Bis(2-amino-4-methyl­pyridinium) bis­(pyridine-2,6-dicarboxyl­ato)cuprate(II)

Aghabozorg, H.; Mofidi Rouchi, A.; Notash, B.; Mirzaei, M.

doi:10.1107/S1600536811001139

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m189

doi:10.1107/S1600536811001139

Open

access

Bis(2-amino-4-methylpyridinium) bis(pyridine-2,6-dicarboxylato)cuprate(II)

Hossein Aghabozorg,^a ^* Azadeh Mofidi Rouchi,^a Behrouz Notash ^b and Masoud Mirzaei ^c

^aFaculty of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran, 1983963113, Iran, and ^cDepartment of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad 917791436, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 25 December 2010; accepted 8 January 2011; online 15 January 2011)

The asymmetric unit of the title compound, (C₆H₉N₂)₂[Cu(C₇H₃NO₄)₂], contains half of a [Cu(pydc)₂]²⁻ (pydcH₂ is pyridine-2,6-dicarboxylic acid) anion and one protonated 2-amino-4-methylpyridine (2a4mpH)⁺ counter-ion. The anion is a six-coordinated complex with a distorted CuN₂O₄ octahedral geometry around the Cu^II ion. N—H⋯O and C—H⋯O hydrogen bonds along with π–π contacts between the pyridine rings of the (2a4mpH)⁺ cations [centroid–centroid distance = 3.573 (2) Å] stabilize the crystal structure.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ). For related structures see: Aghabozorg et al. (2011 ); Eshtiagh-Hosseini, Aghabozorg et al. (2010 ); Eshtiagh-Hosseini, Gschwind et al. (2010 ); Sharif et al. (2010 ).

Experimental

Crystal data

(C₆H₉N₂)₂[Cu(C₇H₃NO₄)₂]
M_r = 612.06
Monoclinic, C 2/c
a = 24.034 (5) Å
b = 14.231 (3) Å
c = 7.9780 (16) Å
β = 107.01 (3)°
V = 2609.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.9 mm⁻¹
T = 298 K
0.45 × 0.15 × 0.10 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical [shape of crystal determined optically (X-RED32; Stoe & Cie, 2005 )] T_min = 0.743, T_max = 0.846
8829 measured reflections
3509 independent reflections
2785 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.119
S = 1.15
3509 reflections
201 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2ⁱ	0.92 (4)	1.77 (4)	2.662 (4)	163 (4)
N4—H4A⋯O1ⁱ	0.85 (5)	2.22 (5)	3.056 (4)	170 (4)
N4—H4B⋯O3	0.89 (5)	1.97 (5)	2.854 (4)	176 (4)
C7—H7⋯O1ⁱⁱ	0.93	2.58	3.250 (4)	130
C14—H14⋯O4ⁱⁱⁱ	0.93	2.42	3.160 (4)	136
Symmetry codes: (i) x, y, z-1; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001139/bt5449sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001139/bt5449Isup2.hkl

checkCIF report

Comment top

Polycarboxylate ligands are widely applied to assemble supramolecular network decorated by coordination bonds, van der Waals interactions, and π –π stacking. Due to the manifold N– and O-donors of pyridine or pyrazine-(di)carboxylic ligands, metal pyridine- or pyrazine dicarboxylates can contrast versatile structural motifs, which finally aggregate to generate various supramolecular architectures with interesting properties. As ones of the dicarboxylate ligands, pydcH₂ have drawn extensive attentions. Continuing with our previous works on synthesizing coordination and proton transfer compounds (Aghabozorg et al. 2008, 2011), (Eshtiagh-Hosseini, Aghabozorg et al., 2010, Eshtiagh-Hosseini, Gschwind et al., 2010), (Sharif et al., 2010), herein, we planned the reaction between pydcH₂, 2a4mp, and copper^II nitrate trihydrate which resulted in the formation of (2a4mpH)⁺₂.[Cu(pydc)₂] crystals (Fig. 1). Crystal packing diagram related to the title compound is also rendered in the Fig. 2. In the anionic fragment, the Cu^II atom is six-coordinated by two nitrogen and four oxygen atoms from the carboxylate groups of two (pydc)^2- ligands, with bond length ranges of 1.911 (3)–2.029 (2) Å. The N1—Cu1—N2 [180.000 (1)°], O1—Cu1—O1 [146.67 (5)°] and O3—Cu1—O3 [160.23 (5)°] angles. The coordination environment around Cu^II is distorted octahedral. In the crystal structure of the title compound, there are intermolecular C—H···O and N—H···O hydrogen bonds (Table 1) and also π-π contacts between pyridine rings of (2a4mpH)⁺ with centroid-centroid distance Cg1···Cg1ⁱ equel to 3.573 (2) Å [symmetry code: (i) 2 - x, 2 - y,1 - z, where Cg1 is the centroid of ring N3/C9—C11/C13—C14]. (Fig. 2) stabilize the structure.

Related literature top

For background to proton-transfer compounds, see: Aghabozorg et al. (2008). For related structures see: Aghabozorg et al. (2011); Eshtiagh-Hosseini, Aghabozorg et al. (2010); Eshtiagh-Hosseini, Gschwind et al. (2010); Sharif et al. (2010).

Experimental top

A solution of pyridine-2,6-dicarboxylic acid (pydcH₂) (167 mg, 1 mmol) in 10 ml me thanol was added to a solution of 2-amino-4-methylpyridine (2a4mp) (216 mg, 0.6 mmol) in 10 ml me thanol and stirred for 4 hrs. Then a solution of Cu(NO₃)₂.3H₂O (240 mg, 1 mmol) in 3 ml me thanol was added to the solution of pydcH₂ and 2a4mp. To the resulted precipitate was added 1 ml of DMSO and stirred for several minutes under heating. By slove evaporation of this solution in room temprature, green crystals of the title compound were obtained after three week which were suitable for X-ray analysis (m.p 265–267 °C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (2a4mpH)⁺₂.[Cu(pydc)₂] with displacement ellipsoids drawn at 30% probability level (symmetry code: i: -x, y, 3/2 - z).
	Fig. 2. The packing diagram of (2a4mpH)⁺₂.[Cu(pydc)₂]. The intermolecular N—H···O and C—H···O hydrogen bonds and π-π contacts are shown as blue and orange dashed lines, respectively.

Bis(2-amino-4-methylpyridinium) bis(pyridine-2,6-dicarboxylato)cuprate(II) top

Crystal data top

(C₆H₉N₂)₂[Cu(C₇H₃NO₄)₂]	F(000) = 1260
M_r = 612.06	D_x = 1.558 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3509 reflections
a = 24.034 (5) Å	θ = 2.9–29.2°
b = 14.231 (3) Å	µ = 0.9 mm⁻¹
c = 7.9780 (16) Å	T = 298 K
β = 107.01 (3)°	Needle, blue
V = 2609.3 (10) Å³	0.45 × 0.15 × 0.1 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	3509 independent reflections
Radiation source: fine-focus sealed tube	2785 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 0.15 mm pixels mm^-1	θ_max = 29.2°, θ_min = 2.9°
rotation method scans	h = −30→32
Absorption correction: numerical [shape of crystal determined optically (X-RED32, Stoe & Cie, 2005)]	k = −19→16
T_min = 0.743, T_max = 0.846	l = −10→10
8829 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.0336P)² + 5.0605P] where P = (F_o² + 2F_c²)/3
3509 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

(C₆H₉N₂)₂[Cu(C₇H₃NO₄)₂]	V = 2609.3 (10) Å³
M_r = 612.06	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.034 (5) Å	µ = 0.9 mm⁻¹
b = 14.231 (3) Å	T = 298 K
c = 7.9780 (16) Å	0.45 × 0.15 × 0.1 mm
β = 107.01 (3)°

Data collection top

Stoe IPDS II diffractometer	3509 independent reflections
Absorption correction: numerical [shape of crystal determined optically (X-RED32, Stoe & Cie, 2005)]	2785 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.846	R_int = 0.061
8829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.39 e Å⁻³
3509 reflections	Δρ_min = −0.30 e Å⁻³
201 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
C2	0.04362 (14)	0.1040 (2)	0.8614 (4)	0.0350 (6)
O2	0.13708 (12)	0.1246 (2)	1.0589 (3)	0.0592 (7)
O1	0.07172 (11)	0.23932 (17)	1.0341 (3)	0.0475 (6)
C7	0.04400 (13)	0.5659 (2)	0.7068 (4)	0.0338 (6)
H7	0.0734	0.5980	0.6770	0.041*
C8	0.0000	0.6143 (3)	0.7500	0.0359 (9)
H8	0.0000	0.6796	0.7500	0.043*
Cu1	0.0000	0.29007 (3)	0.7500	0.02835 (14)
N2	0.0000	0.4244 (2)	0.7500	0.0266 (6)
N4	0.11686 (12)	0.2123 (2)	0.4309 (4)	0.0461 (7)
O3	0.07121 (9)	0.31454 (14)	0.6690 (3)	0.0370 (5)
N3	0.19892 (12)	0.14346 (19)	0.3935 (4)	0.0388 (6)
N1	0.0000	0.1521 (2)	0.7500	0.0318 (7)
C9	0.17056 (13)	0.1785 (2)	0.5020 (4)	0.0345 (6)
C11	0.25320 (16)	0.1393 (2)	0.7462 (4)	0.0444 (7)
C10	0.19805 (15)	0.1743 (2)	0.6831 (4)	0.0420 (7)
H10	0.1786	0.1957	0.7608	0.050*
O4	0.12832 (10)	0.43226 (18)	0.6314 (3)	0.0493 (6)
C6	0.04298 (11)	0.46879 (19)	0.7094 (3)	0.0272 (5)
C5	0.08574 (12)	0.4019 (2)	0.6666 (4)	0.0320 (6)
C13	0.28131 (16)	0.1052 (3)	0.6265 (5)	0.0516 (9)
H13	0.3188	0.0808	0.6665	0.062*
C14	0.25339 (15)	0.1082 (3)	0.4529 (5)	0.0485 (8)
H14	0.2719	0.0859	0.3734	0.058*
C12	0.2851 (2)	0.1384 (3)	0.9394 (5)	0.0679 (12)
H12A	0.3097	0.1927	0.9684	0.102*
H12B	0.3084	0.0826	0.9675	0.102*
H12C	0.2574	0.1393	1.0052	0.102*
C1	0.08860 (15)	0.1616 (2)	0.9957 (4)	0.0395 (7)
C3	0.04539 (18)	0.0064 (2)	0.8605 (5)	0.0485 (8)
H3	0.0770	−0.0255	0.9339	0.058*
C4	0.0000	−0.0425 (3)	0.7500	0.0591 (15)
H4	0.0000	−0.1079	0.7500	0.071*
H3A	0.1810 (18)	0.148 (3)	0.275 (5)	0.057 (11)*
H4B	0.1012 (19)	0.245 (3)	0.501 (6)	0.062 (12)*
H4A	0.108 (2)	0.225 (3)	0.322 (7)	0.074 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0432 (17)	0.0305 (14)	0.0316 (14)	0.0044 (12)	0.0116 (13)	−0.0005 (11)
O2	0.0498 (15)	0.0694 (18)	0.0477 (14)	0.0226 (13)	−0.0024 (12)	−0.0063 (12)
O1	0.0519 (14)	0.0415 (13)	0.0427 (12)	0.0065 (11)	0.0036 (11)	−0.0087 (10)
C7	0.0291 (14)	0.0305 (14)	0.0372 (14)	−0.0073 (11)	0.0026 (12)	0.0014 (11)
C8	0.033 (2)	0.0240 (18)	0.042 (2)	0.000	−0.0011 (18)	0.000
Cu1	0.0325 (3)	0.0218 (2)	0.0336 (2)	0.000	0.01408 (19)	0.000
N2	0.0261 (16)	0.0261 (15)	0.0273 (15)	0.000	0.0072 (13)	0.000
N4	0.0400 (14)	0.0526 (17)	0.0444 (15)	0.0111 (14)	0.0100 (12)	−0.0122 (15)
O3	0.0376 (11)	0.0338 (11)	0.0444 (11)	0.0037 (9)	0.0193 (10)	−0.0036 (9)
N3	0.0367 (14)	0.0414 (14)	0.0378 (13)	0.0074 (11)	0.0102 (11)	−0.0009 (11)
N1	0.042 (2)	0.0233 (15)	0.0304 (16)	0.000	0.0112 (15)	0.000
C9	0.0320 (14)	0.0303 (13)	0.0410 (15)	−0.0003 (11)	0.0104 (12)	−0.0066 (11)
C11	0.0478 (18)	0.0351 (16)	0.0440 (17)	−0.0024 (14)	0.0033 (14)	−0.0012 (14)
C10	0.0445 (18)	0.0415 (16)	0.0399 (16)	0.0009 (14)	0.0120 (14)	−0.0061 (13)
O4	0.0357 (12)	0.0546 (14)	0.0658 (15)	−0.0093 (11)	0.0279 (12)	−0.0084 (12)
C6	0.0249 (13)	0.0304 (13)	0.0254 (11)	−0.0025 (10)	0.0059 (10)	−0.0004 (10)
C5	0.0304 (14)	0.0357 (14)	0.0305 (13)	−0.0020 (11)	0.0098 (11)	−0.0030 (11)
C13	0.0375 (18)	0.049 (2)	0.062 (2)	0.0101 (15)	0.0032 (16)	−0.0013 (16)
C14	0.0394 (18)	0.051 (2)	0.058 (2)	0.0144 (15)	0.0181 (16)	−0.0010 (16)
C12	0.080 (3)	0.058 (2)	0.049 (2)	0.000 (2)	−0.008 (2)	0.0008 (18)
C1	0.0470 (18)	0.0404 (17)	0.0294 (14)	0.0049 (14)	0.0086 (13)	−0.0005 (12)
C3	0.065 (2)	0.0306 (15)	0.0484 (18)	0.0147 (15)	0.0148 (17)	0.0050 (13)
C4	0.088 (4)	0.022 (2)	0.067 (3)	0.000	0.022 (3)	0.000

Geometric parameters (Å, º) top

C2—N1	1.346 (3)	N3—C14	1.351 (4)
C2—C3	1.390 (4)	N3—H3A	0.92 (4)
C2—C1	1.520 (4)	N1—C2ⁱ	1.346 (3)
O2—C1	1.243 (4)	C9—C10	1.403 (4)
O1—C1	1.246 (4)	C11—C10	1.367 (5)
C7—C6	1.382 (4)	C11—C13	1.407 (5)
C7—C8	1.387 (4)	C11—C12	1.507 (5)
C7—H7	0.9300	C10—H10	0.9300
C8—C7ⁱ	1.387 (4)	O4—C5	1.217 (3)
C8—H8	0.9300	C6—C5	1.511 (4)
Cu1—N2	1.911 (3)	C13—C14	1.352 (5)
Cu1—N1	1.964 (3)	C13—H13	0.9300
Cu1—O3	2.029 (2)	C14—H14	0.9300
Cu1—O3ⁱ	2.029 (2)	C12—H12A	0.9600
N2—C6	1.330 (3)	C12—H12B	0.9600
N2—C6ⁱ	1.330 (3)	C12—H12C	0.9600
N4—C9	1.338 (4)	C3—C4	1.374 (5)
N4—H4B	0.89 (5)	C3—H3	0.9300
N4—H4A	0.85 (5)	C4—C3ⁱ	1.374 (5)
O3—C5	1.292 (4)	C4—H4	0.9300
N3—C9	1.344 (4)

N1—C2—C3	121.6 (3)	C10—C11—C12	121.8 (3)
N1—C2—C1	116.5 (3)	C13—C11—C12	119.3 (3)
C3—C2—C1	121.8 (3)	C11—C10—C9	120.5 (3)
C6—C7—C8	118.3 (3)	C11—C10—H10	119.7
C6—C7—H7	120.8	C9—C10—H10	119.7
C8—C7—H7	120.8	N2—C6—C7	119.8 (3)
C7ⁱ—C8—C7	120.5 (4)	N2—C6—C5	112.5 (2)
C7ⁱ—C8—H8	119.8	C7—C6—C5	127.6 (3)
C7—C8—H8	119.8	O4—C5—O3	126.4 (3)
N2—Cu1—N1	180.000 (1)	O4—C5—C6	120.1 (3)
N2—Cu1—O3	80.12 (6)	O3—C5—C6	113.5 (2)
N1—Cu1—O3	99.88 (6)	C14—C13—C11	119.4 (3)
N2—Cu1—O3ⁱ	80.12 (6)	C14—C13—H13	120.3
N1—Cu1—O3ⁱ	99.88 (6)	C11—C13—H13	120.3
O3—Cu1—O3ⁱ	160.24 (12)	N3—C14—C13	120.7 (3)
C6—N2—C6ⁱ	123.2 (3)	N3—C14—H14	119.6
C6—N2—Cu1	118.39 (17)	C13—C14—H14	119.6
C6ⁱ—N2—Cu1	118.39 (17)	C11—C12—H12A	109.5
C9—N4—H4B	117 (3)	C11—C12—H12B	109.5
C9—N4—H4A	116 (3)	H12A—C12—H12B	109.5
H4B—N4—H4A	120 (4)	C11—C12—H12C	109.5
C5—O3—Cu1	115.23 (17)	H12A—C12—H12C	109.5
C9—N3—C14	122.2 (3)	H12B—C12—H12C	109.5
C9—N3—H3A	118 (3)	O2—C1—O1	127.6 (3)
C14—N3—H3A	120 (3)	O2—C1—C2	116.4 (3)
C2ⁱ—N1—C2	118.9 (4)	O1—C1—C2	115.9 (3)
C2ⁱ—N1—Cu1	120.56 (18)	C4—C3—C2	119.3 (3)
C2—N1—Cu1	120.56 (18)	C4—C3—H3	120.3
N4—C9—N3	118.0 (3)	C2—C3—H3	120.3
N4—C9—C10	123.8 (3)	C3ⁱ—C4—C3	119.2 (4)
N3—C9—C10	118.2 (3)	C3ⁱ—C4—H4	120.4
C10—C11—C13	118.8 (3)	C3—C4—H4	120.4

C6—C7—C8—C7ⁱ	−0.48 (18)	Cu1—N2—C6—C7	179.50 (19)
O3—Cu1—N2—C6	−2.65 (14)	C6ⁱ—N2—C6—C5	−179.4 (2)
O3ⁱ—Cu1—N2—C6	177.35 (14)	Cu1—N2—C6—C5	0.6 (2)
O3—Cu1—N2—C6ⁱ	177.35 (14)	C8—C7—C6—N2	1.0 (4)
O3ⁱ—Cu1—N2—C6ⁱ	−2.65 (14)	C8—C7—C6—C5	179.7 (2)
N2—Cu1—O3—C5	4.56 (19)	Cu1—O3—C5—O4	176.0 (3)
N1—Cu1—O3—C5	−175.44 (19)	Cu1—O3—C5—C6	−5.4 (3)
O3ⁱ—Cu1—O3—C5	4.56 (19)	N2—C6—C5—O4	−178.1 (2)
C3—C2—N1—C2ⁱ	1.8 (2)	C7—C6—C5—O4	3.2 (5)
C1—C2—N1—C2ⁱ	−174.4 (3)	N2—C6—C5—O3	3.2 (3)
C3—C2—N1—Cu1	−178.2 (2)	C7—C6—C5—O3	−175.5 (3)
C1—C2—N1—Cu1	5.6 (3)	C10—C11—C13—C14	0.3 (5)
O3—Cu1—N1—C2ⁱ	−114.82 (16)	C12—C11—C13—C14	−178.2 (4)
O3ⁱ—Cu1—N1—C2ⁱ	65.18 (16)	C9—N3—C14—C13	1.3 (5)
O3—Cu1—N1—C2	65.18 (16)	C11—C13—C14—N3	−0.1 (6)
O3ⁱ—Cu1—N1—C2	−114.82 (16)	N1—C2—C1—O2	−157.6 (3)
C14—N3—C9—N4	179.6 (3)	C3—C2—C1—O2	26.2 (5)
C14—N3—C9—C10	−2.6 (5)	N1—C2—C1—O1	24.9 (4)
C13—C11—C10—C9	−1.6 (5)	C3—C2—C1—O1	−151.3 (3)
C12—C11—C10—C9	176.8 (3)	N1—C2—C3—C4	−3.6 (5)
N4—C9—C10—C11	−179.6 (3)	C1—C2—C3—C4	172.4 (3)
N3—C9—C10—C11	2.7 (5)	C2—C3—C4—C3ⁱ	1.7 (2)
C6ⁱ—N2—C6—C7	−0.50 (19)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱⁱ	0.92 (4)	1.77 (4)	2.662 (4)	163 (4)
N4—H4A···O1ⁱⁱ	0.85 (5)	2.22 (5)	3.056 (4)	170 (4)
N4—H4B···O3	0.89 (5)	1.97 (5)	2.854 (4)	176 (4)
C7—H7···O1ⁱⁱⁱ	0.93	2.58	3.250 (4)	130
C14—H14···O4^iv	0.93	2.42	3.160 (4)	136

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

Experimental details

Crystal data
Chemical formula	(C₆H₉N₂)₂[Cu(C₇H₃NO₄)₂]
M_r	612.06
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.034 (5), 14.231 (3), 7.9780 (16)
β (°)	107.01 (3)
V (Å³)	2609.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.9
Crystal size (mm)	0.45 × 0.15 × 0.1

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Numerical [shape of crystal determined optically (X-RED32, Stoe & Cie, 2005)]
T_min, T_max	0.743, 0.846
No. of measured, independent and observed [I > 2σ(I)] reflections	8829, 3509, 2785
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.119, 1.15
No. of reflections	3509
No. of parameters	201
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱ	0.92 (4)	1.77 (4)	2.662 (4)	163 (4)
N4—H4A···O1ⁱ	0.85 (5)	2.22 (5)	3.056 (4)	170 (4)
N4—H4B···O3	0.89 (5)	1.97 (5)	2.854 (4)	176 (4)
C7—H7···O1ⁱⁱ	0.93	2.58	3.250 (4)	130
C14—H14···O4ⁱⁱⁱ	0.93	2.42	3.160 (4)	136

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

Acknowledgements

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc. 5, 184–227. CrossRef CAS Google Scholar
Aghabozorg, H., Mofidi Rouchi, A., Mirzaei, M. & Notash, B. (2011). Acta Cryst. E67, o54. Web of Science CrossRef IUCr Journals Google Scholar
Eshtiagh-Hosseini, H., Aghabozorg, H., Mirzaei, M., Amini, M. M., Chen, Y.-G., Shokrollahi, A. & Aghaei, R. (2010). J. Mol. Struct. 973, 180–189. CAS Google Scholar
Eshtiagh-Hosseini, H., Gschwind, F., Alfi, N. & Mirzaei, M. (2010). Acta Cryst. E66, m826–m827. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sharif, M. A., Tabatabaee, M., Adinehloo, M. & Aghabozorg, H. (2010). Acta Cryst. E66, o3232. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2005). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar