1,1-Dimethyl-biguanidium(2+) dinitrate.

In the crystal structure of the title compound, C(4)H(13)N(5) (2+)·2NO(3) (-), the main inter-molecular inter-actions are the N-H⋯O hydrogen bonds between the cationic amino groups and the O atoms of the nitrate ions. All amino H atoms and nitrate O atoms are involved in the three-dimensional hydrogen-bond network. There are two graph-set motifs R(2) (2)(8), which include the amino groups connected to the N atoms in the biguanide 3-, 4- and 5-positions, and the O atoms of a nitrate ion. They are extended along the a axis. An O atom of the second nitrate ion is involved in a graph-set motif C(4) that is a part of a helix-like N-H⋯O⋯H-N-H⋯O⋯ chain oriented along the b axis. There are also two weak C-H⋯O inter-actions in the crystal structure.

Related literature

For uses of biguanide derivatives in medicine, see: Watkins et al. (1987 ▶). For applications of 1,1-dimethyl­biguanide, see: Bell & Hadden (1997 ▶); Hopker (1961 ▶); Wiernsperger (2000 ▶). For 1,1-dimethyl­biguanide in metal complexes, see: Gheorghiu (1969 ▶); Marchi et al. (1999 ▶); Spacu & Gheorghiu (1968 ▶, 1969 ▶); Viossat et al. (1995 ▶); Zhu et al. (2002 ▶). For related structures of monocation salts, see: Hariharan et al. (1989 ▶); He et al. (2002 ▶); Huang et al. (2008 ▶); Lu et al. (2004a ▶); Zhu et al. (2003 ▶). For related structures of dication salts, see: Lemoine et al. (1994 ▶); Lu et al. (2004b ▶). For related salt materials, see: Fridrichová et al. (2010 ▶); Matulková et al. (2011 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C4H13N5 2+·2NO3 −

M = 255.21

Monoclinic,

a = 7.7850 (2) Å

b = 5.7313 (2) Å

c = 26.5321 (7) Å

β = 101.6020 (15)°

V = 1159.63 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 150 K

0.4 × 0.3 × 0.18 mm

Data collection

Nonius KappaCCD area-detector diffractometer

13222 measured reflections

2228 independent reflections

1913 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.08

2228 reflections

178 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.24 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051105/zq2139sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051105/zq2139Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811051105/zq2139Isup3.smi

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

C4H13N52+·2NO3−	F(000) = 536
Mr = 255.21	Dx = 1.462 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2377 reflections
a = 7.7850 (2) Å	θ = 1–26.0°
b = 5.7313 (2) Å	µ = 0.13 mm−1
c = 26.5321 (7) Å	T = 150 K
β = 101.6020 (15)°	Plate, colourless
V = 1159.63 (6) Å3	0.4 × 0.3 × 0.18 mm
Z = 4

Nonius KappaCCD area-detector diffractometer	1913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.050
graphite	θmax = 26.0°, θmin = 2.7°
Detector resolution: 9.091 pixels mm-1	h = −9→9
φ and ω scans to fill the Ewald sphere	k = −7→7
13222 measured reflections	l = −32→32
2228 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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0581P)2 + 0.3152P] where P = (Fo2 + 2Fc2)/3
2228 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.19 e Å−3
7 restraints	Δρmin = −0.24 e Å−3

Experimental. Vibrational spectra were recorded on a Nicolet Magna 760 FTIR spectrometer: IR spectra using DRIFTS technique in the 100 - 4000 cm-1 region, with 2 cm-1 resolution and Happ-Genzel apodization, Raman spectra using Nicolet Nexus FT Raman module (1064 nm N d:YVO4 laser excitation, 200 mW power at the sample) in the 100–3700 cm-1 region, with 2 cm-1 resolution and Happ-Genzel apodization. For further characterization of the studied compound vibrational spectra are given as a peaklist: IR spectra: 464 m, 505 m, 583 m, 602 m, 722 m, 824 m, 848 w, 937 m, 981 m,1043 m, 1052 m, 1111 m, 1145 m, 1184 m, 1283 m, 1312 m, 1385 m, 1406 s, 1416 s, 1459 m,1486 s, 1574 s, 1600 s, 1630 s, 1659 s, 1748 w, 2080 w, 2134 w, 2340 w, 2445 w, 2471 w, 2619 w, 2737 w, 2797 w, 2879 m, 2953 m, 2981 m, 3177 s, 3327 s. Raman spectra: 158 s, 197 m, 258 w, 332 w, 409 w, 441 w, 476 w, 490 w, 602 m, 709 w, 736 m, 844 m, 939 s, 1042 versus, 1061 m, 1100 m, 1144 w, 1186 w, 1262 w, 1286 w, 1413 m, 1430 w, 1457 m, 1475 m, 1500 m, 1597 w, 1662 w, 1674 w, 2813 w, 2880 m, 2935 s, 2956 m, 3012 w, 3114 w,3220 w, 3294 w, 3340 w.

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	0.31918 (18)	0.4058 (2)	0.08102 (5)	0.0302 (3)
C2	0.18235 (17)	0.5649 (2)	0.14924 (5)	0.0292 (3)
C3	0.0566 (2)	0.8084 (3)	0.20625 (6)	0.0413 (4)
H3A	0.0727	0.6757	0.2300	0.062*
H3B	−0.0587	0.8789	0.2053	0.062*
H3C	0.1484	0.9245	0.2179	0.062*
C4	−0.0215 (2)	0.8737 (3)	0.11244 (6)	0.0390 (4)
H4A	0.0252	0.8402	0.0815	0.059*
H4B	−0.0020	1.0386	0.1217	0.059*
H4C	−0.1475	0.8403	0.1056	0.059*
N1	0.47682 (16)	0.4787 (2)	0.10136 (5)	0.0346 (3)
H11	0.567 (2)	0.428 (3)	0.0891 (7)	0.042*
H12	0.497 (2)	0.586 (3)	0.1260 (6)	0.042*
N2	0.28755 (18)	0.2669 (2)	0.04101 (5)	0.0356 (3)
H21	0.372 (2)	0.217 (3)	0.0291 (7)	0.043*
H22	0.184 (2)	0.210 (3)	0.0295 (7)	0.043*
N3	0.17655 (15)	0.4775 (2)	0.10035 (4)	0.0312 (3)
H3	0.0744 (19)	0.459 (3)	0.0822 (6)	0.037*
N4	0.29198 (17)	0.4743 (2)	0.18829 (5)	0.0349 (3)
H41	0.319 (2)	0.542 (3)	0.2192 (6)	0.042*
H42	0.354 (2)	0.357 (3)	0.1842 (7)	0.042*
N5	0.06775 (15)	0.7280 (2)	0.15485 (4)	0.0315 (3)
N6	0.53721 (16)	0.9772 (2)	0.18120 (4)	0.0338 (3)
O1	0.39367 (14)	0.9879 (2)	0.15067 (4)	0.0453 (3)
O2	0.62993 (15)	0.7999 (2)	0.18337 (5)	0.0505 (4)
O3	0.58703 (17)	1.1475 (2)	0.21013 (4)	0.0495 (3)
N7	0.78091 (15)	0.2624 (2)	0.02958 (5)	0.0327 (3)
O4	0.63326 (15)	0.1814 (2)	0.01442 (5)	0.0581 (4)
O5	0.81006 (13)	0.3970 (2)	0.06767 (4)	0.0412 (3)
O6	0.90260 (14)	0.2106 (2)	0.00741 (4)	0.0446 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0339 (7)	0.0290 (7)	0.0289 (7)	0.0024 (6)	0.0091 (5)	0.0016 (5)
C2	0.0290 (7)	0.0307 (7)	0.0303 (7)	−0.0027 (6)	0.0119 (5)	0.0016 (5)
C3	0.0397 (8)	0.0511 (10)	0.0367 (8)	0.0086 (7)	0.0164 (6)	−0.0039 (7)
C4	0.0417 (8)	0.0349 (8)	0.0411 (8)	0.0073 (7)	0.0099 (6)	0.0040 (6)
N1	0.0315 (7)	0.0381 (7)	0.0371 (7)	−0.0009 (5)	0.0137 (5)	−0.0086 (5)
N2	0.0357 (7)	0.0412 (7)	0.0308 (6)	0.0008 (6)	0.0087 (5)	−0.0071 (5)
N3	0.0273 (6)	0.0373 (7)	0.0298 (6)	0.0026 (5)	0.0074 (5)	−0.0018 (5)
N4	0.0381 (7)	0.0377 (7)	0.0302 (6)	0.0078 (6)	0.0095 (5)	0.0022 (5)
N5	0.0306 (6)	0.0344 (6)	0.0318 (6)	0.0033 (5)	0.0116 (5)	0.0007 (5)
N6	0.0361 (7)	0.0345 (7)	0.0321 (6)	−0.0019 (5)	0.0098 (5)	−0.0009 (5)
O1	0.0395 (6)	0.0408 (7)	0.0513 (7)	−0.0015 (5)	−0.0010 (5)	0.0057 (5)
O2	0.0410 (7)	0.0419 (7)	0.0667 (8)	0.0099 (5)	0.0062 (5)	−0.0108 (6)
O3	0.0708 (8)	0.0346 (6)	0.0387 (6)	−0.0015 (6)	0.0004 (5)	−0.0067 (5)
N7	0.0311 (6)	0.0348 (7)	0.0337 (6)	0.0022 (5)	0.0100 (5)	−0.0032 (5)
O4	0.0355 (6)	0.0671 (8)	0.0749 (9)	−0.0132 (6)	0.0188 (6)	−0.0362 (7)
O5	0.0373 (6)	0.0458 (7)	0.0400 (6)	0.0018 (5)	0.0069 (4)	−0.0150 (5)
O6	0.0345 (6)	0.0628 (8)	0.0403 (6)	0.0094 (5)	0.0163 (5)	−0.0049 (5)

C1—N1	1.3060 (19)	N1—H11	0.878 (14)
C1—N2	1.3100 (19)	N1—H12	0.891 (14)
C1—N3	1.3763 (17)	N2—H21	0.837 (14)
C2—N4	1.3098 (18)	N2—H22	0.867 (14)
C2—N5	1.3212 (18)	N3—H3	0.849 (14)
C2—N3	1.3827 (17)	N4—H41	0.893 (14)
C3—N5	1.4584 (19)	N4—H42	0.846 (14)
C3—H3A	0.9800	N6—O2	1.2411 (17)
C3—H3B	0.9800	N6—O1	1.2428 (16)
C3—H3C	0.9800	N6—O3	1.2538 (16)
C4—N5	1.4601 (19)	N7—O4	1.2301 (16)
C4—H4A	0.9800	N7—O6	1.2474 (15)
C4—H4B	0.9800	N7—O5	1.2551 (16)
C4—H4C	0.9800
N1—C1—N2	122.49 (13)	H11—N1—H12	117.7 (16)
N1—C1—N3	120.79 (13)	C1—N2—H21	118.6 (12)
N2—C1—N3	116.70 (13)	C1—N2—H22	121.5 (12)
N4—C2—N5	122.59 (13)	H21—N2—H22	119.3 (18)
N4—C2—N3	119.46 (13)	C1—N3—C2	125.54 (12)
N5—C2—N3	117.80 (12)	C1—N3—H3	119.0 (12)
N5—C3—H3A	109.5	C2—N3—H3	115.3 (12)
N5—C3—H3B	109.5	C2—N4—H41	123.6 (12)
H3A—C3—H3B	109.5	C2—N4—H42	120.7 (12)
N5—C3—H3C	109.5	H41—N4—H42	115.1 (16)
H3A—C3—H3C	109.5	C2—N5—C3	119.81 (12)
H3B—C3—H3C	109.5	C2—N5—C4	123.05 (12)
N5—C4—H4A	109.5	C3—N5—C4	115.56 (12)
N5—C4—H4B	109.5	O2—N6—O1	120.59 (12)
H4A—C4—H4B	109.5	O2—N6—O3	120.23 (12)
N5—C4—H4C	109.5	O1—N6—O3	119.18 (13)
H4A—C4—H4C	109.5	O4—N7—O6	120.27 (12)
H4B—C4—H4C	109.5	O4—N7—O5	120.08 (11)
C1—N1—H11	119.7 (11)	O6—N7—O5	119.65 (12)
C1—N1—H12	122.4 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H12···O2	0.89 (1)	2.06 (2)	2.9158 (17)	160.(2)
N1—H12···O1	0.89 (1)	2.57 (2)	3.3151 (17)	142.(1)
N1—H11···O5	0.88 (1)	2.09 (2)	2.9463 (16)	164.(2)
N1—H11···O4	0.88 (1)	2.57 (2)	3.2920 (17)	140.(1)
N2—H21···O4	0.84 (1)	2.15 (2)	2.9571 (18)	161.(2)
N2—H21···O4i	0.84 (1)	2.56 (2)	3.0833 (17)	122.(2)
N2—H22···O6ii	0.87 (1)	2.15 (2)	2.9674 (18)	157.(2)
N2—H22···O6i	0.87 (1)	2.64 (2)	3.2503 (18)	128.(2)
N3—H3···O5ii	0.85 (1)	2.05 (2)	2.8479 (16)	157.(2)
N3—H3···O6ii	0.85 (1)	2.59 (2)	3.2947 (17)	142.(2)
N4—H42···O3iii	0.85 (1)	2.17 (2)	2.9300 (18)	149.(2)
N4—H42···O1iii	0.85 (1)	2.34 (2)	3.1164 (18)	153.(2)
N4—H41···O3iv	0.89 (1)	1.97 (2)	2.8487 (17)	170.(2)
C3—H3B···O2ii	0.98	2.42	3.255 (2)	143
C4—H4A···O6v	0.98	2.55	3.519 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H12⋯O2	0.89 (1)	2.06 (2)	2.9158 (17)	160 (2)
N1—H12⋯O1	0.89 (1)	2.57 (2)	3.3151 (17)	142 (1)
N1—H11⋯O5	0.88 (1)	2.09 (2)	2.9463 (16)	164 (2)
N1—H11⋯O4	0.88 (1)	2.57 (2)	3.2920 (17)	140 (1)
N2—H21⋯O4	0.84 (1)	2.15 (2)	2.9571 (18)	161 (2)
N2—H21⋯O4i	0.84 (1)	2.56 (2)	3.0833 (17)	122 (2)
N2—H22⋯O6ii	0.87 (1)	2.15 (2)	2.9674 (18)	157 (2)
N2—H22⋯O6i	0.87 (1)	2.64 (2)	3.2503 (18)	128 (2)
N3—H3⋯O5ii	0.85 (1)	2.05 (2)	2.8479 (16)	157 (2)
N3—H3⋯O6ii	0.85 (1)	2.59 (2)	3.2947 (17)	142 (2)
N4—H42⋯O3iii	0.85 (1)	2.17 (2)	2.9300 (18)	149 (2)
N4—H42⋯O1iii	0.85 (1)	2.34 (2)	3.1164 (18)	153 (2)
N4—H41⋯O3iv	0.89 (1)	1.97 (2)	2.8487 (17)	170 (2)
C3—H3B⋯O2ii	0.98	2.42	3.255 (2)	143
C4—H4A⋯O6v	0.98	2.55	3.519 (2)	170

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