The cocrystal μ-oxalato-κ4O1,O2:O1′,O2′-bis­(aqua­(nitrato-κO){[1-(2-pyridyl-κN)eth­ylidene]hydrazine-κN}copper(II)) μ-oxalato-κ4O1,O2:O1′,O2′-bis­((methanol-κO)(nitrato-κO){[1-(2-pyridyl-κN)eth­ylidene]hydrazine-κN}copper(II)) (1/1)

Diallo, M.; Tamboura, F.B.; Gaye, M.; Barry, A.H.; Bah, Y.

doi:10.1107/S1600536808024550

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1124-m1125

doi:10.1107/S1600536808024550

Open

access

The cocrystal μ-oxalato-κ⁴O¹,O²:O^1′,O^2′-bis(aqua(nitrato-κO){[1-(2-pyridyl-κN)ethylidene]hydrazine-κN}copper(II)) μ-oxalato-κ⁴O¹,O²: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 and Youssouph Bah ^c

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bDépartement de Chimie, Faculté des Sciences, Université de Nouakchott, Nouakchott, Mauritania, and ^cDépartement de Chimie, Faculté des Sciences, Université de Conakry, Conakry, Guinea
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 7 July 2008; accepted 31 July 2008; online 6 August 2008)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.059
wR(F²) = 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

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)

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
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z; (iii) -x+1, -y-1, -z-1.

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Nonius, 1998); data reduction: DENZO (Nonius, 1998); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) (H atoms are omitted for clarity). Displacement ellipsoids are plotted at the 50% probability level. Symmetry codes: (i) -x, -y-1, -z-1; (ii) 2-x, -y, -z.
	Fig. 2. Part of the packing in (I) showing hydrogen bonds as broken lines.

µ-oxalato-κ⁴O¹,O²:O^1',O^2'- bis(aqua(nitrato-κO){[1-(2-pyridyl-κN)ethylidene]hydrazine- κN}copper(II))–µ-oxalato- κ⁴O¹,O²:O^1',O^2'- bis((methanol-κO)(nitrato-κO){[1-(2-pyridyl- κN)ethylidene]hydrazine-κN}copper(II)) (1/1) top

Crystal data top

[Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(H₂O)₂] [Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(CH₄O)₂]	Z = 1
M_r = 1319.04	F(000) = 672
Triclinic, P1	D_x = 1.759 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8358 (9) Å	Cell parameters from 3872 reflections
b = 12.3773 (10) Å	θ = 1.0–26.0°
c = 12.7136 (10) Å	µ = 1.79 mm⁻¹
α = 103.704 (4)°	T = 173 K
β = 112.573 (4)°	Prism, green
γ = 107.821 (4)°	0.03 × 0.02 × 0.02 mm
V = 1245.15 (18) Å³

Data collection top

Nonius KappaCCD diffractometer	3644 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 26.0°, θ_min = 1.9°
π [IS PI CORRECT?] scans	h = −12→11
11826 measured reflections	k = −14→15
4872 independent reflections	l = −15→15

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)] = 0.059	Hydrogen site location: difmap and geom
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0157P)² + 3.8674P] where P = (F_o² + 2F_c²)/3
4872 reflections	(Δ/σ)_max = 0.009
380 parameters	Δρ_max = 0.92 e Å⁻³
6 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(H₂O)₂] [Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(CH₄O)₂]	γ = 107.821 (4)°
M_r = 1319.04	V = 1245.15 (18) Å³
Triclinic, P1	Z = 1
a = 9.8358 (9) Å	Mo Kα radiation
b = 12.3773 (10) Å	µ = 1.79 mm⁻¹
c = 12.7136 (10) Å	T = 173 K
α = 103.704 (4)°	0.03 × 0.02 × 0.02 mm
β = 112.573 (4)°

Data collection top

Nonius KappaCCD diffractometer	3644 reflections with I > 2σ(I)
11826 measured reflections	R_int = 0.057
4872 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	6 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.92 e Å⁻³
4872 reflections	Δρ_min = −0.54 e Å⁻³
380 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
Cu1	0.16109 (7)	−0.43205 (5)	−0.26049 (5)	0.02519 (16)
Cu2	0.80107 (7)	−0.09303 (5)	−0.23584 (5)	0.02536 (16)
O1	0.1705 (4)	−0.3628 (3)	−0.3847 (3)	0.0256 (7)
O2	−0.0358 (4)	−0.5775 (3)	−0.4088 (3)	0.0256 (7)
O3	0.0280 (5)	−0.3375 (4)	−0.1957 (4)	0.0411 (9)
O4	0.3402 (5)	−0.5415 (4)	−0.2903 (3)	0.0421 (9)
O5	0.2179 (6)	−0.7368 (4)	−0.4051 (4)	0.0650 (13)
O6	0.2292 (5)	−0.6055 (3)	−0.4905 (3)	0.0406 (9)
O7	0.8412 (4)	−0.1491 (3)	−0.0993 (3)	0.0260 (7)
O8	0.9916 (4)	0.0660 (3)	−0.1073 (3)	0.0264 (7)
O9	0.9512 (4)	−0.1775 (3)	−0.3019 (3)	0.0342 (8)
H24	0.8965	−0.2413	−0.3686	0.08 (3)*
O10	0.6195 (5)	−0.0053 (4)	−0.1877 (3)	0.0470 (10)
O11	0.7199 (6)	0.1888 (4)	−0.0798 (5)	0.0727 (15)
O12	0.7466 (6)	0.0644 (4)	0.0110 (4)	0.0639 (13)
N1	0.1741 (5)	−0.4997 (4)	−0.1337 (4)	0.0303 (10)
N2	0.3849 (5)	−0.3083 (4)	−0.1229 (4)	0.0306 (10)
N3	0.4829 (6)	−0.2153 (5)	−0.1376 (5)	0.0483 (13)
N4	0.2618 (5)	−0.6290 (4)	−0.3950 (4)	0.0343 (10)
N5	0.7526 (5)	−0.0355 (4)	−0.3705 (4)	0.0287 (9)
N6	0.5987 (5)	−0.2449 (4)	−0.3691 (3)	0.0277 (9)
N7	0.5443 (6)	−0.3515 (4)	−0.3500 (4)	0.0345 (10)
N8	0.6948 (6)	0.0835 (5)	−0.0856 (4)	0.0415 (12)
C1	0.0535 (8)	−0.5935 (5)	−0.1446 (5)	0.0396 (13)
H1	−0.0475	−0.6368	−0.2208	0.048*
C2	0.0702 (9)	−0.6314 (5)	−0.0462 (6)	0.0503 (16)
H2	−0.0178	−0.6988	−0.0545	0.060*
C3	0.2192 (8)	−0.5670 (5)	0.0630 (5)	0.0472 (15)
H3	0.2353	−0.5910	0.1308	0.057*
C4	0.3432 (8)	−0.4695 (6)	0.0739 (5)	0.0468 (15)
H4	0.4456	−0.4256	0.1490	0.056*
C5	0.3192 (7)	−0.4341 (5)	−0.0259 (4)	0.0316 (12)
C6	0.4383 (6)	−0.3281 (5)	−0.0245 (5)	0.0362 (13)
C7	0.6073 (7)	−0.2464 (6)	0.0880 (5)	0.0503 (16)
H7A	0.6882	−0.2226	0.0606	0.076*
H7B	0.6354	−0.2921	0.1398	0.076*
H7C	0.6076	−0.1718	0.1366	0.076*
C8	0.0597 (6)	−0.4386 (4)	−0.4928 (4)	0.0221 (10)
C9	0.8353 (7)	0.0747 (5)	−0.3624 (5)	0.0346 (12)
H9	0.9293	0.1336	−0.2851	0.042*
C10	0.7900 (7)	0.1081 (5)	−0.4626 (5)	0.0425 (14)
H10	0.8512	0.1884	−0.4548	0.051*
C11	0.6536 (7)	0.0212 (6)	−0.5740 (5)	0.0414 (14)
H11	0.6201	0.0418	−0.6442	0.050*
C12	0.5649 (7)	−0.0957 (5)	−0.5847 (5)	0.0374 (13)
H12	0.4699	−0.1549	−0.6613	0.045*
C13	0.6171 (6)	−0.1254 (5)	−0.4813 (4)	0.0292 (11)
C14	0.5375 (6)	−0.2435 (5)	−0.4771 (4)	0.0288 (11)
C15	0.3982 (6)	−0.3556 (5)	−0.5918 (5)	0.0392 (13)
H15A	0.4234	−0.4267	−0.5971	0.059*
H15B	0.3837	−0.3385	−0.6659	0.059*
H15C	0.2969	−0.3744	−0.5871	0.059*
C16	0.9575 (5)	−0.0615 (4)	0.0021 (4)	0.0217 (10)
C17	1.0924 (8)	−0.0986 (6)	−0.2984 (6)	0.0484 (15)
H17A	1.0615	−0.0565	−0.3535	0.073*
H17B	1.1430	−0.1476	−0.3263	0.073*
H17C	1.1708	−0.0368	−0.2131	0.073*
H18	0.107 (6)	−0.277 (4)	−0.112 (3)	0.058 (19)*
H19	−0.001 (7)	−0.277 (4)	−0.220 (5)	0.050 (17)*
H20	0.418 (8)	−0.186 (6)	−0.190 (5)	0.09 (3)*
H21	0.570 (7)	−0.154 (6)	−0.055 (4)	0.12 (3)*
H22	0.437 (4)	−0.406 (4)	−0.420 (4)	0.055 (18)*
H23	0.559 (8)	−0.332 (6)	−0.268 (3)	0.07 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0265 (3)	0.0263 (3)	0.0162 (3)	0.0107 (3)	0.0062 (3)	0.0068 (3)
Cu2	0.0265 (3)	0.0248 (3)	0.0155 (3)	0.0102 (3)	0.0045 (3)	0.0052 (2)
O1	0.0230 (18)	0.0232 (17)	0.0179 (17)	0.0062 (15)	0.0039 (15)	0.0045 (14)
O2	0.0258 (18)	0.0257 (18)	0.0199 (17)	0.0103 (15)	0.0074 (15)	0.0088 (14)
O3	0.056 (3)	0.041 (2)	0.042 (2)	0.033 (2)	0.028 (2)	0.020 (2)
O4	0.042 (2)	0.048 (2)	0.024 (2)	0.024 (2)	0.0072 (18)	0.0050 (18)
O5	0.096 (4)	0.041 (3)	0.067 (3)	0.034 (3)	0.045 (3)	0.023 (2)
O6	0.042 (2)	0.043 (2)	0.027 (2)	0.0173 (19)	0.0132 (18)	0.0070 (17)
O7	0.0223 (18)	0.0228 (17)	0.0191 (17)	0.0053 (15)	0.0038 (15)	0.0042 (14)
O8	0.0283 (19)	0.0267 (18)	0.0164 (16)	0.0106 (16)	0.0054 (15)	0.0082 (14)
O9	0.035 (2)	0.038 (2)	0.026 (2)	0.0173 (18)	0.0145 (17)	0.0090 (18)
O10	0.041 (2)	0.052 (3)	0.029 (2)	0.021 (2)	0.0076 (19)	0.0044 (19)
O11	0.095 (4)	0.042 (3)	0.098 (4)	0.040 (3)	0.057 (4)	0.025 (3)
O12	0.071 (3)	0.078 (3)	0.027 (2)	0.039 (3)	0.012 (2)	0.010 (2)
N1	0.031 (2)	0.035 (2)	0.025 (2)	0.017 (2)	0.013 (2)	0.0117 (19)
N2	0.027 (2)	0.034 (2)	0.023 (2)	0.012 (2)	0.011 (2)	0.0039 (19)
N3	0.034 (3)	0.044 (3)	0.042 (3)	−0.001 (3)	0.015 (3)	0.010 (3)
N4	0.034 (3)	0.034 (3)	0.040 (3)	0.022 (2)	0.018 (2)	0.013 (2)
N5	0.034 (2)	0.032 (2)	0.022 (2)	0.019 (2)	0.012 (2)	0.0122 (19)
N6	0.025 (2)	0.031 (2)	0.020 (2)	0.013 (2)	0.0076 (19)	0.0025 (18)
N7	0.033 (3)	0.027 (2)	0.032 (3)	0.006 (2)	0.014 (2)	0.008 (2)
N8	0.038 (3)	0.045 (3)	0.040 (3)	0.026 (2)	0.017 (2)	0.007 (2)
C1	0.052 (4)	0.041 (3)	0.035 (3)	0.028 (3)	0.023 (3)	0.017 (3)
C2	0.069 (5)	0.035 (3)	0.052 (4)	0.019 (3)	0.033 (4)	0.026 (3)
C3	0.067 (4)	0.040 (3)	0.036 (3)	0.023 (3)	0.022 (3)	0.025 (3)
C4	0.051 (4)	0.057 (4)	0.029 (3)	0.032 (3)	0.011 (3)	0.016 (3)
C5	0.038 (3)	0.043 (3)	0.018 (2)	0.029 (3)	0.011 (2)	0.009 (2)
C6	0.028 (3)	0.043 (3)	0.023 (3)	0.017 (3)	0.008 (2)	−0.002 (2)
C7	0.034 (3)	0.066 (4)	0.035 (3)	0.015 (3)	0.011 (3)	0.014 (3)
C8	0.019 (2)	0.024 (2)	0.017 (2)	0.010 (2)	0.006 (2)	0.005 (2)
C9	0.042 (3)	0.043 (3)	0.025 (3)	0.025 (3)	0.015 (3)	0.018 (2)
C10	0.047 (4)	0.043 (3)	0.046 (3)	0.021 (3)	0.025 (3)	0.028 (3)
C11	0.043 (3)	0.064 (4)	0.034 (3)	0.031 (3)	0.021 (3)	0.032 (3)
C12	0.034 (3)	0.053 (4)	0.026 (3)	0.022 (3)	0.013 (3)	0.018 (3)
C13	0.024 (3)	0.044 (3)	0.019 (2)	0.021 (2)	0.007 (2)	0.010 (2)
C14	0.023 (3)	0.032 (3)	0.022 (3)	0.012 (2)	0.007 (2)	0.002 (2)
C15	0.030 (3)	0.046 (3)	0.023 (3)	0.012 (3)	0.007 (2)	0.003 (2)
C16	0.020 (2)	0.021 (2)	0.021 (2)	0.010 (2)	0.007 (2)	0.005 (2)
C17	0.051 (4)	0.046 (4)	0.052 (4)	0.017 (3)	0.031 (3)	0.021 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.966 (4)	N7—H22	0.96 (2)
Cu1—O1	1.986 (3)	N7—H23	0.95 (2)
Cu1—N2	1.991 (4)	C1—C2	1.406 (8)
Cu1—O2	2.000 (3)	C1—H1	0.9500
Cu1—O3	2.252 (4)	C2—C3	1.382 (9)
Cu1—O4	2.610 (4)	C2—H2	0.9500
Cu2—N5	1.955 (4)	C3—C4	1.362 (8)
Cu2—O7	1.966 (3)	C3—H3	0.9500
Cu2—O8	1.981 (3)	C4—C5	1.397 (7)
Cu2—N6	1.994 (4)	C4—H4	0.9500
Cu2—O9	2.337 (3)	C5—C6	1.458 (8)
Cu2—O10	2.541 (4)	C6—C7	1.514 (7)
O1—C8	1.254 (5)	C7—H7A	0.9800
O2—C8ⁱ	1.258 (5)	C7—H7B	0.9800
O3—H18	0.96 (2)	C7—H7C	0.9800
O3—H19	0.95 (2)	C8—O2ⁱ	1.258 (5)
O4—N4	1.248 (5)	C8—C8ⁱ	1.527 (9)
O5—N4	1.227 (6)	C9—C10	1.386 (7)
O6—N4	1.260 (5)	C9—H9	0.9500
O7—C16	1.262 (5)	C10—C11	1.378 (8)
O8—C16ⁱⁱ	1.258 (5)	C10—H10	0.9500
O9—C17	1.409 (6)	C11—C12	1.384 (8)
O9—H24	0.8400	C11—H11	0.9500
O10—N8	1.237 (5)	C12—C13	1.398 (7)
O11—N8	1.228 (6)	C12—H12	0.9500
O12—N8	1.247 (6)	C13—C14	1.457 (7)
N1—C1	1.315 (7)	C14—C15	1.508 (7)
N1—C5	1.356 (6)	C15—H15A	0.9800
N2—C6	1.273 (7)	C15—H15B	0.9800
N2—N3	1.360 (6)	C15—H15C	0.9800
N3—H20	0.95 (2)	C16—O8ⁱⁱ	1.258 (5)
N3—H21	0.97 (2)	C16—C16ⁱⁱ	1.520 (9)
N5—C9	1.313 (7)	C17—H17A	0.9800
N5—C13	1.381 (6)	C17—H17B	0.9800
N6—C14	1.277 (6)	C17—H17C	0.9800
N6—N7	1.381 (6)

N1—Cu1—O1	174.12 (15)	O11—N8—O10	120.4 (5)
N1—Cu1—N2	80.65 (18)	O11—N8—O12	120.7 (5)
O1—Cu1—N2	95.44 (16)	O10—N8—O12	118.9 (5)
N1—Cu1—O2	98.76 (16)	N1—C1—C2	121.7 (6)
O1—Cu1—O2	84.01 (13)	N1—C1—H1	119.2
N2—Cu1—O2	166.68 (14)	C2—C1—H1	119.2
N1—Cu1—O3	86.33 (15)	C3—C2—C1	117.6 (6)
O1—Cu1—O3	98.48 (13)	C3—C2—H2	121.2
N2—Cu1—O3	95.43 (16)	C1—C2—H2	121.2
O2—Cu1—O3	97.82 (14)	C4—C3—C2	120.4 (5)
N1—Cu1—O4	83.01 (14)	C4—C3—H3	119.8
O1—Cu1—O4	91.90 (12)	C2—C3—H3	119.8
N2—Cu1—O4	78.20 (14)	C3—C4—C5	119.7 (6)
O2—Cu1—O4	88.50 (12)	C3—C4—H4	120.1
O3—Cu1—O4	168.33 (13)	C5—C4—H4	120.1
N5—Cu2—O7	177.14 (15)	N1—C5—C4	119.5 (5)
N5—Cu2—O8	95.30 (15)	N1—C5—C6	115.2 (4)
O7—Cu2—O8	85.09 (13)	C4—C5—C6	125.3 (5)
N5—Cu2—N6	81.51 (17)	N2—C6—C5	114.2 (4)
O7—Cu2—N6	97.92 (15)	N2—C6—C7	123.9 (5)
O8—Cu2—N6	175.14 (15)	C5—C6—C7	121.8 (5)
N5—Cu2—O9	89.35 (14)	C6—C7—H7A	109.5
O7—Cu2—O9	93.43 (13)	C6—C7—H7B	109.5
O8—Cu2—O9	95.95 (13)	H7A—C7—H7B	109.5
N6—Cu2—O9	87.70 (14)	C6—C7—H7C	109.5
N5—Cu2—O10	85.40 (14)	H7A—C7—H7C	109.5
O7—Cu2—O10	91.78 (13)	H7B—C7—H7C	109.5
O8—Cu2—O10	87.50 (13)	O1—C8—O2ⁱ	126.0 (4)
N6—Cu2—O10	88.58 (14)	O1—C8—C8ⁱ	117.4 (5)
O9—Cu2—O10	173.97 (12)	O2ⁱ—C8—C8ⁱ	116.6 (5)
C8—O1—Cu1	111.0 (3)	N5—C9—C10	122.3 (5)
C8ⁱ—O2—Cu1	110.9 (3)	N5—C9—H9	118.9
Cu1—O3—H18	106 (4)	C10—C9—H9	118.9
Cu1—O3—H19	126 (3)	C11—C10—C9	118.0 (5)
H18—O3—H19	92 (5)	C11—C10—H10	121.0
N4—O4—Cu1	110.5 (3)	C9—C10—H10	121.0
C16—O7—Cu2	110.2 (3)	C10—C11—C12	120.7 (5)
C16ⁱⁱ—O8—Cu2	110.3 (3)	C10—C11—H11	119.7
C17—O9—Cu2	119.5 (3)	C12—C11—H11	119.7
C17—O9—H24	109.5	C11—C12—C13	119.1 (5)
Cu2—O9—H24	116.3	C11—C12—H12	120.4
N8—O10—Cu2	113.3 (3)	C13—C12—H12	120.4
C1—N1—C5	121.1 (5)	N5—C13—C12	118.7 (5)
C1—N1—Cu1	125.4 (4)	N5—C13—C14	115.4 (4)
C5—N1—Cu1	113.4 (3)	C12—C13—C14	125.9 (5)
C6—N2—N3	121.3 (5)	N6—C14—C13	114.4 (4)
C6—N2—Cu1	116.4 (4)	N6—C14—C15	123.1 (5)
N3—N2—Cu1	122.0 (3)	C13—C14—C15	122.5 (4)
N2—N3—H20	110 (5)	C14—C15—H15A	109.5
N2—N3—H21	108 (5)	C14—C15—H15B	109.5
H20—N3—H21	116 (7)	H15A—C15—H15B	109.5
O5—N4—O4	120.6 (5)	C14—C15—H15C	109.5
O5—N4—O6	120.2 (5)	H15A—C15—H15C	109.5
O4—N4—O6	119.2 (4)	H15B—C15—H15C	109.5
C9—N5—C13	121.2 (4)	O8ⁱⁱ—C16—O7	125.8 (4)
C9—N5—Cu2	126.3 (3)	O8ⁱⁱ—C16—C16ⁱⁱ	116.7 (5)
C13—N5—Cu2	112.6 (3)	O7—C16—C16ⁱⁱ	117.6 (5)
C14—N6—N7	121.9 (4)	O9—C17—H17A	109.5
C14—N6—Cu2	115.9 (4)	O9—C17—H17B	109.5
N7—N6—Cu2	121.5 (3)	H17A—C17—H17B	109.5
N6—N7—H22	106 (4)	O9—C17—H17C	109.5
N6—N7—H23	111 (4)	H17A—C17—H17C	109.5
H22—N7—H23	119 (5)	H17B—C17—H17C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H18···O11ⁱⁱⁱ	0.96 (2)	2.11 (3)	3.048 (7)	164 (5)
O3—H18···O12ⁱⁱⁱ	0.96 (2)	2.30 (4)	3.084 (6)	138 (5)
O3—H18···N8ⁱⁱⁱ	0.96 (2)	2.53 (2)	3.471 (6)	167 (5)
O3—H19···O9^iv	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···O6^v	0.84	1.89	2.731 (5)	174
O9—H24···N4^v	0.84	2.57	3.367 (6)	158
O9—H24···O5^v	0.84	2.56	3.171 (6)	130

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(H₂O)₂] [Cu₂(C₂O₄)(NO₃)₂(C₇H₉N₃)₂(CH₄O)₂]
M_r	1319.04
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.8358 (9), 12.3773 (10), 12.7136 (10)
α, β, γ (°)	103.704 (4), 112.573 (4), 107.821 (4)
V (Å³)	1245.15 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.03 × 0.02 × 0.02

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11826, 4872, 3644
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.112, 1.07
No. of reflections	4872
No. of parameters	380
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.54

Computer programs: COLLECT (Nonius, 1998), DENZO (Nonius, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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

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

Acknowledgements

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

References

Bulut, A., İçbudak, H., Sezer, G. & Kazak, C. (2005). Acta Cryst. C61, m228–m230. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Du, M., Zou, R.-Q., Zhong, R.-Q. & Xu, Q. (2007). Inorg. Chim. Acta, 360, 3442–3447. Web of Science CSD CrossRef CAS Google Scholar
Kelly, T. L., Milway, V. A., Grove, H., Niel, V., Abedin, T. S. M., Thompson, L. K., Zhao, L., Harvey, R. G., Miller, D. O., Leech, M., Goeta, A. E. & Howard, J. A. K. (2005). Polyhedron, 24, 807–821. Web of Science CSD CrossRef CAS Google Scholar
Moreno, Y., Salgado, Y., Garland, M. T. & Baggio, R. (2007). Acta Cryst. C63, m487–m489. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.