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Acta Cryst. (2008). E64, m1242    [ doi:10.1107/S1600536808027840 ]

Di-[mu]-sulfato-bis{[bis(3,5-dimethylpyrazol-1-yl)methane]copper(II)}

Y. L. Wu, X. C. Wang and X. L. You

Abstract top

The molecule of the title compound, [Cu2(SO4)2(C11H16N4)2], sits on a center of symmetry. The CuII atom has a distorted trigonal-bipyramidal coordination geometry comprising three O atoms of the two symmetry-related SO42- anions and two N atoms from one bis(3,5-dimethylpyrazol-1-yl)methane ligand.

Comment top

SO42- anion-bridged dimeric complexes of Cu(II) are reported extensively (Tamasi & Cini, 2003). In most of these structures the SO42- anion acts as a bidentate bridge (Springsteen et al., 2006; He & Han, 2006; Arnold et al., 2001; Thompson et al., 1998; Endres et al., 1984). However, there are only two known examples of the tridentate bridge form (Hatzidimitriou et al., 2006; Dhar et al., 2004). The crystal structure of the title compound, [Cu(bdmpm)(SO4)]2 (bdmpm = bis(1,1-bis(3,5-dimethylpyrazol-1-yl)methane), shows a perfect centrosymmetric dimer, as two {Cu(bdmpm)}2+ units are bridged by two sulfate anions in the complex (Fig. 1). The Cu···Cu distance is 3.769 (11) Å and the copper atom has a trigonal bipyramidal CuN2O3 coordination geometry with the sulfate O(2) atom and the N(1) atom as axial ligand atoms.

Related literature top

For related literature, see: Arnold et al. (2001); Dhar et al. (2004); Endres et al. (1984); Hatzidimitriou et al. (2006); He & Han (2006); Springsteen et al. (2006); Tamasi & Cini (2003); Thompson et al. (1998).

Experimental top

The reaction of CuSO4.5H2O (25 mg, 0.1 mmol) with bdmpm (22 mg, 0.11 mmol) in MeOH (10 ml) was carried out at ambient temperature for 10 minutes, the mixture was filtered and the filtrate was then left for crystallization.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure with displacement ellipsoids drawn at the 50% probability level. Atoms labeled with the suffix A are related by the (-x, 1 - y, - z) symmetry operator.
Di-µ-sulfato-bis{[bis(3,5-dimethylpyrazol-1-yl)methane]copper(II)} top
Crystal data top
[Cu2(SO4)2(C11H16N4)2]F(000) = 748
Mr = 727.76Dx = 1.710 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4573 reflections
a = 7.5293 (15) Åθ = 3.0–25.4°
b = 10.734 (2) ŵ = 1.71 mm−1
c = 17.740 (4) ÅT = 291 K
β = 99.73 (3)°Block, green
V = 1413.2 (5) Å30.22 × 0.19 × 0.19 mm
Z = 2
Data collection top
Rigaku Mercury
diffractometer		2580 independent reflections
Radiation source: fine-focus sealed tube2253 reflections with I > 2σ(I)
graphiteRint = 0.039
Detector resolution: 14.6306 pixels mm-1θmax = 25.4°, θmin = 3.0°
ω scansh = −9→9
Absorption correction: multi-scan
(Jacobson, 1998)		k = −12→12
Tmin = 0.704, Tmax = 0.737l = −21→21
13344 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.054P)2 + 2.0475P]
where P = (Fo2 + 2Fc2)/3
2580 reflections(Δ/σ)max < 0.001
194 parametersΔρmax = 0.46 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
[Cu2(SO4)2(C11H16N4)2]V = 1413.2 (5) Å3
Mr = 727.76Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.5293 (15) ŵ = 1.71 mm−1
b = 10.734 (2) ÅT = 291 K
c = 17.740 (4) Å0.22 × 0.19 × 0.19 mm
β = 99.73 (3)°
Data collection top
Rigaku Mercury
diffractometer		2580 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		2253 reflections with I > 2σ(I)
Tmin = 0.704, Tmax = 0.737Rint = 0.039
13344 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.46 e Å−3
S = 1.07Δρmin = −0.42 e Å−3
2580 reflectionsAbsolute structure: ?
194 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu1−0.00166 (6)0.33244 (4)0.03099 (2)0.03196 (18)
S1−0.08737 (12)0.41689 (8)−0.10738 (5)0.0301 (2)
O1−0.2040 (4)0.3437 (3)−0.06474 (16)0.0422 (7)
O20.0920 (3)0.4113 (3)−0.05419 (15)0.0431 (7)
O3−0.0756 (4)0.3645 (3)−0.18102 (15)0.0461 (7)
O4−0.1457 (4)0.5477 (3)−0.11429 (16)0.0444 (7)
N1−0.1409 (4)0.2717 (3)0.10764 (17)0.0316 (7)
N2−0.0581 (4)0.1991 (3)0.16697 (17)0.0330 (7)
N30.1848 (4)0.1141 (3)0.11191 (17)0.0316 (7)
N40.1593 (4)0.1722 (3)0.04242 (17)0.0315 (7)
C1−0.3116 (5)0.2839 (4)0.1176 (2)0.0343 (9)
C2−0.3360 (6)0.2205 (4)0.1837 (2)0.0411 (10)
H2−0.44230.21520.20360.049*
C3−0.1745 (6)0.1674 (4)0.2137 (2)0.0365 (9)
C4−0.1213 (7)0.0889 (5)0.2836 (3)0.0557 (13)
H4A−0.08140.00890.26910.084*
H4B−0.22300.07850.30920.084*
H4C−0.02530.12910.31750.084*
C5−0.4425 (5)0.3586 (4)0.0638 (2)0.0433 (10)
H5A−0.38320.43070.04780.065*
H5B−0.53990.38430.08880.065*
H5C−0.48890.30890.01980.065*
C60.1344 (5)0.1810 (4)0.1760 (2)0.0331 (8)
H6A0.17510.13480.22280.040*
H6B0.19390.26150.18070.040*
C70.2597 (5)−0.0001 (4)0.1088 (2)0.0360 (9)
C80.2818 (6)−0.0156 (4)0.0345 (2)0.0418 (10)
H80.3300−0.08510.01400.050*
C90.2187 (5)0.0921 (4)−0.0045 (2)0.0340 (9)
C100.3072 (7)−0.0825 (4)0.1768 (3)0.0509 (11)
H10A0.4025−0.04490.21230.076*
H10B0.3462−0.16190.16090.076*
H10C0.2034−0.09360.20090.076*
C110.2141 (6)0.1216 (5)−0.0874 (2)0.0495 (11)
H11A0.09120.1305−0.11230.074*
H11B0.27010.0552−0.11110.074*
H11C0.27790.1979−0.09200.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0298 (3)0.0404 (3)0.0263 (3)0.00246 (19)0.0063 (2)0.00527 (19)
S10.0345 (5)0.0300 (5)0.0251 (5)−0.0015 (4)0.0034 (4)−0.0014 (4)
O10.0415 (16)0.0482 (17)0.0366 (15)−0.0127 (13)0.0059 (13)0.0060 (13)
O20.0328 (15)0.064 (2)0.0313 (14)−0.0037 (13)0.0025 (12)0.0067 (14)
O30.063 (2)0.0462 (17)0.0285 (14)0.0050 (14)0.0053 (14)−0.0078 (13)
O40.0621 (19)0.0333 (15)0.0372 (15)0.0054 (14)0.0068 (14)0.0024 (12)
N10.0287 (16)0.0381 (18)0.0286 (16)0.0030 (14)0.0066 (13)0.0039 (14)
N20.0355 (18)0.0353 (17)0.0287 (16)0.0059 (14)0.0069 (14)0.0051 (14)
N30.0357 (17)0.0299 (16)0.0297 (16)0.0044 (14)0.0068 (14)−0.0006 (14)
N40.0336 (17)0.0320 (17)0.0293 (16)0.0045 (13)0.0062 (14)0.0010 (13)
C10.033 (2)0.034 (2)0.038 (2)0.0010 (16)0.0112 (17)−0.0067 (17)
C20.041 (2)0.044 (2)0.043 (2)−0.0049 (19)0.0210 (19)0.0026 (19)
C30.044 (2)0.034 (2)0.035 (2)−0.0025 (17)0.0155 (19)0.0045 (17)
C40.068 (3)0.059 (3)0.044 (3)0.004 (2)0.023 (2)0.023 (2)
C50.028 (2)0.057 (3)0.045 (2)0.0065 (19)0.0064 (19)0.002 (2)
C60.039 (2)0.035 (2)0.0249 (18)0.0016 (17)0.0035 (16)0.0009 (16)
C70.034 (2)0.029 (2)0.043 (2)0.0028 (16)0.0017 (17)0.0007 (17)
C80.046 (2)0.035 (2)0.044 (2)0.0067 (18)0.0077 (19)−0.0071 (19)
C90.031 (2)0.034 (2)0.037 (2)0.0013 (16)0.0057 (17)−0.0069 (17)
C100.069 (3)0.035 (2)0.047 (3)0.011 (2)0.003 (2)0.005 (2)
C110.057 (3)0.059 (3)0.034 (2)0.010 (2)0.011 (2)−0.008 (2)
Geometric parameters (Å, °) top
Cu1—N11.963 (3)C2—H20.9300
Cu1—O21.964 (3)C3—C41.497 (6)
Cu1—O12.085 (3)C4—H4A0.9600
Cu1—N42.094 (3)C4—H4B0.9600
Cu1—O4i2.125 (3)C4—H4C0.9600
Cu1—S12.5939 (11)C5—H5A0.9600
S1—O31.439 (3)C5—H5B0.9600
S1—O41.470 (3)C5—H5C0.9600
S1—O11.479 (3)C6—H6A0.9700
S1—O21.513 (3)C6—H6B0.9700
O4—Cu1i2.125 (3)C7—C81.365 (5)
N1—C11.333 (5)C7—C101.489 (6)
N1—N21.372 (4)C8—C91.390 (6)
N2—C31.348 (5)C8—H80.9300
N2—C61.444 (5)C9—C111.499 (5)
N3—C71.354 (5)C10—H10A0.9600
N3—N41.366 (4)C10—H10B0.9600
N3—C61.449 (5)C10—H10C0.9600
N4—C91.326 (5)C11—H11A0.9600
C1—C21.394 (5)C11—H11B0.9600
C1—C51.486 (6)C11—H11C0.9600
C2—C31.367 (6)
N1—Cu1—O2168.29 (12)C3—C2—H2126.4
N1—Cu1—O1100.44 (11)C1—C2—H2126.4
O2—Cu1—O169.90 (11)N2—C3—C2106.4 (3)
N1—Cu1—N491.60 (12)N2—C3—C4122.8 (4)
O2—Cu1—N498.70 (12)C2—C3—C4130.8 (4)
O1—Cu1—N4117.24 (12)C3—C4—H4A109.5
N1—Cu1—O4i89.80 (12)C3—C4—H4B109.5
O2—Cu1—O4i93.50 (11)H4A—C4—H4B109.5
O1—Cu1—O4i139.06 (11)C3—C4—H4C109.5
N4—Cu1—O4i101.80 (12)H4A—C4—H4C109.5
N1—Cu1—S1134.03 (9)H4B—C4—H4C109.5
O2—Cu1—S135.47 (8)C1—C5—H5A109.5
O1—Cu1—S134.73 (8)C1—C5—H5B109.5
N4—Cu1—S1115.22 (9)H5A—C5—H5B109.5
O4i—Cu1—S1117.63 (8)C1—C5—H5C109.5
O3—S1—O4111.17 (17)H5A—C5—H5C109.5
O3—S1—O1112.93 (18)H5B—C5—H5C109.5
O4—S1—O1110.82 (18)N2—C6—N3111.7 (3)
O3—S1—O2111.43 (17)N2—C6—H6A109.3
O4—S1—O2108.23 (17)N3—C6—H6A109.3
O1—S1—O2101.81 (16)N2—C6—H6B109.3
O3—S1—Cu1132.76 (13)N3—C6—H6B109.3
O4—S1—Cu1115.83 (12)H6A—C6—H6B107.9
O1—S1—Cu153.44 (11)N3—C7—C8105.6 (3)
O2—S1—Cu148.89 (11)N3—C7—C10123.2 (4)
S1—O1—Cu191.83 (14)C8—C7—C10131.1 (4)
S1—O2—Cu195.64 (14)C7—C8—C9107.0 (4)
S1—O4—Cu1i114.00 (17)C7—C8—H8126.5
C1—N1—N2106.1 (3)C9—C8—H8126.5
C1—N1—Cu1134.3 (3)N4—C9—C8110.4 (3)
N2—N1—Cu1119.6 (2)N4—C9—C11121.7 (4)
C3—N2—N1110.9 (3)C8—C9—C11127.9 (4)
C3—N2—C6129.9 (3)C7—C10—H10A109.5
N1—N2—C6118.6 (3)C7—C10—H10B109.5
C7—N3—N4111.8 (3)H10A—C10—H10B109.5
C7—N3—C6130.3 (3)C7—C10—H10C109.5
N4—N3—C6117.8 (3)H10A—C10—H10C109.5
C9—N4—N3105.1 (3)H10B—C10—H10C109.5
C9—N4—Cu1136.3 (3)C9—C11—H11A109.5
N3—N4—Cu1117.0 (2)C9—C11—H11B109.5
N1—C1—C2109.3 (3)H11A—C11—H11B109.5
N1—C1—C5121.1 (3)C9—C11—H11C109.5
C2—C1—C5129.6 (4)H11A—C11—H11C109.5
C3—C2—C1107.3 (3)H11B—C11—H11C109.5
Symmetry codes: (i) −x, −y+1, −z.
Acknowledgements top

The authors acknowledge Jiangxi Science and Technology Normal University for funding.

references
References top

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