PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): m1242.
Published online 2008 September 6. doi:  10.1107/S1600536808027840
PMCID: PMC2959271

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

Abstract

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 SO4 2− anions and two N atoms from one bis­(3,5-dimethyl­pyrazol-1-yl)methane ligand.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-m1242-scheme1.jpg

Experimental

Crystal data

  • [Cu2(SO4)2(C11H16N4)2]
  • M r = 727.76
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1242-efi1.jpg
  • a = 7.5293 (15) Å
  • b = 10.734 (2) Å
  • c = 17.740 (4) Å
  • β = 99.73 (3)°
  • V = 1413.2 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.71 mm−1
  • T = 291 (2) K
  • 0.22 × 0.19 × 0.19 mm

Data collection

  • Rigaku Mercury diffractometer
  • Absorption correction: multi-scan (Jacobson, 1998 [triangle]) T min = 0.704, T max = 0.737
  • 13344 measured reflections
  • 2580 independent reflections
  • 2253 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.112
  • S = 1.07
  • 2580 reflections
  • 194 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.42 e Å−3

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027840/cs2085sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027840/cs2085Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

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.

Crystal data

[Cu2(SO4)2(C11H16N4)2]F(000) = 748
Mr = 727.76Dx = 1.710 Mg m3
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 mm1
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

Rigaku Mercury diffractometer2580 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

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 = 1.07w = 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 Å3
0 restraintsΔρmin = −0.42 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2085).

References

  • Arnold, P. J., Davies, S. C., Dilworth, J. R., Durrant, M. C., Griffiths, D. V., Hughes, D. L., Richards, R. L. & Sharpe, P. C. (2001). J. Chem. Soc. Dalton Trans. pp. 736–746.
  • Dhar, S., Nethaji, M. & Chakravarty, A. R. (2004). J. Chem. Soc. Dalton Trans. pp. 4180–4184. [PubMed]
  • Endres, H., Noethe, D., Rossato, E. & Hatfield, W. E. (1984). Inorg. Chem.23, 3467–3473.
  • Hatzidimitriou, A. G., Kapnisti, M. & Voutsas, G. (2006). Z. Kristallogr. New Cryst. Struct.221, 532–534.
  • He, Y.-K. & Han, Z.-B. (2006). Acta Cryst. E62, m2676–m2677.
  • Jacobson, R. (1998). Private communication to the Rigaku Corporation.
  • Rigaku/MSC, (2001). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Rigaku/MSC, (2004). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Springsteen, C. H., Sweeder, R. D. & LaDuca, R. L. (2006). Cryst. Growth Des.6, 2308–2314.
  • Tamasi, G. & Cini, R. (2003). J. Chem. Soc. Dalton Trans. pp. 2928–2936.
  • Thompson, L. K., Xu, Z. Q., Goeta, A. E., Howard, J. A. K., Clase, H. J. & Miller, D. O. (1998). Inorg. Chem.37, 3217–3229.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography