The cocrystal μ-oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­(aqua­(nitrato-κO){[1-(2-pyridyl-κN)eth­ylidene]hydrazine-κN}copper(II)) μ-oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­((methanol-κO)(nitrato-κO){[1-(2-pyridyl-κN)eth­ylidene]hydrazine-κN}copper(II)) (1/1)

Madina Diallo; Farba Bouyagui Tamboura; Mohamed Gaye; Aliou Hamady Barry; Youssouph Bah

doi:10.1107/S1600536808024550

. 2008 Aug 6;64(Pt 9):m1124–m1125. doi: 10.1107/S1600536808024550

The cocrystal μ-oxalato-κ⁴ O ¹,O ²:O ^1′,O ^2′-bis(aqua(nitrato-κO){[1-(2-pyridyl-κN)ethylidene]hydrazine-κN}copper(II)) μ-oxalato-κ⁴ O ¹,O ²:O ^1′,O ^2′-bis((methanol-κO)(nitrato-κO){[1-(2-pyridyl-κN)ethylidene]hydrazine-κN}copper(II)) (1/1)

Madina Diallo ^a, Farba Bouyagui Tamboura ^a, Mohamed Gaye ^a,^*, Aliou Hamady Barry ^b, Youssouph Bah ^c

PMCID: PMC2960478 PMID: 21201585

Abstract

The title cocrystal, [Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(H₂O)₂][Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(CH₄O)₂], is a 1:1 cocrystal of two centrosymmetric Cu^II complexes with oxalate dianions and Schiff base ligands. In each molecule, the Cu^II centre is in a distorted octahedral cis-CuN₂O₄ environment, the donor atoms of the N,N′-bidentate Schiff base ligand and the bridging O,O′-bidentate oxalate group lying in the equatorial plane. In one molecule, a monodentate nitrate anion and a water molecule occupy the axial sites, and in the other, a monodentate nitrate anion and a methanol molecule occupy these sites. In the crystal structure, intermolecular N—H⋯O, O—H⋯O and N—H⋯N hydrogen bonds link the molecules into a network. Weak intramolecular N—H⋯O interactions are also observed.

Related literature

For related structures: see Kelly et al. (2005 ▶); Bulut et al. (2005 ▶); Moreno et al. (2007 ▶); Du et al. (2007 ▶).

Experimental

Crystal data

[Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(H₂O)₂][Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(CH₄O)₂]
M _r = 1319.04
Triclinic,
a = 9.8358 (9) Å
b = 12.3773 (10) Å
c = 12.7136 (10) Å
α = 103.704 (4)°
β = 112.573 (4)°
γ = 107.821 (4)°
V = 1245.15 (18) Å³
Z = 1
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 173 (2) K
0.03 × 0.02 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
11826 measured reflections
4872 independent reflections
3644 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.112
S = 1.06
4872 reflections
380 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO (Nonius, 1998 ▶); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024550/hb2759sup1.cif

e-64-m1124-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024550/hb2759Isup2.hkl

e-64-m1124-Isup2.hkl^{(233.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1	1.966 (4)
Cu1—O1	1.986 (3)
Cu1—N2	1.991 (4)
Cu1—O2	2.000 (3)
Cu1—O3	2.252 (4)
Cu1—O4	2.610 (4)
Cu2—N5	1.955 (4)
Cu2—O7	1.966 (3)
Cu2—O8	1.981 (3)
Cu2—N6	1.994 (4)
Cu2—O9	2.337 (3)
Cu2—O10	2.541 (4)

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H18⋯O11ⁱ	0.96 (2)	2.11 (3)	3.048 (7)	164 (5)
O3—H18⋯O12ⁱ	0.96 (2)	2.30 (4)	3.084 (6)	138 (5)
O3—H18⋯N8ⁱ	0.96 (2)	2.53 (2)	3.471 (6)	167 (5)
O3—H19⋯O9ⁱⁱ	0.95 (2)	1.85 (2)	2.777 (5)	165 (5)
N3—H20⋯O1	0.95 (2)	2.53 (7)	3.014 (6)	112 (5)
N3—H21⋯O12	0.97 (2)	2.44 (7)	3.150 (7)	130 (7)
N7—H22⋯O6	0.96 (2)	2.35 (4)	3.131 (6)	138 (5)
N7—H23⋯N3	0.95 (2)	2.43 (5)	3.196 (7)	138 (5)
N7—H23⋯O7	0.95 (2)	2.59 (6)	3.091 (5)	113 (5)
O9—H24⋯O6ⁱⁱⁱ	0.84	1.89	2.731 (5)	174
O9—H24⋯N4ⁱⁱⁱ	0.84	2.57	3.367 (6)	158
O9—H24⋯O5ⁱⁱⁱ	0.84	2.56	3.171 (6)	130

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No.6314PS804).

supplementary crystallographic information

Comment

The molecular structure of the title compound, (I), (Fig. 1) contains two centrosymmetric binuclear Cu^II complexes (A and B) with the same Schiff base ligand. The coordination spheres around Cu^II in both A and B are slightly distorted octahedra (Table 1), with the coordination plane of each Cu^II formed by the N₂O₂donor atoms of the Schiff base N₂ and the oxalate O₂. The axial positions in A are occupied by an O—NO₂ ion and a water molecule whereas in B these positions are occupied by a O-NO₂ ion and a CH₃OH molecule. The in-plane Cu—O distances are in the range 1.966 (3)–2.000 (3) Å with Cu—N distances 1.955 (4)–1.994 (4) Å, which are slightly larger than distances observed in other Cu^II coordination complexes of the same Schiff base ligand (Kelly et al <i\>., 2005). The elongation of the Cu—O—NO₂ and Cu—O(water) or Cu—O(methanol) axial bonds [2.610 (4) and 2.251 (4) Å in A and 2.541 (4) and 2.338 (3) Å in B] clearly indicate the usual Jahn Teller distortion of the Cu^II as has been found previously (Bulut et al <i\>., 2005; Moreno et al <i\>., 2007; Du et al <i\>., 2007). The basal bond angles O–Cu–O and N–Cu–N are less then 90° [N1–Cu1–N2 = 80.63 (18) ° and N5–Cu2–N6 = 81.50 (17) °; O1–Cu1–O2 = 84.01 (13) ° and O7–Cu2–O8 = 85.09 (17) °] whereas the O–Cu–N angles are largely superior to 90° [N1–Cu1–O2 = 98.76 (16) ° and N2–Cu1–O1 =95.46 (16) ° in A; N5–Cu2–O8 = 95.29 (15) ° and N6–Cu2–O7 =97.93 (15) ° in B]. The axial bonds angles O(water)–Cu1–O—NO₂ and O(methanol)–Cu2–O—NO₂ are also less than the ideal value of 180° [168.34 (14) ° in A and 173.96 (12) ° in B]. A network of hydrogren bonds (Table 2) completes the structure.

Experimental

To a mixture of 0.324 g (1.0 mmol) of the ligand and 50 ml of methanol was added dropwise a solution of 0.463 g (2.0 mmol) of copper nitrate dihydrate in 10 ml of methanol. The resulting mixture was stirred under reflux for 120 min. After cooling the solution was left for slow evaporation and the title compound was obtained in good yield (0.620 g; 94.00°). IR (cm^-1,KBr): 1655, 1625, 1603, 1585, 1484, 1375, 1327, 1030, 829, 783, 699. Analysis calculated for C₃₄H₄₈N₁₆O₂₄Cu₄: C 30.96, H 3.67, N 16.99 °; found: C 30.94, H 3.69, N 16.95 °. Gren prisms of (I) were obtained from slow evaporation of a dimethylformamide solution.