5,7-Dimethyl-2,3-dihydro-1H-1,4-diazepin-4-ium picrate.

In the cation of the title compound, C(7)H(13)N(2) (+)·C(6)H(2)N(3)O(7) (-), the seven-membered 1,4-diazepine ring forms a twist chair conformation. The two o-nitro groups in the anion are twisted by 35.0 (7) and 36.0 (9)° from the benzene ring. In the crystal, N-H⋯O hydrogen bonds between the cation and anion along with weak C-H⋯O hydrogen bonds produce chains along the b axis. C-H⋯O hydrogen bonds connecting the chains are also present.

Related literature

For biological applications of 1,4-diazepine derivatives, see: Andrews et al. (2001 ▶); Block et al. (1989 ▶); Carp (1999 ▶); Moroz (2004 ▶). For treatment of CNS disorders, see: Walser et al. (1978 ▶). For pharmacological profiles, see: Carlos et al. (2004 ▶). For related structures, see: Ferguson et al. (1990 ▶); Harrison et al. (2005 ▶); Peeters et al. (1997 ▶); Petcher et al. (1985 ▶); Rashid et al. (2006 ▶); Yang et al. (2007 ▶). For density functional theory calculations, see: Schmidt & Polik (2007 ▶); Hehre et al. (1986 ▶).

Experimental

Crystal data

C7H13N2 +·C6H2N3O7−

M = 353.30

Monoclinic,

a = 7.2341 (3) Å

b = 27.6458 (6) Å

c = 8.2831 (3) Å

β = 110.611 (4)°

V = 1550.52 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 200 K

0.45 × 0.37 × 0.24 mm

Data collection

Oxford Diffraction Gemini diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.962, T max = 0.970

24773 measured reflections

6353 independent reflections

4493 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.150

S = 1.04

6353 reflections

228 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001487X/is2536sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001487X/is2536Isup2.hkl

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

C7H13N2+·C6H2N3O7−	F(000) = 736
Mr = 353.30	Dx = 1.513 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9544 reflections
a = 7.2341 (3) Å	θ = 4.7–34.7°
b = 27.6458 (6) Å	µ = 0.13 mm−1
c = 8.2831 (3) Å	T = 200 K
β = 110.611 (4)°	Chunk, colorless
V = 1550.52 (9) Å3	0.45 × 0.37 × 0.24 mm
Z = 4

Oxford Diffraction Gemini diffractometer	6353 independent reflections
Radiation source: fine-focus sealed tube	4493 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 10.5081 pixels mm-1	θmax = 34.8°, θmin = 4.7°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −43→44
Tmin = 0.962, Tmax = 0.970	l = −13→13
24773 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.074P)2 + 0.3582P] where P = (Fo2 + 2Fc2)/3
6353 reflections	(Δ/σ)max = 0.001
228 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.23 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
O1A	0.30761 (14)	0.42368 (3)	0.49438 (11)	0.02584 (19)
O21A	0.1166 (2)	0.37603 (5)	0.19050 (14)	0.0569 (4)
O22A	0.2759 (3)	0.30970 (5)	0.20409 (16)	0.0696 (5)
O41A	0.2539 (2)	0.20668 (4)	0.67603 (15)	0.0493 (3)
O42A	0.2899 (2)	0.23953 (4)	0.92133 (14)	0.0444 (3)
O61A	0.4592 (2)	0.41131 (4)	0.99837 (13)	0.0466 (3)
O62A	0.26070 (17)	0.45405 (3)	0.79164 (13)	0.0374 (2)
N2A	0.2123 (2)	0.34203 (4)	0.27069 (14)	0.0367 (3)
N4A	0.27398 (18)	0.24249 (4)	0.76838 (15)	0.0295 (2)
N6A	0.34729 (18)	0.41624 (4)	0.84935 (13)	0.0257 (2)
C1A	0.28914 (16)	0.38355 (4)	0.55484 (14)	0.0188 (2)
C2A	0.25139 (19)	0.33908 (4)	0.45574 (14)	0.0230 (2)
C3A	0.2521 (2)	0.29387 (4)	0.52339 (15)	0.0247 (2)
H3AA	0.2331	0.2660	0.4524	0.030*
C4A	0.28112 (19)	0.28952 (4)	0.69802 (15)	0.0224 (2)
C5A	0.31328 (18)	0.32993 (4)	0.80487 (15)	0.0213 (2)
H5AA	0.3340	0.3265	0.9241	0.026*
C6A	0.31432 (17)	0.37484 (4)	0.73403 (14)	0.0194 (2)
C7B	0.2662 (3)	0.50023 (5)	0.18073 (19)	0.0357 (3)
H7BA	0.2199	0.4691	0.2088	0.054*
H7BB	0.4074	0.4981	0.1993	0.054*
H7BC	0.1929	0.5082	0.0597	0.054*
N1B	0.23246 (16)	0.52460 (3)	0.44657 (14)	0.0252 (2)
H1BC	0.2648	0.4943	0.4762	0.030*
N2B	0.24482 (17)	0.63760 (3)	0.48145 (13)	0.0250 (2)
H2BC	0.2328	0.6674	0.5141	0.030*
C1B	0.1824 (2)	0.55501 (4)	0.56818 (17)	0.0277 (3)
H1BA	0.2014	0.5362	0.6746	0.033*
H1BB	0.0409	0.5638	0.5178	0.033*
C2B	0.3044 (2)	0.60105 (4)	0.61571 (16)	0.0267 (2)
H2BA	0.2927	0.6146	0.7223	0.032*
H2BB	0.4450	0.5929	0.6406	0.032*
C3B	0.20682 (17)	0.63060 (4)	0.31478 (15)	0.0212 (2)
C4B	0.1720 (2)	0.67590 (4)	0.20732 (17)	0.0283 (3)
H4BA	0.1655	0.7038	0.2782	0.042*
H4BB	0.0472	0.6730	0.1098	0.042*
H4BC	0.2806	0.6804	0.1640	0.042*
C5B	0.20560 (19)	0.58659 (4)	0.23242 (15)	0.0236 (2)
H5BA	0.1819	0.5893	0.1125	0.028*
C6B	0.23301 (18)	0.53901 (4)	0.29478 (16)	0.0236 (2)

	U11	U22	U33	U12	U13	U23
O1A	0.0363 (5)	0.0169 (4)	0.0265 (4)	0.0020 (3)	0.0138 (4)	0.0052 (3)
O21A	0.0920 (11)	0.0391 (6)	0.0227 (5)	−0.0056 (6)	−0.0006 (6)	0.0072 (4)
O22A	0.1363 (15)	0.0502 (7)	0.0365 (6)	0.0110 (8)	0.0483 (8)	−0.0054 (5)
O41A	0.0938 (10)	0.0162 (4)	0.0481 (6)	−0.0019 (5)	0.0378 (7)	−0.0017 (4)
O42A	0.0815 (9)	0.0244 (5)	0.0330 (5)	−0.0010 (5)	0.0272 (6)	0.0081 (4)
O61A	0.0723 (8)	0.0370 (6)	0.0193 (5)	0.0035 (5)	0.0023 (5)	−0.0045 (4)
O62A	0.0584 (7)	0.0192 (4)	0.0337 (5)	0.0086 (4)	0.0150 (5)	−0.0019 (4)
N2A	0.0604 (8)	0.0305 (6)	0.0191 (5)	−0.0096 (5)	0.0139 (5)	−0.0011 (4)
N4A	0.0437 (6)	0.0171 (4)	0.0323 (5)	0.0016 (4)	0.0190 (5)	0.0044 (4)
N6A	0.0378 (6)	0.0195 (4)	0.0210 (5)	−0.0017 (4)	0.0119 (4)	−0.0019 (3)
C1A	0.0215 (5)	0.0170 (4)	0.0183 (5)	0.0017 (4)	0.0075 (4)	0.0011 (3)
C2A	0.0325 (6)	0.0205 (5)	0.0165 (5)	−0.0013 (4)	0.0093 (4)	0.0003 (4)
C3A	0.0355 (6)	0.0173 (5)	0.0231 (5)	−0.0019 (4)	0.0127 (5)	−0.0020 (4)
C4A	0.0315 (6)	0.0143 (4)	0.0246 (5)	0.0011 (4)	0.0137 (5)	0.0031 (4)
C5A	0.0277 (5)	0.0182 (4)	0.0197 (5)	0.0015 (4)	0.0105 (4)	0.0024 (4)
C6A	0.0251 (5)	0.0153 (4)	0.0184 (5)	0.0008 (4)	0.0083 (4)	−0.0009 (3)
C7B	0.0506 (9)	0.0219 (5)	0.0345 (7)	0.0020 (5)	0.0146 (7)	−0.0077 (5)
N1B	0.0317 (5)	0.0142 (4)	0.0306 (5)	0.0025 (4)	0.0120 (4)	0.0028 (3)
N2B	0.0366 (6)	0.0156 (4)	0.0234 (5)	0.0027 (4)	0.0115 (4)	−0.0005 (3)
C1B	0.0352 (7)	0.0209 (5)	0.0322 (6)	0.0049 (5)	0.0185 (5)	0.0059 (4)
C2B	0.0371 (7)	0.0217 (5)	0.0213 (5)	0.0045 (5)	0.0104 (5)	0.0008 (4)
C3B	0.0232 (5)	0.0169 (4)	0.0232 (5)	0.0010 (4)	0.0078 (4)	0.0019 (4)
C4B	0.0371 (7)	0.0194 (5)	0.0297 (6)	0.0039 (5)	0.0135 (5)	0.0070 (4)
C5B	0.0308 (6)	0.0190 (5)	0.0198 (5)	0.0013 (4)	0.0074 (5)	−0.0004 (4)
C6B	0.0252 (5)	0.0170 (4)	0.0269 (5)	−0.0002 (4)	0.0071 (5)	−0.0027 (4)

O1A—C1A	1.2438 (13)	C7B—H7BB	0.9800
O21A—N2A	1.2165 (17)	C7B—H7BC	0.9800
O22A—N2A	1.2219 (18)	N1B—C6B	1.3202 (16)
O41A—N4A	1.2281 (15)	N1B—C1B	1.4524 (16)
O42A—N4A	1.2338 (15)	N1B—H1BC	0.8800
O61A—N6A	1.2223 (15)	N2B—C3B	1.3235 (15)
O62A—N6A	1.2257 (14)	N2B—C2B	1.4512 (15)
N2A—C2A	1.4597 (15)	N2B—H2BC	0.8800
N4A—C4A	1.4332 (14)	C1B—C2B	1.5199 (18)
N6A—C6A	1.4558 (14)	C1B—H1BA	0.9900
C1A—C2A	1.4496 (15)	C1B—H1BB	0.9900
C1A—C6A	1.4504 (15)	C2B—H2BA	0.9900
C2A—C3A	1.3692 (16)	C2B—H2BB	0.9900
C3A—C4A	1.3918 (16)	C3B—C5B	1.3935 (15)
C3A—H3AA	0.9500	C3B—C4B	1.5055 (16)
C4A—C5A	1.3929 (15)	C4B—H4BA	0.9800
C5A—C6A	1.3744 (15)	C4B—H4BB	0.9800
C5A—H5AA	0.9500	C4B—H4BC	0.9800
C7B—C6B	1.5031 (17)	C5B—C6B	1.4014 (16)
C7B—H7BA	0.9800	C5B—H5BA	0.9500
O21A—N2A—O22A	123.42 (13)	C6B—N1B—C1B	124.82 (10)
O21A—N2A—C2A	118.62 (12)	C6B—N1B—H1BC	117.6
O22A—N2A—C2A	117.95 (12)	C1B—N1B—H1BC	117.6
O41A—N4A—O42A	122.28 (11)	C3B—N2B—C2B	126.45 (10)
O41A—N4A—C4A	119.43 (11)	C3B—N2B—H2BC	116.8
O42A—N4A—C4A	118.29 (10)	C2B—N2B—H2BC	116.8
O61A—N6A—O62A	123.71 (11)	N1B—C1B—C2B	113.60 (10)
O61A—N6A—C6A	118.17 (10)	N1B—C1B—H1BA	108.8
O62A—N6A—C6A	118.12 (10)	C2B—C1B—H1BA	108.8
O1A—C1A—C2A	123.64 (10)	N1B—C1B—H1BB	108.8
O1A—C1A—C6A	124.58 (10)	C2B—C1B—H1BB	108.8
C2A—C1A—C6A	111.68 (9)	H1BA—C1B—H1BB	107.7
C3A—C2A—C1A	124.72 (10)	N2B—C2B—C1B	113.33 (11)
C3A—C2A—N2A	116.88 (10)	N2B—C2B—H2BA	108.9
C1A—C2A—N2A	118.39 (10)	C1B—C2B—H2BA	108.9
C2A—C3A—C4A	118.80 (10)	N2B—C2B—H2BB	108.9
C2A—C3A—H3AA	120.6	C1B—C2B—H2BB	108.9
C4A—C3A—H3AA	120.6	H2BA—C2B—H2BB	107.7
C3A—C4A—C5A	121.43 (10)	N2B—C3B—C5B	126.98 (10)
C3A—C4A—N4A	119.15 (10)	N2B—C3B—C4B	115.16 (10)
C5A—C4A—N4A	119.41 (10)	C5B—C3B—C4B	117.78 (10)
C6A—C5A—C4A	118.55 (10)	C3B—C4B—H4BA	109.5
C6A—C5A—H5AA	120.7	C3B—C4B—H4BB	109.5
C4A—C5A—H5AA	120.7	H4BA—C4B—H4BB	109.5
C5A—C6A—C1A	124.70 (10)	C3B—C4B—H4BC	109.5
C5A—C6A—N6A	117.03 (10)	H4BA—C4B—H4BC	109.5
C1A—C6A—N6A	118.26 (9)	H4BB—C4B—H4BC	109.5
C6B—C7B—H7BA	109.5	C3B—C5B—C6B	131.55 (11)
C6B—C7B—H7BB	109.5	C3B—C5B—H5BA	114.2
H7BA—C7B—H7BB	109.5	C6B—C5B—H5BA	114.2
C6B—C7B—H7BC	109.5	N1B—C6B—C5B	125.93 (11)
H7BA—C7B—H7BC	109.5	N1B—C6B—C7B	115.97 (11)
H7BB—C7B—H7BC	109.5	C5B—C6B—C7B	118.10 (11)
O1A—C1A—C2A—C3A	172.43 (12)	O1A—C1A—C6A—C5A	−173.26 (12)
C6A—C1A—C2A—C3A	−4.09 (18)	C2A—C1A—C6A—C5A	3.22 (17)
O1A—C1A—C2A—N2A	−6.66 (18)	O1A—C1A—C6A—N6A	5.39 (18)
C6A—C1A—C2A—N2A	176.82 (11)	C2A—C1A—C6A—N6A	−178.13 (10)
O21A—N2A—C2A—C3A	143.77 (15)	O61A—N6A—C6A—C5A	34.74 (17)
O22A—N2A—C2A—C3A	−35.4 (2)	O62A—N6A—C6A—C5A	−145.02 (12)
O21A—N2A—C2A—C1A	−37.07 (19)	O61A—N6A—C6A—C1A	−144.01 (13)
O22A—N2A—C2A—C1A	143.81 (15)	O62A—N6A—C6A—C1A	36.22 (16)
C1A—C2A—C3A—C4A	3.4 (2)	C6B—N1B—C1B—C2B	−55.05 (17)
N2A—C2A—C3A—C4A	−177.54 (12)	C3B—N2B—C2B—C1B	−45.65 (17)
C2A—C3A—C4A—C5A	−1.33 (19)	N1B—C1B—C2B—N2B	75.70 (14)
C2A—C3A—C4A—N4A	177.46 (12)	C2B—N2B—C3B—C5B	3.7 (2)
O41A—N4A—C4A—C3A	4.2 (2)	C2B—N2B—C3B—C4B	−172.89 (12)
O42A—N4A—C4A—C3A	−176.34 (13)	N2B—C3B—C5B—C6B	3.3 (2)
O41A—N4A—C4A—C5A	−176.96 (13)	C4B—C3B—C5B—C6B	179.87 (13)
O42A—N4A—C4A—C5A	2.48 (19)	C1B—N1B—C6B—C5B	6.9 (2)
C3A—C4A—C5A—C6A	0.53 (19)	C1B—N1B—C6B—C7B	−173.08 (13)
N4A—C4A—C5A—C6A	−178.27 (11)	C3B—C5B—C6B—N1B	13.0 (2)
C4A—C5A—C6A—C1A	−1.66 (19)	C3B—C5B—C6B—C7B	−167.02 (14)
C4A—C5A—C6A—N6A	179.67 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H1BC···O1A	0.88	1.98	2.8434 (13)	169
N2B—H2BC···O42Ai	0.88	2.09	2.9657 (14)	176
C5A—H5AA···O22Aii	0.95	2.54	3.4570 (16)	162
C7B—H7BA···O1A	0.98	2.55	3.2817 (17)	131
C1B—H1BA···O62A	0.99	2.45	3.2861 (15)	142
C1B—H1BB···O1Aiii	0.99	2.51	3.4477 (16)	158
C2B—H2BA···O61Aiv	0.99	2.48	3.0678 (16)	117
C2B—H2BB···O1Av	0.99	2.46	3.3135 (16)	144
C4B—H4BA···O42Ai	0.98	2.59	3.4692 (17)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1B—H1BC⋯O1A	0.88	1.98	2.8434 (13)	169
N2B—H2BC⋯O42Ai	0.88	2.09	2.9657 (14)	176
C5A—H5AA⋯O22Aii	0.95	2.54	3.4570 (16)	162
C7B—H7BA⋯O1A	0.98	2.55	3.2817 (17)	131
C1B—H1BA⋯O62A	0.99	2.45	3.2861 (15)	142
C1B—H1BB⋯O1Aiii	0.99	2.51	3.4477 (16)	158
C2B—H2BA⋯O61Aiv	0.99	2.48	3.0678 (16)	117
C2B—H2BB⋯O1Av	0.99	2.46	3.3135 (16)	144
C4B—H4BA⋯O42Ai	0.98	2.59	3.4692 (17)	149

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