(E)-3,3′-(Diazene-1,2-di­yl)bis­(1-methyl-1,4,5,6-tetra­hydro­pyrrolo­[3,4-c]pyrazol-5-ium) dinitrate dihydrate

Abstract

The title compound, C₁₂H₁₈N₈ ²⁺·2NO₃ ⁻·2H₂O, was synthesized unexpectedly from 3-amino-1-methyl-1,4,5,6-tetra­hydro­pyrrolo­[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 mol­ecules 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 _r = 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) ų

• 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

• Δρ_max = 0.28 e Å⁻³

• Δρ_min = −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.

Supplementary Material

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

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

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) .

supplementary crystallographic information

Comment

Tetrahydropyrrolo[3,4-c]pyrazol derivatives are used as anticancer kinase inhibitors (Xia et al., 2011; Fancelli et al., 2005; Gadekar et al., 1968). The title compound was synthesized unexpectedly from 3-amino-1-methyl-1,4,5,6-tetrahydropyrrolo[3,4-c]pyrazol-5-ium chloride and cerium(IV) ammonium nitrate, and its crystal structure is presented herein.

The molecular structure of the title compound is shown in Fig. 1. The cation lies on a crystallographic inversion centre located at the centre of the diazene fragment. The dihedral angle between the fused pyrrole and pyrazole rings is 4.46 (12)°. In the crystal structure, the ions and water molecules are linked via O—H···N, N—H···O and O—H···O hydrogen bonds into a three-dimensional network. (Table 1; Fig. 2).

Experimental

3-Amino-1-methyl-1,4,5,6-tetrahydropyrrolo[3,4-c]pyrazol-5-ium chloride (0.35 g, 2 mmol) and cerium(IV) ammonium nitrate (0.28 g, 0.5 mmol) were dissolved in 95% ethanol (25 ml). The solution was filtered and left at room temperature for 10 days. Yellow prism crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent.

Refinement

The water H atoms were located in a difference Fourier map and refined freely. All other H atoms were placed in calculated positions and refined using a riding model approximation, with C—H=0.96–0.92 Å,N—H=0.97 Å, and with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(C) for methyl groups.

Figures

Fig. 1.

The molecular structure of the title compound showing displacement ellipsoids drawn at the 30% probability level. Atoms with suffix A are generated by the symmetry operation (1-x, 1-y, 1-z).

Fig. 2.

Packing diagram of the title compound, showing the structure along the a axis. Dashed lines indicate hydrogen bonds.

Crystal data

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

Data collection

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

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

Special details

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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)

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