1,4-Diazo-niacyclo-hexane bis-(3-carb-oxy-pyrazine-2-carboxyl-ate) dihydrate.

In the title compound, C(4)H(12)N(2) (2+)·2C(6)H(3)N(2)O(4) (-)·2H(2)O or (1,4-dacH(2))(pyzdcH)(2)·2H(2)O, the complete dication is generated by crystallographic inversion symmetry. An intra-molecular O-H⋯O hydrogen bond occurs in the anion. In the crystal, O-H⋯O, O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds result in the formation of a three-dimensional network. Additionally, π-π stacking inter-actions between the pyrazine rings with centroid-centroid distances of 3.7065 (2) Å are observed.

Related literature

For related structures dereived from pyrazine-2,3-dicarb­oxy­lic acid with various organic bases, see: Eshtiagh-Hosseini et al. (2010a ▶,b ▶,c ▶,d ▶). For the biological properties of derivatives of 1,4-diazo­nia-cyclo­hexane derivatives, see Iqbal et al. (2001 ▶), Greenberg et al. (1981 ▶).

Experimental

Crystal data

C4H12N2 2+·2C6H3N2O4 −·2H2O

M = 458.40

Monoclinic,

a = 7.7519 (4) Å

b = 18.4576 (8) Å

c = 7.0292 (4) Å

β = 111.974 (6)°

V = 932.68 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.14 mm−1

T = 120 K

0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 detector

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T min = 0.990, T max = 1.000

4000 measured reflections

2006 independent reflections

1696 reflections with I > 2σ(I)

R int = 0.010

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.02

2006 reflections

165 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.38 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis 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/S1600536810040109/im2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040109/im2230Isup2.hkl

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

C4H12N22+·2C6H3N2O4−·2H2O	F(000) = 480
Mr = 458.40	Dx = 1.632 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2589 reflections
a = 7.7519 (4) Å	θ = 3.0–27.5°
b = 18.4576 (8) Å	µ = 0.14 mm−1
c = 7.0292 (4) Å	T = 120 K
β = 111.974 (6)°	Prism, colourless
V = 932.68 (8) Å3	0.40 × 0.40 × 0.30 mm
Z = 2

Oxford Diffraction Xcalibur with a Sapphire2 detector diffractometer	2006 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1696 reflections with I > 2σ(I)
graphite	Rint = 0.010
Detector resolution: 8.4353 pixels mm-1	θmax = 27.6°, θmin = 3.0°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −15→23
Tmin = 0.990, Tmax = 1.000	l = −6→8
4000 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0601P)2] where P = (Fo2 + 2Fc2)/3
2006 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.38 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
O1	0.66092 (11)	0.30115 (5)	0.67977 (14)	0.0214 (2)
O2	0.47664 (11)	0.38022 (4)	0.74880 (14)	0.0213 (2)
O3	0.70151 (11)	0.17141 (5)	0.70969 (13)	0.0198 (2)
O4	0.54415 (12)	0.07636 (5)	0.74616 (13)	0.0219 (2)
N1	0.19076 (13)	0.29280 (5)	0.62615 (15)	0.0149 (2)
N2	0.22265 (13)	0.14348 (6)	0.61232 (14)	0.0156 (2)
N3	0.15261 (14)	0.46005 (6)	0.64194 (15)	0.0157 (2)
C1	0.35741 (15)	0.26185 (6)	0.66012 (16)	0.0126 (2)
C2	0.04412 (16)	0.24966 (6)	0.58448 (18)	0.0159 (3)
H2	−0.0743	0.2704	0.5607	0.019*
C3	0.05966 (16)	0.17478 (7)	0.57477 (18)	0.0162 (3)
H3	−0.0487	0.1456	0.5406	0.019*
C4	0.37356 (15)	0.18606 (6)	0.65666 (17)	0.0133 (3)
C5	0.51081 (16)	0.31916 (7)	0.70094 (17)	0.0151 (3)
C6	0.55073 (16)	0.14025 (7)	0.70888 (17)	0.0160 (3)
C7	−0.04171 (16)	0.44630 (7)	0.62525 (19)	0.0190 (3)
H7A	−0.0416	0.4307	0.7600	0.023*
H7B	−0.0968	0.4069	0.5252	0.023*
C8	0.15674 (16)	0.48597 (7)	0.44316 (18)	0.0176 (3)
H8A	0.1073	0.4478	0.3378	0.021*
H8B	0.2868	0.4961	0.4588	0.021*
O5	0.23627 (12)	0.52146 (5)	0.03053 (14)	0.0190 (2)
H3B	0.202 (2)	0.4944 (9)	0.742 (2)	0.027 (4)*
H3A	0.222 (2)	0.4184 (9)	0.675 (2)	0.032 (4)*
H5B	0.271 (2)	0.4805 (10)	0.089 (3)	0.045 (5)*
H5A	0.330 (3)	0.5564 (11)	0.092 (3)	0.071 (6)*
H1O	0.683 (3)	0.2317 (12)	0.687 (3)	0.070 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.0147 (4)	0.0176 (5)	0.0344 (5)	−0.0009 (4)	0.0120 (4)	0.0005 (4)
O2	0.0144 (4)	0.0146 (5)	0.0303 (5)	−0.0010 (4)	0.0032 (4)	−0.0039 (4)
O3	0.0130 (4)	0.0185 (5)	0.0284 (5)	0.0008 (4)	0.0083 (4)	−0.0032 (4)
O4	0.0200 (5)	0.0152 (5)	0.0284 (5)	0.0037 (4)	0.0067 (4)	0.0011 (4)
N1	0.0132 (5)	0.0164 (5)	0.0153 (5)	0.0006 (4)	0.0054 (4)	0.0004 (4)
N2	0.0157 (5)	0.0156 (5)	0.0164 (5)	−0.0010 (4)	0.0070 (4)	−0.0007 (4)
N3	0.0141 (5)	0.0145 (5)	0.0166 (5)	0.0030 (4)	0.0034 (4)	−0.0006 (4)
C1	0.0123 (6)	0.0155 (6)	0.0100 (5)	0.0005 (5)	0.0041 (4)	0.0002 (4)
C2	0.0117 (6)	0.0189 (6)	0.0173 (6)	0.0016 (5)	0.0056 (4)	0.0017 (5)
C3	0.0131 (6)	0.0181 (6)	0.0176 (6)	−0.0023 (5)	0.0060 (4)	0.0002 (5)
C4	0.0138 (6)	0.0158 (6)	0.0108 (5)	0.0005 (5)	0.0052 (4)	−0.0002 (4)
C5	0.0132 (6)	0.0150 (6)	0.0144 (6)	−0.0005 (5)	0.0022 (4)	0.0012 (5)
C6	0.0150 (6)	0.0168 (6)	0.0149 (6)	0.0007 (5)	0.0042 (4)	−0.0041 (4)
C7	0.0174 (6)	0.0179 (6)	0.0222 (6)	−0.0003 (5)	0.0080 (5)	0.0037 (5)
C8	0.0158 (6)	0.0208 (6)	0.0162 (6)	0.0024 (5)	0.0060 (5)	−0.0009 (5)
O5	0.0186 (5)	0.0156 (5)	0.0215 (5)	−0.0016 (4)	0.0059 (4)	0.0002 (4)

O1—C5	1.2713 (14)	C1—C4	1.4054 (16)
O1—H1O	1.29 (2)	C1—C5	1.5362 (16)
O2—C5	1.2330 (14)	C2—C3	1.3912 (16)
O3—C6	1.3007 (14)	C2—H2	0.9500
O3—H1O	1.13 (2)	C3—H3	0.9500
O4—C6	1.2133 (15)	C4—C6	1.5359 (16)
N1—C2	1.3277 (15)	C7—C8i	1.5061 (17)
N1—C1	1.3496 (14)	C7—H7A	0.9900
N2—C3	1.3230 (15)	C7—H7B	0.9900
N2—C4	1.3455 (14)	C8—C7i	1.5061 (17)
N3—C7	1.4883 (15)	C8—H8A	0.9900
N3—C8	1.4886 (15)	C8—H8B	0.9900
N3—H3B	0.915 (16)	O5—H5B	0.852 (19)
N3—H3A	0.917 (17)	O5—H5A	0.95 (2)
C5—O1—H1O	111.5 (8)	C1—C4—C6	128.41 (10)
C6—O3—H1O	111.6 (10)	O2—C5—O1	124.78 (11)
C2—N1—C1	117.97 (10)	O2—C5—C1	116.74 (10)
C3—N2—C4	118.28 (10)	O1—C5—C1	118.47 (10)
C7—N3—C8	110.95 (9)	O4—C6—O3	122.63 (11)
C7—N3—H3B	107.4 (9)	O4—C6—C4	118.73 (10)
C8—N3—H3B	110.3 (9)	O3—C6—C4	118.64 (10)
C7—N3—H3A	110.9 (9)	N3—C7—C8i	110.15 (10)
C8—N3—H3A	107.0 (9)	N3—C7—H7A	109.6
H3B—N3—H3A	110.4 (14)	C8i—C7—H7A	109.6
N1—C1—C4	120.25 (10)	N3—C7—H7B	109.6
N1—C1—C5	111.37 (10)	C8i—C7—H7B	109.6
C4—C1—C5	128.37 (10)	H7A—C7—H7B	108.1
N1—C2—C3	121.59 (11)	N3—C8—C7i	110.39 (9)
N1—C2—H2	119.2	N3—C8—H8A	109.6
C3—C2—H2	119.2	C7i—C8—H8A	109.6
N2—C3—C2	121.18 (11)	N3—C8—H8B	109.6
N2—C3—H3	119.4	C7i—C8—H8B	109.6
C2—C3—H3	119.4	H8A—C8—H8B	108.1
N2—C4—C1	120.67 (10)	H5B—O5—H5A	109.8 (17)
N2—C4—C6	110.85 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O5ii	0.92 (2)	2.01 (2)	2.800 (1)	144 (1)
N3—H3B···O4iii	0.92 (2)	2.46 (2)	3.061 (1)	124 (1)
N3—H3A···O2	0.92 (2)	1.97 (2)	2.763 (1)	143 (1)
N3—H3A···N1	0.92 (2)	2.34 (2)	3.107 (2)	141 (1)
O5—H5B···O4iv	0.85 (2)	2.25 (2)	2.923 (1)	136 (2)
O5—H5B···N2iv	0.85 (2)	2.34 (2)	3.107 (1)	151 (2)
O5—H5A···O2v	0.95 (2)	1.90 (2)	2.841 (1)	172 (2)
O3—H1O···O1	1.13 (2)	1.29 (2)	2.414 (1)	174 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O5i	0.92 (2)	2.01 (2)	2.800 (1)	144 (1)
N3—H3B⋯O4ii	0.92 (2)	2.46 (2)	3.061 (1)	124 (1)
N3—H3A⋯O2	0.92 (2)	1.97 (2)	2.763 (1)	143 (1)
N3—H3A⋯N1	0.92 (2)	2.34 (2)	3.107 (2)	141 (1)
O5—H5B⋯O4iii	0.85 (2)	2.25 (2)	2.923 (1)	136 (2)
O5—H5B⋯N2iii	0.85 (2)	2.34 (2)	3.107 (1)	151 (2)
O5—H5A⋯O2iv	0.95 (2)	1.90 (2)	2.841 (1)	172 (2)
O3—H1O⋯O1	1.13 (2)	1.29 (2)	2.414 (1)	174 (2)

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