1,1-Dimethyl­biguanidium(2+) dinitrate

Fridrichová, M.; Císařová, I.; Němec, I.

doi:10.1107/S1600536811051105

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages o18-o19

doi:10.1107/S1600536811051105

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1,1-Dimethylbiguanidium(2+) dinitrate

Michaela Fridrichová,^a ^* Ivana Císařová ^a and Ivan Němec ^a

^aDepartment of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12843 Prague 2, Czech Republic
^*Correspondence e-mail: fantom.ag@seznam.cz

(Received 18 November 2011; accepted 28 November 2011; online 3 December 2011)

In the crystal structure of the title compound, C₄H₁₃N₅²⁺·2NO₃⁻, the main intermolecular interactions 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 R₂²(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 interactions 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

C₄H₁₃N₅²⁺·2NO₃⁻
M_r = 255.21
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.041
wR(F²) = 0.113
S = 1.08
2228 reflections
178 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

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⋯O3^iv	0.89 (1)	1.97 (2)	2.8487 (17)	170 (2)
C3—H3B⋯O2ⁱⁱ	0.98	2.42	3.255 (2)	143
C4—H4A⋯O6^v	0.98	2.55	3.519 (2)	170
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z; (iii) x, y-1, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811051105/zq2139sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811051105/zq2139Isup3.smi

checkCIF report

Comment top

Among derivatives of biguanide widely used in medicine (Watkins et al., 1987), 1,1-dimethylbiguanide, known also under common name metformin, is an important component of drugs for diabetes treatment (Hopker, 1961; Wiernsperger, 2000). An overview of the investigation and use of 1,1-dimethylbiguanide has been published by Bell & Hadden (1997).

Complexes of 1,1-dimethylbiguanide, namely Cu(II) (Viossat et al., 1995; Zhu et al., 2002), Rh(III) (Spacu & Gheorghiu, 1968), Ir(III) (Gheorghiu, 1969), Os(II) and Os(III) (Spacu & Gheorghiu, 1969), Tc(V) and Re(V) complexes (Marchi et al., 1999) have been studied.

Surprisingly only eight structures concerning 1,1-dimethylbiguanide are available in the current version of the Cambridge Structure Database (Allen, 2002). Five of them contain a monocation: chloride (Hariharan et al., 1989), bromide (Lu et al., 2004a), nitrate (Zhu et al., 2003), [TlBr₄]^3- salt (He et al., 2002) and perchlorate, with the cation enclosed in a large complex (Huang et al., 2008). Other three salts contain dications: oxalate (Lu et al., 2004b), sulfate (Lu et al., 2004b) and a [CuCl₄]^2- complex (Lemoine et al., 1994).

In the crystal structure of the title compound, 1,1-Dimethylbiguanidium(2+) dinitrate, the main intermolecular interactions are the N—H···O hydrogen bonds between the amino groups of the cations and the O atoms of the nitrate anions with distances ranging from 2.848 (2) to 3.315 (2) Å, forming a three dimensional network (Fig. 2). Along the a axis there are extended two graph set motifs R²₂(8) (Etter et al., 1990; Fig. 3). The atoms involved in these two graph set motifs are N7—O5···H11—N1—C1—N2—H21···O4-(N7) and C1—N3—H3···O5(i)-N7(i)-O6(i)···H22—N22-(C1) with the symmetry code (i) = 1 - x, y, z. Along the b axis there is a chain O3(i)···H42—N4—H41···O3(ii)··· (Fig. 4; symmetry codes (i) = x, y - 1, z; (ii) = 1 - x, -1/2 + y, 1/2 - z) containing the graph set motif C(4). This chain forms a helix with the axis parallel to b. Two consecutive graph set motifs C(4) correspond to the pitch of this helix which equals to the unit-cell length b. O1 and O2 are involved in N1—H12···O1 and N1—H12···O2, respectively. In comparison to the monocation nitrate (Zhu et al., 2003), there are no important hydrogen bonds between the cations.

The title compound was prepared during the primary research oriented on salt materials with delocalized π electrons for applications in non-linear optics. For comparison, see similar salt materials (Fridrichová et al., 2010; Matulková et al., 2011).

Related literature top

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 top

A solution of the title compound was prepared by neutralization of stoichiometric amounts of dimethylbiguanidium hydroxide and nitric acid. The hydroxide was prepared from dimethylbiguanide hydrochloride (97%, Sigma-Aldrich) by the exchange reaction on an anex. Small transparent colourless crystals were obtained from water solution first after two years of crystallization. They were stable on air and non-hygroscopic.

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); 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).

Figures top

	Fig. 1. Atom-labelling scheme of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing scheme of the title compound along the monoclinic axis (blue: N; red: O; large grey spheres: C; small grey spheres: H). The dashed lines indicate the hydrogen bonds.
	Fig. 3. Section of the structure showing the graph-set motifs R₂²(8) extended along the a axis. The hydrogen bonds involved in these graph-set motifs are enhanced (blue: N; red: O; large grey spheres: C; small grey spheres: H; symmetry code (i) = 1 - x, y, z).
	Fig. 4. View of the graph set motif C(4). The atoms involved are H42—N4—H41···O3(ii)···H42—N4(iii) etc. The hydrogen bonds pertinent to the C(4) motif are enhanced (blue: N; red: O; large grey spheres: C; small grey spheres: H; symmetry codes (i) = x, y - 1, z; (ii) = 1 - x, -1/2 + y, 1/2 - z; (iii) = 1 - x, 1/2 + y, 1/2 - z; (iv) = x, y + 1, z).

1,1-Dimethylbiguanidium(2+) dinitrate top

Crystal data top

C₄H₁₃N₅²⁺·2NO₃⁻	F(000) = 536
M_r = 255.21	D_x = 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

Data collection top

Nonius KappaCCD area-detector diffractometer	1913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 26.0°, θ_min = 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 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)] = 0.041	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(F_o²) + (0.0581P)² + 0.3152P] where P = (F_o² + 2F_c²)/3
2228 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.19 e Å⁻³
7 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₁₃N₅²⁺·2NO₃⁻	V = 1159.63 (6) Å³
M_r = 255.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7850 (2) Å	µ = 0.13 mm⁻¹
b = 5.7313 (2) Å	T = 150 K
c = 26.5321 (7) Å	0.4 × 0.3 × 0.18 mm
β = 101.6020 (15)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1913 reflections with I > 2σ(I)
13222 measured reflections	R_int = 0.050
2228 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	7 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.19 e Å⁻³
2228 reflections	Δρ_min = −0.24 e Å⁻³
178 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.89 (1)	1.97 (2)	2.8487 (17)	170 (2)
C3—H3B···O2ⁱⁱ	0.98	2.42	3.255 (2)	143
C4—H4A···O6^v	0.98	2.55	3.519 (2)	170

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

Experimental details

Crystal data
Chemical formula	C₄H₁₃N₅²⁺·2NO₃⁻
M_r	255.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.7850 (2), 5.7313 (2), 26.5321 (7)
β (°)	101.6020 (15)
V (Å³)	1159.63 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.4 × 0.3 × 0.18

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13222, 2228, 1913
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.08
No. of reflections	2228
No. of parameters	178
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H12···O2	0.891 (14)	2.062 (15)	2.9158 (17)	160.3 (16)
N1—H12···O1	0.891 (14)	2.565 (16)	3.3151 (17)	142.4 (14)
N1—H11···O5	0.878 (14)	2.091 (15)	2.9463 (16)	164.2 (16)
N1—H11···O4	0.878 (14)	2.571 (16)	3.2920 (17)	139.9 (14)
N2—H21···O4	0.837 (14)	2.154 (15)	2.9571 (18)	160.9 (17)
N2—H21···O4ⁱ	0.837 (14)	2.557 (17)	3.0833 (17)	122.0 (15)
N2—H22···O6ⁱⁱ	0.867 (14)	2.149 (15)	2.9674 (18)	157.2 (17)
N2—H22···O6ⁱ	0.867 (14)	2.640 (17)	3.2503 (18)	128.4 (15)
N3—H3···O5ⁱⁱ	0.849 (14)	2.047 (15)	2.8479 (16)	156.9 (16)
N3—H3···O6ⁱⁱ	0.849 (14)	2.586 (15)	3.2947 (17)	141.7 (15)
N4—H42···O3ⁱⁱⁱ	0.846 (14)	2.171 (15)	2.9300 (18)	149.3 (16)
N4—H42···O1ⁱⁱⁱ	0.846 (14)	2.340 (16)	3.1164 (18)	152.9 (16)
N4—H41···O3^iv	0.893 (14)	1.965 (15)	2.8487 (17)	169.8 (17)
C3—H3B···O2ⁱⁱ	0.98	2.42	3.255 (2)	143
C4—H4A···O6^v	0.98	2.55	3.519 (2)	170

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

Acknowledgements

This work was supported by the Grant Agency of Charles University in Prague (grant No. 58608), the Czech Science Foundation (grant No. 203/09/0878) and it is a part of the long term Research Plan of the Ministry of Education of the Czech Republic (No. MSM0021620857). We would like to thank Dr Jan Fábry for his careful supervision and inspiring critique.

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