Bis(2-amino-4-methyl-pyridinium) trans-diaqua-bis-(pyrazine-2,3-dicarboxyl-ato)cuprate(II) hexa-hydrate.

The title compound, (C(6)H(9)N(2))(2)[Cu(C(6)H(2)N(2)O(4))(2)(H(2)O)(2)]·6H(2)O, consists of a mononuclear trans-[Cu(pzdc)(2)(H(2)O)(2)](2-) dianion (pzdc is pyrazine-2,3-dicarboxyl-ate) and two [ampyH](+) cations (ampy is 2-amino-4-methyl-pyridine) with six water mol-ecules of solvation. The Cu(II) atom is hexa-coordinated by two pzdc groups and two water mol-ecules. The coordinated water mol-ecules are in trans-diaxial positions and the pzdc dianion acts as a bidentate ligand through an O atom of the carboxyl-ate group and the N atom of the pyrazine ring. There are diverse hydrogen-bonding inter-actions, such as N-H⋯O and O-H⋯O contacts, which lead to the formation of a three-dimensional supra-molecular architecture.

Related literature

For the crystal structure of pyrazine-2,3-dicarb­oxy­lic acid (pzdcH2), see: Takusagawa & Shimada (1973 ▶). For complexes of pzdcH2 with manganese and zinc, see: Eshtiagh-Hosseini et al. (2010a ▶,b ▶). For the structure of bis­(2,4,6-triamino-1,3,5-triazin-1-ium) pyrazine-2,3-dicarboxyl­ate tetra­hydrate, see: Eshtiagh-Hosseini et al. (2010c ▶). For a review articleon water cluster chemistry, see: Aghabozorg et al. (2010 ▶).

Experimental

Crystal data

(C6H9N2)2[Cu(C6H2N2O4)2(H2O)2]·6H2O

M = 758.17

Triclinic,

a = 6.9075 (14) Å

b = 8.4710 (17) Å

c = 14.505 (3) Å

α = 78.28 (3)°

β = 83.62 (3)°

γ = 85.81 (3)°

V = 824.8 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.75 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Stoe IPDS 2 diffractometer

Absorption correction: for a sphere [modified Dwiggins (1975 ▶) interpolation procedure] T min = 0.743, T max = 0.745

17015 measured reflections

4684 independent reflections

4282 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.092

S = 1.04

4684 reflections

268 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.52 e Å−3

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-RED (Stoe & Cie, 2009 ▶); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023081/fj2310sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023081/fj2310Isup2.hkl

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

(C6H9N2)2[Cu(C6H2N2O4)2(H2O)2]·6H2O	Z = 1
Mr = 758.17	F(000) = 395.0
Triclinic, P1	Dx = 1.526 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9075 (14) Å	Cell parameters from 34097 reflections
b = 8.4710 (17) Å	θ = 3,8–59,7°
c = 14.505 (3) Å	µ = 0.75 mm−1
α = 78.28 (3)°	T = 293 K
β = 83.62 (3)°	Block, blue
γ = 85.81 (3)°	0.3 × 0.2 × 0.1 mm
V = 824.8 (3) Å3

Stoe IPDS 2 diffractometer	4684 independent reflections
Radiation source: fine-focus sealed tube	4282 reflections with I > 2σ(I)
graphite	Rint = 0.046
Detector resolution: 6.67 pixels mm-1	θmax = 29.8°, θmin = 2.5°
rotation method scans	h = −9→9
Absorption correction: for a sphere modified Dwiggins (1975) interpolation procedure	k = −11→11
Tmin = 0.743, Tmax = 0.745	l = −20→20
17015 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0453P)2 + 0.5453P] where P = (Fo2 + 2Fc2)/3
4684 reflections	(Δ/σ)max = 0.001
268 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.52 e Å−3

Experimental. Absorption correction: Interpolation using Int. Tab. Vol. C (1992) p. 523, Tab. 6.3.3.3 for values of muR in the range 0-2.5, and Int. Tab. Vol. II (1959) p. 302; Table 5.3.6 B for muR in the range 2.6-10.0. The interpolation procedure of C. W. Dwiggins Jr is used with some modification.

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.

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.5000	0.01658 (8)
O3	0.30782 (17)	0.49841 (13)	0.17617 (8)	0.0195 (2)
O4	0.11843 (16)	0.64677 (13)	0.26546 (8)	0.0180 (2)
O1	−0.09643 (16)	0.33706 (13)	0.27415 (8)	0.0190 (2)
O5	0.1806 (2)	−0.17345 (17)	0.40519 (9)	0.0258 (3)
O2	−0.12649 (16)	0.11778 (13)	0.38957 (8)	0.0189 (2)
N1	0.19550 (18)	0.16670 (15)	0.45776 (8)	0.0147 (2)
N2	0.43093 (18)	0.41844 (16)	0.37769 (9)	0.0173 (2)
C1	−0.0415 (2)	0.24286 (17)	0.34432 (10)	0.0144 (2)
C2	0.1458 (2)	0.27423 (16)	0.38093 (9)	0.0134 (2)
C5	0.2651 (2)	0.40007 (17)	0.34084 (10)	0.0139 (2)
C4	0.4760 (2)	0.31081 (19)	0.45398 (11)	0.0187 (3)
H4	0.5897	0.3212	0.4806	0.022*
C3	0.3583 (2)	0.18338 (18)	0.49501 (10)	0.0171 (3)
H3	0.3936	0.1103	0.5483	0.021*
C6	0.2244 (2)	0.52402 (17)	0.25287 (10)	0.0148 (2)
N3	0.17729 (19)	−0.08982 (15)	0.12469 (9)	0.0175 (2)
H13	0.1634	−0.1765	0.1614	0.021*
N4	0.2985 (2)	−0.23942 (16)	0.01280 (10)	0.0200 (3)
H14A	0.3217	−0.2450	−0.0394	0.024*
C10	0.2467 (2)	−0.09571 (18)	0.03481 (10)	0.0160 (3)
C9	0.2613 (2)	0.05143 (19)	−0.03132 (11)	0.0184 (3)
C8	0.2056 (2)	0.19545 (18)	−0.00370 (11)	0.0197 (3)
C11	0.1206 (2)	0.05082 (19)	0.15352 (11)	0.0212 (3)
H11	0.0728	0.0489	0.2162	0.025*
C12	0.1332 (3)	0.19396 (19)	0.09169 (12)	0.0223 (3)
C7	0.2186 (3)	0.3528 (2)	−0.07308 (14)	0.0288 (4)
H7A	0.2698	0.4314	−0.0443	0.043*
H7B	0.0911	0.3898	−0.0912	0.043*
H7C	0.3034	0.3379	−0.1281	0.043*
O6	0.7121 (2)	0.67499 (18)	0.32078 (13)	0.0381 (4)
O7	0.4817 (2)	0.9530 (2)	0.28417 (12)	0.0385 (3)
O8	0.60159 (18)	0.25375 (14)	0.18411 (8)	0.0203 (2)
H12	0.097 (4)	0.287 (3)	0.1154 (19)	0.040 (7)*
H14B	0.289 (3)	−0.322 (3)	0.0565 (17)	0.024 (5)*
H9	0.311 (3)	0.045 (2)	−0.0939 (15)	0.017 (5)*
H5B	0.267 (4)	−0.130 (3)	0.372 (2)	0.040 (7)*
H5A	0.138 (4)	−0.236 (3)	0.377 (2)	0.040 (7)*
H8A	0.516 (4)	0.326 (3)	0.1824 (19)	0.039 (7)*
H8B	0.677 (4)	0.279 (3)	0.2116 (19)	0.034 (6)*
H6B	0.823 (5)	0.645 (4)	0.306 (2)	0.057 (9)*
H6A	0.632 (6)	0.606 (5)	0.333 (3)	0.076 (11)*
H17A	0.570 (5)	0.885 (4)	0.288 (2)	0.049 (8)*
H17B	0.524 (5)	1.032 (4)	0.259 (3)	0.062 (10)*

	U11	U22	U33	U12	U13	U23
Cu1	0.01841 (13)	0.01479 (13)	0.01464 (12)	−0.00519 (9)	−0.00398 (9)	0.00436 (9)
O3	0.0237 (5)	0.0173 (5)	0.0150 (5)	0.0014 (4)	0.0007 (4)	0.0003 (4)
O4	0.0203 (5)	0.0131 (5)	0.0190 (5)	0.0006 (4)	−0.0017 (4)	−0.0002 (4)
O1	0.0208 (5)	0.0176 (5)	0.0172 (5)	−0.0032 (4)	−0.0062 (4)	0.0032 (4)
O5	0.0265 (6)	0.0295 (6)	0.0239 (6)	−0.0017 (5)	−0.0016 (5)	−0.0116 (5)
O2	0.0193 (5)	0.0175 (5)	0.0185 (5)	−0.0068 (4)	−0.0056 (4)	0.0037 (4)
N1	0.0172 (5)	0.0131 (5)	0.0129 (5)	−0.0012 (4)	−0.0023 (4)	0.0003 (4)
N2	0.0158 (5)	0.0174 (6)	0.0179 (6)	−0.0020 (4)	−0.0023 (4)	−0.0007 (5)
C1	0.0154 (6)	0.0140 (6)	0.0134 (6)	−0.0015 (5)	−0.0013 (5)	−0.0014 (5)
C2	0.0149 (6)	0.0124 (6)	0.0121 (6)	−0.0004 (5)	−0.0013 (5)	−0.0006 (5)
C5	0.0149 (6)	0.0125 (6)	0.0133 (6)	0.0006 (5)	−0.0005 (5)	−0.0014 (5)
C4	0.0165 (6)	0.0196 (7)	0.0196 (7)	−0.0020 (5)	−0.0051 (5)	−0.0009 (5)
C3	0.0193 (6)	0.0165 (6)	0.0148 (6)	0.0005 (5)	−0.0044 (5)	−0.0006 (5)
C6	0.0154 (6)	0.0127 (6)	0.0154 (6)	−0.0035 (5)	−0.0015 (5)	0.0004 (5)
N3	0.0221 (6)	0.0146 (5)	0.0143 (5)	−0.0001 (4)	−0.0021 (4)	0.0007 (4)
N4	0.0262 (6)	0.0161 (6)	0.0162 (6)	0.0006 (5)	−0.0010 (5)	−0.0009 (5)
C10	0.0155 (6)	0.0175 (6)	0.0149 (6)	−0.0022 (5)	−0.0036 (5)	−0.0010 (5)
C9	0.0185 (6)	0.0192 (7)	0.0156 (6)	−0.0020 (5)	−0.0021 (5)	0.0014 (5)
C8	0.0194 (7)	0.0159 (7)	0.0223 (7)	−0.0034 (5)	−0.0057 (5)	0.0022 (5)
C11	0.0277 (8)	0.0199 (7)	0.0161 (6)	0.0016 (6)	−0.0033 (6)	−0.0043 (6)
C12	0.0282 (8)	0.0164 (7)	0.0232 (7)	−0.0002 (6)	−0.0067 (6)	−0.0044 (6)
C7	0.0340 (9)	0.0173 (7)	0.0308 (9)	−0.0031 (6)	−0.0035 (7)	0.0058 (6)
O6	0.0263 (7)	0.0240 (7)	0.0620 (10)	−0.0045 (5)	0.0142 (7)	−0.0127 (7)
O7	0.0273 (7)	0.0304 (7)	0.0498 (9)	−0.0033 (6)	−0.0024 (6)	0.0108 (7)
O8	0.0208 (5)	0.0204 (5)	0.0203 (5)	0.0013 (4)	−0.0044 (4)	−0.0051 (4)

Cu1—O2	1.9644 (13)	N3—C11	1.358 (2)
Cu1—O2i	1.9644 (12)	N3—H13	0.8202
Cu1—N1	1.9840 (14)	N4—C10	1.335 (2)
Cu1—N1i	1.9840 (14)	N4—H14A	0.7669
Cu1—O5	2.4038 (15)	N4—H14B	0.84 (2)
Cu1—O5i	2.4038 (15)	C10—C9	1.412 (2)
O3—C6	1.2467 (18)	C9—C8	1.376 (2)
O4—C6	1.2597 (18)	C9—H9	0.95 (2)
O1—C1	1.2364 (18)	C8—C12	1.416 (2)
O5—H5B	0.79 (3)	C8—C7	1.500 (2)
O5—H5A	0.82 (3)	C11—C12	1.356 (2)
O2—C1	1.2732 (18)	C11—H11	0.9300
N1—C3	1.3291 (19)	C12—H12	0.93 (3)
N1—C2	1.3477 (18)	C7—H7A	0.9600
N2—C4	1.333 (2)	C7—H7B	0.9600
N2—C5	1.3486 (18)	C7—H7C	0.9600
C1—C2	1.5119 (19)	O6—H6B	0.81 (4)
C2—C5	1.387 (2)	O6—H6A	0.81 (4)
C5—C6	1.517 (2)	O7—H17A	0.80 (3)
C4—C3	1.393 (2)	O7—H17B	0.76 (4)
C4—H4	0.9300	O8—H8A	0.81 (3)
C3—H3	0.9300	O8—H8B	0.76 (3)
N3—C10	1.3475 (19)
O2—Cu1—O2i	180.00 (4)	N1—C3—H3	120.1
O2—Cu1—N1	83.31 (5)	C4—C3—H3	120.1
O2i—Cu1—N1	96.69 (5)	O3—C6—O4	126.59 (14)
O2—Cu1—N1i	96.69 (5)	O3—C6—C5	116.73 (13)
O2i—Cu1—N1i	83.31 (5)	O4—C6—C5	116.56 (13)
N1—Cu1—N1i	180.00 (7)	C10—N3—C11	122.73 (14)
O2—Cu1—O5	90.70 (5)	C10—N3—H13	116.8
O2i—Cu1—O5	89.30 (5)	C11—N3—H13	120.3
N1—Cu1—O5	90.80 (6)	C10—N4—H14A	119.0
N1i—Cu1—O5	89.20 (6)	C10—N4—H14B	117.9 (15)
O2—Cu1—O5i	89.30 (5)	H14A—N4—H14B	122.6
O2i—Cu1—O5i	90.70 (5)	N4—C10—N3	118.61 (14)
N1—Cu1—O5i	89.20 (6)	N4—C10—C9	123.36 (14)
N1i—Cu1—O5i	90.80 (6)	N3—C10—C9	118.02 (14)
O5—Cu1—O5i	180.00 (5)	C8—C9—C10	120.30 (14)
Cu1—O5—H5B	113 (2)	C8—C9—H9	123.0 (12)
Cu1—O5—H5A	127.8 (19)	C10—C9—H9	116.7 (12)
H5B—O5—H5A	107 (3)	C9—C8—C12	119.11 (14)
C1—O2—Cu1	114.87 (9)	C9—C8—C7	121.06 (15)
C3—N1—C2	119.43 (13)	C12—C8—C7	119.83 (15)
C3—N1—Cu1	129.00 (10)	C12—C11—N3	120.60 (15)
C2—N1—Cu1	111.57 (10)	C12—C11—H11	119.7
C4—N2—C5	117.45 (13)	N3—C11—H11	119.7
O1—C1—O2	126.27 (13)	C11—C12—C8	119.24 (15)
O1—C1—C2	118.40 (13)	C11—C12—H12	117.2 (17)
O2—C1—C2	115.33 (12)	C8—C12—H12	123.5 (17)
N1—C2—C5	120.04 (13)	C8—C7—H7A	109.5
N1—C2—C1	114.86 (12)	C8—C7—H7B	109.5
C5—C2—C1	125.09 (12)	H7A—C7—H7B	109.5
N2—C5—C2	121.23 (13)	C8—C7—H7C	109.5
N2—C5—C6	114.89 (13)	H7A—C7—H7C	109.5
C2—C5—C6	123.87 (13)	H7B—C7—H7C	109.5
N2—C4—C3	122.10 (14)	H6B—O6—H6A	117 (3)
N2—C4—H4	118.9	H17A—O7—H17B	107 (3)
C3—C4—H4	118.9	H8A—O8—H8B	105 (3)
N1—C3—C4	119.74 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H13···O4ii	0.82	1.91	2.7221 (19)	169
N4—H14A···O8iii	0.77	2.12	2.8879 (19)	177
N4—H14B···O3ii	0.84 (2)	2.07 (2)	2.903 (2)	168 (2)
O5—H5B···O7ii	0.79 (3)	1.92 (3)	2.703 (2)	173 (3)
O5—H5A···O4ii	0.82 (3)	2.09 (3)	2.8556 (18)	157 (3)
O8—H8B···O1iv	0.76 (3)	2.03 (3)	2.7838 (18)	173 (3)
O6—H6B···O4iv	0.81 (4)	2.06 (4)	2.839 (2)	162 (3)
O7—H17B···O8v	0.76 (4)	2.04 (4)	2.797 (2)	172 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H13⋯O4i	0.82	1.91	2.7221 (19)	169
N4—H14A⋯O8ii	0.77	2.12	2.8879 (19)	177
N4—H14B⋯O3i	0.84 (2)	2.07 (2)	2.903 (2)	168 (2)
O5—H5B⋯O7i	0.79 (3)	1.92 (3)	2.703 (2)	173 (3)
O5—H5A⋯O4i	0.82 (3)	2.09 (3)	2.8556 (18)	157 (3)
O8—H8B⋯O1iii	0.76 (3)	2.03 (3)	2.7838 (18)	173 (3)
O6—H6B⋯O4iii	0.81 (4)	2.06 (4)	2.839 (2)	162 (3)
O7—H17B⋯O8iv	0.76 (4)	2.04 (4)	2.797 (2)	172 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .