Hexa-μ(2)-chlorido-μ(4)-oxido-tetra-kis-[(3-methyl-5-phenyl-1H-pyrazole-κN)copper(II)].

The title compound, [Cu(4)Cl(6)O(C(10)H(10)N(2))(4)], contains four Cu(II) atoms which are bridged by six chloride anions. The central O atom is located on a crystallographic fourfold roto-inversion axis. Each Cu(II) atom is coordinated by an N atom of a neutral monodentate 3-methyl-5-phenyl-pyrazole ligand, three Cl(-) anions, and one O(2-) anion. The geometry at each Cu(II) atom is distorted trigonal-bipyramidal, with the three Cl(-) ions in the equatorial plane and the N and O atoms in the axial positions.

Related literature

For the formation of tris­pyrazolylborate anions, see: Tekeste & Vahrenkamp (2007 ▶); Jacobsen & Cohen (2004 ▶); Puerta & Cohen (2003 ▶); Parkin (2004 ▶). For the formation of dinuclear copper compounds, see: He & Sykes (2007 ▶). For the formation of tetranuclear compounds, see: Keij et al. (1991 ▶); Liu et al. (2003 ▶); Chiarella et al. (2009 ▶).

Experimental

Crystal data

[Cu4Cl6O(C10H10N2)4]

M = 1115.66

Tetragonal,

a = 14.5460 (6) Å

c = 11.1686 (7) Å

V = 2363.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 2.16 mm−1

T = 293 K

0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.564, T max = 0.564

14047 measured reflections

2072 independent reflections

1184 reflections with I > 2σ(I)

R int = 0.080

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.194

S = 1.17

2072 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.72 e Å−3

Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053663/is2649sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053663/is2649Isup2.hkl

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

[Cu4Cl6O(C10H10N2)4]	Dx = 1.568 Mg m−3
Mr = 1115.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 16570 reflections
Hall symbol: -P 4a	θ = 2.3–25.0°
a = 14.5460 (6) Å	µ = 2.16 mm−1
c = 11.1686 (7) Å	T = 293 K
V = 2363.1 (3) Å3	Block, brown
Z = 2	0.30 × 0.30 × 0.30 mm
F(000) = 1124

Bruker APEXII CCD area-detector diffractometer	2072 independent reflections
Radiation source: fine-focus sealed tube	1184 reflections with I > 2σ(I)
graphite	Rint = 0.080
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −17→17
Tmin = 0.564, Tmax = 0.564	k = −17→17
14047 measured reflections	l = −13→13

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)] = 0.067	H-atom parameters constrained
wR(F2) = 0.194	w = 1/[σ2(Fo2) + (0.0526P)2 + 14.3478P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max < 0.001
2072 reflections	Δρmax = 0.72 e Å−3
136 parameters	Δρmin = −0.56 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: 0.0028 (8)

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.

	x	y	z	Uiso*/Ueq
Cu1	0.72083 (7)	0.14541 (7)	0.90461 (11)	0.0567 (5)
Cl2	0.57726 (15)	0.14864 (15)	1.0031 (3)	0.0729 (8)
Cl1	0.7500	0.2500	0.7295 (3)	0.0705 (10)
N2	0.6784 (5)	0.0507 (5)	0.6812 (8)	0.070 (2)
H2	0.6890	0.1006	0.6424	0.084*
N1	0.6896 (5)	0.0413 (5)	0.8019 (8)	0.063 (2)
O1	0.7500	0.2500	1.0000	0.052 (3)
C1	0.6666 (7)	−0.0801 (7)	0.9515 (11)	0.079 (3)
H1A	0.6904	−0.0337	1.0042	0.119*
H1B	0.7046	−0.1340	0.9560	0.119*
H1C	0.6050	−0.0954	0.9749	0.119*
C2	0.6663 (6)	−0.0449 (6)	0.8269 (10)	0.063 (3)
C3	0.6412 (7)	−0.0918 (7)	0.7231 (11)	0.075 (3)
H3	0.6232	−0.1530	0.7177	0.090*
C4	0.6481 (7)	−0.0296 (7)	0.6292 (11)	0.072 (3)
C5	0.6268 (7)	−0.0344 (7)	0.5035 (11)	0.075 (3)
C6	0.5923 (10)	−0.1170 (9)	0.4580 (14)	0.120 (5)
H6	0.5854	−0.1677	0.5079	0.143*
C7	0.5686 (12)	−0.1228 (12)	0.3385 (15)	0.139 (6)
H7	0.5476	−0.1786	0.3084	0.166*
C8	0.5748 (10)	−0.0512 (12)	0.2651 (15)	0.122 (5)
H8	0.5571	−0.0566	0.1854	0.146*
C9	0.6072 (10)	0.0301 (11)	0.3078 (14)	0.120 (5)
H9	0.6116	0.0811	0.2579	0.144*
C10	0.6331 (9)	0.0355 (9)	0.4244 (13)	0.104 (4)
H10	0.6568	0.0911	0.4516	0.125*

	U11	U22	U33	U12	U13	U23
Cu1	0.0436 (6)	0.0403 (6)	0.0863 (9)	−0.0028 (4)	−0.0010 (6)	−0.0064 (5)
Cl2	0.0424 (12)	0.0602 (14)	0.116 (2)	−0.0100 (10)	0.0079 (13)	−0.0219 (14)
Cl1	0.088 (2)	0.0405 (17)	0.082 (2)	−0.0115 (16)	0.000	0.000
N2	0.074 (5)	0.056 (5)	0.081 (6)	−0.014 (4)	0.002 (5)	−0.006 (4)
N1	0.051 (4)	0.043 (4)	0.096 (7)	−0.004 (3)	0.011 (4)	0.000 (4)
O1	0.039 (3)	0.039 (3)	0.077 (8)	0.000	0.000	0.000
C1	0.065 (6)	0.058 (6)	0.114 (10)	−0.016 (5)	0.001 (6)	0.009 (6)
C2	0.046 (5)	0.051 (5)	0.092 (8)	−0.001 (4)	0.009 (5)	0.008 (5)
C3	0.076 (7)	0.047 (5)	0.102 (9)	−0.013 (5)	0.000 (6)	−0.012 (6)
C4	0.066 (6)	0.054 (6)	0.097 (9)	−0.016 (5)	0.009 (6)	−0.012 (6)
C5	0.073 (7)	0.074 (7)	0.078 (8)	−0.017 (5)	0.013 (6)	−0.017 (6)
C6	0.149 (13)	0.090 (9)	0.119 (12)	−0.040 (9)	0.014 (10)	−0.039 (8)
C7	0.180 (16)	0.130 (14)	0.106 (13)	−0.057 (12)	0.008 (12)	−0.049 (11)
C8	0.108 (11)	0.142 (14)	0.115 (12)	−0.035 (10)	0.011 (9)	−0.029 (12)
C9	0.128 (12)	0.127 (12)	0.104 (11)	−0.037 (10)	−0.004 (9)	0.003 (10)
C10	0.122 (11)	0.096 (9)	0.095 (10)	−0.032 (8)	−0.014 (8)	0.004 (8)

Cu1—O1	1.9052 (10)	C1—H1C	0.9600
Cu1—N1	1.953 (8)	C2—C3	1.394 (14)
Cu1—Cl2	2.361 (2)	C3—C4	1.388 (14)
Cu1—Cl2i	2.377 (2)	C3—H3	0.9300
Cu1—Cl1	2.514 (3)	C4—C5	1.439 (15)
Cl2—Cu1ii	2.377 (2)	C5—C10	1.350 (15)
Cl1—Cu1iii	2.514 (3)	C5—C6	1.397 (15)
N2—N1	1.365 (11)	C6—C7	1.38 (2)
N2—C4	1.377 (11)	C6—H6	0.9300
N2—H2	0.8600	C7—C8	1.33 (2)
N1—C2	1.328 (10)	C7—H7	0.9300
O1—Cu1iii	1.9052 (10)	C8—C9	1.359 (18)
O1—Cu1i	1.9052 (10)	C8—H8	0.9300
O1—Cu1ii	1.9052 (10)	C9—C10	1.358 (18)
C1—C2	1.482 (15)	C9—H9	0.9300
C1—H1A	0.9600	C10—H10	0.9300
C1—H1B	0.9600
O1—Cu1—N1	177.9 (3)	H1B—C1—H1C	109.5
O1—Cu1—Cl2	85.45 (7)	N1—C2—C3	110.7 (10)
N1—Cu1—Cl2	94.8 (2)	N1—C2—C1	121.5 (10)
O1—Cu1—Cl2i	84.98 (7)	C3—C2—C1	127.8 (9)
N1—Cu1—Cl2i	96.7 (2)	C4—C3—C2	106.9 (8)
Cl2—Cu1—Cl2i	120.86 (5)	C4—C3—H3	126.6
O1—Cu1—Cl1	85.08 (7)	C2—C3—H3	126.6
N1—Cu1—Cl1	93.0 (3)	N2—C4—C3	104.9 (9)
Cl2—Cu1—Cl1	119.98 (8)	N2—C4—C5	121.4 (10)
Cl2i—Cu1—Cl1	117.06 (8)	C3—C4—C5	133.6 (9)
Cu1—Cl2—Cu1ii	81.32 (8)	C10—C5—C6	115.7 (12)
Cu1iii—Cl1—Cu1	77.85 (12)	C10—C5—C4	126.0 (10)
N1—N2—C4	111.7 (8)	C6—C5—C4	118.3 (12)
N1—N2—H2	124.1	C7—C6—C5	119.6 (15)
C4—N2—H2	124.1	C7—C6—H6	120.2
C2—N1—N2	105.8 (8)	C5—C6—H6	120.2
C2—N1—Cu1	131.9 (8)	C8—C7—C6	122.0 (15)
N2—N1—Cu1	122.0 (6)	C8—C7—H7	119.0
Cu1iii—O1—Cu1	112.00 (7)	C6—C7—H7	119.0
Cu1iii—O1—Cu1i	108.22 (3)	C7—C8—C9	119.3 (16)
Cu1—O1—Cu1i	108.22 (3)	C7—C8—H8	120.3
Cu1iii—O1—Cu1ii	108.22 (3)	C9—C8—H8	120.3
Cu1—O1—Cu1ii	108.22 (3)	C10—C9—C8	118.9 (15)
Cu1i—O1—Cu1ii	112.00 (7)	C10—C9—H9	120.6
C2—C1—H1A	109.5	C8—C9—H9	120.6
C2—C1—H1B	109.5	C5—C10—C9	124.4 (13)
H1A—C1—H1B	109.5	C5—C10—H10	117.8
C2—C1—H1C	109.5	C9—C10—H10	117.8
H1A—C1—H1C	109.5
O1—Cu1—Cl2—Cu1ii	1.12 (6)	Cl1—Cu1—O1—Cu1ii	119.21 (2)
N1—Cu1—Cl2—Cu1ii	−176.7 (3)	N2—N1—C2—C3	0.8 (10)
Cl2i—Cu1—Cl2—Cu1ii	82.50 (10)	Cu1—N1—C2—C3	174.0 (6)
Cl1—Cu1—Cl2—Cu1ii	−80.53 (11)	N2—N1—C2—C1	−177.8 (8)
O1—Cu1—Cl1—Cu1iii	0.0	Cu1—N1—C2—C1	−4.6 (13)
N1—Cu1—Cl1—Cu1iii	179.1 (2)	N1—C2—C3—C4	−1.1 (11)
Cl2—Cu1—Cl1—Cu1iii	81.86 (9)	C1—C2—C3—C4	177.3 (9)
Cl2i—Cu1—Cl1—Cu1iii	−81.80 (9)	N1—N2—C4—C3	−0.6 (11)
C4—N2—N1—C2	−0.1 (10)	N1—N2—C4—C5	176.7 (9)
C4—N2—N1—Cu1	−174.1 (6)	C2—C3—C4—N2	1.0 (11)
Cl2—Cu1—N1—C2	−60.9 (8)	C2—C3—C4—C5	−175.8 (11)
Cl2i—Cu1—N1—C2	61.0 (8)	N2—C4—C5—C10	−0.3 (18)
Cl1—Cu1—N1—C2	178.7 (8)	C3—C4—C5—C10	176.0 (13)
Cl2—Cu1—N1—N2	111.4 (6)	N2—C4—C5—C6	−177.1 (11)
Cl2i—Cu1—N1—N2	−126.7 (6)	C3—C4—C5—C6	−0.7 (19)
Cl1—Cu1—N1—N2	−9.0 (6)	C10—C5—C6—C7	1(2)
Cl2—Cu1—O1—Cu1iii	−120.66 (8)	C4—C5—C6—C7	178.0 (13)
Cl2i—Cu1—O1—Cu1iii	117.77 (8)	C5—C6—C7—C8	−2(3)
Cl1—Cu1—O1—Cu1iii	0.0	C6—C7—C8—C9	1(3)
Cl2—Cu1—O1—Cu1i	120.13 (9)	C7—C8—C9—C10	1(2)
Cl2i—Cu1—O1—Cu1i	−1.44 (8)	C6—C5—C10—C9	1(2)
Cl1—Cu1—O1—Cu1i	−119.21 (2)	C4—C5—C10—C9	−175.8 (13)
Cl2—Cu1—O1—Cu1ii	−1.45 (8)	C8—C9—C10—C5	−2(2)
Cl2i—Cu1—O1—Cu1ii	−123.01 (9)