{4,6-Bis[(E)-1-methyl-2-(pyridin-2-yl­methyl­idene-κN)hydrazinyl-κN2]pyrimidine-κN1}dichloridocopper(II) methanol disolvate monohydrate

Marzec, B.; Mariyatra, M.B.; McCabe, T.; Schmitt, W.

doi:10.1107/S1600536811025414

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1073-m1074

doi:10.1107/S1600536811025414

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{4,6-Bis[(E)-1-methyl-2-(pyridin-2-ylmethylidene-κN)hydrazinyl-κN²]pyrimidine-κN¹}dichloridocopper(II) methanol disolvate monohydrate

Bartosz Marzec,^a M. Baby Mariyatra,^a Thomas McCabe ^a and Wolfgang Schmitt ^a ^*

^aSchool of Chemistry & CRANN, The University of Dublin, Trinity College, Dublin 2, Ireland
^*Correspondence e-mail: schmittw@tcd.ie

(Received 23 June 2011; accepted 28 June 2011; online 9 July 2011)

The title compound, [CuCl₂(C₁₈H₁₈N₈)]·2CH₃OH·H₂O, contains a pentacoordinated Cu(II) atom bonded to the tridentate 4,6-bis[(E)-1-methyl-2-(pyridin-2-ylmethylidene)hydrazinyl]pyrimidine ligand and two Cl atoms. The geometry around the Cu^II atom is distorted square-pyramidal. The molecules pack in the crystal structure via O—H⋯Cl, O—H⋯N, C—H⋯Cl and C—H⋯O hydrogen bonds, C—H⋯π and π–π interactions [centroid–centroid distances of the pyrimidine–pyridine and pyridine–pyridine interactions are 3.750 (3) and 3.850 (3) Å, respectively], forming sheet-like assemblies.

Related literature

For the coordination chemistry of similar ligand-types, see: Stadler et al. (2005 , 2006 ). For additional geometric analysis, see: Addison et al. (1984 ).

Experimental

Crystal data

[CuCl₂(C₁₈H₁₈N₈)]·2CH₄O·H₂O
M_r = 560.94
Triclinic, $[P \overline 1]$
a = 7.430 (5) Å
b = 11.627 (8) Å
c = 14.026 (9) Å
α = 95.848 (7)°
β = 93.477 (13)°
γ = 92.920 (9)°
V = 1201.2 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 116 K
0.30 × 0.25 × 0.10 mm

Data collection

Rigaku Saturn724 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.786, T_max = 1.000
26094 measured reflections
7050 independent reflections
4093 reflections with I > 2σ(I)
R_int = 0.091

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.104
S = 0.82
7050 reflections
311 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—Cl1	2.2306 (15)
Cu1—Cl2	2.5353 (16)
Cu1—N1	2.038 (3)
Cu1—N2	1.989 (2)
Cu1—N4	2.011 (2)

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N4,N5,C16–C19 and N1,C15,C28,C29–C31 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl2ⁱ	0.84	2.36	3.144 (3)	155
O3—H3a⋯N8ⁱⁱ	0.84	1.96	2.773 (4)	164
C2—H2⋯Cl1ⁱⁱⁱ	0.95	2.78	3.683 (4)	158
C32—H32⋯Cl2^iv	0.95	2.64	3.480 (3)	148
C33—H33⋯Cl2^v	0.95	2.80	3.694 (4)	158
C36—H36b⋯O3ⁱⁱ	0.98	2.26	3.225 (4)	169
C29—H29⋯O5	0.95	2.47	3.289 (5)	145
C20—H20b⋯Cg1^v	0.98	2.58	3.381 (4)	139
C36—H36c⋯Cg2^iv	0.98	2.81	3.646 (4)	144
Symmetry codes: (i) x-1, y, z; (ii) -x, -y, -z+1; (iii) x-1, y-1, z; (iv) -x+1, -y, -z+1; (v) -x+1, -y, -z+2.

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ), DIAMOND (Brandenburg, 1998 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025414/tk2760sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025414/tk2760Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025414/tk2760Isup3.mol

checkCIF report

Comment top

Heterocyclic N-containing ligands have been heavily exploited to create metallo-supramolecular structures such as helicates, grids, molecular ladders, etc. Lehn and co-workers recently reported (pyridin-2-ylmethylene)hydrazinyl)pyrimidine-based ligands and their Pb^II, Zn^II, Hg^II and La^III complexes (Stadler et al., 2005; Stadler et al. 2006).

The asymmetric unit in the title compound contains a mononuclear Cu^II complex of 4,6-bis[(E)-1-methyl-2-(pyrindin-2-ylmethylene)hydrazinyl]pyrimidine (Fig. 1), two solvent methanol molecules and a water solvent molecule. The Cu^II atom is penta-coordinated by three N atoms of the organic ligand and two chloride atoms, Table 1. The coordination geometry of the central Cu^II is best described as distorted square pyramid. The structural distortion index (Addison et al., 1984), τ, is 0.08 compared with an ideal τ value of 0.0 for a square pyramid. In this description, the N1 N2 N4 Cl2 atoms form the basal plane, and Cl1 occupies the apical position . The bond angles around the central Cu atom range between 78.04 (10)–159.90 (7)°. The configuration around both imine bonds is assigned to be E.

The crystal structure is stabilized by hydrogen bonds between the Cu^II complex and the constitutional solvent molecules, Table 2, and π–π interactions between the pyrimidine and pyridine rings of symmetry related molecules (Figs 2 & 3). The centroid-centroid distances of the pyrimidine···pyridine (symmetry code:-x, -y, 2 - z) and pyridine···pyridine (symmetry code: -x, -1 - y, 2 - z) interactions are 3.750 (3) and 3.850 (3) Å, respectively. In addition, weak C—H···π interactions are also observed, Table 2.

Related literature top

For the coordination chemistry of similar ligand-types, see: Stadler et al. (2005, 2006). For additional geometric analysis, see: Addison et al. (1984);

Experimental top

4,6-bis[N-Methyl-2-(pyrindin-2-ylmethylene)hydrazinyl]pyrimidine (0.007 g. 0.025 mmol) was dissolved in 5 ml of chloroform and 4.75 ml of ethanol. Then, 0.25 ml of an ethanolic 0.1 M copper(II) chloride dihydrate solution was added and the mixture was left for slow evaporation. Green blocks of the title compound were collected after 2 days. Yield: ca 75%.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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), DIAMOND (Brandenburg, 1998) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound drawn at 50% probability thermal ellipsoids. Solvent molecules are omitted for clarity.
	Fig. 2. Packing of the Cu^II complex and constitutional solvent molecules; views in the direction of the crystallographic b- (left) and c-axes.
	Fig. 3. π–π Stacking between the Cu^II complexes; view in the direction of the c-axis.

{4,6-Bis[(E)-1-methyl-2-(pyridin-2-ylmethylidene-κN)hydrazinyl- κN²]pyrimidine-κN¹}dichloridocopper(II) methanol disolvate monohydrate top

Crystal data top

[CuCl₂(C₂₀H₁₈N₈)]·2CH₄O·H₂O	Z = 2
M_r = 560.94	F(000) = 578
Triclinic, P1	D_x = 1.551 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.430 (5) Å	Cell parameters from 4091 reflections
b = 11.627 (8) Å	θ = 1.5–31.2°
c = 14.026 (9) Å	µ = 1.17 mm⁻¹
α = 95.848 (7)°	T = 116 K
β = 93.477 (13)°	Block, green
γ = 92.920 (9)°	0.30 × 0.25 × 0.10 mm
V = 1201.2 (14) Å³

Data collection top

Rigaku Saturn724 diffractometer	7050 independent reflections
Radiation source: fine-focus sealed tube	4093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.091
Detector resolution: 28.5714 pixels mm^-1	θ_max = 31.0°, θ_min = 2.8°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −16→16
T_min = 0.786, T_max = 1.000	l = −20→20
26094 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.0252P)²] where P = (F_o² + 2F_c²)/3
7050 reflections	(Δ/σ)_max = 0.001
311 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[CuCl₂(C₂₀H₁₈N₈)]·2CH₄O·H₂O	γ = 92.920 (9)°
M_r = 560.94	V = 1201.2 (14) Å³
Triclinic, P1	Z = 2
a = 7.430 (5) Å	Mo Kα radiation
b = 11.627 (8) Å	µ = 1.17 mm⁻¹
c = 14.026 (9) Å	T = 116 K
α = 95.848 (7)°	0.30 × 0.25 × 0.10 mm
β = 93.477 (13)°

Data collection top

Rigaku Saturn724 diffractometer	7050 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	4093 reflections with I > 2σ(I)
T_min = 0.786, T_max = 1.000	R_int = 0.091
26094 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 0.82	Δρ_max = 1.20 e Å⁻³
7050 reflections	Δρ_min = −0.64 e Å⁻³
311 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cu1	0.51669 (5)	0.23008 (3)	0.67322 (2)	0.02337 (11)
Cl1	0.60610 (11)	0.40752 (6)	0.74048 (5)	0.03137 (19)
Cl2	0.80299 (10)	0.12043 (6)	0.67078 (5)	0.02719 (17)
N8	−0.0738 (3)	−0.3088 (2)	0.95926 (17)	0.0257 (6)
N7	0.1465 (3)	−0.1045 (2)	0.99451 (17)	0.0224 (5)
N6	0.2460 (3)	−0.00054 (19)	1.01525 (16)	0.0212 (5)
N5	0.4077 (3)	0.15083 (19)	0.95650 (16)	0.0218 (5)
N4	0.4243 (3)	0.16279 (19)	0.78868 (16)	0.0212 (5)
N1	0.5074 (3)	0.2629 (2)	0.53308 (16)	0.0235 (5)
N2	0.3547 (3)	0.09759 (19)	0.61299 (16)	0.0210 (5)
N3	0.2856 (3)	0.02344 (19)	0.67263 (17)	0.0236 (5)
C1	−0.0123 (4)	−0.2672 (2)	1.0503 (2)	0.0222 (6)
C2	−0.1852 (4)	−0.4043 (2)	0.9493 (2)	0.0298 (7)
H2	−0.2286	−0.4348	0.8862	0.036*
C3	−0.2412 (4)	−0.4615 (3)	1.0258 (2)	0.0306 (7)
H3	−0.3217	−0.5284	1.0149	0.037*
C4	−0.1776 (4)	−0.4193 (3)	1.1175 (2)	0.0308 (7)
H4	−0.2136	−0.4565	1.1711	0.037*
C5	−0.0597 (4)	−0.3212 (2)	1.1308 (2)	0.0264 (7)
H5	−0.0122	−0.2915	1.1933	0.032*
C15	0.5832 (4)	0.3533 (3)	0.4945 (2)	0.0284 (7)
H15	0.6540	0.4107	0.5356	0.034*
C16	0.3030 (4)	0.0512 (2)	0.9371 (2)	0.0205 (6)
C17	0.2558 (4)	0.0018 (2)	0.84227 (19)	0.0205 (6)
H17	0.1839	−0.0686	0.8288	0.025*
C18	0.4602 (4)	0.2000 (2)	0.8816 (2)	0.0224 (6)
H18	0.5322	0.2704	0.8951	0.027*
C19	0.3201 (4)	0.0616 (2)	0.7704 (2)	0.0211 (6)
C20	0.2746 (4)	0.0561 (2)	1.11368 (19)	0.0246 (6)
H20A	0.3352	0.1328	1.1128	0.037*
H20B	0.3500	0.0091	1.1522	0.037*
H20C	0.1578	0.0644	1.1418	0.037*
C28	0.5623 (4)	0.3661 (3)	0.3978 (2)	0.0312 (7)
H28	0.6165	0.4318	0.3733	0.037*
C29	0.4617 (4)	0.2825 (3)	0.3368 (2)	0.0321 (7)
H29	0.4466	0.2899	0.2700	0.039*
C30	0.3827 (4)	0.1872 (3)	0.3747 (2)	0.0299 (7)
H30	0.3135	0.1282	0.3344	0.036*
C31	0.4081 (4)	0.1808 (3)	0.4734 (2)	0.0252 (7)
C32	0.3240 (4)	0.0875 (2)	0.5211 (2)	0.0237 (6)
H32	0.2526	0.0247	0.4869	0.028*
C33	0.1001 (3)	−0.1588 (2)	1.0661 (2)	0.0212 (6)
H33	0.1396	−0.1281	1.1297	0.025*
C36	0.1671 (4)	−0.0758 (2)	0.6330 (2)	0.0250 (6)
H36A	0.0583	−0.0487	0.6013	0.037*
H36B	0.1328	−0.1212	0.6849	0.037*
H36C	0.2304	−0.1243	0.5861	0.037*
O1	0.0092 (3)	0.26564 (19)	0.52994 (16)	0.0421 (6)
H1	−0.0750	0.2342	0.5572	0.063*
C37	0.0780 (4)	0.3696 (3)	0.5842 (3)	0.0458 (9)
H37A	−0.0173	0.4030	0.6217	0.069*
H37B	0.1195	0.4247	0.5407	0.069*
H37C	0.1794	0.3531	0.6277	0.069*
O3	−0.0217 (4)	0.24581 (19)	0.21711 (17)	0.0615 (8)
H3A	0.0257	0.2578	0.1659	0.092*
C38	−0.0030 (4)	0.3467 (3)	0.2806 (2)	0.0374 (8)
H38A	−0.0155	0.3271	0.3462	0.056*
H38B	−0.0968	0.3988	0.2638	0.056*
H38C	0.1163	0.3850	0.2762	0.056*
O5	0.6024 (5)	0.2970 (3)	0.1203 (2)	0.0990 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0281 (2)	0.0221 (2)	0.01938 (19)	−0.00223 (15)	0.00150 (15)	0.00127 (14)
Cl1	0.0424 (5)	0.0232 (4)	0.0269 (4)	−0.0065 (3)	−0.0001 (3)	0.0000 (3)
Cl2	0.0285 (4)	0.0287 (4)	0.0238 (4)	0.0021 (3)	0.0010 (3)	−0.0002 (3)
N8	0.0256 (14)	0.0267 (14)	0.0242 (13)	0.0000 (11)	0.0023 (11)	−0.0005 (11)
N7	0.0199 (13)	0.0239 (13)	0.0233 (13)	0.0009 (10)	0.0029 (10)	0.0013 (10)
N6	0.0232 (13)	0.0205 (12)	0.0195 (12)	0.0000 (10)	0.0023 (10)	0.0004 (10)
N5	0.0210 (13)	0.0221 (13)	0.0217 (13)	−0.0005 (10)	0.0017 (10)	0.0003 (10)
N4	0.0203 (13)	0.0211 (12)	0.0221 (12)	−0.0015 (10)	0.0025 (10)	0.0022 (10)
N1	0.0230 (14)	0.0268 (13)	0.0212 (13)	−0.0004 (11)	0.0023 (10)	0.0049 (11)
N2	0.0217 (13)	0.0192 (12)	0.0212 (12)	−0.0018 (10)	0.0035 (10)	−0.0013 (10)
N3	0.0284 (15)	0.0221 (13)	0.0190 (12)	−0.0042 (11)	0.0017 (10)	−0.0012 (10)
C1	0.0205 (16)	0.0222 (15)	0.0239 (15)	0.0029 (12)	0.0034 (12)	0.0000 (12)
C2	0.0251 (18)	0.0288 (17)	0.0336 (18)	−0.0020 (14)	−0.0005 (14)	−0.0023 (14)
C3	0.0274 (18)	0.0231 (16)	0.041 (2)	−0.0029 (13)	0.0035 (15)	0.0037 (14)
C4	0.0292 (18)	0.0286 (17)	0.0364 (19)	−0.0004 (14)	0.0059 (14)	0.0110 (15)
C5	0.0236 (17)	0.0302 (17)	0.0252 (16)	0.0008 (13)	0.0005 (13)	0.0032 (13)
C15	0.0281 (18)	0.0277 (17)	0.0289 (17)	−0.0002 (13)	0.0033 (14)	0.0002 (14)
C16	0.0185 (15)	0.0218 (14)	0.0212 (14)	0.0030 (12)	0.0022 (12)	0.0008 (12)
C17	0.0172 (15)	0.0222 (14)	0.0215 (15)	−0.0027 (11)	0.0010 (11)	0.0009 (12)
C18	0.0205 (16)	0.0185 (14)	0.0264 (15)	−0.0025 (12)	−0.0007 (12)	−0.0031 (12)
C19	0.0201 (15)	0.0223 (15)	0.0204 (14)	0.0032 (12)	0.0004 (12)	−0.0016 (12)
C20	0.0304 (17)	0.0228 (15)	0.0199 (15)	−0.0025 (13)	0.0017 (12)	0.0006 (12)
C28	0.0331 (19)	0.0321 (18)	0.0295 (17)	0.0005 (14)	0.0053 (14)	0.0082 (14)
C29	0.038 (2)	0.0390 (19)	0.0200 (15)	−0.0006 (15)	0.0019 (14)	0.0062 (14)
C30	0.0351 (19)	0.0316 (17)	0.0219 (16)	−0.0001 (14)	0.0016 (14)	−0.0008 (13)
C31	0.0239 (16)	0.0298 (16)	0.0230 (15)	0.0041 (13)	0.0052 (12)	0.0047 (13)
C32	0.0229 (16)	0.0246 (15)	0.0227 (15)	−0.0020 (12)	−0.0004 (12)	0.0004 (12)
C33	0.0181 (15)	0.0238 (15)	0.0207 (14)	−0.0008 (12)	−0.0001 (12)	−0.0002 (12)
C36	0.0264 (17)	0.0249 (15)	0.0220 (15)	−0.0066 (13)	−0.0002 (12)	−0.0004 (12)
O1	0.0430 (15)	0.0446 (15)	0.0378 (14)	−0.0067 (12)	0.0104 (11)	−0.0002 (12)
C37	0.038 (2)	0.043 (2)	0.054 (2)	−0.0052 (17)	−0.0018 (18)	0.0018 (19)
O3	0.112 (2)	0.0336 (14)	0.0366 (15)	−0.0247 (15)	0.0352 (15)	−0.0096 (12)
C38	0.043 (2)	0.040 (2)	0.0297 (18)	0.0002 (16)	0.0058 (15)	0.0024 (15)
O5	0.115 (3)	0.101 (3)	0.079 (3)	−0.008 (2)	0.018 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Cu1—Cl1	2.2306 (15)	C15—H15	0.9500
Cu1—Cl2	2.5353 (16)	C16—C17	1.410 (4)
Cu1—N1	2.038 (3)	C17—C19	1.377 (4)
Cu1—N2	1.989 (2)	C17—H17	0.9500
Cu1—N4	2.011 (2)	C18—H18	0.9500
N8—C2	1.342 (3)	C20—H20A	0.9800
N8—C1	1.362 (4)	C20—H20B	0.9800
N7—C33	1.294 (3)	C20—H20C	0.9800
N7—N6	1.380 (3)	C28—C29	1.384 (4)
N6—C16	1.381 (3)	C28—H28	0.9500
N6—C20	1.466 (3)	C29—C30	1.395 (4)
N5—C18	1.317 (3)	C29—H29	0.9500
N5—C16	1.356 (3)	C30—C31	1.397 (4)
N4—C18	1.337 (3)	C30—H30	0.9500
N4—C19	1.368 (3)	C31—C32	1.464 (4)
N1—C15	1.344 (3)	C32—H32	0.9500
N1—C31	1.358 (4)	C33—H33	0.9500
N2—C32	1.288 (3)	C36—H36A	0.9800
N2—N3	1.364 (3)	C36—H36B	0.9800
N3—C19	1.402 (3)	C36—H36C	0.9800
N3—C36	1.457 (3)	O1—C37	1.416 (4)
C1—C5	1.401 (4)	O1—H1	0.8400
C1—C33	1.465 (4)	C37—H37A	0.9800
C2—C3	1.392 (4)	C37—H37B	0.9800
C2—H2	0.9500	C37—H37C	0.9800
C3—C4	1.377 (4)	O3—C38	1.394 (4)
C3—H3	0.9500	O3—H3A	0.8399
C4—C5	1.391 (4)	C38—H38A	0.9800
C4—H4	0.9500	C38—H38B	0.9800
C5—H5	0.9500	C38—H38C	0.9800
C15—C28	1.381 (4)

N2—Cu1—N4	78.01 (10)	C16—C17—H17	122.0
N2—Cu1—N1	79.32 (10)	N5—C18—N4	127.7 (3)
N4—Cu1—N1	155.14 (9)	N5—C18—H18	116.1
N2—Cu1—Cl1	159.91 (7)	N4—C18—H18	116.1
N4—Cu1—Cl1	99.43 (8)	N4—C19—C17	122.7 (3)
N1—Cu1—Cl1	98.34 (8)	N4—C19—N3	114.5 (2)
N2—Cu1—Cl2	95.54 (8)	C17—C19—N3	122.8 (3)
N4—Cu1—Cl2	95.41 (7)	N6—C20—H20A	109.5
N1—Cu1—Cl2	96.80 (7)	N6—C20—H20B	109.5
Cl1—Cu1—Cl2	104.54 (5)	H20A—C20—H20B	109.5
C2—N8—C1	116.9 (3)	N6—C20—H20C	109.5
C33—N7—N6	117.5 (2)	H20A—C20—H20C	109.5
C16—N6—N7	115.9 (2)	H20B—C20—H20C	109.5
C16—N6—C20	122.2 (2)	C15—C28—C29	119.4 (3)
N7—N6—C20	121.7 (2)	C15—C28—H28	120.3
C18—N5—C16	116.1 (2)	C29—C28—H28	120.3
C18—N4—C19	115.4 (2)	C28—C29—C30	119.2 (3)
C18—N4—Cu1	128.5 (2)	C28—C29—H29	120.4
C19—N4—Cu1	115.97 (18)	C30—C29—H29	120.4
C15—N1—C31	118.0 (3)	C29—C30—C31	118.1 (3)
C15—N1—Cu1	128.7 (2)	C29—C30—H30	120.9
C31—N1—Cu1	113.24 (18)	C31—C30—H30	120.9
C32—N2—N3	124.9 (2)	N1—C31—C30	122.6 (3)
C32—N2—Cu1	118.0 (2)	N1—C31—C32	114.9 (3)
N3—N2—Cu1	117.15 (17)	C30—C31—C32	122.5 (3)
N2—N3—C19	113.7 (2)	N2—C32—C31	114.5 (3)
N2—N3—C36	119.9 (2)	N2—C32—H32	122.8
C19—N3—C36	125.9 (2)	C31—C32—H32	122.8
N8—C1—C5	122.4 (3)	N7—C33—C1	120.9 (3)
N8—C1—C33	119.3 (3)	N7—C33—H33	119.6
C5—C1—C33	118.2 (3)	C1—C33—H33	119.6
N8—C2—C3	124.0 (3)	N3—C36—H36A	109.5
N8—C2—H2	118.0	N3—C36—H36B	109.5
C3—C2—H2	118.0	H36A—C36—H36B	109.5
C4—C3—C2	118.7 (3)	N3—C36—H36C	109.5
C4—C3—H3	120.7	H36A—C36—H36C	109.5
C2—C3—H3	120.7	H36B—C36—H36C	109.5
C3—C4—C5	119.1 (3)	C37—O1—H1	110.9
C3—C4—H4	120.5	O1—C37—H37A	109.5
C5—C4—H4	120.5	O1—C37—H37B	109.5
C4—C5—C1	118.9 (3)	H37A—C37—H37B	109.5
C4—C5—H5	120.5	O1—C37—H37C	109.5
C1—C5—H5	120.5	H37A—C37—H37C	109.5
N1—C15—C28	122.7 (3)	H37B—C37—H37C	109.5
N1—C15—H15	118.7	C38—O3—H3A	109.4
C28—C15—H15	118.7	O3—C38—H38A	109.5
N5—C16—N6	116.5 (2)	O3—C38—H38B	109.5
N5—C16—C17	122.1 (2)	H38A—C38—H38B	109.5
N6—C16—C17	121.4 (3)	O3—C38—H38C	109.5
C19—C17—C16	116.0 (3)	H38A—C38—H38C	109.5
C19—C17—H17	122.0	H38B—C38—H38C	109.5

C33—N7—N6—C16	175.9 (2)	Cu1—N1—C15—C28	−178.4 (2)
C33—N7—N6—C20	−9.5 (4)	C18—N5—C16—N6	−179.5 (2)
N2—Cu1—N4—C18	−178.6 (2)	C18—N5—C16—C17	1.2 (4)
N1—Cu1—N4—C18	−154.0 (2)	N7—N6—C16—N5	−177.2 (2)
Cl1—Cu1—N4—C18	−18.9 (2)	C20—N6—C16—N5	8.3 (4)
Cl2—Cu1—N4—C18	86.9 (2)	N7—N6—C16—C17	2.2 (4)
N2—Cu1—N4—C19	5.93 (18)	C20—N6—C16—C17	−172.4 (2)
N1—Cu1—N4—C19	30.6 (3)	N5—C16—C17—C19	−0.9 (4)
Cl1—Cu1—N4—C19	165.64 (18)	N6—C16—C17—C19	179.8 (2)
Cl2—Cu1—N4—C19	−88.61 (19)	C16—N5—C18—N4	−0.8 (4)
N2—Cu1—N1—C15	176.8 (3)	C19—N4—C18—N5	0.2 (4)
N4—Cu1—N1—C15	152.3 (2)	Cu1—N4—C18—N5	−175.3 (2)
Cl1—Cu1—N1—C15	17.1 (3)	C18—N4—C19—C17	0.1 (4)
Cl2—Cu1—N1—C15	−88.8 (2)	Cu1—N4—C19—C17	176.2 (2)
N2—Cu1—N1—C31	−2.32 (19)	C18—N4—C19—N3	−179.4 (2)
N4—Cu1—N1—C31	−26.8 (3)	Cu1—N4—C19—N3	−3.3 (3)
Cl1—Cu1—N1—C31	−162.08 (18)	C16—C17—C19—N4	0.3 (4)
Cl2—Cu1—N1—C31	92.1 (2)	C16—C17—C19—N3	179.7 (2)
N4—Cu1—N2—C32	172.7 (2)	N2—N3—C19—N4	−3.2 (3)
N1—Cu1—N2—C32	2.9 (2)	C36—N3—C19—N4	−174.6 (2)
Cl1—Cu1—N2—C32	88.0 (3)	N2—N3—C19—C17	177.3 (2)
Cl2—Cu1—N2—C32	−93.0 (2)	C36—N3—C19—C17	5.9 (4)
N4—Cu1—N2—N3	−7.87 (18)	N1—C15—C28—C29	−0.9 (5)
N1—Cu1—N2—N3	−177.6 (2)	C15—C28—C29—C30	0.3 (5)
Cl1—Cu1—N2—N3	−92.5 (3)	C28—C29—C30—C31	0.4 (5)
Cl2—Cu1—N2—N3	86.50 (18)	C15—N1—C31—C30	0.1 (4)
C32—N2—N3—C19	−172.1 (3)	Cu1—N1—C31—C30	179.3 (2)
Cu1—N2—N3—C19	8.5 (3)	C15—N1—C31—C32	−177.7 (2)
C32—N2—N3—C36	−0.1 (4)	Cu1—N1—C31—C32	1.6 (3)
Cu1—N2—N3—C36	−179.56 (18)	C29—C30—C31—N1	−0.6 (5)
C2—N8—C1—C5	0.9 (4)	C29—C30—C31—C32	177.0 (3)
C2—N8—C1—C33	−176.0 (2)	N3—N2—C32—C31	177.7 (2)
C1—N8—C2—C3	0.4 (4)	Cu1—N2—C32—C31	−2.9 (3)
N8—C2—C3—C4	−0.9 (5)	N1—C31—C32—N2	0.8 (4)
C2—C3—C4—C5	−0.1 (4)	C30—C31—C32—N2	−176.9 (3)
C3—C4—C5—C1	1.3 (4)	N6—N7—C33—C1	177.3 (2)
N8—C1—C5—C4	−1.7 (4)	N8—C1—C33—N7	−2.3 (4)
C33—C1—C5—C4	175.2 (3)	C5—C1—C33—N7	−179.3 (3)
C31—N1—C15—C28	0.7 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N4,N5,C16–C19 and N1,C15,C28,C29–C31 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl2ⁱ	0.84	2.36	3.144 (3)	155
O3—H3a···N8ⁱⁱ	0.84	1.96	2.773 (4)	164
C2—H2···Cl1ⁱⁱⁱ	0.95	2.78	3.683 (4)	158
C32—H32···Cl2^iv	0.95	2.64	3.480 (3)	148
C33—H33···Cl2^v	0.95	2.80	3.694 (4)	158
C36—H36b···O3ⁱⁱ	0.98	2.26	3.225 (4)	169
C29—H29···O5	0.95	2.47	3.289 (5)	145
C20—H20b···Cg1^v	0.98	2.58	3.381 (4)	139
C36—H36c···Cg2^iv	0.98	2.81	3.646 (4)	144

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

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₂₀H₁₈N₈)]·2CH₄O·H₂O
M_r	560.94
Crystal system, space group	Triclinic, P1
Temperature (K)	116
a, b, c (Å)	7.430 (5), 11.627 (8), 14.026 (9)
α, β, γ (°)	95.848 (7), 93.477 (13), 92.920 (9)
V (Å³)	1201.2 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.30 × 0.25 × 0.10

Data collection
Diffractometer	Rigaku Saturn724 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.786, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	26094, 7050, 4093
R_int	0.091
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.104, 0.82
No. of reflections	7050
No. of parameters	311
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.64

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), DIAMOND (Brandenburg, 1998) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cu1—Cl1	2.2306 (15)	Cu1—N2	1.989 (2)
Cu1—Cl2	2.5353 (16)	Cu1—N4	2.011 (2)
Cu1—N1	2.038 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N4,N5,C16–C19 and N1,C15,C28,C29–C31 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl2ⁱ	0.84	2.36	3.144 (3)	155
O3—H3a···N8ⁱⁱ	0.84	1.96	2.773 (4)	164
C2—H2···Cl1ⁱⁱⁱ	0.95	2.78	3.683 (4)	158
C32—H32···Cl2^iv	0.95	2.64	3.480 (3)	148
C33—H33···Cl2^v	0.95	2.80	3.694 (4)	158
C36—H36b···O3ⁱⁱ	0.98	2.26	3.225 (4)	169
C29—H29···O5	0.95	2.47	3.289 (5)	145
C20—H20b···Cg1^v	0.98	2.58	3.381 (4)	139
C36—H36c···Cg2^iv	0.98	2.81	3.646 (4)	144

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

Acknowledgements

The authors thank the Science Foundation Ireland for financial support (SFI; 06/RFP/CHE174 and 08/IN.1/I2047). Financial support from DRHEA (BM) and Trinity College is gratefully acknowledged.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stadler, A.-M., Kyritsakas, N., Graff, R. & Lehn, J.-M. (2006). Chem. Eur. J. 12, 4503–4522. Web of Science CSD CrossRef PubMed CAS Google Scholar
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Volume 67| Part 8| August 2011| Pages m1073-m1074

doi:10.1107/S1600536811025414

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