2-Methyl-benzene-1,3-di-ammonium dinitrate.

In the crystal structure of the title salt, C7H12N2 (2+)·2NO3 (-), the nitrate ions are located in the vicinity of the protonated amine groups, accepting strong N-H⋯O hydrogen bonds. Each ammonium group is involved in a total of three such inter-actions with neighbouring nitrate ions, generating a three-dimensional network. In addition, there are π-π inter-actions between the aromatic rings of centrosymmetrically related di-ammonium moieties, with a centroid-centroid distance of 3.682 (1) Å.

Related literature

For applications of amine salts, see: Jayaraman et al. (2002 ▶). For hydrogen bonding, see: Steiner (2002 ▶). For related structures, see: Garza Rodríguez et al. (2013 ▶); Gao & Ng (2012 ▶); Riahi et al. (2012 ▶). For comparable crystal packing arrangements, see: Abrahams et al. (2013 ▶); Glidewell et al. (2004 ▶).

Experimental

Crystal data

C7H12N2 2+·2NO3 −

M = 248.21

Monoclinic,

a = 10.494 (3) Å

b = 7.417 (2) Å

c = 13.487 (4) Å

β = 91.46 (5)°

V = 1049.4 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.36 × 0.30 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T min = 0.708, T max = 0.982

11810 measured reflections

2400 independent reflections

1617 reflections with I > 2σ(I)

R int = 0.000

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.091

S = 0.84

2400 reflections

179 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814001561/lr2121sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001561/lr2121Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C7H12N22+·2NO3−	F(000) = 520
Mr = 248.21	Dx = 1.571 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11810 reflections
a = 10.494 (3) Å	θ = 3.1–27.5°
b = 7.417 (2) Å	µ = 0.14 mm−1
c = 13.487 (4) Å	T = 293 K
β = 91.46 (5)°	Prism, brown
V = 1049.4 (5) Å3	0.36 × 0.30 × 0.16 mm
Z = 4

Nonius KappaCCD diffractometer	2400 independent reflections
Radiation source: fine-focus sealed tube	1617 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.000
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD rotation images, thick slices scans	h = −13→13
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = 0→9
Tmin = 0.708, Tmax = 0.982	l = 0→17
11810 measured 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3
2400 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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
N1	0.32257 (14)	0.5382 (2)	0.04883 (13)	0.0161 (3)
H11	0.330 (2)	0.416 (3)	0.0529 (16)	0.034 (6)*
H12	0.3819 (19)	0.590 (3)	0.0923 (16)	0.029 (6)*
H13	0.338 (2)	0.573 (3)	−0.0094 (18)	0.033 (6)*
N2	−0.03954 (14)	0.5320 (2)	0.27455 (11)	0.0154 (3)
H21	0.0007 (18)	0.582 (3)	0.3308 (15)	0.021 (5)*
H22	−0.0346 (18)	0.413 (3)	0.2809 (14)	0.023 (5)*
H23	−0.124 (2)	0.558 (3)	0.2749 (15)	0.031 (5)*
C1	0.02007 (15)	0.5914 (2)	0.18309 (12)	0.0143 (3)
C2	−0.04968 (15)	0.7016 (2)	0.11933 (13)	0.0174 (4)
HC2	−0.1311	0.7390	0.1357	0.021*
C3	0.00273 (15)	0.7559 (2)	0.03071 (13)	0.0189 (4)
HC3	−0.0441	0.8288	−0.0129	0.023*
C4	0.12492 (15)	0.7017 (2)	0.00712 (13)	0.0173 (4)
HC4	0.1606	0.7373	−0.0522	0.021*
C5	0.19263 (14)	0.5937 (2)	0.07346 (12)	0.0142 (3)
C6	0.14394 (15)	0.5344 (2)	0.16332 (12)	0.0135 (3)
C7	0.21965 (15)	0.4140 (2)	0.23249 (12)	0.0160 (3)
H1	0.3076	0.4499	0.2331	0.024*
H2	0.2124	0.2913	0.2103	0.024*
H3	0.1873	0.4240	0.2982	0.024*
O1	0.00268 (10)	0.15667 (16)	0.30012 (10)	0.0216 (3)
O2	−0.18762 (11)	0.13185 (17)	0.23748 (9)	0.0237 (3)
O3	−0.11592 (13)	−0.06969 (16)	0.34182 (9)	0.0260 (3)
N3	−0.10232 (13)	0.07181 (18)	0.29321 (11)	0.0171 (3)
O4	0.37995 (10)	−0.08942 (15)	0.01918 (9)	0.0212 (3)
O5	0.37031 (11)	0.17901 (15)	0.08249 (9)	0.0203 (3)
O6	0.31797 (11)	0.13625 (18)	−0.07227 (9)	0.0257 (3)
N4	0.35592 (12)	0.07296 (19)	0.00802 (10)	0.0158 (3)

	U11	U22	U33	U12	U13	U23
N1	0.0172 (7)	0.0150 (8)	0.0161 (8)	−0.0007 (6)	0.0037 (6)	0.0003 (6)
N2	0.0128 (7)	0.0164 (8)	0.0170 (8)	0.0001 (6)	0.0014 (6)	0.0007 (6)
C1	0.0162 (7)	0.0126 (7)	0.0141 (8)	−0.0036 (6)	−0.0002 (6)	−0.0014 (7)
C2	0.0130 (7)	0.0157 (8)	0.0234 (10)	0.0005 (6)	−0.0016 (7)	0.0001 (7)
C3	0.0192 (8)	0.0159 (8)	0.0213 (10)	0.0000 (6)	−0.0063 (7)	0.0031 (7)
C4	0.0225 (9)	0.0149 (8)	0.0143 (9)	−0.0036 (6)	−0.0013 (7)	0.0012 (7)
C5	0.0132 (7)	0.0118 (8)	0.0176 (9)	−0.0012 (6)	−0.0010 (6)	−0.0026 (7)
C6	0.0153 (8)	0.0098 (7)	0.0154 (9)	−0.0025 (6)	−0.0023 (6)	−0.0025 (6)
C7	0.0150 (7)	0.0155 (8)	0.0176 (9)	0.0008 (6)	0.0019 (6)	0.0007 (7)
O1	0.0135 (6)	0.0183 (6)	0.0329 (7)	−0.0023 (5)	−0.0030 (5)	0.0016 (5)
O2	0.0155 (6)	0.0332 (7)	0.0223 (7)	−0.0006 (5)	−0.0038 (5)	0.0015 (6)
O3	0.0429 (8)	0.0146 (6)	0.0209 (7)	−0.0057 (6)	0.0086 (6)	0.0019 (5)
N3	0.0184 (7)	0.0156 (7)	0.0172 (7)	−0.0013 (6)	0.0025 (6)	−0.0027 (6)
O4	0.0195 (6)	0.0116 (6)	0.0327 (7)	−0.0002 (5)	0.0041 (5)	−0.0021 (5)
O5	0.0292 (7)	0.0166 (6)	0.0151 (6)	0.0035 (5)	0.0002 (5)	−0.0037 (5)
O6	0.0246 (7)	0.0360 (8)	0.0163 (7)	0.0093 (6)	−0.0041 (5)	0.0017 (6)
N4	0.0124 (6)	0.0170 (7)	0.0181 (8)	0.0005 (5)	0.0014 (5)	−0.0009 (6)

N1—C5	1.470 (2)	C4—C5	1.384 (2)
N1—H11	0.91 (2)	C4—HC4	0.9300
N1—H12	0.93 (2)	C5—C6	1.398 (2)
N1—H13	0.85 (2)	C6—C7	1.504 (2)
N2—C1	1.465 (2)	C7—H1	0.9600
N2—H21	0.94 (2)	C7—H2	0.9600
N2—H22	0.89 (2)	C7—H3	0.9600
N2—H23	0.91 (2)	O1—N3	1.2703 (17)
C1—C2	1.382 (2)	O2—N3	1.2371 (19)
C1—C6	1.399 (2)	O3—N3	1.2475 (19)
C2—C3	1.388 (2)	O4—N4	1.2388 (18)
C2—HC2	0.9300	O5—N4	1.2817 (18)
C3—C4	1.389 (2)	O6—N4	1.2367 (18)
C3—HC3	0.9300
C5—N1—H11	110.0 (13)	C5—C4—C3	118.78 (15)
C5—N1—H12	110.8 (12)	C5—C4—HC4	120.6
H11—N1—H12	108.5 (19)	C3—C4—HC4	120.6
C5—N1—H13	109.0 (15)	C4—C5—C6	123.34 (14)
H11—N1—H13	110 (2)	C4—C5—N1	118.67 (15)
H12—N1—H13	108.4 (19)	C6—C5—N1	117.99 (15)
C1—N2—H21	111.6 (11)	C5—C6—C1	115.58 (15)
C1—N2—H22	110.8 (13)	C5—C6—C7	121.71 (14)
H21—N2—H22	107.1 (18)	C1—C6—C7	122.69 (14)
C1—N2—H23	112.2 (13)	C6—C7—H1	109.5
H21—N2—H23	109.3 (17)	C6—C7—H2	109.5
H22—N2—H23	105.5 (18)	H1—C7—H2	109.5
C2—C1—C6	122.68 (15)	C6—C7—H3	109.5
C2—C1—N2	118.10 (14)	H1—C7—H3	109.5
C6—C1—N2	119.22 (15)	H2—C7—H3	109.5
C1—C2—C3	119.49 (15)	O2—N3—O3	122.10 (14)
C1—C2—HC2	120.3	O2—N3—O1	118.62 (14)
C3—C2—HC2	120.3	O3—N3—O1	119.27 (14)
C2—C3—C4	120.11 (16)	O6—N4—O4	122.38 (14)
C2—C3—HC3	119.9	O6—N4—O5	118.82 (14)
C4—C3—HC3	119.9	O4—N4—O5	118.80 (14)
C6—C1—C2—C3	1.5 (3)	N1—C5—C6—C1	179.86 (14)
N2—C1—C2—C3	−178.15 (15)	C4—C5—C6—C7	178.77 (15)
C1—C2—C3—C4	−0.8 (3)	N1—C5—C6—C7	−1.4 (2)
C2—C3—C4—C5	−0.2 (2)	C2—C1—C6—C5	−1.1 (2)
C3—C4—C5—C6	0.6 (2)	N2—C1—C6—C5	178.57 (14)
C3—C4—C5—N1	−179.28 (15)	C2—C1—C6—C7	−179.79 (15)
C4—C5—C6—C1	0.0 (2)	N2—C1—C6—C7	−0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O5	0.91 (2)	1.85 (2)	2.746 (2)	168 (2)
N1—H12···O1i	0.93 (2)	1.93 (2)	2.845 (2)	168 (2)
N1—H13···O3ii	0.85 (2)	2.07 (2)	2.891 (2)	161 (2)
N2—H21···O5i	0.94 (2)	1.91 (2)	2.808 (2)	161 (2)
N2—H22···O1	0.89 (2)	1.96 (2)	2.839 (2)	172 (2)
N2—H23···O2iii	0.91 (2)	2.05 (3)	2.958 (2)	174 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O5	0.91 (2)	1.85 (2)	2.746 (2)	168 (2)
N1—H12⋯O1i	0.93 (2)	1.93 (2)	2.845 (2)	168 (2)
N1—H13⋯O3ii	0.85 (2)	2.07 (2)	2.891 (2)	161 (2)
N2—H21⋯O5i	0.94 (2)	1.91 (2)	2.808 (2)	161 (2)
N2—H22⋯O1	0.89 (2)	1.96 (2)	2.839 (2)	172 (2)
N2—H23⋯O2iii	0.91 (2)	2.05 (3)	2.958 (2)	174 (2)

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