Bis(2-amino-4-methyl-pyridinium) bis-(pyridine-2,6-dicarboxyl-ato)cuprate(II).

The asymmetric unit of the title compound, (C(6)H(9)N(2))(2)[Cu(C(7)H(3)NO(4))(2)], contains half of a [Cu(pydc)(2)](2-) (pydcH(2) is pyridine-2,6-dicarb-oxy-lic acid) anion and one protonated 2-amino-4-methyl-pyridine (2a4mpH)(+) counter-ion. The anion is a six-coordinated complex with a distorted CuN(2)O(4) octa-hedral 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 = 612.06

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.119

S = 1.15

3509 reflections

201 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.30 e Å−3

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 ▶).

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

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

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

(C6H9N2)2[Cu(C7H3NO4)2]	F(000) = 1260
Mr = 612.06	Dx = 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

Stoe IPDS II diffractometer	3509 independent reflections
Radiation source: fine-focus sealed tube	2785 reflections with I > 2σ(I)
graphite	Rint = 0.061
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.2°, θmin = 2.9°
rotation method scans	h = −30→32
Absorption correction: numerical [shape of crystal determined optically (X-RED32, Stoe & Cie, 2005)]	k = −19→16
Tmin = 0.743, Tmax = 0.846	l = −10→10
8829 measured reflections

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(Fo2) + (0.0336P)2 + 5.0605P] where P = (Fo2 + 2Fc2)/3
3509 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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

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)

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···O4iv	0.93	2.42	3.160 (4)	136

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) ; (ii) ; (iii) .