Di-μ-chlorido-bis-[dichlorido(3,3',5,5'-tetra-methyl-4,4'-bipyrazol-1-ium-κN)copper(II)] dihydrate.

The structure of the centrosymmetric title compound, [Cu(2)Cl(6)(C(10)H(15)N(4))(2)]·2H(2)O, consists of a dimeric [{(HMe(4)bpz)CuCl(3)}(2)] unit (HMe(4)bpz is 3,3',5,5'-tetra-methyl-4,4'-bipyrazol-1-ium) with two solvent water molecules. Each [HMe(4)bpz](+) cation is bonded to a CuCl(3) 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.

Related literature

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 an exploration of N—H⋯Cl interactions in the design and synthesis of crystal structures with desired properties such as unit-cell metrics or defined reactivity, see: Adams et al. (2005 ▶).

Experimental

Crystal data

[Cu2Cl6(C10H15N4)2]·2H2O

M = 758.35

Triclinic,

a = 8.2837 (4) Å

b = 10.5907 (6) Å

c = 10.9058 (6) Å

α = 102.4385 (9)°

β = 108.4401 (9)°

γ = 110.2613 (8)°

V = 792.70 (7) Å3

Z = 1

Mo Kα radiation

μ = 1.88 mm−1

T = 173 (2) K

0.2 × 0.13 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.787, T max = 0.87

8466 measured reflections

3609 independent reflections

3242 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.064

S = 1.04

3609 reflections

182 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022605/rn2046sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022605/rn2046Isup2.hkl

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

[Cu2Cl6(C10H15N4)2]·2H2O	Z = 1
Mr = 758.35	F000 = 386
Triclinic, P1	Dx = 1.589 Mg m−3
a = 8.2837 (4) Å	Mo Kα radiation λ = 0.71073 Å
b = 10.5907 (6) Å	Cell parameters from 5647 reflections
c = 10.9058 (6) Å	θ = 2.4–27.5º
α = 102.4385 (9)º	µ = 1.88 mm−1
β = 108.4401 (9)º	T = 173 (2) K
γ = 110.2613 (8)º	Plate, green
V = 792.70 (7) Å3	0.2 × 0.13 × 0.08 mm

Bruker SMART CCD area-detector diffractometer	3609 independent reflections
Radiation source: fine-focus sealed tube	3242 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.023
T = 173(2) K	θmax = 27.5º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 2008a)	h = −10→10
Tmin = 0.787, Tmax = 0.87	k = −13→13
8466 measured reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024	H 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 reflections	Δρmax = 0.39 e Å−3
182 parameters	Δρmin = −0.33 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
Cu1	1.11358 (3)	1.463916 (19)	0.381212 (19)	0.01706 (7)
Cl1	1.38009 (6)	1.67695 (4)	0.47299 (5)	0.02431 (10)
Cl2	1.16045 (6)	1.45959 (4)	0.60262 (4)	0.02086 (9)
Cl3	1.04245 (6)	1.46073 (4)	0.15868 (4)	0.02189 (10)
N1	0.7878 (2)	1.19314 (14)	0.32487 (14)	0.0185 (3)
H1A	0.7400	1.2435	0.3637	0.022*
N2	0.9482 (2)	1.25267 (14)	0.30738 (14)	0.0178 (3)
N3	0.7030 (2)	0.64464 (15)	0.01465 (15)	0.0210 (3)
H3A	0.6352	0.5632	−0.0579	0.025*
N4	0.8615 (2)	0.67473 (15)	0.12509 (15)	0.0217 (3)
H4A	0.9136	0.6159	0.1356	0.026*
C1	0.5323 (3)	0.9567 (2)	0.2828 (2)	0.0291 (4)
H1B	0.5223	1.0103	0.3631	0.044*
H1C	0.5358	0.8677	0.2923	0.044*
H1D	0.4220	0.9325	0.1977	0.044*
C2	0.7099 (2)	1.04760 (17)	0.27573 (17)	0.0185 (3)
C3	0.8267 (2)	1.01087 (17)	0.22334 (16)	0.0167 (3)
C4	0.9734 (2)	1.14256 (17)	0.24501 (16)	0.0172 (3)
C5	1.1377 (3)	1.16715 (19)	0.2077 (2)	0.0261 (4)
H5A	1.1436	1.2324	0.1559	0.039*
H5B	1.1210	1.0746	0.1501	0.039*
H5C	1.2561	1.2106	0.2926	0.039*
C6	0.4994 (3)	0.7602 (2)	−0.0706 (2)	0.0310 (4)
H6A	0.4776	0.7067	−0.1642	0.047*
H6B	0.5248	0.8602	−0.0607	0.047*
H6C	0.3862	0.7144	−0.0553	0.047*
C7	0.6656 (2)	0.75913 (17)	0.03346 (17)	0.0192 (3)
C8	0.8057 (2)	0.86539 (17)	0.16027 (17)	0.0171 (3)
C9	0.9272 (2)	0.80751 (17)	0.21604 (18)	0.0194 (3)
C10	1.0961 (3)	0.8699 (2)	0.3517 (2)	0.0290 (4)
H10A	1.1679	0.8134	0.3499	0.044*
H10B	1.0542	0.8671	0.4260	0.044*
H10C	1.1775	0.9703	0.3684	0.044*
O1	0.50412 (19)	0.40901 (14)	0.78153 (14)	0.0258 (3)
H11	0.570 (3)	0.402 (2)	0.741 (2)	0.031*
H12	0.413 (3)	0.410 (2)	0.729 (2)	0.031*

	U11	U22	U33	U12	U13	U23
Cu1	0.02091 (11)	0.01281 (11)	0.01527 (11)	0.00629 (8)	0.00744 (8)	0.00371 (8)
Cl1	0.0229 (2)	0.01816 (19)	0.0263 (2)	0.00477 (16)	0.01237 (17)	0.00262 (16)
Cl2	0.0242 (2)	0.0218 (2)	0.0157 (2)	0.01139 (16)	0.00700 (16)	0.00580 (15)
Cl3	0.0302 (2)	0.0242 (2)	0.0190 (2)	0.01682 (18)	0.01283 (17)	0.01042 (16)
N1	0.0212 (7)	0.0162 (7)	0.0193 (7)	0.0090 (6)	0.0104 (6)	0.0050 (5)
N2	0.0208 (7)	0.0148 (6)	0.0168 (7)	0.0072 (6)	0.0085 (6)	0.0045 (5)
N3	0.0246 (7)	0.0150 (7)	0.0197 (7)	0.0082 (6)	0.0085 (6)	0.0026 (6)
N4	0.0265 (7)	0.0186 (7)	0.0239 (8)	0.0138 (6)	0.0112 (6)	0.0080 (6)
C1	0.0264 (9)	0.0215 (9)	0.0384 (11)	0.0074 (7)	0.0192 (8)	0.0069 (8)
C2	0.0202 (8)	0.0166 (8)	0.0171 (8)	0.0085 (7)	0.0068 (6)	0.0051 (6)
C3	0.0180 (7)	0.0152 (7)	0.0144 (8)	0.0074 (6)	0.0049 (6)	0.0042 (6)
C4	0.0204 (8)	0.0157 (7)	0.0145 (8)	0.0087 (6)	0.0061 (6)	0.0047 (6)
C5	0.0269 (9)	0.0202 (8)	0.0331 (10)	0.0099 (7)	0.0172 (8)	0.0075 (7)
C6	0.0270 (9)	0.0258 (9)	0.0267 (10)	0.0127 (8)	−0.0001 (8)	0.0012 (8)
C7	0.0214 (8)	0.0163 (8)	0.0197 (8)	0.0084 (6)	0.0093 (7)	0.0056 (6)
C8	0.0194 (7)	0.0148 (7)	0.0183 (8)	0.0081 (6)	0.0086 (6)	0.0065 (6)
C9	0.0217 (8)	0.0177 (8)	0.0206 (8)	0.0094 (7)	0.0095 (7)	0.0087 (7)
C10	0.0264 (9)	0.0269 (9)	0.0284 (10)	0.0125 (8)	0.0040 (8)	0.0110 (8)
O1	0.0243 (7)	0.0271 (7)	0.0245 (7)	0.0119 (6)	0.0117 (6)	0.0043 (5)

Cu1—N2	1.9834 (13)	C2—C3	1.388 (2)
Cu1—Cl1	2.2684 (5)	C3—C4	1.407 (2)
Cu1—Cl3	2.2988 (4)	C3—C8	1.470 (2)
Cu1—Cl2	2.3345 (4)	C4—C5	1.495 (2)
Cu1—Cl2i	2.7029 (5)	C5—H5A	0.9800
Cl2—Cu1i	2.7029 (5)	C5—H5B	0.9800
N1—C2	1.348 (2)	C5—H5C	0.9800
N1—N2	1.3538 (19)	C6—C7	1.487 (2)
N1—H1A	0.8800	C6—H6A	0.9800
N2—C4	1.335 (2)	C6—H6B	0.9800
N3—C7	1.342 (2)	C6—H6C	0.9800
N3—N4	1.349 (2)	C7—C8	1.391 (2)
N3—H3A	0.8800	C8—C9	1.400 (2)
N4—C9	1.336 (2)	C9—C10	1.487 (2)
N4—H4A	0.8800	C10—H10A	0.9800
C1—C2	1.490 (2)	C10—H10B	0.9800
C1—H1B	0.9800	C10—H10C	0.9800
C1—H1C	0.9800	O1—H11	0.811 (15)
C1—H1D	0.9800	O1—H12	0.800 (15)
N2—Cu1—Cl1	159.99 (4)	C2—C3—C8	127.73 (15)
N2—Cu1—Cl3	90.16 (4)	C4—C3—C8	126.42 (14)
Cl1—Cu1—Cl3	92.769 (17)	N2—C4—C3	109.72 (14)
N2—Cu1—Cl2	87.45 (4)	N2—C4—C5	121.50 (15)
Cl1—Cu1—Cl2	90.762 (17)	C3—C4—C5	128.78 (14)
Cl3—Cu1—Cl2	175.537 (17)	C4—C5—H5A	109.5
N2—Cu1—Cl2i	95.31 (4)	C4—C5—H5B	109.5
Cl1—Cu1—Cl2i	104.333 (16)	H5A—C5—H5B	109.5
Cl3—Cu1—Cl2i	92.434 (14)	C4—C5—H5C	109.5
Cl2—Cu1—Cl2i	84.042 (14)	H5A—C5—H5C	109.5
Cu1—Cl2—Cu1i	95.958 (14)	H5B—C5—H5C	109.5
C2—N1—N2	111.89 (13)	C7—C6—H6A	109.5
C2—N1—H1A	124.1	C7—C6—H6B	109.5
N2—N1—H1A	124.1	H6A—C6—H6B	109.5
C4—N2—N1	106.26 (13)	C7—C6—H6C	109.5
C4—N2—Cu1	130.17 (11)	H6A—C6—H6C	109.5
N1—N2—Cu1	123.33 (10)	H6B—C6—H6C	109.5
C7—N3—N4	108.88 (13)	N3—C7—C8	107.84 (14)
C7—N3—H3A	125.6	N3—C7—C6	122.10 (15)
N4—N3—H3A	125.6	C8—C7—C6	130.06 (15)
C9—N4—N3	109.65 (13)	C7—C8—C9	106.25 (14)
C9—N4—H4A	125.2	C7—C8—C3	127.55 (14)
N3—N4—H4A	125.2	C9—C8—C3	126.19 (15)
C2—C1—H1B	109.5	N4—C9—C8	107.39 (15)
C2—C1—H1C	109.5	N4—C9—C10	122.58 (15)
H1B—C1—H1C	109.5	C8—C9—C10	130.00 (15)
C2—C1—H1D	109.5	C9—C10—H10A	109.5
H1B—C1—H1D	109.5	C9—C10—H10B	109.5
H1C—C1—H1D	109.5	H10A—C10—H10B	109.5
N1—C2—C3	106.28 (15)	C9—C10—H10C	109.5
N1—C2—C1	122.23 (15)	H10A—C10—H10C	109.5
C3—C2—C1	131.49 (15)	H10B—C10—H10C	109.5
C2—C3—C4	105.84 (14)	H11—O1—H12	107 (2)
N2—Cu1—Cl2—Cu1i	−95.61 (4)	N1—N2—C4—C5	179.50 (15)
Cl1—Cu1—Cl2—Cu1i	104.331 (16)	Cu1—N2—C4—C5	−6.1 (2)
Cl2i—Cu1—Cl2—Cu1i	0.0	C2—C3—C4—N2	0.31 (18)
C2—N1—N2—C4	0.25 (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—C5	1.5 (3)
Cl3—Cu1—N2—C4	71.20 (14)	N4—N3—C7—C8	0.06 (19)
Cl2—Cu1—N2—C4	−112.57 (14)	N4—N3—C7—C6	179.90 (16)
Cl2i—Cu1—N2—C4	163.66 (14)	N3—C7—C8—C9	−0.39 (19)
Cl1—Cu1—N2—N1	146.16 (10)	C6—C7—C8—C9	179.78 (18)
Cl3—Cu1—N2—N1	−115.29 (12)	N3—C7—C8—C3	178.39 (16)
Cl2—Cu1—N2—N1	60.94 (12)	C6—C7—C8—C3	−1.4 (3)
Cl2i—Cu1—N2—N1	−22.83 (12)	C2—C3—C8—C7	69.0 (3)
C7—N3—N4—C9	0.32 (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—C1	179.98 (15)	C4—C3—C8—C9	66.3 (2)
N1—C2—C3—C4	−0.15 (18)	N3—N4—C9—C8	−0.56 (19)
C1—C2—C3—C4	179.81 (18)	N3—N4—C9—C10	177.32 (16)
N1—C2—C3—C8	178.83 (15)	C7—C8—C9—N4	0.58 (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—C3	174.02 (11)	C3—C8—C9—C10	4.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.88	2.43	3.2625 (14)	157
N3—H3A···O1ii	0.88	1.80	2.6786 (19)	173
N4—H4A···Cl3iii	0.88	2.26	3.1435 (14)	179
O1—H11···Cl1iv	0.811 (15)	2.519 (17)	3.2640 (14)	153 (2)
O1—H11···Cl3iv	0.811 (15)	2.74 (2)	3.3031 (14)	128.5 (19)
O1—H12···Cl2v	0.800 (15)	2.404 (16)	3.1923 (14)	169 (2)

Table 1

Selected bond lengths (Å)

Cu1—N2	1.9834 (13)
Cu1—Cl1	2.2684 (5)
Cu1—Cl3	2.2988 (4)
Cu1—Cl2	2.3345 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.88	2.43	3.2625 (14)	157
N3—H3A⋯O1ii	0.88	1.80	2.6786 (19)	173
N4—H4A⋯Cl3iii	0.88	2.26	3.1435 (14)	179
O1—H11⋯Cl1iv	0.811 (15)	2.519 (17)	3.2640 (14)	153 (2)
O1—H11⋯Cl3iv	0.811 (15)	2.74 (2)	3.3031 (14)	128.5 (19)
O1—H12⋯Cl2v	0.800 (15)	2.404 (16)	3.1923 (14)	169 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .