Chloridobis[2-(1,5-dimethyl-1H-pyrazol-3-yl-κN2)-1-methyl-1H-imidazole-κN3]copper(II) chloride methanol hemisolvate tetra­hydrate

El Ghayati, L.; Tjiou, E.M.; El Ammari, L.

doi:10.1107/S1600536810000048

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m134-m135

https://doi.org/10.1107/S1600536810000048

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Chloridobis[2-(1,5-dimethyl-1H-pyrazol-3-yl-κN²)-1-methyl-1H-imidazole-κN³]copper(II) chloride methanol hemisolvate tetrahydrate

Lhoussaine El Ghayati,^a El Mostafa Tjiou ^a and Lahcen El Ammari ^b ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences, Pharmacochimie, Avenue Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V-Agdal, Rabat, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: l_elammari@fsr.ac.ma

(Received 20 December 2009; accepted 1 January 2010; online 9 January 2010)

In the title compound, [CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₃OH·4H₂O, the Cu^II ion adopts a distorted trigonal-bipyramidal coordination arising from two bidentate ligands and a Cl⁻ anion. The two heterocyclic ligands are planar with dihedral angles of 3.4 (1) and 0.7 (1)° between the pyrazole and imidazole rings. In the crystal, water molecules and uncoordinated chloride anions form an O—H⋯Cl and O—H⋯O hydrogen-bonded sheet parallel to (100) which lies between two layers of complex molecules. The packing is further stabilized by C—H⋯Cl and C—H⋯O hydrogen bonds. The methanol solvent molecule is disordered across a centre of inversion.

Related literature

For applications of transition metal complexes with biheterocyclic ligands, see: Allen & Wilson (1963 ); El-Khawass & Bistawroos (1990 ); Pearson (1975 ); Trofimenko (1993 ); Tsuboi et al. (1994 ); Hartfiel et al. (1993 ). For the preparation of biheterocyclic ligands, see: Tjiou et al. (1989 ); Bouhaddioui (1993 ).

Experimental

Crystal data

[CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₄O·4H₂O
M_r = 574.98
Monoclinic, P 2₁ /c
a = 12.5213 (3) Å
b = 15.5386 (4) Å
c = 14.1806 (4) Å
β = 100.883 (1)°
V = 2709.40 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 298 K
0.44 × 0.33 × 0.19 mm

Data collection

Bruker X8 APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.668, T_max = 0.820
47954 measured reflections
7884 independent reflections
5480 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.124
S = 1.01
7884 reflections
323 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9531 (17)
Cu1—N5	1.9545 (17)
Cu1—N4	2.2161 (14)
Cu1—N8	2.2415 (14)
Cu1—Cl1	2.2739 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl2ⁱ	0.85	2.33	3.162 (2)	167
O1—H1B⋯Cl2	0.84	2.34	3.186 (2)	175
O2—H2A⋯Cl2	0.83	2.39	3.205 (3)	165
O3—H3B⋯Cl2ⁱⁱ	0.85	2.38	3.234 (3)	174
O4—H4A⋯O1	0.84	1.98	2.793 (3)	165
O4—H4B⋯O2ⁱⁱⁱ	0.83	1.89	2.706 (4)	165
C11—H11⋯Cl2^iv	0.93	2.75	3.592 (2)	151
C18—H18C⋯Cl1^v	0.96	2.76	3.708 (3)	177
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810000048/ci2996sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000048/ci2996Isup2.hkl

checkCIF report

Comment top

The ability of biheterocycles to form stable and biochemically interesting complexes, with transition metals has prompted several researchers to test them in several areas: medicine (El-Khawass & Bistawroos, 1990, Trofimenko, 1993), agriculture (Tsuboi et al., 1994, Hartfiel et al., 1993) and the photography industry (Allen & Wilson, 1963; Pearson, 1975). To contribute to the understanding of interaction of these heterocyclic compounds with transition metals, we have studied a copper complex of a biheterocycle prepared by Tjiou et al. (1989) and methylated using phase transfer catalysis process (Bouhaddioui, 1993).

The Cu^II ion adopts a distorted trigonal bipyramidal coordination arising from two bidentate ligands and a Cl^- anion (Fig. 1). The axial positions are occupied by N1 and N5 [N1—Cu1—N5 = 173.03 (7)°], while atoms Cu1, Cl1, N4 and N8 lie in the equatorial plane [N4—Cu1—Cl1 = 128.60 (4)°, N8—Cu1—Cl1 = 132.50 (4)° and N4—Cu1—N8 = 98.90 (6)°]. The two organic ligands are almost planar; the dihedral angle between N1/C1/C2/N2/C3 and N3/N4/C4-C6 planes is 3.4 (1)° and that between N5/C10/C11/N6/C12 and N7/N8/C13-C15 planes is 0.7 (1)°.

In the crystal, the water molecules and uncoordinated chloride ions form a O—H···Cl and O—H···O hydrogen-bonded sheet parallel to the (100) and it lies between two layers of complex molecules. The packing is further stabilized by C—H···Cl and C—H···O hydrogen bonds (Table 2 and Fig.2).

Related literature top

For applications of transition metal complexes with biheterocyclic ligands, see: Allen & Wilson (1963); El-Khawass & Bistawroos (1990); Pearson (1975); Trofimenko (1993); Tsuboi et al. (1994); Hartfiel et al. (1993). For the preparation of biheterocyclic ligands, see: Tjiou et al. (1989); Bouhaddioui (1993).

Experimental top

The title compound was synthesized by mixing a solution of biheterocycle in methanol and an aqueous solution of cupric chloride with a ligand/metal ratio of 2. Heating was maintained for few minutes until dissolution of all ligand. Then a pinch of NaCl was added and the heating was continued. When the solution became clear, it was left to stand at room temperature. After a few days, green crystals were collected by filtration. They were dried over P₂O₅ in a desiccator for 48 h.

Structure description top

For applications of transition metal complexes with biheterocyclic ligands, see: Allen & Wilson (1963); El-Khawass & Bistawroos (1990); Pearson (1975); Trofimenko (1993); Tsuboi et al. (1994); Hartfiel et al. (1993). For the preparation of biheterocyclic ligands, see: Tjiou et al. (1989); Bouhaddioui (1993).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia,1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing diagram showing hydrogen-bonded (dashed lines) layer of solvent molecules between the complex molecules.

Chloridobis[2-(1,5-dimethyl-1H-pyrazol-3-yl-κN²)-1-methyl- 1H-imidazole-κN³]copper(II) chloride methanol hemisolvate tetrahydrate top

Crystal data top

[CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₄O·4H₂O	F(000) = 1200
M_r = 574.98	D_x = 1.410 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4291 reflections
a = 12.5213 (3) Å	θ = 2.6–29.8°
b = 15.5386 (4) Å	µ = 1.04 mm⁻¹
c = 14.1806 (4) Å	T = 298 K
β = 100.883 (1)°	Block, green
V = 2709.40 (12) Å³	0.44 × 0.33 × 0.19 mm
Z = 4

Data collection top

Bruker X8 APEXII area-detector diffractometer	7884 independent reflections
Radiation source: fine-focus sealed tube	5480 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 30.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
T_min = 0.668, T_max = 0.820	k = −20→21
47954 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0649P)² + 0.7437P] where P = (F_o² + 2F_c²)/3
7884 reflections	(Δ/σ)_max = 0.001
323 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₄O·4H₂O	V = 2709.40 (12) Å³
M_r = 574.98	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5213 (3) Å	µ = 1.04 mm⁻¹
b = 15.5386 (4) Å	T = 298 K
c = 14.1806 (4) Å	0.44 × 0.33 × 0.19 mm
β = 100.883 (1)°

Data collection top

Bruker X8 APEXII area-detector diffractometer	7884 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5480 reflections with I > 2σ(I)
T_min = 0.668, T_max = 0.820	R_int = 0.029
47954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	Δρ_max = 0.39 e Å⁻³
7884 reflections	Δρ_min = −0.26 e Å⁻³
323 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.900612 (18)	0.233115 (15)	0.118071 (16)	0.04439 (9)
Cl1	0.90806 (7)	0.08691 (4)	0.12169 (4)	0.0800 (2)
N1	0.78145 (13)	0.23508 (10)	0.00716 (12)	0.0454 (3)
N2	0.70109 (13)	0.28521 (11)	−0.13260 (12)	0.0477 (4)
N3	1.05116 (12)	0.37246 (10)	0.01121 (11)	0.0417 (3)
N4	0.96472 (12)	0.32276 (9)	0.02067 (10)	0.0393 (3)
N5	1.01880 (13)	0.24643 (10)	0.22878 (12)	0.0450 (4)
N6	1.09451 (12)	0.30513 (12)	0.36557 (12)	0.0486 (4)
N7	0.74464 (12)	0.38061 (10)	0.21093 (10)	0.0399 (3)
N8	0.83164 (11)	0.32983 (9)	0.20746 (10)	0.0379 (3)
C1	0.68255 (17)	0.19476 (15)	−0.01803 (16)	0.0570 (5)
H1	0.6547	0.1532	0.0179	0.068*
C2	0.63247 (18)	0.22604 (15)	−0.10454 (17)	0.0571 (5)
H2	0.5643	0.2102	−0.1384	0.068*
C3	0.79083 (15)	0.28850 (11)	−0.06320 (12)	0.0403 (4)
C4	0.89033 (15)	0.33733 (10)	−0.05888 (12)	0.0379 (3)
C5	0.92968 (17)	0.39587 (12)	−0.11883 (13)	0.0452 (4)
H5	0.8937	0.4163	−0.1780	0.054*
C6	1.03251 (16)	0.41695 (11)	−0.07205 (13)	0.0443 (4)
C7	0.6782 (2)	0.33629 (16)	−0.22015 (15)	0.0620 (6)
H7A	0.6052	0.3252	−0.2531	0.093*
H7B	0.7283	0.3211	−0.2609	0.093*
H7C	0.6859	0.3963	−0.2042	0.093*
C8	1.11508 (19)	0.47529 (14)	−0.10149 (17)	0.0588 (5)
H8A	1.0878	0.4972	−0.1648	0.088*
H8B	1.1811	0.4439	−0.1016	0.088*
H8C	1.1295	0.5224	−0.0571	0.088*
C9	1.14876 (18)	0.37281 (16)	0.08480 (18)	0.0626 (6)
H9A	1.1915	0.4227	0.0771	0.094*
H9B	1.1904	0.3218	0.0791	0.094*
H9C	1.1290	0.3741	0.1470	0.094*
C10	1.12060 (17)	0.21135 (15)	0.25698 (17)	0.0567 (5)
H10	1.1517	0.1696	0.2236	0.068*
C11	1.16802 (17)	0.24752 (15)	0.34115 (18)	0.0583 (5)
H11	1.2372	0.2357	0.3759	0.070*
C12	1.00555 (14)	0.30198 (12)	0.29551 (13)	0.0410 (4)
C13	0.90411 (14)	0.34939 (11)	0.28650 (12)	0.0373 (3)
C14	0.86365 (16)	0.41194 (12)	0.34037 (13)	0.0463 (4)
H14	0.8983	0.4359	0.3982	0.056*
C15	0.76163 (16)	0.43081 (12)	0.28999 (13)	0.0446 (4)
C16	0.64923 (17)	0.37722 (16)	0.13561 (16)	0.0570 (5)
H16A	0.6096	0.4302	0.1345	0.086*
H16B	0.6038	0.3302	0.1474	0.086*
H16C	0.6710	0.3690	0.0748	0.086*
C17	0.6784 (2)	0.49353 (17)	0.31146 (19)	0.0672 (6)
H17A	0.7067	0.5233	0.3702	0.101*
H17B	0.6135	0.4631	0.3181	0.101*
H17C	0.6618	0.5343	0.2599	0.101*
C18	1.1111 (2)	0.35786 (17)	0.45289 (17)	0.0655 (6)
H18A	1.1821	0.3467	0.4902	0.098*
H18B	1.0569	0.3438	0.4900	0.098*
H18C	1.1053	0.4176	0.4356	0.098*
O5	0.6547 (5)	−0.0238 (4)	0.0811 (5)	0.130 (2)	0.50
H5A	0.6516	0.0148	0.1199	0.195*	0.50
C19	0.5593 (8)	−0.0440 (7)	0.0398 (6)	0.123 (3)	0.50
H19A	0.5173	0.0073	0.0231	0.185*	0.50
H19B	0.5258	−0.0785	0.0823	0.185*	0.50
H19C	0.5626	−0.0762	−0.0174	0.185*	0.50
O1	0.38934 (14)	0.50044 (13)	0.08744 (14)	0.0760 (5)
H1A	0.3877	0.4702	0.0374	0.114*
H1B	0.4383	0.5370	0.0841	0.114*
O2	0.6051 (2)	0.73482 (18)	0.27534 (18)	0.1147 (9)
H2A	0.6107	0.7026	0.2296	0.172*
H2B	0.6581	0.7289	0.3199	0.172*
O3	0.6009 (3)	0.6933 (2)	0.46268 (19)	0.1391 (11)
H3A	0.5428	0.6909	0.4210	0.209*
H3B	0.5919	0.7388	0.4938	0.209*
O4	0.3845 (3)	0.4064 (2)	0.25444 (18)	0.1355 (10)
H4A	0.3913	0.4417	0.2114	0.203*
H4B	0.3836	0.3559	0.2350	0.203*
Cl2	0.58501 (5)	0.62937 (4)	0.07857 (5)	0.07005 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.05202 (15)	0.03657 (13)	0.04530 (14)	−0.00040 (9)	0.01102 (10)	0.00375 (9)
Cl1	0.1459 (7)	0.0368 (3)	0.0565 (3)	0.0098 (3)	0.0171 (4)	0.0002 (2)
N1	0.0476 (9)	0.0430 (8)	0.0478 (8)	−0.0077 (7)	0.0150 (7)	−0.0046 (6)
N2	0.0480 (9)	0.0485 (9)	0.0462 (8)	0.0079 (7)	0.0078 (7)	−0.0106 (7)
N3	0.0440 (8)	0.0371 (7)	0.0465 (8)	−0.0030 (6)	0.0150 (6)	0.0028 (6)
N4	0.0412 (7)	0.0366 (7)	0.0423 (8)	−0.0017 (6)	0.0132 (6)	0.0050 (6)
N5	0.0451 (8)	0.0440 (8)	0.0481 (9)	0.0087 (6)	0.0147 (7)	0.0099 (7)
N6	0.0430 (9)	0.0481 (9)	0.0521 (9)	−0.0002 (7)	0.0025 (7)	0.0122 (7)
N7	0.0399 (8)	0.0383 (8)	0.0425 (7)	0.0049 (6)	0.0106 (6)	0.0043 (6)
N8	0.0379 (7)	0.0365 (7)	0.0405 (7)	0.0032 (6)	0.0101 (6)	0.0033 (6)
C1	0.0536 (12)	0.0569 (13)	0.0624 (13)	−0.0135 (10)	0.0162 (10)	−0.0089 (10)
C2	0.0450 (10)	0.0635 (14)	0.0624 (13)	−0.0067 (9)	0.0094 (9)	−0.0179 (10)
C3	0.0449 (9)	0.0368 (8)	0.0403 (9)	0.0034 (7)	0.0108 (7)	−0.0082 (7)
C4	0.0479 (9)	0.0322 (8)	0.0356 (8)	0.0038 (7)	0.0131 (7)	−0.0027 (6)
C5	0.0636 (12)	0.0383 (9)	0.0364 (8)	0.0039 (8)	0.0161 (8)	0.0031 (7)
C6	0.0598 (11)	0.0327 (8)	0.0463 (9)	0.0000 (7)	0.0248 (8)	0.0012 (7)
C7	0.0657 (14)	0.0666 (15)	0.0504 (11)	0.0174 (11)	0.0029 (10)	−0.0034 (10)
C8	0.0776 (15)	0.0408 (11)	0.0663 (13)	−0.0104 (9)	0.0347 (11)	0.0020 (9)
C9	0.0494 (12)	0.0639 (14)	0.0715 (14)	−0.0105 (10)	0.0036 (10)	0.0135 (11)
C10	0.0514 (11)	0.0585 (12)	0.0633 (13)	0.0173 (9)	0.0188 (10)	0.0174 (10)
C11	0.0438 (11)	0.0633 (13)	0.0666 (14)	0.0114 (9)	0.0073 (9)	0.0216 (11)
C12	0.0393 (9)	0.0391 (9)	0.0452 (9)	0.0011 (7)	0.0096 (7)	0.0129 (7)
C13	0.0418 (9)	0.0335 (8)	0.0373 (8)	−0.0018 (6)	0.0097 (7)	0.0066 (6)
C14	0.0544 (11)	0.0415 (10)	0.0427 (9)	0.0012 (8)	0.0084 (8)	−0.0016 (7)
C15	0.0533 (11)	0.0377 (9)	0.0459 (9)	0.0048 (7)	0.0172 (8)	0.0016 (7)
C16	0.0481 (11)	0.0620 (13)	0.0577 (12)	0.0108 (9)	0.0016 (9)	−0.0007 (10)
C17	0.0730 (15)	0.0591 (14)	0.0723 (15)	0.0229 (11)	0.0205 (12)	−0.0053 (11)
C18	0.0644 (14)	0.0619 (14)	0.0622 (13)	−0.0024 (11)	−0.0085 (11)	0.0021 (11)
O5	0.141 (5)	0.120 (5)	0.152 (5)	0.030 (4)	0.087 (4)	0.050 (4)
C19	0.127 (7)	0.145 (8)	0.113 (6)	0.004 (6)	0.060 (5)	0.030 (5)
O1	0.0805 (12)	0.0732 (11)	0.0803 (11)	−0.0101 (9)	0.0307 (9)	−0.0129 (10)
O2	0.139 (2)	0.123 (2)	0.0857 (16)	−0.0216 (16)	0.0300 (15)	−0.0303 (14)
O3	0.176 (3)	0.147 (3)	0.0957 (17)	0.028 (2)	0.0274 (18)	−0.0217 (18)
O4	0.195 (3)	0.115 (2)	0.0959 (17)	−0.022 (2)	0.0239 (18)	0.0127 (15)
Cl2	0.0692 (4)	0.0644 (4)	0.0750 (4)	−0.0088 (3)	0.0097 (3)	−0.0167 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.9531 (17)	C8—H8B	0.96
Cu1—N5	1.9545 (17)	C8—H8C	0.96
Cu1—N4	2.2161 (14)	C9—H9A	0.96
Cu1—N8	2.2415 (14)	C9—H9B	0.96
Cu1—Cl1	2.2739 (6)	C9—H9C	0.96
N1—C3	1.320 (2)	C10—C11	1.351 (4)
N1—C1	1.374 (3)	C10—H10	0.93
N2—C3	1.348 (2)	C11—H11	0.93
N2—C2	1.368 (3)	C12—C13	1.453 (2)
N2—C7	1.456 (3)	C13—C14	1.390 (3)
N3—C6	1.350 (2)	C14—C15	1.372 (3)
N3—N4	1.357 (2)	C14—H14	0.93
N3—C9	1.450 (3)	C15—C17	1.499 (3)
N4—C4	1.340 (2)	C16—H16A	0.96
N5—C12	1.314 (3)	C16—H16B	0.96
N5—C10	1.374 (3)	C16—H16C	0.96
N6—C12	1.346 (2)	C17—H17A	0.96
N6—C11	1.374 (3)	C17—H17B	0.96
N6—C18	1.467 (3)	C17—H17C	0.96
N7—C15	1.349 (2)	C18—H18A	0.96
N7—N8	1.354 (2)	C18—H18B	0.96
N7—C16	1.445 (3)	C18—H18C	0.96
N8—C13	1.337 (2)	O5—C19	1.266 (10)
C1—C2	1.358 (3)	O5—H5A	0.82
C1—H1	0.93	C19—H19A	0.96
C2—H2	0.93	C19—H19B	0.96
C3—C4	1.450 (3)	C19—H19C	0.96
C4—C5	1.397 (2)	O1—H1A	0.85
C5—C6	1.372 (3)	O1—H1B	0.84
C5—H5	0.93	O2—H2A	0.83
C6—C8	1.493 (3)	O2—H2B	0.83
C7—H7A	0.96	O3—H3A	0.85
C7—H7B	0.96	O3—H3B	0.85
C7—H7C	0.96	O4—H4A	0.84
C8—H8A	0.96	O4—H4B	0.83

N1—Cu1—N5	173.03 (7)	C6—C8—H8B	109.5
N1—Cu1—N4	78.45 (6)	H8A—C8—H8B	109.5
N5—Cu1—N4	97.22 (6)	C6—C8—H8C	109.5
N1—Cu1—N8	97.33 (6)	H8A—C8—H8C	109.5
N5—Cu1—N8	77.82 (6)	H8B—C8—H8C	109.5
N4—Cu1—N8	98.90 (6)	N3—C9—H9A	109.5
N1—Cu1—Cl1	93.19 (5)	N3—C9—H9B	109.5
N5—Cu1—Cl1	93.78 (5)	H9A—C9—H9B	109.5
N4—Cu1—Cl1	128.60 (4)	N3—C9—H9C	109.5
N8—Cu1—Cl1	132.50 (4)	H9A—C9—H9C	109.5
C3—N1—C1	107.14 (17)	H9B—C9—H9C	109.5
C3—N1—Cu1	117.07 (13)	C11—C10—N5	108.7 (2)
C1—N1—Cu1	135.76 (15)	C11—C10—H10	125.6
C3—N2—C2	107.22 (17)	N5—C10—H10	125.6
C3—N2—C7	127.23 (19)	C10—C11—N6	106.85 (18)
C2—N2—C7	125.53 (19)	C10—C11—H11	126.6
C6—N3—N4	111.62 (15)	N6—C11—H11	126.6
C6—N3—C9	127.65 (16)	N5—C12—N6	110.84 (16)
N4—N3—C9	120.72 (15)	N5—C12—C13	119.79 (16)
C4—N4—N3	105.15 (14)	N6—C12—C13	129.37 (18)
C4—N4—Cu1	110.79 (11)	N8—C13—C14	111.07 (16)
N3—N4—Cu1	144.00 (11)	N8—C13—C12	113.71 (15)
C12—N5—C10	106.69 (18)	C14—C13—C12	135.21 (17)
C12—N5—Cu1	117.93 (12)	C15—C14—C13	105.27 (16)
C10—N5—Cu1	135.37 (15)	C15—C14—H14	127.4
C12—N6—C11	106.90 (18)	C13—C14—H14	127.4
C12—N6—C18	127.53 (18)	N7—C15—C14	107.11 (16)
C11—N6—C18	125.55 (18)	N7—C15—C17	122.55 (19)
C15—N7—N8	111.44 (15)	C14—C15—C17	130.34 (19)
C15—N7—C16	127.86 (16)	N7—C16—H16A	109.5
N8—N7—C16	120.70 (15)	N7—C16—H16B	109.5
C13—N8—N7	105.10 (14)	H16A—C16—H16B	109.5
C13—N8—Cu1	110.70 (11)	N7—C16—H16C	109.5
N7—N8—Cu1	144.10 (11)	H16A—C16—H16C	109.5
C2—C1—N1	108.2 (2)	H16B—C16—H16C	109.5
C2—C1—H1	125.9	C15—C17—H17A	109.5
N1—C1—H1	125.9	C15—C17—H17B	109.5
C1—C2—N2	107.16 (19)	H17A—C17—H17B	109.5
C1—C2—H2	126.4	C15—C17—H17C	109.5
N2—C2—H2	126.4	H17A—C17—H17C	109.5
N1—C3—N2	110.32 (17)	H17B—C17—H17C	109.5
N1—C3—C4	119.69 (16)	N6—C18—H18A	109.5
N2—C3—C4	129.94 (17)	N6—C18—H18B	109.5
N4—C4—C5	110.70 (16)	H18A—C18—H18B	109.5
N4—C4—C3	113.73 (15)	N6—C18—H18C	109.5
C5—C4—C3	135.56 (17)	H18A—C18—H18C	109.5
C6—C5—C4	105.54 (16)	H18B—C18—H18C	109.5
C6—C5—H5	127.2	C19—O5—H5A	109.5
C4—C5—H5	127.2	O5—C19—H19A	109.5
N3—C6—C5	106.99 (16)	O5—C19—H19B	109.5
N3—C6—C8	122.76 (19)	H19A—C19—H19B	109.5
C5—C6—C8	130.25 (18)	O5—C19—H19C	109.5
N2—C7—H7A	109.5	H19A—C19—H19C	109.5
N2—C7—H7B	109.5	H19B—C19—H19C	109.5
H7A—C7—H7B	109.5	H1A—O1—H1B	103.3
N2—C7—H7C	109.5	H2A—O2—H2B	110.7
H7A—C7—H7C	109.5	H3A—O3—H3B	102.6
H7B—C7—H7C	109.5	H4A—O4—H4B	111.9
C6—C8—H8A	109.5

N4—Cu1—N1—C3	−4.61 (13)	C2—N2—C3—C4	176.81 (18)
N8—Cu1—N1—C3	93.03 (14)	C7—N2—C3—C4	−4.9 (3)
Cl1—Cu1—N1—C3	−133.39 (13)	N3—N4—C4—C5	0.24 (19)
N4—Cu1—N1—C1	177.6 (2)	Cu1—N4—C4—C5	178.19 (11)
N8—Cu1—N1—C1	−84.8 (2)	N3—N4—C4—C3	179.21 (14)
Cl1—Cu1—N1—C1	48.8 (2)	Cu1—N4—C4—C3	−2.84 (17)
C6—N3—N4—C4	−0.30 (19)	N1—C3—C4—N4	−0.8 (2)
C9—N3—N4—C4	−179.64 (18)	N2—C3—C4—N4	−178.02 (17)
C6—N3—N4—Cu1	−177.04 (15)	N1—C3—C4—C5	177.79 (19)
C9—N3—N4—Cu1	3.6 (3)	N2—C3—C4—C5	0.6 (3)
N1—Cu1—N4—C4	4.05 (12)	N4—C4—C5—C6	−0.1 (2)
N5—Cu1—N4—C4	−170.41 (12)	C3—C4—C5—C6	−178.75 (19)
N8—Cu1—N4—C4	−91.68 (12)	N4—N3—C6—C5	0.2 (2)
Cl1—Cu1—N4—C4	88.86 (12)	C9—N3—C6—C5	179.53 (19)
N1—Cu1—N4—N3	−179.3 (2)	N4—N3—C6—C8	−178.74 (17)
N5—Cu1—N4—N3	6.2 (2)	C9—N3—C6—C8	0.5 (3)
N8—Cu1—N4—N3	84.9 (2)	C4—C5—C6—N3	−0.1 (2)
Cl1—Cu1—N4—N3	−94.5 (2)	C4—C5—C6—C8	178.80 (19)
N4—Cu1—N5—C12	95.69 (14)	C12—N5—C10—C11	−0.5 (2)
N8—Cu1—N5—C12	−1.91 (13)	Cu1—N5—C10—C11	178.32 (15)
Cl1—Cu1—N5—C12	−134.62 (13)	N5—C10—C11—N6	0.4 (3)
N4—Cu1—N5—C10	−83.1 (2)	C12—N6—C11—C10	−0.1 (2)
N8—Cu1—N5—C10	179.3 (2)	C18—N6—C11—C10	178.7 (2)
Cl1—Cu1—N5—C10	46.61 (19)	C10—N5—C12—N6	0.5 (2)
C15—N7—N8—C13	−0.05 (19)	Cu1—N5—C12—N6	−178.63 (12)
C16—N7—N8—C13	179.66 (17)	C10—N5—C12—C13	−179.30 (16)
C15—N7—N8—Cu1	−175.72 (15)	Cu1—N5—C12—C13	1.6 (2)
C16—N7—N8—Cu1	4.0 (3)	C11—N6—C12—N5	−0.2 (2)
N1—Cu1—N8—C13	−172.90 (11)	C18—N6—C12—N5	−179.04 (19)
N5—Cu1—N8—C13	2.02 (11)	C11—N6—C12—C13	179.52 (18)
N4—Cu1—N8—C13	−93.51 (11)	C18—N6—C12—C13	0.7 (3)
Cl1—Cu1—N8—C13	85.92 (12)	N7—N8—C13—C14	0.25 (18)
N1—Cu1—N8—N7	2.63 (19)	Cu1—N8—C13—C14	177.54 (12)
N5—Cu1—N8—N7	177.6 (2)	N7—N8—C13—C12	−179.07 (13)
N4—Cu1—N8—N7	82.02 (19)	Cu1—N8—C13—C12	−1.78 (17)
Cl1—Cu1—N8—N7	−98.55 (19)	N5—C12—C13—N8	0.3 (2)
C3—N1—C1—C2	−0.7 (2)	N6—C12—C13—N8	−179.36 (17)
Cu1—N1—C1—C2	177.22 (15)	N5—C12—C13—C14	−178.76 (19)
N1—C1—C2—N2	0.4 (2)	N6—C12—C13—C14	1.5 (3)
C3—N2—C2—C1	0.1 (2)	N8—C13—C14—C15	−0.4 (2)
C7—N2—C2—C1	−178.17 (19)	C12—C13—C14—C15	178.76 (19)
C1—N1—C3—N2	0.8 (2)	N8—N7—C15—C14	−0.2 (2)
Cu1—N1—C3—N2	−177.57 (11)	C16—N7—C15—C14	−179.86 (19)
C1—N1—C3—C4	−176.90 (16)	N8—N7—C15—C17	179.76 (18)
Cu1—N1—C3—C4	4.7 (2)	C16—N7—C15—C17	0.1 (3)
C2—N2—C3—N1	−0.6 (2)	C13—C14—C15—N7	0.3 (2)
C7—N2—C3—N1	177.67 (18)	C13—C14—C15—C17	−179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱ	0.85	2.33	3.162 (2)	167
O1—H1B···Cl2	0.84	2.34	3.186 (2)	175
O2—H2A···Cl2	0.83	2.39	3.205 (3)	165
O3—H3B···Cl2ⁱⁱ	0.85	2.38	3.234 (3)	174
O4—H4A···O1	0.84	1.98	2.793 (3)	165
O4—H4B···O2ⁱⁱⁱ	0.83	1.89	2.706 (4)	165
C11—H11···Cl2^iv	0.93	2.75	3.592 (2)	151
C18—H18C···Cl1^v	0.96	2.76	3.708 (3)	177

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₄O·4H₂O
M_r	574.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.5213 (3), 15.5386 (4), 14.1806 (4)
β (°)	100.883 (1)
V (Å³)	2709.40 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.44 × 0.33 × 0.19

Data collection
Diffractometer	Bruker X8 APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.668, 0.820
No. of measured, independent and observed [I > 2σ(I)] reflections	47954, 7884, 5480
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.124, 1.01
No. of reflections	7884
No. of parameters	323
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia,1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—N1	1.9531 (17)	Cu1—N8	2.2415 (14)
Cu1—N5	1.9545 (17)	Cu1—Cl1	2.2739 (6)
Cu1—N4	2.2161 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2ⁱ	0.85	2.33	3.162 (2)	167
O1—H1B···Cl2	0.84	2.34	3.186 (2)	175
O2—H2A···Cl2	0.83	2.39	3.205 (3)	165
O3—H3B···Cl2ⁱⁱ	0.85	2.38	3.234 (3)	174
O4—H4A···O1	0.84	1.98	2.793 (3)	165
O4—H4B···O2ⁱⁱⁱ	0.83	1.89	2.706 (4)	165
C11—H11···Cl2^iv	0.93	2.75	3.592 (2)	151
C18—H18C···Cl1^v	0.96	2.76	3.708 (3)	177

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for making this work possible. They also thank H. Zouihri for his helpful technical assistance during the X-ray measurements.

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