0.1057	0.7580	0.116*
C12	1.2070 (5)	−0.1896 (3)	0.7354 (3)	0.1034 (15)
H12	1.1926	−0.2199	0.7845	0.124*
C13	1.2888 (5)	−0.2128 (3)	0.6784 (4)	0.1056 (15)
H13	1.3310	−0.2597	0.6873	0.127*
C14	1.3087 (4)	−0.1667 (2)	0.6077 (3)	0.0893 (12)
H14	1.3652	−0.1821	0.5684	0.107*
C15	1.2458 (3)	−0.0972 (2)	0.5940 (3)	0.0633 (9)
C16	1.2631 (3)	−0.0431 (2)	0.5204 (2)	0.0617 (9)
C17	1.3361 (4)	−0.0580 (2)	0.4522 (3)	0.0811 (11)
H17	1.3769	−0.1049	0.4504	0.097*
C18	1.3487 (4)	−0.0046 (3)	0.3876 (3)	0.0975 (13)
H18	1.3981	−0.0147	0.3418	0.117*
C19	1.2890 (4)	0.0634 (3)	0.3904 (3)	0.0954 (12)
H19	1.2972	0.1009	0.3473	0.114*
C20	1.2164 (4)	0.0755 (2)	0.4580 (3)	0.0903 (12)
H20	1.1742	0.1221	0.4593	0.108*
C21	0.3923 (3)	0.0802 (2)	0.7580 (2)	0.0658 (9)
C22	0.4283 (3)	0.24393 (18)	0.5130 (2)	0.0536 (8)
C23	1.0047 (4)	0.09831 (19)	0.6881 (3)	0.0706 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0947 (3)	0.0914 (4)	0.0562 (3)	−0.0338 (3)	0.0130 (2)	0.0137 (2)
Cu2	0.0880 (3)	0.0867 (4)	0.1408 (5)	0.0024 (3)	0.0487 (3)	−0.0510 (3)
Cu3	0.0990 (3)	0.0733 (3)	0.0532 (3)	0.0211 (2)	0.0318 (2)	0.0187 (2)
Cu4	0.0725 (3)	0.0637 (3)	0.0520 (2)	−0.0044 (2)	0.02109 (19)	−0.0135 (2)
Br1	0.0697 (2)	0.0949 (3)	0.0768 (3)	0.0063 (2)	0.00151 (19)	0.0136 (2)
N1	0.0643 (16)	0.0648 (19)	0.0558 (17)	−0.0068 (14)	0.0085 (13)	0.0070 (15)
N2	0.0630 (16)	0.073 (2)	0.0557 (17)	−0.0154 (14)	0.0176 (13)	−0.0033 (15)
N3	0.0662 (17)	0.072 (2)	0.095 (2)	−0.0112 (15)	0.0324 (17)	−0.0206 (18)
N4	0.0713 (18)	0.056 (2)	0.088 (2)	0.0030 (15)	0.0171 (16)	−0.0208 (17)
N5	0.093 (2)	0.075 (2)	0.0492 (17)	−0.0009 (16)	0.0170 (15)	0.0079 (15)
N6	0.0674 (18)	0.069 (2)	0.072 (2)	−0.0068 (14)	0.0151 (15)	−0.0024 (16)
N7	0.0760 (18)	0.0662 (19)	0.0627 (18)	0.0042 (15)	0.0169 (15)	−0.0111 (15)
C1	0.077 (2)	0.058 (2)	0.079 (3)	−0.0036 (19)	0.004 (2)	0.012 (2)
C2	0.078 (2)	0.071 (3)	0.078 (3)	0.001 (2)	0.011 (2)	−0.010 (2)
C3	0.078 (2)	0.080 (3)	0.059 (2)	−0.008 (2)	0.0191 (18)	−0.011 (2)
C4	0.066 (2)	0.063 (2)	0.052 (2)	−0.0099 (17)	0.0114 (16)	0.0017 (17)
C5	0.0533 (17)	0.057 (2)	0.0477 (19)	−0.0139 (15)	0.0061 (14)	0.0019 (16)
C6	0.0524 (17)	0.061 (2)	0.0503 (19)	−0.0149 (15)	0.0090 (14)	−0.0022 (16)
C7	0.066 (2)	0.066 (2)	0.070 (2)	−0.0063 (18)	0.0191 (17)	0.0082 (19)
C8	0.076 (3)	0.073 (3)	0.104 (3)	0.005 (2)	0.017 (2)	0.007 (2)
C9	0.076 (3)	0.088 (3)	0.095 (3)	−0.005 (2)	0.024 (2)	−0.022 (3)
C10	0.079 (3)	0.099 (3)	0.068 (3)	−0.019 (2)	0.027 (2)	−0.011 (2)
C11	0.082 (3)	0.108 (4)	0.108 (4)	−0.022 (3)	0.039 (3)	−0.016 (3)
C12	0.083 (3)	0.108 (4)	0.116 (4)	−0.020 (3)	0.015 (3)	0.026 (3)
C13	0.083 (3)	0.092 (4)	0.138 (4)	0.013 (2)	0.018 (3)	0.022 (3)
C14	0.078 (3)	0.082 (3)	0.108 (3)	0.015 (2)	0.021 (2)	−0.001 (3)
C15	0.0484 (17)	0.061 (2)	0.079 (2)	−0.0021 (16)	0.0100 (16)	−0.0222 (19)
C16	0.0492 (17)	0.061 (2)	0.071 (2)	0.0034 (16)	0.0059 (16)	−0.0193 (19)
C17	0.083 (3)	0.082 (3)	0.079 (3)	0.018 (2)	0.020 (2)	−0.014 (2)
C18	0.100 (3)	0.120 (4)	0.075 (3)	0.011 (3)	0.025 (2)	−0.009 (3)
C19	0.098 (3)	0.099 (4)	0.084 (3)	−0.005 (3)	0.011 (2)	0.005 (3)
C20	0.100 (3)	0.057 (3)	0.112 (4)	0.008 (2)	0.018 (3)	−0.008 (3)
C21	0.073 (2)	0.073 (2)	0.050 (2)	−0.0087 (18)	0.0102 (16)	0.0081 (18)
C22	0.0647 (19)	0.059 (2)	0.0359 (17)	−0.0024 (15)	0.0098 (14)	0.0112 (15)
C23	0.075 (2)	0.059 (2)	0.082 (3)	−0.0009 (18)	0.027 (2)	−0.019 (2)

Geometric parameters (Å, º) top

Cu1—N1	2.025 (3)	C4—C5	1.383 (4)
Cu1—N2	2.029 (3)	C4—H4	0.9300
Cu1—C21	1.836 (4)	C5—C6	1.480 (4)
Cu2—N3	2.055 (3)	C6—C7	1.381 (4)
Cu2—N4	2.010 (3)	C7—C8	1.370 (5)
Cu2—C23	1.836 (3)	C7—H7	0.9300
Cu3—N5	1.876 (3)	C8—C9	1.385 (5)
Cu3—Br1	2.5163 (6)	C8—H8	0.9300
Cu3—C22	1.842 (3)	C9—C10	1.357 (5)
Cu4—N6ⁱ	1.906 (3)	C9—H9	0.9300
Cu4—N7	1.878 (3)	C10—H10	0.9300
Cu4—Br1	2.4650 (6)	C11—C12	1.354 (6)
N1—C1	1.334 (4)	C11—H11	0.9300
N1—C5	1.347 (4)	C12—C13	1.351 (6)
N2—C10	1.339 (4)	C12—H12	0.9300
N2—C6	1.341 (3)	C13—C14	1.362 (5)
N3—C15	1.336 (4)	C13—H13	0.9300
N3—C11	1.338 (5)	C14—C15	1.379 (5)
N4—C20	1.337 (5)	C14—H14	0.9300
N4—C16	1.344 (4)	C15—C16	1.474 (5)
N5—C21	1.141 (4)	C16—C17	1.381 (4)
N6—C22	1.141 (4)	C17—C18	1.360 (5)
N7—C23	1.140 (4)	C17—H17	0.9300
C1—C2	1.374 (5)	C18—C19	1.351 (6)
C1—H1	0.9300	C18—H18	0.9300
C2—C3	1.363 (5)	C19—C20	1.363 (5)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.387 (5)	C20—H20	0.9300
C3—H3	0.9300

C21—Cu1—N1	138.90 (14)	C8—C7—C6	119.2 (3)
C21—Cu1—N2	139.10 (13)	C8—C7—H7	120.4
N1—Cu1—N2	80.99 (11)	C6—C7—H7	120.4
C23—Cu2—N4	146.27 (15)	C7—C8—C9	119.4 (4)
C23—Cu2—N3	132.60 (15)	C7—C8—H8	120.3
N4—Cu2—N3	81.13 (13)	C9—C8—H8	120.3
C22—Cu3—N5	145.80 (13)	C10—C9—C8	117.8 (4)
C22—Cu3—Br1	106.87 (10)	C10—C9—H9	121.1
N5—Cu3—Br1	107.33 (9)	C8—C9—H9	121.1
N7—Cu4—N6ⁱ	139.32 (12)	N2—C10—C9	124.0 (4)
N7—Cu4—Br1	114.45 (9)	N2—C10—H10	118.0
N6ⁱ—Cu4—Br1	106.16 (8)	C9—C10—H10	118.0
Cu4—Br1—Cu3	119.81 (2)	N3—C11—C12	123.4 (4)
C1—N1—C5	118.5 (3)	N3—C11—H11	118.3
C1—N1—Cu1	126.9 (2)	C12—C11—H11	118.3
C5—N1—Cu1	113.4 (2)	C13—C12—C11	118.4 (5)
C10—N2—C6	117.8 (3)	C13—C12—H12	120.8
C10—N2—Cu1	127.9 (2)	C11—C12—H12	120.8
C6—N2—Cu1	114.2 (2)	C12—C13—C14	119.3 (4)
C15—N3—C11	118.6 (3)	C12—C13—H13	120.4
C15—N3—Cu2	112.8 (3)	C14—C13—H13	120.4
C11—N3—Cu2	128.3 (3)	C13—C14—C15	120.5 (4)
C20—N4—C16	118.1 (3)	C13—C14—H14	119.7
C20—N4—Cu2	127.7 (3)	C15—C14—H14	119.7
C16—N4—Cu2	114.1 (3)	N3—C15—C14	119.8 (4)
C21—N5—Cu3	175.6 (3)	N3—C15—C16	115.9 (3)
C22—N6—Cu4ⁱⁱ	174.1 (3)	C14—C15—C16	124.3 (3)
C23—N7—Cu4	175.3 (3)	N4—C16—C17	120.1 (4)
N1—C1—C2	123.4 (3)	N4—C16—C15	115.8 (3)
N1—C1—H1	118.3	C17—C16—C15	124.1 (3)
C2—C1—H1	118.3	C18—C17—C16	120.4 (4)
C3—C2—C1	118.2 (4)	C18—C17—H17	119.8
C3—C2—H2	120.9	C16—C17—H17	119.8
C1—C2—H2	120.9	C19—C18—C17	119.5 (4)
C2—C3—C4	119.6 (3)	C19—C18—H18	120.3
C2—C3—H3	120.2	C17—C18—H18	120.3
C4—C3—H3	120.2	C18—C19—C20	118.4 (4)
C5—C4—C3	119.2 (3)	C18—C19—H19	120.8
C5—C4—H4	120.4	C20—C19—H19	120.8
C3—C4—H4	120.4	N4—C20—C19	123.5 (4)
N1—C5—C4	121.0 (3)	N4—C20—H20	118.2
N1—C5—C6	115.5 (3)	C19—C20—H20	118.2
C4—C5—C6	123.5 (3)	N5—C21—Cu1	175.3 (3)
N2—C6—C7	121.7 (3)	N6—C22—Cu3	175.7 (3)
N2—C6—C5	114.8 (3)	N7—C23—Cu2	175.0 (3)
C7—C6—C5	123.5 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu₄Br(CN)₃(C₁₀H₈N₂)₂]
M_r	724.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	273
a, b, c (Å)	10.0074 (10), 17.7556 (17), 14.5125 (14)
β (°)	102.924 (1)
V (Å³)	2513.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.96
Crystal size (mm)	0.24 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.383, 0.409
No. of measured, independent and observed [I > 2σ(I)] reflections	23142, 6171, 3491
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.084, 1.00
No. of reflections	6171
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.41

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	2.025 (3)	Cu3—N5	1.876 (3)
Cu1—N2	2.029 (3)	Cu3—Br1	2.5163 (6)
Cu1—C21	1.836 (4)	Cu3—C22	1.842 (3)
Cu2—N3	2.055 (3)	Cu4—N6ⁱ	1.906 (3)
Cu2—N4	2.010 (3)	Cu4—N7	1.878 (3)
Cu2—C23	1.836 (3)	Cu4—Br1	2.4650 (6)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 20971032).

References

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