Dichloridobis[3-methyl-4-phenyl-5-(2-pyrid-yl)-4H-1,2,4-triazole-κN,N]copper(II) 3.33-hydrate.

In the title compound, [CuCl(2)(C(14)H(12)N(4))(2)]·3.33H(2)O, the Cu(II) atom is coordinated by two chelating 3-methyl-4-phenyl-5-(2-pyrid-yl)-1,2,4-triazole ligands and two chloride anions in a distorted octa-hedral geometry with a CuN(2)N(') (2)Cl(2) chromophore. The Cu atom is located on an inversion center. Two uncoordinated water mol-ecules lie on threefold rotation axes with disordered H atoms. Two hydrogen bonds are formed between the water mol-ecules, and another between water and a chlorido ligand.

Related literature

For related literature, see: Bencini et al. (1987 ▶); Koningsbruggen et al. (1995 ▶); Moliner et al. (1998 ▶, 2001 ▶); Klingele & Brooker (2003 ▶); Klingele et al. (2005 ▶); Garcia et al. (1997 ▶); Lavrenova & Larionov (1998 ▶); Kahn & Martinez (1998 ▶); Koningsbruggen (2004 ▶); Matouzenko et al. (2004 ▶); Wang et al. (2005 ▶); Zhou et al. (2006a ▶,b ▶).

Experimental

Crystal data

[CuCl2(C14H12N4)2]·3.33H2O

M = 667.04

Rhombohedral,

a = 21.5496 (13) Å

c = 17.619 (2) Å

V = 7086.0 (10) Å3

Z = 9

Mo Kα radiation

μ = 0.91 mm−1

T = 293 (2) K

0.28 × 0.26 × 0.22 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.78, T max = 0.82

12784 measured reflections

3091 independent reflections

2155 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.114

S = 1.06

3091 reflections

194 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.82 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808007630/cf2182sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007630/cf2182Isup2.hkl

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

[CuCl2(C14H12N4)2]·3.33H2O	Z = 9
Mr = 667.04	F000 = 3099
Rhombohedral, R3	Dx = 1.407 Mg m−3
Hall symbol: -R 3	Mo Kα radiation λ = 0.71073 Å
a = 21.5496 (13) Å	Cell parameters from 3501 reflections
b = 21.5496 (13) Å	θ = 2.5–23.9º
c = 17.619 (2) Å	µ = 0.91 mm−1
α = 90º	T = 293 (2) K
β = 90º	Polyhedron, blue
γ = 120º	0.28 × 0.26 × 0.22 mm
V = 7086.0 (10) Å3

Bruker SMART APEX CCD diffractometer	3091 independent reflections
Radiation source: sealed tube	2155 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.055
T = 293(2) K	θmax = 26.0º
φ and ω scans	θmin = 1.9º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −26→26
Tmin = 0.78, Tmax = 0.82	k = −21→26
12784 measured reflections	l = −21→19

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)] = 0.057	H-atom parameters constrained
wR(F2) = 0.114	w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3091 reflections	Δρmax = 0.31 e Å−3
194 parameters	Δρmin = −0.82 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	Occ. (<1)
Cu1	0.5000	1.0000	1.0000	0.04781 (19)
C1	0.56211 (17)	0.87212 (17)	0.88733 (16)	0.0408 (7)
C2	0.54547 (13)	0.96307 (14)	0.86885 (15)	0.0280 (6)
C3	0.53495 (14)	1.02034 (15)	0.84128 (15)	0.0292 (6)
C4	0.54676 (16)	1.04762 (16)	0.76855 (16)	0.0366 (7)
H4	0.5626	1.0287	0.7307	0.044*
C5	0.53496 (19)	1.10252 (19)	0.75306 (16)	0.0459 (8)
H5	0.5416	1.1206	0.7040	0.055*
C6	0.51311 (18)	1.13172 (19)	0.80953 (16)	0.0444 (8)
H6	0.5053	1.1696	0.7995	0.053*
C7	0.50315 (17)	1.10251 (16)	0.88239 (17)	0.0412 (7)
H7	0.4894	1.1222	0.9214	0.049*
C8	0.57362 (19)	0.81162 (17)	0.87105 (17)	0.0445 (8)
H8A	0.6136	0.8167	0.9001	0.067*
H8B	0.5834	0.8112	0.8179	0.067*
H8C	0.5314	0.7675	0.8845	0.067*
C9	0.56300 (18)	0.90787 (16)	0.74991 (16)	0.0380 (7)
C10	0.4997 (2)	0.86341 (18)	0.71288 (19)	0.0504 (8)
H10	0.4565	0.8395	0.7389	0.061*
C11	0.5032 (2)	0.8556 (2)	0.6345 (2)	0.0574 (9)
H11	0.4617	0.8262	0.6072	0.069*
C12	0.56770 (19)	0.89132 (18)	0.59789 (17)	0.0458 (8)
H12	0.5696	0.8859	0.5457	0.055*
C13	0.6281 (2)	0.9340 (2)	0.6358 (2)	0.0563 (9)
H13	0.6711	0.9579	0.6093	0.068*
C14	0.62835 (19)	0.94346 (18)	0.71455 (19)	0.0509 (8)
H14	0.6704	0.9722	0.7413	0.061*
N4	0.54193 (13)	0.94977 (13)	0.94163 (13)	0.0361 (6)
N5	0.55287 (15)	0.89213 (14)	0.95473 (14)	0.0411 (6)
N6	0.55975 (13)	0.91589 (13)	0.83203 (13)	0.0333 (5)
N7	0.51276 (12)	1.04744 (13)	0.89762 (13)	0.0356 (6)
Cl1	0.37209 (5)	0.88666 (5)	0.95079 (5)	0.0581 (3)
O1	0.38596 (12)	0.77383 (11)	0.85941 (11)	0.0424 (5)
H1D	0.3825	0.8054	0.8850	0.051*
H1A	0.3444	0.7409	0.8465	0.051*
O2	0.3333	0.6667	0.7377 (2)	0.0567 (11)
H2A	0.2895	0.6359	0.7304	0.068*	0.334
H2B	0.3504	0.6925	0.6983	0.068*	0.334
O3	0.6667	0.3333	0.70495 (19)	0.0428 (9)
H3A	0.6650	0.3103	0.6651	0.051*	0.3333
H3C	0.6474	0.3042	0.7416	0.051*	0.3333

	U11	U22	U33	U12	U13	U23
Cu1	0.0484 (3)	0.0501 (4)	0.0456 (4)	0.0251 (3)	0.0044 (3)	0.0055 (3)
C1	0.0531 (19)	0.0518 (18)	0.0298 (17)	0.0356 (16)	0.0098 (14)	0.0032 (14)
C2	0.0275 (14)	0.0340 (15)	0.0229 (13)	0.0158 (12)	0.0030 (11)	−0.0039 (11)
C3	0.0295 (14)	0.0369 (15)	0.0227 (13)	0.0178 (12)	0.0003 (11)	−0.0025 (11)
C4	0.0469 (17)	0.0542 (18)	0.0184 (13)	0.0326 (15)	−0.0003 (12)	−0.0004 (13)
C5	0.062 (2)	0.068 (2)	0.0205 (14)	0.0417 (19)	0.0051 (14)	0.0132 (15)
C6	0.064 (2)	0.062 (2)	0.0292 (15)	0.0477 (18)	0.0059 (15)	0.0107 (15)
C7	0.060 (2)	0.0531 (19)	0.0302 (15)	0.0429 (16)	0.0118 (14)	0.0119 (14)
C8	0.065 (2)	0.052 (2)	0.0315 (17)	0.0406 (18)	0.0071 (15)	0.0038 (14)
C9	0.064 (2)	0.0440 (17)	0.0176 (14)	0.0356 (16)	0.0047 (14)	−0.0010 (12)
C10	0.064 (2)	0.053 (2)	0.0408 (18)	0.0341 (18)	0.0118 (17)	0.0035 (16)
C11	0.062 (2)	0.070 (2)	0.0377 (19)	0.031 (2)	−0.0055 (18)	−0.0072 (18)
C12	0.070 (2)	0.057 (2)	0.0244 (16)	0.0420 (19)	0.0051 (16)	−0.0025 (14)
C13	0.063 (2)	0.068 (2)	0.042 (2)	0.036 (2)	−0.0001 (18)	0.0004 (18)
C14	0.050 (2)	0.055 (2)	0.0416 (19)	0.0214 (17)	−0.0045 (16)	−0.0022 (16)
N4	0.0456 (14)	0.0424 (14)	0.0237 (13)	0.0245 (12)	0.0007 (10)	0.0104 (10)
N5	0.0589 (17)	0.0484 (15)	0.0291 (13)	0.0367 (14)	0.0058 (12)	0.0062 (11)
N6	0.0484 (15)	0.0400 (13)	0.0197 (11)	0.0282 (12)	0.0069 (10)	−0.0004 (10)
N7	0.0401 (13)	0.0454 (14)	0.0329 (13)	0.0303 (12)	−0.0029 (11)	−0.0059 (11)
Cl1	0.0439 (5)	0.0671 (6)	0.0520 (5)	0.0191 (4)	0.0020 (4)	0.0033 (4)
O1	0.0534 (13)	0.0488 (13)	0.0327 (11)	0.0313 (11)	0.0046 (10)	0.0029 (10)
O2	0.0633 (16)	0.0633 (16)	0.043 (3)	0.0317 (8)	0.000	0.000
O3	0.0519 (14)	0.0519 (14)	0.0245 (18)	0.0259 (7)	0.000	0.000

Cu1—N4i	2.006 (2)	C8—H8A	0.960
Cu1—N4	2.006 (2)	C8—H8B	0.960
Cu1—N7	2.023 (2)	C8—H8C	0.960
Cu1—N7i	2.023 (2)	C9—C14	1.371 (5)
Cu1—Cl1	2.7537 (9)	C9—C10	1.377 (5)
Cu1—Cl1i	2.7537 (9)	C9—N6	1.463 (3)
C1—N5	1.312 (4)	C10—C11	1.398 (5)
C1—N6	1.375 (4)	C10—H10	0.930
C1—C8	1.472 (4)	C11—C12	1.368 (5)
C2—N4	1.308 (3)	C11—H11	0.930
C2—N6	1.365 (3)	C12—C13	1.338 (5)
C2—C3	1.446 (4)	C12—H12	0.930
C3—N7	1.354 (3)	C13—C14	1.402 (5)
C3—C4	1.380 (4)	C13—H13	0.930
C4—C5	1.356 (4)	C14—H14	0.930
C4—H4	0.930	N4—N5	1.395 (3)
C5—C6	1.380 (4)	O1—H1D	0.850
C5—H5	0.930	O1—H1A	0.850
C6—C7	1.398 (4)	O2—H2A	0.850
C6—H6	0.930	O2—H2B	0.8499
C7—N7	1.330 (4)	O3—H3A	0.850
C7—H7	0.930	O3—H3C	0.850
N4i—Cu1—N4	180.000 (1)	C1—C8—H8B	109.5
N4i—Cu1—N7	99.70 (9)	H8A—C8—H8B	109.5
N4—Cu1—N7	80.30 (9)	C1—C8—H8C	109.5
N4i—Cu1—N7i	80.30 (9)	H8A—C8—H8C	109.5
N4—Cu1—N7i	99.70 (9)	H8B—C8—H8C	109.5
N7—Cu1—N7i	180.000 (1)	C14—C9—C10	123.8 (3)
N4i—Cu1—Cl1	96.83 (8)	C14—C9—N6	118.7 (3)
N4—Cu1—Cl1	83.17 (8)	C10—C9—N6	117.5 (3)
N7—Cu1—Cl1	89.45 (7)	C9—C10—C11	117.3 (3)
N4i—Cu1—Cl1i	83.17 (8)	C9—C10—H10	121.4
N4—Cu1—Cl1i	96.83 (8)	C11—C10—H10	121.4
N7—Cu1—Cl1i	90.55 (7)	C12—C11—C10	119.9 (3)
N7i—Cu1—Cl1i	89.45 (7)	C12—C11—H11	120.1
Cl1—Cu1—Cl1i	180.00 (4)	C10—C11—H11	120.1
N5—C1—N6	110.6 (3)	C13—C12—C11	121.2 (3)
N5—C1—C8	126.0 (3)	C13—C12—H12	119.4
N6—C1—C8	123.4 (3)	C11—C12—H12	119.4
N4—C2—N6	108.2 (2)	C12—C13—C14	121.7 (3)
N4—C2—C3	120.0 (2)	C12—C13—H13	119.2
N6—C2—C3	131.8 (2)	C14—C13—H13	119.2
N7—C3—C4	121.8 (3)	C9—C14—C13	116.1 (3)
N7—C3—C2	111.2 (2)	C9—C14—H14	121.9
C4—C3—C2	127.0 (2)	C13—C14—H14	121.9
C5—C4—C3	118.9 (3)	C2—N4—N5	109.9 (2)
C5—C4—H4	120.5	C2—N4—Cu1	112.15 (18)
C3—C4—H4	120.5	N5—N4—Cu1	135.90 (18)
C4—C5—C6	120.6 (3)	C1—N5—N4	105.3 (2)
C4—C5—H5	119.7	C2—N6—C1	105.9 (2)
C6—C5—H5	119.7	C2—N6—C9	126.9 (2)
C5—C6—C7	117.9 (3)	C1—N6—C9	126.8 (2)
C5—C6—H6	121.1	C7—N7—C3	118.9 (3)
C7—C6—H6	121.1	C7—N7—Cu1	126.0 (2)
N7—C7—C6	122.0 (3)	C3—N7—Cu1	115.07 (19)
N7—C7—H7	119.0	H1D—O1—H1A	109.5
C6—C7—H7	119.0	H2A—O2—H2B	109.5
C1—C8—H8A	109.5	H3A—O3—H3C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···Cl1	0.85	2.20	3.053 (2)	179
O1—H1A···O2	0.85	2.43	2.932 (3)	119
O2—H2B···O2ii	0.85	1.88	2.505 (8)	130

Cu1—N4	2.006 (2)
Cu1—N7	2.023 (2)
Cu1—Cl1	2.7537 (9)

N4i—Cu1—N7	99.70 (9)
N4—Cu1—N7	80.30 (9)
N4i—Cu1—Cl1	96.83 (8)
N4—Cu1—Cl1	83.17 (8)
N7—Cu1—Cl1	89.45 (7)
N7—Cu1—Cl1i	90.55 (7)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1D⋯Cl1	0.85	2.20	3.053 (2)	179
O1—H1A⋯O2	0.85	2.43	2.932 (3)	119
O2—H2B⋯O2ii	0.85	1.88	2.505 (8)	130

Symmetry code: (ii) .