Hexa-μ₂-chlorido-μ₄-oxido-tetra­kis­[(3-methyl-5-phenyl-1H-pyrazole-κN²)copper(II)]

The title compound, [Cu₄Cl₆O(C₁₀H₁₀N₂)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-phenyl­pyrazole ligand, three Cl⁻ anions, and one O²⁻ 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.018 Å
• R factor = 0.067
• wR factor = 0.194
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT341_ALERT_3_B Low Bond Precision on  C-C Bonds (x 1000) Ang ..         18

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C5     -C10           1.36 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      73.00 A   3 
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         16

Alert level G
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      14.35
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.28 Ratio
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     .......       2.11

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

5-Methyl-3-phenylpyrazole has been widely used as starting material for the preparation of the trispyrazolylborate anion (Tekeste & Vahrenkamp, 2007; Jacobsen & Cohen, 2004; Puerta & Cohen, 2003; Parkin, 2004). It can form a dimeric complex (He & Sykes, 2007). Reported here is a new complex when it reacts with copper chloride.

In the title compound, (I), six chloride ions hold four copper ions together with an O atom encapsulated in the center (Fig. 1). The coordination geometry around each Cu^II is identical to each other with three Cl^- in the equatorial positions and N and O atoms in the axial positions. The distances between Cu1 and three Cl atoms are 2.361 (2), 2.514 (3) and 2.377 (2) Å. The distances between Cu1 and O1 and N1 are 1.9052 (10) and 1.953 (8) Å, respectively. The N1, Cu1 and O1 atoms fall almost in a line with an angle of 177.9 (5)°. The oxygen atom is located on a crystallographic fourfold roto-inversion axis.

Related literature

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

S2. Experimental

5-Methyl-3-phenylpyrazole (16.0 mg, 0.1 mmol), prepared according to the literature (Puerta & Cohen, 2003), was dissolved in dichloromethane (10 ml) at room temperature. To this solution, copper(II) chloride dihydrate (8.7 mg, 0.05 mmol) in methanol (2 ml) was added. The resulting solution was stirred for two hours. The mixture was filtered and the filtrate kept at room temperature. Brown crystals were obtained after one week by slow evaporation.

S3. Refinement

All H atoms are geometrically constrained and refined in riding mode as follows: methyl d(C—H) = 0.96 Å, U_iso(H) = 1.5U_eq(C); aromatic d(C—H) = 0.93 Å, U_iso(H) = 1.2U_eq(C); d(N—H) = 0.86 Å, U_iso(H) = 1.5U_eq(N).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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).

Figures

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are drawn as small circles of arbitrary radii.

Hexa-µ₂-chlorido-µ₄-oxido-tetrakis[(3-methyl-5-phenyl-1H-pyrazole- κN²)copper(II)]

Crystal data

[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) Å^3	Block, brown
Z = 2	0.30 × 0.30 × 0.30 mm
F(000) = 1124

Data collection

Bruker APEXII CCD area-detector diffractometer	2072 independent reflections
Radiation source: fine-focus sealed tube	1184 reflections with I > 2σ(I)
Graphite monochromator	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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.194	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 14.3478P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (8)

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—Cl2^i	2.377 (2)	C3—H3	0.9300
Cu1—Cl1	2.514 (3)	C4—C5	1.439 (15)
Cl2—Cu1^ii	2.377 (2)	C5—C10	1.350 (15)
Cl1—Cu1^iii	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—Cu1^iii	1.9052 (10)	C8—C9	1.359 (18)
O1—Cu1^i	1.9052 (10)	C8—H8	0.9300
O1—Cu1^ii	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—Cl2^i	84.98 (7)	C3—C2—C1	127.8 (9)
N1—Cu1—Cl2^i	96.7 (2)	C4—C3—C2	106.9 (8)
Cl2—Cu1—Cl2^i	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)
Cl2^i—Cu1—Cl1	117.06 (8)	C3—C4—C5	133.6 (9)
Cu1—Cl2—Cu1^ii	81.32 (8)	C10—C5—C6	115.7 (12)
Cu1^iii—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
Cu1^iii—O1—Cu1	112.00 (7)	C6—C7—H7	119.0
Cu1^iii—O1—Cu1^i	108.22 (3)	C7—C8—C9	119.3 (16)
Cu1—O1—Cu1^i	108.22 (3)	C7—C8—H8	120.3
Cu1^iii—O1—Cu1^ii	108.22 (3)	C9—C8—H8	120.3
Cu1—O1—Cu1^ii	108.22 (3)	C10—C9—C8	118.9 (15)
Cu1^i—O1—Cu1^ii	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—Cu1^ii	1.12 (6)	Cl1—Cu1—O1—Cu1^ii	119.21 (2)
N1—Cu1—Cl2—Cu1^ii	−176.7 (3)	N2—N1—C2—C3	0.8 (10)
Cl2^i—Cu1—Cl2—Cu1^ii	82.50 (10)	Cu1—N1—C2—C3	174.0 (6)
Cl1—Cu1—Cl2—Cu1^ii	−80.53 (11)	N2—N1—C2—C1	−177.8 (8)
O1—Cu1—Cl1—Cu1^iii	0.0	Cu1—N1—C2—C1	−4.6 (13)
N1—Cu1—Cl1—Cu1^iii	179.1 (2)	N1—C2—C3—C4	−1.1 (11)
Cl2—Cu1—Cl1—Cu1^iii	81.86 (9)	C1—C2—C3—C4	177.3 (9)
Cl2^i—Cu1—Cl1—Cu1^iii	−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)
Cl2^i—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)
Cl2^i—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—Cu1^iii	−120.66 (8)	C4—C5—C6—C7	178.0 (13)
Cl2^i—Cu1—O1—Cu1^iii	117.77 (8)	C5—C6—C7—C8	−2 (3)
Cl1—Cu1—O1—Cu1^iii	0.0	C6—C7—C8—C9	1 (3)
Cl2—Cu1—O1—Cu1^i	120.13 (9)	C7—C8—C9—C10	1 (2)
Cl2^i—Cu1—O1—Cu1^i	−1.44 (8)	C6—C5—C10—C9	1 (2)
Cl1—Cu1—O1—Cu1^i	−119.21 (2)	C4—C5—C10—C9	−175.8 (13)
Cl2—Cu1—O1—Cu1^ii	−1.45 (8)	C8—C9—C10—C5	−2 (2)
Cl2^i—Cu1—O1—Cu1^ii	−123.01 (9)

Symmetry codes: (i) −y+1, x−1/2, −z+2; (ii) y+1/2, −x+1, −z+2; (iii) −x+3/2, −y+1/2, z.