supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1979    [ doi:10.1107/S1600536807024671 ]

Bis[tris(1-pyrazolyl)methane-[kappa]3N,N',N'']copper(II) dichloride methanol disolvate

T. F. S. Silva, L. M. D. R. Martins, M. F. C. Guedes da Silva and A. J. L. Pombeiro

Abstract top

The reaction between copper(II) chloride dihydrate and excess tris(1-pyrazolyl)methane results in the formation of the title complex, [Cu(C10H10N6)2]Cl2·2CH3OH. The centrosymmetric complex cation is mononuclear with octahedral coordination for Cu and two tridentate ligands. Two short and one long Cu-N distances [2.002 (3), 2.011 (2) and 2.413 (2) Å] are found, as expected for Jahn-Teller distortion.

Comment top

Copper complexes of tripodal N3-donor ligands are of significance from a bioinorganic point of view since, for example, the N3–1igand coordination can mimic some spectroscopic features of blue copper proteins (Kitajima et al., 1990; Qiu et al., 1994). Compared with the enormous number of synthetic and structural studies of poly(1-pyrazolyl)borate Cu(II) comp1exes, only a few studies have been reported on the analogous poly(1-pyrazolyl)methane derivatives (Astley et al., 1993; Martini et al., 2002). We describe here a copper(II) complex containing tris(1-pyrazolyl)methane ligands, (I).

The structure of (I) (Fig. 1) consists of discrete centrosymmetric octahedral mononuclear CuII species with two tris(1-pyrazolyl)methane ligands, Cl− counter-ions, and methanol of crystallization. The bonding parameters are similar to those of the analogous complexes [Cu{HC(pz)3}2](NO3)2 and [Cu{HC(pz)3}2](ClO4)2 (Martini et al., 2002).

The Cu—N distances are close to those for [Cu{HC(pz)3}2](ClO4)2 (Martini et al., 2002). Two short Cu—N distances, approximately 2.0 Å, and one long, approximately 2.4 Å, are observed in both cases, consistent with Jahn-Teller distortion. All other bond lengths are normal (Allen et al., 1987; Orpen et al., 1989).

Related literature top

For related literature, see: Allen et al. (1987); Astley et al. (1993); Kitajima et al. (1990); Martini et al. (2002); Orpen et al. (1989); Qiu et al. (1994).

Experimental top

The title compound was prepared by the previously published procedure (Martini et al., 2002) using copper(II) chloride dihydrate and tris(1-pyrazolyl)methane as starting materials and a reaction time of 24 h. Suitable crystals for X-ray study were obtained by vapour diffusion of diethyl ether into a methanol solution of (I) at 278 K. Anal. Cal. for CuC22H28N12Cl2O: C, 42.1; H, 4.5; N, 26.8. Found: C, 42.4; H, 4.0; N, 28.4%. IR (KBr pellet): 3092.0 [s, ν (C–H)], 1630.2 and 1518.4 [s, ν (C═C), ν (N═C), HC(pz)3]. EPR (90 K): g = 2.0732; aCu = 168; aN = 12.5. FAB+—MS, m/z: 626 [M]+, 611 [M – O]+, 561 [M – pz]+, 528 [M – 2pz +Cl]+, 493 [M – 2pz]+. FAB−–MS, m/z: 35 [Cl]−–.

Refinement top

All H atoms were located in a difference map and refined freely, giving C—H = 0.86 (3)–0.99 (4)° and O—H = 0.76 (4) Å.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of the cation of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size. [Symmetry code: (a) −x, −y, −z.]
Bis[tris(1-pyrazolyl)methane-κ3N,N',N'']copper(II) dichloride methanol disolvate top
Crystal data top
[Cu(C10H10N6)2]Cl2·2CH4OF000 = 646
Mr = 627.00Dx = 1.458 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71069 Å
a = 8.5069 (13) ÅCell parameters from 829 reflections
b = 10.4307 (16) Åθ = 2.5–22.6º
c = 16.101 (3) ŵ = 1.00 mm−1
β = 91.574 (8)ºT = 150 (2) K
V = 1428.1 (4) Å3Block, blue
Z = 20.10 × 0.08 × 0.06 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2497 independent reflections
Radiation source: fine-focus sealed tube1871 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.058
T = 150(2) Kθmax = 25.3º
φ and ω scansθmin = 3.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −9→8
Tmin = 0.907, Tmax = 0.943k = −12→8
6690 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040All H-atom parameters refined
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0365P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.001
2497 reflectionsΔρmax = 0.33 e Å−3
234 parametersΔρmin = −0.34 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C10H10N6)2]Cl2·2CH4OV = 1428.1 (4) Å3
Mr = 627.00Z = 2
Monoclinic, P21/cMo Kα
a = 8.5069 (13) ŵ = 1.00 mm−1
b = 10.4307 (16) ÅT = 150 (2) K
c = 16.101 (3) Å0.10 × 0.08 × 0.06 mm
β = 91.574 (8)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2497 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1871 reflections with I > 2σ(I)
Tmin = 0.907, Tmax = 0.943Rint = 0.058
6690 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040234 parameters
wR(F2) = 0.085All H-atom parameters refined
S = 0.97Δρmax = 0.33 e Å−3
2497 reflectionsΔρmin = −0.34 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.1681 (4)0.2505 (3)−0.05452 (19)0.0131 (7)
C10−0.0476 (7)0.3472 (4)0.2225 (3)0.0405 (11)
C110.2292 (4)−0.0536 (3)−0.1423 (2)0.0181 (8)
C120.3208 (4)0.1382 (3)−0.16536 (19)0.0173 (8)
C130.3323 (4)0.0143 (3)−0.1904 (2)0.0198 (8)
C210.2827 (4)0.1359 (3)0.1412 (2)0.0169 (7)
C220.3558 (4)0.2975 (3)0.0643 (2)0.0163 (7)
C230.3904 (4)0.2372 (3)0.1373 (2)0.0200 (8)
C31−0.2408 (4)0.2123 (3)−0.0468 (2)0.0183 (8)
C32−0.0855 (4)0.3708 (3)−0.0796 (2)0.0182 (8)
C33−0.2401 (4)0.3394 (3)−0.0739 (2)0.0209 (8)
N110.1550 (3)0.0229 (2)−0.09019 (15)0.0142 (6)
N120.2121 (3)0.1422 (2)−0.10577 (15)0.0135 (6)
N210.1868 (3)0.1328 (2)0.07567 (16)0.0154 (6)
N220.2318 (3)0.2345 (2)0.02865 (16)0.0139 (6)
N31−0.0963 (3)0.1681 (2)−0.03537 (16)0.0143 (6)
N320.0001 (3)0.2665 (2)−0.05655 (16)0.0141 (6)
O10−0.0946 (3)0.3534 (2)0.13793 (16)0.0265 (6)
Cl10.38445 (10)0.47169 (6)−0.14522 (5)0.0183 (2)
Cu10.00000.00000.00000.01293 (17)
H10.214 (3)0.329 (3)−0.0776 (17)0.008 (7)*
H10−0.170 (5)0.390 (3)0.132 (2)0.031 (13)*
H10A−0.138 (8)0.321 (6)0.254 (4)0.14 (3)*
H10B−0.018 (5)0.434 (4)0.243 (3)0.050 (12)*
H10C0.036 (7)0.293 (5)0.229 (3)0.11 (2)*
H110.205 (4)−0.141 (3)−0.1439 (19)0.021 (9)*
H120.366 (4)0.207 (3)−0.181 (2)0.020 (9)*
H130.396 (4)−0.016 (3)−0.2311 (19)0.015 (9)*
H210.280 (4)0.074 (3)0.185 (2)0.021 (9)*
H220.397 (4)0.370 (3)0.0392 (18)0.017 (8)*
H230.468 (4)0.258 (3)0.173 (2)0.029 (10)*
H31−0.331 (4)0.159 (3)−0.038 (2)0.029 (10)*
H32−0.027 (4)0.444 (3)−0.0968 (18)0.010 (8)*
H33−0.334 (4)0.391 (3)−0.0892 (19)0.023 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.013 (2)0.0095 (15)0.0171 (17)−0.0023 (13)0.0011 (14)0.0012 (13)
C100.041 (3)0.040 (2)0.040 (3)0.008 (2)−0.015 (2)−0.006 (2)
C110.018 (2)0.0151 (16)0.0214 (19)0.0027 (14)0.0051 (15)−0.0027 (14)
C120.018 (2)0.0179 (17)0.0165 (18)0.0002 (14)0.0068 (15)0.0042 (13)
C130.020 (2)0.0203 (17)0.0194 (18)0.0031 (15)0.0116 (16)−0.0001 (15)
C210.018 (2)0.0168 (16)0.0159 (18)−0.0037 (14)0.0023 (15)0.0014 (13)
C220.015 (2)0.0128 (16)0.0215 (18)−0.0038 (14)0.0059 (15)−0.0021 (13)
C230.017 (2)0.0245 (17)0.0189 (19)−0.0029 (15)−0.0024 (16)−0.0042 (15)
C310.014 (2)0.0191 (16)0.0220 (19)0.0024 (15)0.0014 (15)−0.0013 (14)
C320.028 (2)0.0092 (15)0.0175 (17)0.0017 (14)0.0008 (15)0.0029 (13)
C330.016 (2)0.0179 (16)0.029 (2)0.0073 (15)0.0013 (16)0.0046 (15)
N110.0165 (17)0.0097 (12)0.0166 (14)−0.0024 (11)0.0029 (12)0.0037 (10)
N120.0163 (17)0.0104 (12)0.0140 (14)−0.0027 (11)0.0043 (12)0.0015 (10)
N210.0144 (17)0.0157 (13)0.0160 (14)−0.0033 (11)0.0015 (12)0.0017 (11)
N220.0144 (16)0.0096 (12)0.0180 (15)−0.0020 (11)0.0035 (12)0.0028 (11)
N310.0098 (17)0.0117 (12)0.0216 (15)−0.0038 (11)0.0041 (12)0.0020 (11)
N320.0119 (17)0.0114 (12)0.0191 (15)0.0014 (11)0.0029 (12)0.0013 (11)
O100.0262 (18)0.0226 (13)0.0306 (15)0.0054 (12)−0.0027 (13)−0.0015 (11)
Cl10.0164 (5)0.0161 (4)0.0225 (4)−0.0028 (3)0.0027 (4)0.0023 (3)
Cu10.0121 (3)0.0095 (3)0.0174 (3)0.0000 (2)0.0042 (2)0.0027 (2)
Geometric parameters (Å, °) top
C1—N321.438 (4)C22—H220.93 (3)
C1—N221.440 (4)C23—H230.89 (4)
C1—N121.454 (4)C31—N311.321 (4)
C1—H10.99 (3)C31—C331.396 (4)
C10—O101.411 (5)C31—H310.96 (3)
C10—H10A0.98 (7)C32—N321.355 (4)
C10—H10B0.99 (4)C32—C331.361 (5)
C10—H10C0.91 (6)C32—H320.96 (3)
C11—N111.329 (4)C33—H330.98 (3)
C11—C131.382 (5)N11—N121.362 (3)
C11—H110.93 (3)N11—Cu12.002 (3)
C12—N121.352 (4)N21—N221.364 (3)
C12—C131.358 (4)N21—Cu12.413 (2)
C12—H120.86 (3)N31—N321.363 (3)
C13—H130.92 (3)N31—Cu12.011 (2)
C21—N211.316 (4)O10—H100.76 (4)
C21—C231.401 (4)Cu1—N11i2.002 (3)
C21—H210.95 (3)Cu1—N31i2.011 (2)
C22—N221.357 (4)Cu1—N21i2.413 (2)
C22—C231.357 (5)
N32—C1—N22112.5 (3)C32—C33—H33128.9 (18)
N32—C1—N12110.4 (2)C31—C33—H33125.7 (18)
N22—C1—N12110.0 (2)C11—N11—N12104.7 (2)
N32—C1—H1107.5 (17)C11—N11—Cu1136.0 (2)
N22—C1—H1107.7 (16)N12—N11—Cu1119.17 (18)
N12—C1—H1108.6 (16)C12—N12—N11110.9 (2)
O10—C10—H10A108 (4)C12—N12—C1128.2 (2)
O10—C10—H10B110 (2)N11—N12—C1120.5 (2)
H10A—C10—H10B106 (4)C21—N21—N22104.4 (2)
O10—C10—H10C110 (4)C21—N21—Cu1143.5 (2)
H10A—C10—H10C113 (5)N22—N21—Cu1110.92 (18)
H10B—C10—H10C109 (4)C22—N22—N21111.6 (3)
N11—C11—C13111.5 (3)C22—N22—C1127.3 (3)
N11—C11—H11120 (2)N21—N22—C1120.1 (2)
C13—C11—H11129 (2)C31—N31—N32105.5 (2)
N12—C12—C13107.3 (3)C31—N31—Cu1135.5 (2)
N12—C12—H12121 (2)N32—N31—Cu1118.98 (19)
C13—C12—H12132 (2)C32—N32—N31110.5 (3)
C12—C13—C11105.6 (3)C32—N32—C1128.8 (3)
C12—C13—H13126.0 (19)N31—N32—C1120.7 (2)
C11—C13—H13128.4 (19)C10—O10—H10112 (3)
N21—C21—C23111.9 (3)N11—Cu1—N11i180.00 (14)
N21—C21—H21123 (2)N11—Cu1—N3187.82 (10)
C23—C21—H21125 (2)N11i—Cu1—N3192.18 (10)
N22—C22—C23106.8 (3)N11—Cu1—N31i92.18 (10)
N22—C22—H22120.5 (19)N11i—Cu1—N31i87.82 (10)
C23—C22—H22132.6 (19)N31—Cu1—N31i180.00 (15)
C22—C23—C21105.2 (3)N11—Cu1—N2181.95 (9)
C22—C23—H23126 (2)N11i—Cu1—N2198.05 (9)
C21—C23—H23129 (2)N31—Cu1—N2184.24 (9)
N31—C31—C33111.3 (3)N31i—Cu1—N2195.76 (9)
N31—C31—H31121 (2)N11—Cu1—N21i98.05 (9)
C33—C31—H31127 (2)N11i—Cu1—N21i81.95 (9)
N32—C32—C33107.6 (3)N31—Cu1—N21i95.76 (9)
N32—C32—H32116.0 (18)N31i—Cu1—N21i84.24 (9)
C33—C32—H32136.4 (18)N21—Cu1—N21i180.00 (14)
C32—C33—C31105.2 (3)
N12—C12—C13—C11−1.2 (4)C31—N31—N32—C1−177.7 (3)
N11—C11—C13—C120.6 (4)Cu1—N31—N32—C10.6 (3)
N22—C22—C23—C211.0 (4)N22—C1—N32—C32114.0 (3)
N21—C21—C23—C22−0.2 (4)N12—C1—N32—C32−122.7 (3)
N32—C32—C33—C31−0.2 (4)N22—C1—N32—N31−67.7 (3)
N31—C31—C33—C320.8 (4)N12—C1—N32—N3155.6 (3)
C13—C11—N11—N120.2 (4)C11—N11—Cu1—N11i22 (5)
C13—C11—N11—Cu1−177.0 (2)N12—N11—Cu1—N11i−155 (5)
C13—C12—N12—N111.4 (4)C11—N11—Cu1—N31−145.0 (3)
C13—C12—N12—C1174.0 (3)N12—N11—Cu1—N3138.1 (2)
C11—N11—N12—C12−1.0 (3)C11—N11—Cu1—N31i35.0 (3)
Cu1—N11—N12—C12176.8 (2)N12—N11—Cu1—N31i−141.9 (2)
C11—N11—N12—C1−174.2 (3)C11—N11—Cu1—N21130.5 (3)
Cu1—N11—N12—C13.5 (4)N12—N11—Cu1—N21−46.4 (2)
N32—C1—N12—C12129.8 (3)C11—N11—Cu1—N21i−49.5 (3)
N22—C1—N12—C12−105.5 (3)N12—N11—Cu1—N21i133.6 (2)
N32—C1—N12—N11−58.3 (3)C31—N31—Cu1—N11137.2 (3)
N22—C1—N12—N1166.4 (3)N32—N31—Cu1—N11−40.4 (2)
C23—C21—N21—N22−0.6 (3)C31—N31—Cu1—N11i−42.8 (3)
C23—C21—N21—Cu1164.7 (3)N32—N31—Cu1—N11i139.6 (2)
C23—C22—N22—N21−1.4 (4)C31—N31—Cu1—N31i−14 (25)
C23—C22—N22—C1−169.9 (3)N32—N31—Cu1—N31i169 (25)
C21—N21—N22—C221.2 (3)C31—N31—Cu1—N21−140.7 (3)
Cu1—N21—N22—C22−169.5 (2)N32—N31—Cu1—N2141.7 (2)
C21—N21—N22—C1170.6 (3)C31—N31—Cu1—N21i39.3 (3)
Cu1—N21—N22—C10.0 (3)N32—N31—Cu1—N21i−138.3 (2)
N32—C1—N22—C22−131.0 (3)C21—N21—Cu1—N11−118.9 (4)
N12—C1—N22—C22105.5 (3)N22—N21—Cu1—N1145.76 (19)
N32—C1—N22—N2161.4 (3)C21—N21—Cu1—N11i61.1 (4)
N12—C1—N22—N21−62.1 (4)N22—N21—Cu1—N11i−134.24 (19)
C33—C31—N31—N32−1.0 (4)C21—N21—Cu1—N31152.5 (4)
C33—C31—N31—Cu1−178.9 (2)N22—N21—Cu1—N31−42.85 (19)
C33—C32—N32—N31−0.5 (4)C21—N21—Cu1—N31i−27.5 (4)
C33—C32—N32—C1178.0 (3)N22—N21—Cu1—N31i137.15 (19)
C31—N31—N32—C320.9 (3)C21—N21—Cu1—N21i−1.5 (4)
Cu1—N31—N32—C32179.2 (2)N22—N21—Cu1—N21i163.16 (15)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

This work has been partially supported by the IPL 41/2003 and the Fundação para a Ciência e a Tecnologia (FCT), Portugal, and its POCI 2010 programme (FEDER funded).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Astley, T., Gulbis, J. M., Hitchman, M. A. & Tiekink, E. R. T. (1993). J. Chem. Soc. Dalton Trans. pp. 509–515.

Bruker, (2000). SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Kitajima, N., Fujisawa, K. & Moro-oka, Y. (1990). J. Am. Chem. Soc. 112, 3210–3212.

Martini, D., Pellei, M., Pettinari, C., Skelton, B. & White, A. (2002). Inorg. Chim. Acta, 333, 72–82.

Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1–83.

Qiu, D., Kilpatrick, L., Kitajima, N. & Spiro, T. G. (1994). J. Am. Chem. Soc. 116, 2585–2590.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.