Poly[tetra-μ(1,1)-azido-bis-(μ(2)-pyrimidine-2-carboxyl-ato)tricopper(II)].

In the title compound, [Cu(3)(C(5)H(3)N(2)O(2))(2)(N(3))(4)](n), one of the Cu(II) atoms lies on an inversion centre and is octa-hedrally coordinated by two bidentate chelating pyrimidine-2-carboxyl-ate 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-carboxyl-ate 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 = 604.96

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.134

S = 1.24

1572 reflections

151 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027030/zs2045Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu3(C5H3N2O2)2(N3)4]	F(000) = 594
Mr = 604.96	Dx = 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

Rigaku SCXmini CCD diffractometer	1572 independent reflections
Radiation source: fine-focus sealed tube	1305 reflections with I > 2σ(I)
graphite	Rint = 0.061
ω scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.625, Tmax = 1.000	k = −17→17
7028 measured reflections	l = −11→11

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(Fo2) + (0.0543P)2 + 2.0516P] where P = (Fo2 + 2Fc2)/3
1572 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)