Amino-(5-{2-[amino-(iminio)meth-yl]hydrazin-1-yl}-3,5-dimethyl-4,5-dihydro-1H-pyrazol-1-yl)methaniminium dinitrate.

The reaction of aqueous solutions of amino-guanidine hydrogennitrate and acetyl-acetone produces the title pyrazole salt, C(7)H(18)N(8) (2+)·2NO(3) (-). The crystal structure is stabilized by a complex N-H⋯O hydrogen-bonding network. The difference in the engagement of the two nitrate anions in hydrogen bonding is reflected in the variation of the corresponding N-O bond lengths.

Related literature

For the biological activity of pyrazole derivatives, see: Farag et al. (2008 ▶); Stauffer et al. (2000 ▶). For the coordination chemistry of pyrazole derivatives, see: Mukherjee (2000 ▶); Mani (1992 ▶). For related structures, see: Cousson et al. (1991a ▶,b ▶); Kettmann & Světlík (2002 ▶); Khudoyarov et al. (1995 ▶). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶). Thiele & Dralle (1898 ▶) reported that the reaction of aqueous amino­guanidine hydrogennitrate and acetyl­acetone solutions led to the formation of acetyl­acetonebis(amino­guanidine) dihydrogendinitrate (C7H16N8·2HNO3). However, our investigations of the crystal and molecular structure of the obtained product have shown that this reaction did not form the cited Schiff base but a cyclic product of the same chemical composition.

Experimental

Crystal data

C7H18N8 2+·2NO3 −

M = 338.31

Orthorhombic,

a = 7.5025 (2) Å

b = 13.8946 (4) Å

c = 14.2477 (3) Å

V = 1485.24 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 293 K

0.42 × 0.35 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 (Gemini Mo) diffractometer

4760 measured reflections

1997 independent reflections

1548 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.114

S = 1.03

1997 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PLATON (Spek, 2009 ▶) and PARST (Nardelli, 1983 ▶, 1995 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025006/dn2584sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025006/dn2584Isup2.hkl

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

C7H18N82+·2NO3−	F(000) = 712
Mr = 338.31	Dx = 1.513 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2501 reflections
a = 7.5025 (2) Å	θ = 3.1–29.1°
b = 13.8946 (4) Å	µ = 0.13 mm−1
c = 14.2477 (3) Å	T = 293 K
V = 1485.24 (7) Å3	Prism, white
Z = 4	0.42 × 0.35 × 0.26 mm

Oxford Diffraction Xcalibur Sapphire3 (Gemini Mo) diffractometer	1548 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
graphite	θmax = 29.2°, θmin = 3.1°
Detector resolution: 16.3280 pixels mm-1	h = −10→7
ω scans	k = −16→17
4760 measured reflections	l = −19→19
1997 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0719P)2] where P = (Fo2 + 2Fc2)/3
1997 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
N1	0.6023 (3)	0.23138 (16)	0.72769 (15)	0.0309 (5)
N2	0.5967 (3)	0.19338 (16)	0.63655 (16)	0.0322 (5)
N3	0.6670 (3)	0.39564 (15)	0.76413 (15)	0.0296 (5)
H3	0.6855	0.4255	0.8161	0.036*
N4	0.5571 (3)	0.43172 (16)	0.69281 (15)	0.0312 (5)
H4	0.5944	0.4349	0.6359	0.037*
N5	0.3293 (3)	0.44897 (18)	0.79956 (16)	0.0382 (6)
H5A	0.2228	0.4676	0.8127	0.046*
H5B	0.3938	0.4222	0.8421	0.046*
N6	0.2960 (3)	0.50226 (18)	0.64889 (17)	0.0412 (6)
H6A	0.1894	0.5212	0.6611	0.049*
H6B	0.3394	0.5100	0.5935	0.049*
N7	0.3393 (3)	0.15173 (18)	0.75060 (18)	0.0427 (6)
H7A	0.2524	0.1339	0.7860	0.051*
H7B	0.3423	0.1341	0.6928	0.051*
N8	0.4640 (3)	0.23279 (18)	0.87330 (18)	0.0410 (6)
H8A	0.3773	0.2151	0.9088	0.049*
H8B	0.5481	0.2681	0.8956	0.049*
C1	0.7481 (3)	0.30221 (18)	0.74174 (19)	0.0283 (5)
C2	0.8406 (4)	0.2956 (2)	0.6454 (2)	0.0340 (6)
H2A	0.8451	0.3581	0.6152	0.041*
H2B	0.9610	0.2710	0.6517	0.041*
C3	0.7278 (4)	0.22799 (19)	0.59131 (19)	0.0318 (6)
C4	0.7588 (5)	0.2006 (2)	0.4917 (2)	0.0477 (8)
H4A	0.6762	0.1511	0.4740	0.071*
H4B	0.8784	0.1772	0.4846	0.071*
H4C	0.7418	0.2559	0.4523	0.071*
C5	0.4681 (3)	0.20601 (18)	0.78507 (19)	0.0306 (6)
C6	0.8751 (4)	0.2760 (2)	0.8205 (2)	0.0426 (7)
H6C	0.9766	0.3181	0.8188	0.064*
H6D	0.9139	0.2106	0.8129	0.064*
H6E	0.8153	0.2828	0.8797	0.064*
C7	0.3929 (3)	0.46119 (18)	0.71523 (17)	0.0268 (5)
N9	0.0699 (3)	0.09061 (19)	0.95468 (15)	0.0364 (6)
O1	0.0933 (3)	0.05303 (16)	0.87444 (13)	0.0442 (5)
O2	0.1651 (3)	0.15852 (17)	0.97976 (16)	0.0521 (6)
N10	−0.0557 (4)	0.52379 (19)	0.92350 (18)	0.0418 (6)
O3	−0.0469 (3)	0.0598 (3)	1.00527 (15)	0.0752 (9)
O4	0.0522 (4)	0.4704 (3)	0.9632 (2)	0.0828 (9)
O5	−0.0419 (3)	0.52961 (19)	0.83639 (16)	0.0562 (6)
O6	−0.1669 (5)	0.5670 (2)	0.9663 (3)	0.1010 (12)

	U11	U22	U33	U12	U13	U23
N1	0.0339 (11)	0.0319 (11)	0.0268 (10)	−0.0079 (10)	0.0053 (10)	−0.0029 (10)
N2	0.0347 (11)	0.0323 (11)	0.0295 (10)	−0.0007 (10)	−0.0011 (11)	−0.0039 (10)
N3	0.0314 (11)	0.0302 (11)	0.0273 (10)	0.0030 (10)	−0.0032 (10)	−0.0059 (10)
N4	0.0311 (12)	0.0389 (12)	0.0238 (9)	0.0040 (11)	0.0021 (10)	0.0021 (10)
N5	0.0331 (11)	0.0514 (15)	0.0302 (10)	0.0120 (12)	0.0026 (11)	0.0029 (12)
N6	0.0418 (14)	0.0496 (14)	0.0323 (12)	0.0167 (13)	−0.0042 (10)	0.0003 (12)
N7	0.0363 (12)	0.0479 (13)	0.0440 (14)	−0.0148 (12)	0.0069 (12)	0.0011 (13)
N8	0.0413 (13)	0.0484 (14)	0.0334 (12)	−0.0106 (12)	0.0098 (12)	0.0002 (12)
C1	0.0249 (12)	0.0282 (11)	0.0318 (13)	−0.0012 (11)	−0.0016 (11)	−0.0002 (12)
C2	0.0293 (13)	0.0360 (14)	0.0365 (14)	0.0026 (12)	0.0068 (12)	−0.0006 (13)
C3	0.0342 (14)	0.0291 (12)	0.0320 (13)	0.0052 (12)	0.0005 (12)	−0.0022 (12)
C4	0.0491 (17)	0.0572 (19)	0.0367 (15)	0.0090 (17)	0.0088 (15)	−0.0050 (16)
C5	0.0320 (13)	0.0259 (12)	0.0338 (13)	0.0012 (11)	0.0035 (12)	0.0037 (11)
C6	0.0338 (15)	0.0535 (18)	0.0403 (16)	0.0079 (15)	−0.0081 (13)	0.0023 (15)
C7	0.0272 (12)	0.0267 (12)	0.0265 (11)	0.0001 (11)	−0.0026 (11)	−0.0047 (10)
N9	0.0317 (12)	0.0526 (15)	0.0249 (10)	−0.0043 (12)	0.0015 (11)	−0.0007 (11)
O1	0.0482 (11)	0.0567 (13)	0.0277 (9)	−0.0101 (11)	0.0064 (10)	−0.0083 (10)
O2	0.0543 (13)	0.0573 (13)	0.0448 (12)	−0.0216 (12)	0.0073 (11)	−0.0166 (12)
N10	0.0405 (14)	0.0442 (15)	0.0405 (13)	−0.0054 (13)	−0.0008 (12)	−0.0085 (12)
O3	0.0620 (15)	0.130 (3)	0.0335 (11)	−0.0500 (18)	0.0185 (12)	−0.0166 (15)
O4	0.094 (2)	0.097 (2)	0.0578 (15)	0.012 (2)	−0.0325 (17)	0.0030 (16)
O5	0.0557 (14)	0.0699 (15)	0.0430 (11)	−0.0017 (14)	−0.0097 (11)	0.0007 (12)
O6	0.092 (2)	0.0797 (19)	0.131 (3)	0.007 (2)	0.061 (2)	−0.035 (2)

N1—C5	1.344 (3)	N8—H8B	0.8605
N1—N2	1.403 (3)	C1—C6	1.517 (4)
N1—C1	1.485 (3)	C1—C2	1.541 (4)
N2—C3	1.271 (4)	C2—C3	1.480 (4)
N3—N4	1.402 (3)	C2—H2A	0.9700
N3—C1	1.469 (3)	C2—H2B	0.9700
N3—H3	0.8601	C3—C4	1.488 (4)
N4—C7	1.336 (3)	C4—H4A	0.9600
N4—H4	0.8593	C4—H4B	0.9600
N5—C7	1.304 (3)	C4—H4C	0.9600
N5—H5A	0.8606	C6—H6C	0.9600
N5—H5B	0.8597	C6—H6D	0.9600
N6—C7	1.322 (3)	C6—H6E	0.9600
N6—H6A	0.8597	N9—O3	1.212 (3)
N6—H6B	0.8606	N9—O2	1.236 (3)
N7—C5	1.320 (4)	N9—O1	1.269 (3)
N7—H7A	0.8605	N10—O6	1.195 (4)
N7—H7B	0.8594	N10—O4	1.235 (4)
N8—C5	1.311 (4)	N10—O5	1.248 (3)
N8—H8A	0.8597
C5—N1—N2	116.2 (2)	C3—C2—H2B	110.9
C5—N1—C1	130.1 (2)	C1—C2—H2B	110.9
N2—N1—C1	113.4 (2)	H2A—C2—H2B	109.0
C3—N2—N1	107.7 (2)	N2—C3—C2	114.8 (2)
N4—N3—C1	113.7 (2)	N2—C3—C4	120.5 (3)
N4—N3—H3	123.2	C2—C3—C4	124.7 (3)
C1—N3—H3	123.1	C3—C4—H4A	109.5
C7—N4—N3	118.6 (2)	C3—C4—H4B	109.5
C7—N4—H4	120.7	H4A—C4—H4B	109.5
N3—N4—H4	120.7	C3—C4—H4C	109.5
C7—N5—H5A	120.0	H4A—C4—H4C	109.5
C7—N5—H5B	120.0	H4B—C4—H4C	109.5
H5A—N5—H5B	120.0	N8—C5—N7	120.1 (3)
C7—N6—H6A	120.0	N8—C5—N1	121.7 (3)
C7—N6—H6B	120.1	N7—C5—N1	118.2 (2)
H6A—N6—H6B	120.0	C1—C6—H6C	109.5
C5—N7—H7A	120.0	C1—C6—H6D	109.5
C5—N7—H7B	120.0	H6C—C6—H6D	109.5
H7A—N7—H7B	120.0	C1—C6—H6E	109.5
C5—N8—H8A	120.0	H6C—C6—H6E	109.5
C5—N8—H8B	119.9	H6D—C6—H6E	109.5
H8A—N8—H8B	120.0	N5—C7—N6	120.9 (2)
N3—C1—N1	108.1 (2)	N5—C7—N4	121.2 (2)
N3—C1—C6	108.1 (2)	N6—C7—N4	117.9 (2)
N1—C1—C6	113.8 (2)	O3—N9—O2	121.0 (3)
N3—C1—C2	115.6 (2)	O3—N9—O1	119.3 (3)
N1—C1—C2	99.90 (19)	O2—N9—O1	119.6 (2)
C6—C1—C2	111.2 (2)	O6—N10—O4	121.7 (3)
C3—C2—C1	104.1 (2)	O6—N10—O5	122.2 (3)
C3—C2—H2A	110.9	O4—N10—O5	116.1 (3)
C1—C2—H2A	110.9
C5—N1—N2—C3	177.1 (2)	N1—C1—C2—C3	3.4 (2)
C1—N1—N2—C3	3.2 (3)	C6—C1—C2—C3	123.9 (2)
C1—N3—N4—C7	129.5 (2)	N1—N2—C3—C2	−0.6 (3)
N4—N3—C1—N1	−61.2 (3)	N1—N2—C3—C4	179.7 (2)
N4—N3—C1—C6	175.2 (2)	C1—C2—C3—N2	−1.9 (3)
N4—N3—C1—C2	49.7 (3)	C1—C2—C3—C4	177.7 (3)
C5—N1—C1—N3	−55.7 (3)	N2—N1—C5—N8	176.2 (2)
N2—N1—C1—N3	117.2 (2)	C1—N1—C5—N8	−11.1 (4)
C5—N1—C1—C6	64.4 (4)	N2—N1—C5—N7	−2.9 (4)
N2—N1—C1—C6	−122.7 (3)	C1—N1—C5—N7	169.8 (2)
C5—N1—C1—C2	−176.9 (3)	N3—N4—C7—N5	−6.1 (4)
N2—N1—C1—C2	−4.1 (3)	N3—N4—C7—N6	174.6 (2)
N3—C1—C2—C3	−112.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O5i	0.86	2.52	3.048 (3)	120
N4—H4···O6ii	0.86	2.48	3.331 (5)	173
N5—H5A···O4	0.86	2.50	3.138 (4)	132
N5—H5A···O5	0.86	2.19	3.048 (4)	174
N5—H5B···O3iii	0.86	2.23	2.934 (3)	139
N6—H6A···O1iv	0.86	2.22	3.022 (3)	154
N6—H6B···O4ii	0.86	2.04	2.905 (4)	179
N7—H7A···O1	0.86	2.07	2.899 (3)	162
N8—H8A···O2	0.86	2.04	2.897 (3)	172
N8—H8B···O2iii	0.86	2.23	2.990 (3)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O5i	0.86	2.52	3.048 (3)	120
N4—H4⋯O6ii	0.86	2.48	3.331 (5)	173
N5—H5A⋯O4	0.86	2.50	3.138 (4)	132
N5—H5A⋯O5	0.86	2.19	3.048 (4)	174
N5—H5B⋯O3iii	0.86	2.23	2.934 (3)	139
N6—H6A⋯O1iv	0.86	2.22	3.022 (3)	154
N6—H6B⋯O4ii	0.86	2.04	2.905 (4)	179
N7—H7A⋯O1	0.86	2.07	2.899 (3)	162
N8—H8A⋯O2	0.86	2.04	2.897 (3)	172
N8—H8B⋯O2iii	0.86	2.23	2.990 (3)	148

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