Poly[tetra-μ1,1-azido-bis­(μ2-pyrimidine-2-carboxyl­ato)tricopper(II)]

Zhao, J.-P.; Liu, F.-C.

doi:10.1107/S1600536810027030

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m973

https://doi.org/10.1107/S1600536810027030

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Poly[tetra-μ_1,1-azido-bis(μ₂-pyrimidine-2-carboxylato)tricopper(II)]

Jiong-Peng Zhao ^a and Fu-Chen Liu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: fuchenliutj@yahoo.com

(Received 2 June 2010; accepted 8 July 2010; online 21 July 2010)

In the title compound, [Cu₃(C₅H₃N₂O₂)₂(N₃)₄]_n, one of the Cu^II atoms lies on an inversion centre and is octahedrally coordinated by two bidentate chelating pyrimidine-2-carboxylate ligands and two azide anions, each of which gives an N:N-bridge to the second inversion-related Cu^II centre in the formula unit. The second Cu^II atom is five-coordinated with a distorted square-pyramidal coordination sphere comprising a single bidentate chelating pyrimidine-2-carboxylate anion and three azide N anions, two of which doubly bridge centrosymmetric Cu^II centres, giving a two-dimensional network structure extending parallel to (010).

Related literature

Copper azide complexes have attracted much attention in recent years because the azide anions can mediate magnetic interactions effectively between the copper ions, see: Zhao et al. (2009 ). The structures of the complexes are dependant on the co-ligand and conditions employed in the synthesis, see: Zeng et al. (2009 ). For azide complexes with 2,2′-bipyrimidine or oxalate as co-ligands, see: Cortes et al. (1996 ); Escuer et al. (1994 ) and for an azide complex with a pyrimidine-2-carboxylate ligand, see: Suarez-Varela et al. (2008 ).

Experimental

Crystal data

[Cu₃(C₅H₃N₂O₂)₂(N₃)₄]
M_r = 604.96
Monoclinic, P 2₁ /c
a = 7.4743 (15) Å
b = 14.997 (3) Å
c = 9.479 (4) Å
β = 122.31 (2)°
V = 898.0 (5) Å³
Z = 2
Mo Kα radiation
μ = 3.59 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.18 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.625, T_max = 1.000
7028 measured reflections
1572 independent reflections
1305 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.134
S = 1.24
1572 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006 ); cell refinement: PROCESS-AUTO (Rigaku, 1998 ); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027030/zs2045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027030/zs2045Isup2.hkl

checkCIF report

Comment top

Copper azide complexes have attracted much attention in recent years because the azide anions can mediate magnetic interactions effectively between the copper ions (Zhao et al., 2009). The structures of those complexes are dependant on the co-ligand and conditions employed in the synthesis (Zeng et al., 2009). Some azide complexes with 2,2'-bipyrimidine or oxalate as co-ligands have been reported (Cortes et al., 1996); Escuer et al., 1994). The pyrimidine-2-carboxylate ligand can be considered as the combination of 2,2'-bipyrimidine and oxalate, and a new metal azide complex with it as ligand has been reported (Suarez-Varela et al., 2008). In this work we report a new copper(II) azide complex with pyrimidine-2-carboxylate as co-ligand, [Cu₃(C₅H₃N₂O₂)₂(N₃)₄]_n (I), prepared under hydrothermal conditions and its structure is reported here.

In the asymmetric units of the title compound, there are one and a half copper(II) cations, two azido anions and two pyrimidine-2-carboxylate ligands (Fig. 1). One of the cations (Cu2) lies on an inversion centre and is octahedrally coordinated by two bidentate chelate pyrimidine-2-carboxylato-N,O ligands and two azido anions, each giving an N bridge to the inversion-related Cu1 centres in the formula unit [Cu2—Cu1, 3.4652 (14) Å]. A second weak contact between a carboxyl O (O1) to Cu1 is also present [Cu1···O1, 2.950 (4) Å] but is too long to be considered a bridging (Cu–O) bond. The coordination sphere about Cu1 is five-coordinate with a distorted square pyramidal coordination sphere comprising a single bidentate chelate pyrimidine-2-carboxylate anion and three azido N anions, one bridging to Cu2, the other two giving double N bridges to centrosymmetrically related Cu centres [Cu1—Cu1ⁱⁱⁱ, 3.329 (2) Å] [symmetry code: (iii) x -1, y, z]. Structure extension results in a two-dimensional network (Figs. 2, 3).

Related literature top

Copper azide complexes have attracted much attention in recent years because the azide anions can mediate magnetic interactions effectively between the copper ions, see: Zhao et al. (2009). The structures of the complexes are dependant on the co-ligand and conditions employed in the synthesis, see: Zeng et al. (2009). For azide complexes with 2,2'-bipyrimidine or oxalate as co-ligands, see: Cortes et al. (1996); Escuer et al. (1994) and for an azide complex with a pyrimidine-2-carboxylate ligand, see: Suarez-Varela et al. (2008).

Experimental top

A mixture of copper(II) nitrate (1.5mmol) and sodium azide (2 mmol), and pyrimidine-2-carboxylic acid (0.5 mmol) in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 413 K for 48 h. Black crystals of the title complex were collected after the bomb was allowed to cool to room temperature (yield 20% based on Cu). Caution: azides may be explosive: although we have had no problems in this work, only small quantities should be prepared and should be handled with great caution.

Structure description top

Copper azide complexes have attracted much attention in recent years because the azide anions can mediate magnetic interactions effectively between the copper ions, see: Zhao et al. (2009). The structures of the complexes are dependant on the co-ligand and conditions employed in the synthesis, see: Zeng et al. (2009). For azide complexes with 2,2'-bipyrimidine or oxalate as co-ligands, see: Cortes et al. (1996); Escuer et al. (1994) and for an azide complex with a pyrimidine-2-carboxylate ligand, see: Suarez-Varela et al. (2008).

Computing details top

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination mode and linkage of the metal ions and ligands in (I). Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (A) -x + 2, -y, -z; (B) -x + 1, -y, -z - 1; (C) -x + 1, -y, -z; (D) x - 1, y, z].
	Fig. 2. The two-dimensional network structure of (I).
	Fig. 3. The packing mode of the complex in the unit cell.

Poly[tetra-µ_1,1-azido-bis(µ₂-pyrimidine-2-carboxylato)tricopper(II)] top

Crystal data top

[Cu₃(C₅H₃N₂O₂)₂(N₃)₄]	F(000) = 594
M_r = 604.96	D_x = 2.237 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7433 reflections
a = 7.4743 (15) Å	θ = 3.2–27.5°
b = 14.997 (3) Å	µ = 3.59 mm⁻¹
c = 9.479 (4) Å	T = 293 K
β = 122.31 (2)°	Block, black
V = 898.0 (5) Å³	0.20 × 0.18 × 0.18 mm
Z = 2

Data collection top

Rigaku SCXmini CCD diffractometer	1572 independent reflections
Radiation source: fine-focus sealed tube	1305 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.625, T_max = 1.000	k = −17→17
7028 measured reflections	l = −11→11

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.0543P)² + 2.0516P] where P = (F_o² + 2F_c²)/3
1572 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Cu₃(C₅H₃N₂O₂)₂(N₃)₄]	V = 898.0 (5) Å³
M_r = 604.96	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4743 (15) Å	µ = 3.59 mm⁻¹
b = 14.997 (3) Å	T = 293 K
c = 9.479 (4) Å	0.20 × 0.18 × 0.18 mm
β = 122.31 (2)°

Data collection top

Rigaku SCXmini CCD diffractometer	1572 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1305 reflections with I > 2σ(I)
T_min = 0.625, T_max = 1.000	R_int = 0.061
7028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.24	Δρ_max = 0.71 e Å⁻³
1572 reflections	Δρ_min = −0.46 e Å⁻³
151 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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	0.64025 (11)	−0.01316 (5)	−0.29370 (10)	0.0259 (3)
Cu2	0.50000	0.00000	0.00000	0.0221 (3)
O1	0.7728 (6)	−0.0882 (3)	0.0359 (5)	0.0278 (12)
O2	1.1215 (6)	−0.0703 (3)	0.1528 (5)	0.0234 (12)
N1	0.4612 (8)	0.0444 (4)	−0.2223 (7)	0.0279 (17)
N2	0.4377 (9)	0.1253 (4)	−0.2455 (7)	0.0344 (19)
N3	0.4134 (13)	0.2001 (5)	−0.2695 (10)	0.063 (3)
N4	0.4241 (9)	−0.0895 (4)	−0.4673 (7)	0.0365 (19)
N5	0.2454 (9)	−0.0933 (4)	−0.4977 (6)	0.035 (2)
N6	0.0719 (11)	−0.0987 (6)	−0.5367 (8)	0.064 (3)
N7	1.1181 (8)	0.0896 (3)	0.2648 (6)	0.0245 (17)
N8	0.7462 (8)	0.0827 (3)	0.1309 (6)	0.0224 (17)
C1	0.9407 (9)	−0.0464 (4)	0.1173 (7)	0.0214 (17)
C2	0.9320 (9)	0.0481 (4)	0.1760 (7)	0.0221 (17)
C3	0.7414 (11)	0.1682 (4)	0.1722 (9)	0.033 (2)
C4	0.9286 (12)	0.2167 (5)	0.2647 (9)	0.038 (3)
C5	1.1161 (11)	0.1746 (4)	0.3094 (8)	0.032 (2)
H3A	0.61250	0.19510	0.13880	0.0390*
H4A	0.92720	0.27550	0.29530	0.0460*
H5A	1.24310	0.20550	0.37130	0.0390*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0184 (4)	0.0326 (5)	0.0258 (5)	−0.0030 (3)	0.0112 (4)	−0.0039 (3)
Cu2	0.0168 (6)	0.0274 (6)	0.0215 (6)	−0.0014 (4)	0.0099 (5)	−0.0009 (4)
O1	0.026 (2)	0.026 (2)	0.030 (2)	−0.0038 (19)	0.014 (2)	−0.0047 (19)
O2	0.018 (2)	0.028 (2)	0.023 (2)	−0.0004 (17)	0.0102 (18)	−0.0010 (18)
N1	0.025 (3)	0.031 (3)	0.034 (3)	−0.001 (2)	0.020 (3)	0.001 (3)
N2	0.029 (3)	0.048 (4)	0.035 (3)	−0.001 (3)	0.023 (3)	−0.001 (3)
N3	0.091 (6)	0.032 (4)	0.092 (6)	0.014 (4)	0.066 (5)	0.011 (4)
N4	0.026 (3)	0.045 (4)	0.035 (3)	−0.003 (3)	0.014 (3)	−0.010 (3)
N5	0.035 (4)	0.050 (4)	0.018 (3)	−0.012 (3)	0.012 (3)	−0.002 (3)
N6	0.034 (4)	0.114 (7)	0.040 (4)	−0.025 (4)	0.018 (3)	−0.001 (4)
N7	0.021 (3)	0.024 (3)	0.026 (3)	−0.005 (2)	0.011 (2)	−0.003 (2)
N8	0.021 (3)	0.025 (3)	0.022 (3)	−0.001 (2)	0.012 (2)	−0.002 (2)
C1	0.021 (3)	0.026 (3)	0.016 (3)	−0.001 (3)	0.009 (3)	0.000 (3)
C2	0.027 (3)	0.020 (3)	0.022 (3)	0.000 (3)	0.015 (3)	0.002 (2)
C3	0.035 (4)	0.029 (4)	0.037 (4)	0.007 (3)	0.021 (3)	0.002 (3)
C4	0.047 (5)	0.025 (4)	0.041 (4)	0.000 (3)	0.022 (4)	−0.004 (3)
C5	0.030 (4)	0.035 (4)	0.026 (4)	−0.011 (3)	0.012 (3)	−0.004 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.991 (7)	N2—N3	1.140 (10)
Cu1—N4	1.946 (6)	N4—N5	1.208 (10)
Cu1—N4ⁱ	2.563 (6)	N5—N6	1.146 (12)
Cu1—O2ⁱⁱ	1.995 (5)	N7—C2	1.334 (9)
Cu1—N7ⁱⁱ	2.030 (6)	N7—C5	1.346 (8)
Cu2—O1	2.298 (5)	N8—C2	1.321 (10)
Cu2—N1	2.077 (6)	N8—C3	1.347 (8)
Cu2—N8	2.006 (6)	C1—C2	1.537 (9)
Cu2—O1ⁱⁱⁱ	2.298 (5)	C3—C4	1.394 (12)
Cu2—N1ⁱⁱⁱ	2.077 (6)	C4—C5	1.381 (13)
Cu2—N8ⁱⁱⁱ	2.006 (5)	C3—H3A	0.9300
O1—C1	1.236 (8)	C4—H4A	0.9300
O2—C1	1.258 (9)	C5—H5A	0.9300
N1—N2	1.229 (8)

N1—Cu1—N4	97.9 (3)	Cu1—N1—N2	115.2 (5)
N1—Cu1—N4ⁱ	101.4 (2)	Cu2—N1—N2	115.3 (5)
O2ⁱⁱ—Cu1—N1	91.3 (2)	N1—N2—N3	178.9 (8)
N1—Cu1—N7ⁱⁱ	155.5 (2)	Cu1—N4—N5	122.8 (5)
N4—Cu1—N4ⁱ	85.8 (2)	Cu1—N4—Cu1ⁱ	94.2 (2)
O2ⁱⁱ—Cu1—N4	167.4 (2)	Cu1ⁱ—N4—N5	99.0 (4)
N4—Cu1—N7ⁱⁱ	93.4 (3)	N4—N5—N6	175.6 (7)
O2ⁱⁱ—Cu1—N4ⁱ	83.89 (19)	C2—N7—C5	117.2 (6)
N4ⁱ—Cu1—N7ⁱⁱ	101.0 (2)	Cu1ⁱⁱ—N7—C2	112.0 (4)
O2ⁱⁱ—Cu1—N7ⁱⁱ	81.5 (2)	Cu1ⁱⁱ—N7—C5	130.6 (5)
O1—Cu2—N1	88.1 (2)	Cu2—N8—C2	114.5 (4)
O1—Cu2—N8	79.4 (2)	Cu2—N8—C3	127.6 (6)
O1—Cu2—O1ⁱⁱⁱ	180.00	C2—N8—C3	117.8 (6)
O1—Cu2—N1ⁱⁱⁱ	91.9 (2)	O1—C1—O2	127.6 (6)
O1—Cu2—N8ⁱⁱⁱ	100.6 (2)	O1—C1—C2	117.9 (6)
N1—Cu2—N8	90.8 (2)	O2—C1—C2	114.4 (6)
O1ⁱⁱⁱ—Cu2—N1	91.9 (2)	N7—C2—N8	125.6 (6)
N1—Cu2—N1ⁱⁱⁱ	180.00	N7—C2—C1	115.3 (6)
N1—Cu2—N8ⁱⁱⁱ	89.2 (2)	N8—C2—C1	119.1 (6)
O1ⁱⁱⁱ—Cu2—N8	100.6 (2)	N8—C3—C4	120.4 (8)
N1ⁱⁱⁱ—Cu2—N8	89.2 (2)	C3—C4—C5	117.9 (7)
N8—Cu2—N8ⁱⁱⁱ	180.00	N7—C5—C4	121.1 (7)
O1ⁱⁱⁱ—Cu2—N1ⁱⁱⁱ	88.1 (2)	N8—C3—H3A	120.00
O1ⁱⁱⁱ—Cu2—N8ⁱⁱⁱ	79.4 (2)	C4—C3—H3A	120.00
N1ⁱⁱⁱ—Cu2—N8ⁱⁱⁱ	90.8 (2)	C3—C4—H4A	121.00
Cu2—O1—C1	109.0 (4)	C5—C4—H4A	121.00
Cu1ⁱⁱ—O2—C1	116.6 (4)	N7—C5—H5A	119.00
Cu1—N1—Cu2	116.8 (3)	C4—C5—H5A	119.00

O1—Cu1—N1—N2	136.0 (5)	N8—Cu2—N1—Cu1	84.3 (3)
N4—Cu1—N1—Cu2	103.7 (3)	N8—Cu2—N1—N2	−55.7 (6)
N4—Cu1—N1—N2	−116.3 (5)	O1ⁱⁱⁱ—Cu2—N1—Cu1	−175.1 (3)
N4ⁱ—Cu1—N1—Cu2	−169.0 (3)	O1ⁱⁱⁱ—Cu2—N1—N2	44.9 (6)
N4ⁱ—Cu1—N1—N2	−28.9 (5)	N8ⁱⁱⁱ—Cu2—N1—Cu1	−95.7 (3)
O2ⁱⁱ—Cu1—N1—Cu2	−84.9 (3)	N8ⁱⁱⁱ—Cu2—N1—N2	124.3 (6)
O2ⁱⁱ—Cu1—N1—N2	55.1 (5)	O1—Cu2—N8—C2	−2.2 (4)
N7ⁱⁱ—Cu1—N1—Cu2	−12.9 (8)	O1—Cu2—N8—C3	175.8 (6)
N7ⁱⁱ—Cu1—N1—N2	127.2 (6)	N1—Cu2—N8—C2	−90.1 (5)
O1—Cu1—N4—N5	72.4 (6)	N1—Cu2—N8—C3	87.9 (6)
O1—Cu1—N4—Cu1ⁱ	175.86 (15)	O1ⁱⁱⁱ—Cu2—N8—C2	177.8 (4)
N1—Cu1—N4—N5	−2.6 (6)	O1ⁱⁱⁱ—Cu2—N8—C3	−4.3 (6)
N1—Cu1—N4—Cu1ⁱ	100.9 (2)	N1ⁱⁱⁱ—Cu2—N8—C2	89.9 (5)
N4ⁱ—Cu1—N4—N5	−103.5 (6)	N1ⁱⁱⁱ—Cu2—N8—C3	−92.2 (6)
N4ⁱ—Cu1—N4—Cu1ⁱ	0.0 (2)	Cu1—O1—C1—O2	−91.6 (6)
N7ⁱⁱ—Cu1—N4—N5	155.7 (6)	Cu1—O1—C1—C2	84.7 (5)
N7ⁱⁱ—Cu1—N4—Cu1ⁱ	−100.8 (2)	Cu2—O1—C1—O2	−175.2 (5)
N1—Cu1—N4ⁱ—Cu1ⁱ	−97.2 (3)	Cu2—O1—C1—C2	1.2 (6)
N1—Cu1—N4ⁱ—N5ⁱ	138.6 (4)	Cu1ⁱⁱ—O2—C1—O1	−178.1 (5)
N4—Cu1—N4ⁱ—Cu1ⁱ	0.0 (3)	Cu1ⁱⁱ—O2—C1—C2	5.5 (6)
N4—Cu1—N4ⁱ—N5ⁱ	−124.2 (5)	C5—N7—C2—N8	−1.4 (9)
O1—Cu1—O2ⁱⁱ—C1ⁱⁱ	87.9 (4)	C5—N7—C2—C1	175.8 (5)
N1—Cu1—O2ⁱⁱ—C1ⁱⁱ	160.8 (4)	Cu1ⁱⁱ—N7—C2—N8	−176.8 (5)
O1—Cu1—N7ⁱⁱ—C2ⁱⁱ	−84.5 (4)	Cu1ⁱⁱ—N7—C2—C1	0.4 (6)
O1—Cu1—N7ⁱⁱ—C5ⁱⁱ	90.1 (6)	C2—N7—C5—C4	0.0 (10)
N1—Cu1—N7ⁱⁱ—C2ⁱⁱ	−75.9 (7)	Cu1ⁱⁱ—N7—C5—C4	174.4 (5)
N1—Cu1—N7ⁱⁱ—C5ⁱⁱ	98.7 (7)	Cu2—N8—C2—N7	−179.3 (5)
N4—Cu1—N7ⁱⁱ—C2ⁱⁱ	166.6 (4)	Cu2—N8—C2—C1	3.6 (7)
N4—Cu1—N7ⁱⁱ—C5ⁱⁱ	−18.8 (6)	C3—N8—C2—N7	2.6 (9)
N1—Cu2—O1—Cu1	−2.98 (18)	C3—N8—C2—C1	−174.6 (6)
N1—Cu2—O1—C1	91.6 (4)	Cu2—N8—C3—C4	179.9 (5)
N8—Cu2—O1—Cu1	−94.14 (17)	C2—N8—C3—C4	−2.2 (10)
N8—Cu2—O1—C1	0.4 (4)	O1—C1—C2—N7	179.3 (5)
N1ⁱⁱⁱ—Cu2—O1—Cu1	177.02 (18)	O1—C1—C2—N8	−3.3 (8)
N1ⁱⁱⁱ—Cu2—O1—C1	−88.4 (4)	O2—C1—C2—N7	−3.9 (8)
N8ⁱⁱⁱ—Cu2—O1—Cu1	85.86 (17)	O2—C1—C2—N8	173.5 (5)
N8ⁱⁱⁱ—Cu2—O1—C1	−179.6 (4)	N8—C3—C4—C5	1.0 (11)
O1—Cu2—N1—Cu1	4.9 (3)	C3—C4—C5—N7	0.2 (11)
O1—Cu2—N1—N2	−135.1 (6)

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

Experimental details

Crystal data
Chemical formula	[Cu₃(C₅H₃N₂O₂)₂(N₃)₄]
M_r	604.96
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4743 (15), 14.997 (3), 9.479 (4)
β (°)	122.31 (2)
V (Å³)	898.0 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.59
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Rigaku SCXmini CCD diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.625, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7028, 1572, 1305
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.134, 1.24
No. of reflections	1572
No. of parameters	151
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.46

Computer programs: SCXmini Benchtop Crystallography System Software (Rigaku, 2006), PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge financial support from Tianjin Municipal Education Commission (grant No. 20060503).

References

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