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

Chen, J.-M.; Zhao, H.

doi:10.1107/S1600536811053347

organic compounds

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

Jin-Mei Chen ^a and Hong Zhao ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 28 November 2011; accepted 12 December 2011; online 17 December 2011)

The title compound, C₁₂H₁₈N₈²⁺·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

C₁₂H₁₈N₈²⁺·2NO₃⁻·2H₂O
M_r = 434.40
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.048
wR(F²) = 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

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⋯O3^iv	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.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053347/rz2680sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811053347/rz2680Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

C₁₂H₁₈N₈²⁺·2NO₃⁻·2H₂O	Z = 1
M_r = 434.40	F(000) = 228
Triclinic, P1	D_x = 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 top

Rigaku SCXmini diffractometer	1479 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 26.0°, θ_min = 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 top

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(F_o²) + (0.060P)² + 0.1401P] where P = (F_o² + 2F_c²)/3
1811 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₈N₈²⁺·2NO₃⁻·2H₂O	γ = 92.84 (3)°
M_r = 434.40	V = 462.64 (16) Å³
Triclinic, P1	Z = 1
a = 6.2344 (12) Å	Mo Kα radiation
b = 7.7725 (16) Å	µ = 0.13 mm⁻¹
c = 9.7071 (19) Å	T = 295 K
α = 99.56 (3)°	0.22 × 0.16 × 0.12 mm
β = 92.49 (3)°

Data collection top

Rigaku SCXmini diffractometer	1479 reflections with I > 2σ(I)
4322 measured reflections	R_int = 0.034
1811 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.28 e Å⁻³
1811 reflections	Δρ_min = −0.21 e Å⁻³
145 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O3^iv	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.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₈N₈²⁺·2NO₃⁻·2H₂O
M_r	434.40
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.2344 (12), 7.7725 (16), 9.7071 (19)
α, β, γ (°)	99.56 (3), 92.49 (3), 92.84 (3)
V (Å³)	462.64 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.22 × 0.16 × 0.12

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4322, 1811, 1479
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.08
No. of reflections	1811
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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)	159.2
N2—H2A···O1ⁱⁱⁱ	0.90	2.44	2.970 (2)	118.0
N2—H2A···O3^iv	0.90	2.18	2.894 (3)	136.2
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.

Acknowledgements

This work was supported financially by the Southeast University Fund for Young Researchers (4007041027).

References

Fancelli, D., Berta, D., Bindi, S., Cameron, A., Cappella, P., Carpinelli, P., et al. (2005). J. Med. Chem. 48, 3080–3084. Web of Science CrossRef PubMed CAS Google Scholar
Gadekar, S. M., Johnson, B. D. & Cohen, E. (1968). J. Med. Chem. 11, 616–618. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xia, W.-B., Bai, X.-G., Liu, H.-T. & Wang, J.-X. (2011). Acta Cryst. E67, o1150. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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