(E)-3,3'-(Diazene-1,2-di-yl)bis-(1-methyl-1,4,5,6-tetra-hydro-pyrrolo-[3,4-c]pyrazol-5-ium) dinitrate dihydrate.

The title compound, C(12)H(18)N(8) (2+)·2NO(3) (-)·2H(2)O, was synthesized unexpectedly from 3-amino-1-methyl-1,4,5,6-tetra-hydro-pyrrolo-[3,4-c]pyrazol-5-ium chloride and cerium(IV) ammonium nitrate. The cation has a crystallographically imposed centre of symmetry. In the crystal, the ions and water mol-ecules are linked via O-H⋯N, N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For background to potential anti­cancer kinase inhibitors, see: Fancelli et al. (2005 ▶); Gadekar et al. (1968 ▶). For a related structure, see: Xia et al. (2011 ▶).

Experimental

Crystal data

C12H18N8 2+·2NO3 −·2H2O

M = 434.40

Triclinic,

a = 6.2344 (12) Å

b = 7.7725 (16) Å

c = 9.7071 (19) Å

α = 99.56 (3)°

β = 92.49 (3)°

γ = 92.84 (3)°

V = 462.64 (16) Å3

Z = 1

Mo Kα radiation

μ = 0.13 mm−1

T = 295 K

0.22 × 0.16 × 0.12 mm

Data collection

Rigaku SCXmini diffractometer

4322 measured reflections

1811 independent reflections

1479 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.131

S = 1.08

1811 reflections

145 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053347/rz2680sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053347/rz2680Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053347/rz2680Isup3.cml

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

C12H18N82+·2NO3−·2H2O	Z = 1
Mr = 434.40	F(000) = 228
Triclinic, P1	Dx = 1.559 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2344 (12) Å	Cell parameters from 4309 reflections
b = 7.7725 (16) Å	θ = 3.1–27.2°
c = 9.7071 (19) Å	µ = 0.13 mm−1
α = 99.56 (3)°	T = 295 K
β = 92.49 (3)°	Prism, yellow
γ = 92.84 (3)°	0.22 × 0.16 × 0.12 mm
V = 462.64 (16) Å3

Rigaku SCXmini diffractometer	1479 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
graphite	θmax = 26.0°, θmin = 3.1°
Detector resolution: 13.6612 pixels mm-1	h = −7→7
CCD_Profile_fitting scans	k = −9→9
4322 measured reflections	l = −11→11
1811 independent 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.060P)2 + 0.1401P] where P = (Fo2 + 2Fc2)/3
1811 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.21 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
C1	0.7436 (3)	0.6228 (2)	0.52005 (18)	0.0324 (4)
C2	0.8295 (3)	0.6536 (2)	0.65780 (17)	0.0301 (4)
C3	1.0187 (3)	0.7441 (2)	0.65097 (18)	0.0308 (4)
C4	0.7930 (3)	0.6264 (3)	0.80235 (18)	0.0370 (5)
H4A	0.7592	0.5043	0.8065	0.044*
H4B	0.6790	0.6959	0.8426	0.044*
C5	1.1457 (3)	0.7872 (3)	0.78510 (19)	0.0388 (5)
H5A	1.1556	0.9119	0.8199	0.047*
H5B	1.2891	0.7446	0.7779	0.047*
C7	1.2218 (3)	0.8565 (3)	0.4629 (2)	0.0467 (5)
H7A	1.3142	0.9190	0.5383	0.070*
H7B	1.1674	0.9371	0.4068	0.070*
H7C	1.3016	0.7717	0.4062	0.070*
N1	0.5569 (2)	0.5305 (2)	0.45680 (15)	0.0353 (4)
N2	1.0105 (3)	0.6894 (2)	0.87401 (16)	0.0404 (4)
H2A	0.9912	0.7595	0.9556	0.049*
H2B	1.0803	0.5968	0.8932	0.049*
N3	0.6426 (3)	0.1158 (3)	0.86872 (18)	0.0456 (5)
N4	0.8749 (3)	0.6936 (2)	0.43628 (16)	0.0363 (4)
N5	1.0436 (2)	0.7685 (2)	0.51941 (15)	0.0340 (4)
O1	0.1944 (3)	0.3662 (2)	0.86511 (17)	0.0527 (4)
O2	0.6074 (3)	0.2635 (2)	0.93400 (19)	0.0651 (5)
O3	0.8117 (3)	0.0492 (3)	0.89667 (19)	0.0733 (6)
O5	0.5152 (3)	0.0407 (3)	0.77657 (19)	0.0761 (6)
H1E	0.167 (4)	0.323 (3)	0.769 (3)	0.068 (8)*
H1F	0.323 (6)	0.344 (4)	0.886 (3)	0.084 (10)*

	U11	U22	U33	U12	U13	U23
C1	0.0333 (9)	0.0308 (9)	0.0313 (9)	0.0052 (8)	−0.0060 (7)	0.0007 (7)
C2	0.0293 (9)	0.0284 (9)	0.0310 (9)	0.0027 (7)	−0.0034 (7)	0.0012 (7)
C3	0.0301 (9)	0.0286 (9)	0.0325 (9)	0.0031 (7)	−0.0016 (7)	0.0024 (7)
C4	0.0318 (9)	0.0437 (11)	0.0341 (10)	−0.0039 (8)	−0.0051 (8)	0.0065 (8)
C5	0.0311 (9)	0.0456 (11)	0.0379 (10)	−0.0057 (8)	−0.0047 (8)	0.0061 (8)
C7	0.0461 (12)	0.0463 (12)	0.0498 (12)	0.0040 (10)	0.0094 (10)	0.0122 (9)
N1	0.0359 (9)	0.0330 (8)	0.0347 (8)	0.0038 (7)	−0.0089 (6)	0.0009 (6)
N2	0.0365 (9)	0.0528 (10)	0.0302 (8)	−0.0027 (8)	−0.0063 (7)	0.0052 (7)
N3	0.0430 (10)	0.0540 (11)	0.0378 (9)	−0.0108 (9)	−0.0043 (8)	0.0078 (8)
N4	0.0403 (9)	0.0373 (9)	0.0301 (8)	0.0048 (7)	−0.0042 (7)	0.0034 (6)
N5	0.0353 (8)	0.0332 (8)	0.0336 (8)	0.0042 (7)	0.0007 (6)	0.0051 (6)
O1	0.0513 (10)	0.0694 (11)	0.0375 (8)	0.0156 (8)	0.0006 (7)	0.0056 (7)
O2	0.0619 (11)	0.0573 (11)	0.0706 (11)	0.0123 (9)	−0.0215 (8)	−0.0018 (9)
O3	0.0658 (11)	0.0726 (12)	0.0727 (12)	0.0239 (10)	−0.0173 (9)	−0.0139 (9)
O5	0.0587 (11)	0.0946 (14)	0.0639 (11)	−0.0315 (10)	−0.0129 (9)	−0.0043 (10)

C1—N4	1.340 (3)	C7—N5	1.451 (3)
C1—C2	1.397 (2)	C7—H7A	0.9600
C1—N1	1.398 (2)	C7—H7B	0.9600
C2—C3	1.353 (3)	C7—H7C	0.9600
C2—C4	1.479 (2)	N1—N1i	1.258 (3)
C3—N5	1.336 (2)	N2—H2A	0.9000
C3—C5	1.474 (2)	N2—H2B	0.9000
C4—N2	1.517 (2)	N3—O5	1.221 (2)
C4—H4A	0.9700	N3—O3	1.237 (2)
C4—H4B	0.9700	N3—O2	1.250 (2)
C5—N2	1.500 (3)	N4—N5	1.344 (2)
C5—H5A	0.9700	O1—H1E	0.95 (3)
C5—H5B	0.9700	O1—H1F	0.85 (4)
N4—C1—C2	110.64 (16)	N5—C7—H7A	109.5
N4—C1—N1	116.89 (16)	N5—C7—H7B	109.5
C2—C1—N1	132.44 (17)	H7A—C7—H7B	109.5
C3—C2—C1	104.04 (16)	N5—C7—H7C	109.5
C3—C2—C4	111.36 (15)	H7A—C7—H7C	109.5
C1—C2—C4	144.60 (17)	H7B—C7—H7C	109.5
N5—C3—C2	109.44 (16)	N1i—N1—C1	112.49 (18)
N5—C3—C5	136.16 (17)	C5—N2—C4	111.95 (14)
C2—C3—C5	114.38 (16)	C5—N2—H2A	109.2
C2—C4—N2	100.74 (14)	C4—N2—H2A	109.2
C2—C4—H4A	111.6	C5—N2—H2B	109.2
N2—C4—H4A	111.6	C4—N2—H2B	109.2
C2—C4—H4B	111.6	H2A—N2—H2B	107.9
N2—C4—H4B	111.6	O5—N3—O3	120.6 (2)
H4A—C4—H4B	109.4	O5—N3—O2	120.7 (2)
C3—C5—N2	99.89 (14)	O3—N3—O2	118.73 (18)
C3—C5—H5A	111.8	C1—N4—N5	105.67 (14)
N2—C5—H5A	111.8	C3—N5—N4	110.19 (15)
C3—C5—H5B	111.8	C3—N5—C7	128.79 (17)
N2—C5—H5B	111.8	N4—N5—C7	120.99 (16)
H5A—C5—H5B	109.5	H1E—O1—H1F	107 (3)
N4—C1—C2—C3	−0.7 (2)	N4—C1—N1—N1i	−179.69 (18)
N1—C1—C2—C3	176.94 (18)	C2—C1—N1—N1i	2.8 (3)
N4—C1—C2—C4	179.0 (2)	C3—C5—N2—C4	−11.9 (2)
N1—C1—C2—C4	−3.4 (4)	C2—C4—N2—C5	13.2 (2)
C1—C2—C3—N5	0.9 (2)	C2—C1—N4—N5	0.20 (19)
C4—C2—C3—N5	−178.88 (15)	N1—C1—N4—N5	−177.85 (14)
C1—C2—C3—C5	−177.86 (15)	C2—C3—N5—N4	−0.9 (2)
C4—C2—C3—C5	2.3 (2)	C5—C3—N5—N4	177.5 (2)
C3—C2—C4—N2	−9.2 (2)	C2—C3—N5—C7	−179.34 (17)
C1—C2—C4—N2	171.1 (2)	C5—C3—N5—C7	−0.9 (3)
N5—C3—C5—N2	−172.5 (2)	C1—N4—N5—C3	0.39 (19)
C2—C3—C5—N2	5.9 (2)	C1—N4—N5—C7	179.01 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1E···N4i	0.95 (3)	1.98 (3)	2.895 (2)	163 (2)
N2—H2B···O1ii	0.90	1.94	2.802 (3)	159.
N2—H2A···O1iii	0.90	2.44	2.970 (2)	118.
N2—H2A···O3iv	0.90	2.18	2.894 (3)	136.
O1—H1F···O2	0.85 (4)	1.97 (4)	2.819 (2)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1E⋯N4i	0.95 (3)	1.98 (3)	2.895 (2)	163 (2)
N2—H2B⋯O1ii	0.90	1.94	2.802 (3)	159
N2—H2A⋯O1iii	0.90	2.44	2.970 (2)	118
N2—H2A⋯O3iv	0.90	2.18	2.894 (3)	136
O1—H1F⋯O2	0.85 (4)	1.97 (4)	2.819 (2)	173 (3)

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