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Acta Cryst. (2008). E64, m1053-m1054    [ doi:10.1107/S1600536808022605 ]

Di-[mu]-chlorido-bis[dichlorido(3,3',5,5'-tetramethyl-4,4'-bipyrazol-1-ium-[kappa]N2')copper(II)] dihydrate

M. A. Kurawa, C. J. Adams and A. G. Orpen

Abstract top

The structure of the centrosymmetric title compound, [Cu2Cl6(C10H15N4)2]·2H2O, consists of a dimeric [{(HMe4bpz)CuCl3}2] unit (HMe4bpz is 3,3',5,5'-tetramethyl-4,4'-bipyrazol-1-ium) with two solvent water molecules. Each [HMe4bpz]+ cation is bonded to a CuCl3 unit through a Cu-N dative bond, effectively making square-planar geometry at the Cu atom. Two of these units then undergo a face-to-face dimerization so that the Cu atoms have a Jahn-Teller distorted square-pyramidal geometry with three chlorides and an N atom in the basal plane and one chloride weakly bound in the apical position. Several N-H...Cl, O-H...Cl and N-H...O hydrogen bonds form a three-dimensional network.

Comment top

We have sought to explore N—H···Cl interactions in designing and synthesizing crystal structures with desired properties such as unit cell metrics or defined reactivity (Adams et al., 2005). We aimed to utilize these interactions by reacting 3,3',5,5'- tetramethylbipyrazole dihydrochloride and copper(II) chloride dihydrate in a 1:1 ratio to synthesize (C10H16N4)[CuCl4]. However, the title compound I was obtained instead, crystallizing in the triclinic system with the P1 space group, with a [HMe4bpz]+ cation bonded to a CuCl3- unit through a Cu—N bond, forming a zwitterion. In the crystal structure, water molecules bridge adjacent [{(HMe4bpz)CuCl3}2] dimers through O—H···Cl hydrogen bonds forming a hydrogen bonded ribbon (Fig. 2) along the a-axis.

Related literature top

We have been unable to find any references in the literature to any other compound containing a monoprotonated 3,3',5,5'- tetramethylbipyrazole ligand coordinated only to one metal atom through a single nitrogen donor, but Komarchuk et al. (2004) reported a compound containing two unprotonated tetramethylbipyrazole ligands acting as ligands to a single copper atom.

For related literature, see: Adams et al. (2005).

Experimental top

An attempt to synthesize tetramethylbipyrazolium tetrachlorocuprate(II) by slow evaporation at room temperature of a solution of equimolar amounts of tetramethylbipyrazole hydrochloride and copper(II) chloride dihydrate in concentrated HCl resulted in the formation of the title compound as a by-product in the form of pale green, plate-like crystals.

Refinement top

H atoms bonded to O atoms were located in a difference map and refined with distance restraints of O—H = 0.84 (2) Å with Uiso(H) = 1.2Ueq(O). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.98 Å and N—H = 0.88 Å, with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C, N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. The molecular structure of I with atom labels and 50% probability displacement ellipsoids for non-H atoms. [Symmetry codes: (A) -x + 2, -y + 3, -z + 1; (B) x, y - 1, z]
[Figure 2] Fig. 2. Packing of I viewed down the c axis, with O—H···Cl bonds connecting the dimeric units.
Di-µ-chlorido-bis[dichlorido(3,3',5,5'- tetramethyl-4,4'-bipyrazol-1-ium-κN2')copper(II)] dihydrate top
Crystal data top
[Cu2Cl6(C10H15N4)2]·2H2OZ = 1
Mr = 758.35F000 = 386
Triclinic, P1Dx = 1.589 Mg m−3
a = 8.2837 (4) ÅMo Kα radiation
λ = 0.71073 Å
b = 10.5907 (6) ÅCell parameters from 5647 reflections
c = 10.9058 (6) Åθ = 2.4–27.5º
α = 102.4385 (9)ºµ = 1.88 mm−1
β = 108.4401 (9)ºT = 173 (2) K
γ = 110.2613 (8)ºPlate, green
V = 792.70 (7) Å30.2 × 0.13 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3609 independent reflections
Radiation source: fine-focus sealed tube3242 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 173(2) Kθmax = 27.5º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		h = −10→10
Tmin = 0.787, Tmax = 0.87k = −13→13
8466 measured reflectionsl = −14→14
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)] = 0.024H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.064  w = 1/[σ2(Fo2) + (0.0305P)2 + 0.3154P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
3609 reflectionsΔρmax = 0.39 e Å−3
182 parametersΔρmin = −0.33 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu2Cl6(C10H15N4)2]·2H2Oγ = 110.2613 (8)º
Mr = 758.35V = 792.70 (7) Å3
Triclinic, P1Z = 1
a = 8.2837 (4) ÅMo Kα
b = 10.5907 (6) ŵ = 1.88 mm−1
c = 10.9058 (6) ÅT = 173 (2) K
α = 102.4385 (9)º0.2 × 0.13 × 0.08 mm
β = 108.4401 (9)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3609 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		3242 reflections with I > 2σ(I)
Tmin = 0.787, Tmax = 0.87Rint = 0.023
8466 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0242 restraints
wR(F2) = 0.064H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.39 e Å−3
3609 reflectionsΔρmin = −0.33 e Å−3
182 parameters
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
Cu11.11358 (3)1.463916 (19)0.381212 (19)0.01706 (7)
Cl11.38009 (6)1.67695 (4)0.47299 (5)0.02431 (10)
Cl21.16045 (6)1.45959 (4)0.60262 (4)0.02086 (9)
Cl31.04245 (6)1.46073 (4)0.15868 (4)0.02189 (10)
N10.7878 (2)1.19314 (14)0.32487 (14)0.0185 (3)
H1A0.74001.24350.36370.022*
N20.9482 (2)1.25267 (14)0.30738 (14)0.0178 (3)
N30.7030 (2)0.64464 (15)0.01465 (15)0.0210 (3)
H3A0.63520.5632−0.05790.025*
N40.8615 (2)0.67473 (15)0.12509 (15)0.0217 (3)
H4A0.91360.61590.13560.026*
C10.5323 (3)0.9567 (2)0.2828 (2)0.0291 (4)
H1B0.52231.01030.36310.044*
H1C0.53580.86770.29230.044*
H1D0.42200.93250.19770.044*
C20.7099 (2)1.04760 (17)0.27573 (17)0.0185 (3)
C30.8267 (2)1.01087 (17)0.22334 (16)0.0167 (3)
C40.9734 (2)1.14256 (17)0.24501 (16)0.0172 (3)
C51.1377 (3)1.16715 (19)0.2077 (2)0.0261 (4)
H5A1.14361.23240.15590.039*
H5B1.12101.07460.15010.039*
H5C1.25611.21060.29260.039*
C60.4994 (3)0.7602 (2)−0.0706 (2)0.0310 (4)
H6A0.47760.7067−0.16420.047*
H6B0.52480.8602−0.06070.047*
H6C0.38620.7144−0.05530.047*
C70.6656 (2)0.75913 (17)0.03346 (17)0.0192 (3)
C80.8057 (2)0.86539 (17)0.16027 (17)0.0171 (3)
C90.9272 (2)0.80751 (17)0.21604 (18)0.0194 (3)
C101.0961 (3)0.8699 (2)0.3517 (2)0.0290 (4)
H10A1.16790.81340.34990.044*
H10B1.05420.86710.42600.044*
H10C1.17750.97030.36840.044*
O10.50412 (19)0.40901 (14)0.78153 (14)0.0258 (3)
H110.570 (3)0.402 (2)0.741 (2)0.031*
H120.413 (3)0.410 (2)0.729 (2)0.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02091 (11)0.01281 (11)0.01527 (11)0.00629 (8)0.00744 (8)0.00371 (8)
Cl10.0229 (2)0.01816 (19)0.0263 (2)0.00477 (16)0.01237 (17)0.00262 (16)
Cl20.0242 (2)0.0218 (2)0.0157 (2)0.01139 (16)0.00700 (16)0.00580 (15)
Cl30.0302 (2)0.0242 (2)0.0190 (2)0.01682 (18)0.01283 (17)0.01042 (16)
N10.0212 (7)0.0162 (7)0.0193 (7)0.0090 (6)0.0104 (6)0.0050 (5)
N20.0208 (7)0.0148 (6)0.0168 (7)0.0072 (6)0.0085 (6)0.0045 (5)
N30.0246 (7)0.0150 (7)0.0197 (7)0.0082 (6)0.0085 (6)0.0026 (6)
N40.0265 (7)0.0186 (7)0.0239 (8)0.0138 (6)0.0112 (6)0.0080 (6)
C10.0264 (9)0.0215 (9)0.0384 (11)0.0074 (7)0.0192 (8)0.0069 (8)
C20.0202 (8)0.0166 (8)0.0171 (8)0.0085 (7)0.0068 (6)0.0051 (6)
C30.0180 (7)0.0152 (7)0.0144 (8)0.0074 (6)0.0049 (6)0.0042 (6)
C40.0204 (8)0.0157 (7)0.0145 (8)0.0087 (6)0.0061 (6)0.0047 (6)
C50.0269 (9)0.0202 (8)0.0331 (10)0.0099 (7)0.0172 (8)0.0075 (7)
C60.0270 (9)0.0258 (9)0.0267 (10)0.0127 (8)−0.0001 (8)0.0012 (8)
C70.0214 (8)0.0163 (8)0.0197 (8)0.0084 (6)0.0093 (7)0.0056 (6)
C80.0194 (7)0.0148 (7)0.0183 (8)0.0081 (6)0.0086 (6)0.0065 (6)
C90.0217 (8)0.0177 (8)0.0206 (8)0.0094 (7)0.0095 (7)0.0087 (7)
C100.0264 (9)0.0269 (9)0.0284 (10)0.0125 (8)0.0040 (8)0.0110 (8)
O10.0243 (7)0.0271 (7)0.0245 (7)0.0119 (6)0.0117 (6)0.0043 (5)
Geometric parameters (Å, °) top
Cu1—N21.9834 (13)C2—C31.388 (2)
Cu1—Cl12.2684 (5)C3—C41.407 (2)
Cu1—Cl32.2988 (4)C3—C81.470 (2)
Cu1—Cl22.3345 (4)C4—C51.495 (2)
Cu1—Cl2i2.7029 (5)C5—H5A0.9800
Cl2—Cu1i2.7029 (5)C5—H5B0.9800
N1—C21.348 (2)C5—H5C0.9800
N1—N21.3538 (19)C6—C71.487 (2)
N1—H1A0.8800C6—H6A0.9800
N2—C41.335 (2)C6—H6B0.9800
N3—C71.342 (2)C6—H6C0.9800
N3—N41.349 (2)C7—C81.391 (2)
N3—H3A0.8800C8—C91.400 (2)
N4—C91.336 (2)C9—C101.487 (2)
N4—H4A0.8800C10—H10A0.9800
C1—C21.490 (2)C10—H10B0.9800
C1—H1B0.9800C10—H10C0.9800
C1—H1C0.9800O1—H110.811 (15)
C1—H1D0.9800O1—H120.800 (15)
N2—Cu1—Cl1159.99 (4)C2—C3—C8127.73 (15)
N2—Cu1—Cl390.16 (4)C4—C3—C8126.42 (14)
Cl1—Cu1—Cl392.769 (17)N2—C4—C3109.72 (14)
N2—Cu1—Cl287.45 (4)N2—C4—C5121.50 (15)
Cl1—Cu1—Cl290.762 (17)C3—C4—C5128.78 (14)
Cl3—Cu1—Cl2175.537 (17)C4—C5—H5A109.5
N2—Cu1—Cl2i95.31 (4)C4—C5—H5B109.5
Cl1—Cu1—Cl2i104.333 (16)H5A—C5—H5B109.5
Cl3—Cu1—Cl2i92.434 (14)C4—C5—H5C109.5
Cl2—Cu1—Cl2i84.042 (14)H5A—C5—H5C109.5
Cu1—Cl2—Cu1i95.958 (14)H5B—C5—H5C109.5
C2—N1—N2111.89 (13)C7—C6—H6A109.5
C2—N1—H1A124.1C7—C6—H6B109.5
N2—N1—H1A124.1H6A—C6—H6B109.5
C4—N2—N1106.26 (13)C7—C6—H6C109.5
C4—N2—Cu1130.17 (11)H6A—C6—H6C109.5
N1—N2—Cu1123.33 (10)H6B—C6—H6C109.5
C7—N3—N4108.88 (13)N3—C7—C8107.84 (14)
C7—N3—H3A125.6N3—C7—C6122.10 (15)
N4—N3—H3A125.6C8—C7—C6130.06 (15)
C9—N4—N3109.65 (13)C7—C8—C9106.25 (14)
C9—N4—H4A125.2C7—C8—C3127.55 (14)
N3—N4—H4A125.2C9—C8—C3126.19 (15)
C2—C1—H1B109.5N4—C9—C8107.39 (15)
C2—C1—H1C109.5N4—C9—C10122.58 (15)
H1B—C1—H1C109.5C8—C9—C10130.00 (15)
C2—C1—H1D109.5C9—C10—H10A109.5
H1B—C1—H1D109.5C9—C10—H10B109.5
H1C—C1—H1D109.5H10A—C10—H10B109.5
N1—C2—C3106.28 (15)C9—C10—H10C109.5
N1—C2—C1122.23 (15)H10A—C10—H10C109.5
C3—C2—C1131.49 (15)H10B—C10—H10C109.5
C2—C3—C4105.84 (14)H11—O1—H12107 (2)
N2—Cu1—Cl2—Cu1i−95.61 (4)N1—N2—C4—C5179.50 (15)
Cl1—Cu1—Cl2—Cu1i104.331 (16)Cu1—N2—C4—C5−6.1 (2)
Cl2i—Cu1—Cl2—Cu1i0.0C2—C3—C4—N20.31 (18)
C2—N1—N2—C40.25 (18)C8—C3—C4—N2−178.69 (15)
C2—N1—N2—Cu1−174.59 (11)C2—C3—C4—C5−179.52 (17)
Cl1—Cu1—N2—C4−27.4 (2)C8—C3—C4—C51.5 (3)
Cl3—Cu1—N2—C471.20 (14)N4—N3—C7—C80.06 (19)
Cl2—Cu1—N2—C4−112.57 (14)N4—N3—C7—C6179.90 (16)
Cl2i—Cu1—N2—C4163.66 (14)N3—C7—C8—C9−0.39 (19)
Cl1—Cu1—N2—N1146.16 (10)C6—C7—C8—C9179.78 (18)
Cl3—Cu1—N2—N1−115.29 (12)N3—C7—C8—C3178.39 (16)
Cl2—Cu1—N2—N160.94 (12)C6—C7—C8—C3−1.4 (3)
Cl2i—Cu1—N2—N1−22.83 (12)C2—C3—C8—C769.0 (3)
C7—N3—N4—C90.32 (19)C4—C3—C8—C7−112.3 (2)
N2—N1—C2—C3−0.06 (18)C2—C3—C8—C9−112.5 (2)
N2—N1—C2—C1179.98 (15)C4—C3—C8—C966.3 (2)
N1—C2—C3—C4−0.15 (18)N3—N4—C9—C8−0.56 (19)
C1—C2—C3—C4179.81 (18)N3—N4—C9—C10177.32 (16)
N1—C2—C3—C8178.83 (15)C7—C8—C9—N40.58 (19)
C1—C2—C3—C8−1.2 (3)C3—C8—C9—N4−178.22 (16)
N1—N2—C4—C3−0.34 (17)C7—C8—C9—C10−177.09 (18)
Cu1—N2—C4—C3174.02 (11)C3—C8—C9—C104.1 (3)
Symmetry codes: (i) −x+2, −y+3, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.882.433.2625 (14)157
N3—H3A···O1ii0.881.802.6786 (19)173
N4—H4A···Cl3iii0.882.263.1435 (14)179
O1—H11···Cl1iv0.811 (15)2.519 (17)3.2640 (14)153 (2)
O1—H11···Cl3iv0.811 (15)2.74 (2)3.3031 (14)128.5 (19)
O1—H12···Cl2v0.800 (15)2.404 (16)3.1923 (14)169 (2)
Symmetry codes: (i) −x+2, −y+3, −z+1; (ii) x, y, z−1; (iii) x, y−1, z; (iv) −x+2, −y+2, −z+1; (v) x−1, y−1, z.
Table 1
Selected geometric parameters (Å) top
Cu1—N21.9834 (13)Cu1—Cl32.2988 (4)
Cu1—Cl12.2684 (5)Cu1—Cl22.3345 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.882.433.2625 (14)157
N3—H3A···O1ii0.881.802.6786 (19)173
N4—H4A···Cl3iii0.882.263.1435 (14)179
O1—H11···Cl1iv0.811 (15)2.519 (17)3.2640 (14)153 (2)
O1—H11···Cl3iv0.811 (15)2.74 (2)3.3031 (14)128.5 (19)
O1—H12···Cl2v0.800 (15)2.404 (16)3.1923 (14)169 (2)
Symmetry codes: (i) −x+2, −y+3, −z+1; (ii) x, y, z−1; (iii) x, y−1, z; (iv) −x+2, −y+2, −z+1; (v) x−1, y−1, z.
Acknowledgements top

MAK thanks Bayero University, Kano, Nigeria for funding.

references
References top

Adams, C. J., Crawford, P. C., Orpen, A. G., Podesta, T. J. & Salt, B. (2005). Chem. Commun. pp. 2457–2458.

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Komarchuk, V. V., Ponomarova, V. V., Krautscheid, H. & Domasevitch, K. V. (2004). Z. Anorg. Allg. Chem. 630, 1413–1418.

Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.