Di-μ-azido-di-azidodi-μ-oxalato-di-histamine-tetra-copper(II) 0.9-hydrate.

The title compound, [Cu4(C2O4)2(N3)4(C5H9N3)2]·0.9H2O, contains a tetranuclear Cu(II)-based molecule composed of two oxalate-bridged Cu(II) dimers linked through end-on azide ions and related by an inversion center. The tetranuclear unit contains two crystallographically independent Cu(II) ions. One Cu(II) ion coordinates to two N atoms of a histamine mol-ecule, two O atoms of a bridging oxalate ligand, and an N atom of an end-on bridging azide ligand, leading to an elongated square-pyramidal coordination geometry in which the azide ion occupies the axial position. The other Cu(II) ion, which has a square-planar coordination geometry, is coordinated by two O atoms of a bridging oxalate ligand and two N atoms of two different azide ligands, one which is bridging. In the crystal, a two-dimensional network parallel to (010) is formed by N-H⋯N and N-H⋯O hydrogen bonds. A partially occupied solvent water mol-ecule refined to an occupancy of 0.447 (5). Two of the azide ligands were refined as disordered over two sets of sites with refined occupancies in the ratios 0.517 (8):0.483 (8) and 0.553 (5):0.447 (5).

Related literature

For background to bridging oxalate and azide ligands, see: Coronado et al. (2003 ▶); Ribas et al. (1999 ▶); Pardo et al. (2010 ▶); Sun et al. (1997 ▶).

Experimental

Crystal data

[Cu4(C2O4)2(N3)4(C5H9N3)2]·0.9H2O

M = 838.62

Triclinic,

a = 7.7003 (10) Å

b = 8.2841 (11) Å

c = 11.8677 (15) Å

α = 106.005 (2)°

β = 91.715 (2)°

γ = 115.010 (2)°

V = 650.07 (15) Å3

Z = 1

Mo Kα radiation

μ = 3.31 mm−1

T = 173 K

0.12 × 0.11 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: integration [based on measured indexed crystal faces (SHELXTL; Sheldrick, 2008 ▶)] T min = 0.654, T max = 0.877

5770 measured reflections

2885 independent reflections

2442 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.073

S = 1.03

2885 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.60 e Å−3

Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013329/lh5597sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013329/lh5597Isup2.hkl

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

[Cu4(C2O4)2(N3)4(C5H9N3)2]·0.9H2O	Z = 1
Mr = 838.62	F(000) = 416
Triclinic, P1	Dx = 2.137 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7003 (10) Å	Cell parameters from 29 reflections
b = 8.2841 (11) Å	θ = 2.0–28.0°
c = 11.8677 (15) Å	µ = 3.31 mm−1
α = 106.005 (2)°	T = 173 K
β = 91.715 (2)°	Plate, green
γ = 115.010 (2)°	0.12 × 0.11 × 0.04 mm
V = 650.07 (15) Å3

Bruker SMART CCD area-detector diffractometer	2885 independent reflections
Radiation source: fine-focus sealed tube	2442 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω and φ scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: integration [based on measured indexed crystal faces (SHELXTL; Sheldrick, 2008)]	h = −9→9
Tmin = 0.654, Tmax = 0.877	k = −10→10
5770 measured reflections	l = −15→15

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0327P)2 + 0.5471P] where P = (Fo2 + 2Fc2)/3
2885 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.10361 (5)	0.35821 (5)	0.26714 (3)	0.0187 (1)
Cu2	0.45210 (4)	0.78190 (4)	0.47013 (3)	0.0146 (1)
O1	0.1735 (3)	0.3957 (2)	0.44160 (16)	0.0177 (4)
O2	0.2983 (3)	0.2567 (3)	0.24786 (16)	0.0196 (4)
O3	0.4798 (3)	0.1874 (3)	0.35955 (16)	0.0194 (4)
O4	0.3611 (3)	0.3319 (3)	0.55217 (16)	0.0172 (4)
O5	−0.0013 (8)	0.9226 (8)	0.3473 (5)	0.0304 (14)	0.447 (5)
N1	0.3411 (3)	0.6717 (3)	0.3003 (2)	0.0217 (5)
N2	0.4238 (7)	0.6559 (8)	0.2176 (4)	0.0181 (11)*	0.517 (8)
N3	0.5044 (9)	0.6493 (9)	0.1379 (5)	0.0389 (17)*	0.517 (8)
N2'	0.4711 (8)	0.7391 (9)	0.2413 (5)	0.0189 (12)*	0.483 (8)
N3'	0.5775 (9)	0.7833 (9)	0.1768 (6)	0.0378 (18)*	0.483 (8)
N4	0.2809 (4)	0.9047 (3)	0.5128 (2)	0.0218 (5)
N5'	0.1670 (6)	0.8882 (5)	0.4349 (3)	0.0153 (10)	0.553 (5)
N6'	0.0499 (8)	0.8764 (8)	0.3687 (5)	0.0245 (11)	0.553 (5)
N5	0.2251 (7)	0.9251 (7)	0.6159 (4)	0.0182 (12)	0.447 (5)
N6	0.1813 (7)	0.9522 (7)	0.7129 (5)	0.0228 (13)	0.447 (5)
N7	−0.1142 (4)	0.4201 (5)	0.3030 (2)	0.0455 (9)
H7B	−0.2026	0.3281	0.3293	0.055*
H7C	−0.0665	0.5310	0.3651	0.055*
H7A	0.245 (4)	0.240 (4)	0.028 (3)	0.016 (7)*
N8	0.0241 (3)	0.2683 (3)	0.09526 (19)	0.0183 (5)
N9	0.0241 (4)	0.1696 (3)	−0.0948 (2)	0.0215 (5)
H9	0.064 (5)	0.142 (5)	−0.155 (3)	0.036 (10)*
C1	0.3613 (4)	0.2501 (3)	0.3439 (2)	0.0163 (5)
C2	0.2908 (3)	0.3308 (3)	0.4554 (2)	0.0137 (5)
C3	−0.2212 (4)	0.4403 (5)	0.2049 (3)	0.0296 (7)
H3B	−0.1315	0.5458	0.1795	0.035*
H3A	−0.3275	0.4689	0.2337	0.035*
C4	−0.3049 (4)	0.2605 (4)	0.1001 (2)	0.0258 (6)
H4B	−0.3748	0.1526	0.1291	0.031*
H4A	−0.4004	0.2647	0.0446	0.031*
C5	−0.1530 (4)	0.2306 (4)	0.0346 (2)	0.0186 (5)
C6	−0.1515 (4)	0.1704 (4)	−0.0830 (3)	0.0226 (6)
H6A	−0.237 (5)	0.131 (5)	−0.143 (3)	0.027 (9)*
C7	0.1261 (4)	0.2291 (4)	0.0137 (2)	0.0205 (6)

	U11	U22	U33	U12	U13	U23
Cu1	0.01983 (18)	0.02819 (19)	0.01006 (17)	0.01687 (15)	−0.00150 (12)	−0.00048 (13)
Cu2	0.01364 (16)	0.01637 (16)	0.01463 (17)	0.00709 (13)	0.00059 (12)	0.00577 (12)
O1	0.0189 (9)	0.0221 (9)	0.0142 (9)	0.0132 (8)	0.0004 (7)	0.0024 (7)
O2	0.0227 (10)	0.0281 (10)	0.0110 (9)	0.0176 (8)	−0.0011 (7)	0.0010 (7)
O3	0.0239 (10)	0.0238 (9)	0.0135 (9)	0.0169 (8)	−0.0001 (7)	0.0004 (8)
O4	0.0188 (9)	0.0212 (9)	0.0140 (9)	0.0108 (8)	0.0038 (7)	0.0058 (7)
O5	0.026 (3)	0.041 (3)	0.014 (2)	0.009 (2)	0.003 (2)	0.003 (2)
N1	0.0218 (12)	0.0337 (13)	0.0138 (11)	0.0166 (10)	0.0024 (9)	0.0071 (10)
N4	0.0303 (13)	0.0213 (11)	0.0163 (11)	0.0162 (10)	−0.0019 (10)	0.0030 (9)
N5'	0.017 (2)	0.0134 (18)	0.014 (2)	0.0076 (16)	0.0051 (16)	0.0018 (15)
N6'	0.020 (3)	0.034 (3)	0.023 (3)	0.015 (2)	−0.001 (2)	0.010 (2)
N5	0.018 (3)	0.018 (2)	0.023 (3)	0.012 (2)	0.004 (2)	0.007 (2)
N6	0.019 (3)	0.025 (3)	0.029 (3)	0.015 (2)	0.006 (2)	0.007 (2)
N7	0.0454 (17)	0.089 (2)	0.0143 (13)	0.0549 (18)	−0.0038 (12)	−0.0055 (14)
N8	0.0199 (11)	0.0245 (11)	0.0121 (10)	0.013 (1)	0.0009 (8)	0.0034 (9)
N9	0.0298 (13)	0.0263 (12)	0.0104 (11)	0.0157 (11)	0.004 (1)	0.0037 (10)
C1	0.0168 (12)	0.0147 (11)	0.0140 (12)	0.0068 (10)	−0.0002 (10)	0.0003 (10)
C2	0.0131 (12)	0.0117 (11)	0.0126 (12)	0.0042 (9)	−0.0007 (9)	0.0011 (9)
C3	0.0287 (16)	0.0449 (18)	0.0234 (15)	0.0297 (15)	0.0015 (12)	0.0019 (13)
C4	0.0208 (14)	0.0399 (16)	0.0176 (14)	0.0168 (13)	0.0009 (11)	0.0053 (12)
C5	0.0194 (13)	0.0202 (12)	0.0143 (12)	0.0104 (11)	−0.0042 (10)	0.0011 (10)
C6	0.0252 (15)	0.0252 (14)	0.0151 (13)	0.0127 (12)	−0.0038 (11)	0.0017 (11)
C7	0.0220 (14)	0.0272 (14)	0.0155 (13)	0.0164 (12)	0.0034 (11)	0.0029 (11)

Cu1—N8	1.947 (2)	N5'—N6'	1.132 (7)
Cu1—N7	1.977 (2)	N5—N6	1.197 (7)
Cu1—O2	1.9970 (18)	N7—C3	1.493 (4)
Cu1—O1	2.0275 (18)	N7—H7B	0.9200
Cu1—N1	2.371 (3)	N7—H7C	0.9200
Cu2—N1	1.962 (2)	N8—C7	1.322 (3)
Cu2—N4	1.980 (2)	N8—C5	1.390 (3)
Cu2—O3i	1.9915 (18)	N9—C7	1.334 (4)
Cu2—O4i	2.0148 (18)	N9—C6	1.366 (4)
O1—C2	1.258 (3)	N9—H9	0.80 (4)
O2—C1	1.249 (3)	C1—C2	1.534 (3)
O3—C1	1.258 (3)	C3—C4	1.516 (4)
O3—Cu2i	1.9915 (18)	C3—H3B	0.9900
O4—C2	1.251 (3)	C3—H3A	0.9900
O4—Cu2i	2.0148 (18)	C4—C5	1.493 (4)
N1—N2	1.192 (5)	C4—H4B	0.9900
N1—N2'	1.260 (6)	C4—H4A	0.9900
N2—N3	1.149 (7)	C5—C6	1.348 (4)
N2'—N3'	1.153 (7)	C6—H6A	0.84 (3)
N4—N5'	1.192 (4)	C7—H7A	0.88 (3)
N4—N5	1.300 (5)
N8—Cu1—N7	95.03 (10)	Cu1—N7—H7C	107.9
N8—Cu1—O2	90.05 (8)	H7B—N7—H7C	107.2
N7—Cu1—O2	168.22 (12)	C7—N8—C5	106.7 (2)
N8—Cu1—O1	168.11 (8)	C7—N8—Cu1	126.94 (19)
N7—Cu1—O1	89.88 (9)	C5—N8—Cu1	126.40 (18)
O2—Cu1—O1	83.23 (7)	C7—N9—C6	108.3 (2)
N8—Cu1—N1	101.85 (9)	C7—N9—H9	124 (3)
N7—Cu1—N1	95.97 (12)	C6—N9—H9	127 (3)
O2—Cu1—N1	93.37 (8)	O2—C1—O3	126.8 (2)
O1—Cu1—N1	88.36 (8)	O2—C1—C2	117.0 (2)
N1—Cu2—N4	94.99 (9)	O3—C1—C2	116.2 (2)
N1—Cu2—O3i	162.53 (9)	O4—C2—O1	126.1 (2)
N4—Cu2—O3i	90.34 (8)	O4—C2—C1	116.7 (2)
N1—Cu2—O4i	91.90 (8)	O1—C2—C1	117.1 (2)
N4—Cu2—O4i	173.09 (8)	N7—C3—C4	110.3 (3)
O3i—Cu2—O4i	82.91 (7)	N7—C3—H3B	109.6
C2—O1—Cu1	110.59 (16)	C4—C3—H3B	109.6
C1—O2—Cu1	111.93 (17)	N7—C3—H3A	109.6
C1—O3—Cu2i	112.47 (16)	C4—C3—H3A	109.6
C2—O4—Cu2i	111.66 (16)	H3B—C3—H3A	108.1
N2—N1—Cu2	128.1 (3)	C5—C4—C3	112.7 (2)
N2'—N1—Cu2	109.1 (3)	C5—C4—H4B	109.0
N2—N1—Cu1	102.3 (3)	C3—C4—H4B	109.0
N2'—N1—Cu1	130.6 (3)	C5—C4—H4A	109.0
Cu2—N1—Cu1	107.77 (10)	C3—C4—H4A	109.0
N3—N2—N1	176.5 (6)	H4B—C4—H4A	107.8
N3'—N2'—N1	172.4 (7)	C6—C5—N8	108.1 (2)
N5'—N4—N5	114.0 (3)	C6—C5—C4	130.8 (2)
N5'—N4—Cu2	117.9 (2)	N8—C5—C4	121.0 (2)
N5—N4—Cu2	121.0 (3)	C5—C6—N9	106.8 (2)
N6'—N5'—N4	173.9 (5)	C5—C6—H6A	132 (2)
N6—N5—N4	176.8 (5)	N9—C6—H6A	121 (2)
C3—N7—Cu1	117.6 (2)	N8—C7—N9	110.1 (2)
C3—N7—H7B	107.9	N8—C7—H7A	125.6 (19)
Cu1—N7—H7B	107.9	N9—C7—H7A	124.4 (19)
C3—N7—H7C	107.9

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O5ii	0.80 (4)	2.18 (4)	2.861 (6)	143 (3)
N9—H9···N6′ii	0.80 (4)	2.59 (4)	3.171 (6)	130 (3)
N9—H9···N3′iii	0.80 (4)	2.60 (4)	3.145 (7)	127 (3)
N9—H9···N6iv	0.80 (4)	2.38 (4)	3.108 (6)	151 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O5i	0.80 (4)	2.18 (4)	2.861 (6)	143 (3)
N9—H9⋯N6′i	0.80 (4)	2.59 (4)	3.171 (6)	130 (3)
N9—H9⋯N3′ii	0.80 (4)	2.60 (4)	3.145 (7)	127 (3)
N9—H9⋯N6iii	0.80 (4)	2.38 (4)	3.108 (6)	151 (3)

Symmetry codes: (i) ; (ii) ; (iii) .