2,2,4-Trimethyl-7-nitro-2,3-dihydro-1H-1,5-benzodiazepin-5-ium perchlorate.

In the title mol-ecular salt, C(12)H(16)N(3)O(2) (+)·ClO(4) (-), the nitro group is close to being coplanar with the benzene ring [dihedral angle = 8.1 (3)°]. The seven-membered ring has a maximum deviation of 0.502 (3) Å at the C atom between the dimethyl- and methyl-substituted C atoms. In the crystal, the components are linked into infinite sheets lying parallel to the bc plane by N-H⋯O and C-H⋯O hydrogen bonds. A short O⋯N contact of 2.896 (4) Å occurs within the sheets and a short O⋯O contact of 2.608 (4) Å occurs between the sheets.

Related literature

For general background and applications of benzimidazole derivatives, see: Landquist (1984 ▶); Insuasty et al. (2010 ▶); Balakrishna & Kaboudin (2001 ▶); Ballo et al. (2010 ▶). For the preparation of the title compound, see: Grech et al. (1994 ▶). For ring conformations, see Cremer & Pople (1975 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C12H16N3O2 +·ClO4 −

M = 333.73

Monoclinic,

a = 21.046 (7) Å

b = 11.818 (3) Å

c = 15.636 (6) Å

β = 132.176 (9)°

V = 2882.0 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.30 × 0.17 × 0.08 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.915, T max = 0.976

24582 measured reflections

3323 independent reflections

2816 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.138

S = 1.05

3323 reflections

210 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.69 e Å−3

Δρmin = −0.69 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024475/hb5507sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024475/hb5507Isup2.hkl

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

C12H16N3O2+·ClO4−	F(000) = 1392
Mr = 333.73	Dx = 1.538 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7331 reflections
a = 21.046 (7) Å	θ = 2.2–29.8°
b = 11.818 (3) Å	µ = 0.30 mm−1
c = 15.636 (6) Å	T = 100 K
β = 132.176 (9)°	Plate, brown
V = 2882.0 (16) Å3	0.30 × 0.17 × 0.08 mm
Z = 8

Bruker APEXII DUO CCD diffractometer	3323 independent reflections
Radiation source: fine-focus sealed tube	2816 reflections with I > 2σ(I)
graphite	Rint = 0.066
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −27→27
Tmin = 0.915, Tmax = 0.976	k = −15→15
24582 measured reflections	l = −20→20

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0714P)2 + 7.0069P] where P = (Fo2 + 2Fc2)/3
3323 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.69 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Cl1	0.15021 (3)	0.71202 (4)	0.49658 (4)	0.01923 (16)
O1	0.13150 (11)	0.68718 (14)	0.56727 (14)	0.0259 (4)
O2	0.19403 (11)	0.82394 (13)	0.52807 (14)	0.0245 (4)
O3	0.21587 (10)	0.62367 (14)	0.52533 (14)	0.0256 (4)
O4	0.07604 (10)	0.70691 (14)	0.37336 (13)	0.0234 (4)
O5	0.08273 (11)	1.21240 (13)	0.25797 (14)	0.0249 (4)
O6	0.09384 (11)	1.07773 (14)	0.36195 (13)	0.0246 (4)
N1	0.11724 (12)	0.79665 (15)	0.04379 (16)	0.0183 (4)
N2	0.10204 (12)	0.72103 (15)	0.21588 (15)	0.0176 (4)
N3	0.08881 (11)	1.11171 (16)	0.28211 (15)	0.0194 (4)
C1	0.10956 (12)	0.86625 (17)	0.10449 (16)	0.0152 (4)
C2	0.10763 (13)	0.98440 (18)	0.08478 (17)	0.0166 (4)
H2A	0.1127	1.0079	0.0328	0.020*
C3	0.09866 (12)	1.06450 (17)	0.13882 (17)	0.0166 (4)
H3A	0.0967	1.1410	0.1232	0.020*
C4	0.09241 (12)	1.02892 (18)	0.21822 (17)	0.0172 (4)
C5	0.09300 (13)	0.91616 (18)	0.24014 (17)	0.0172 (4)
H5A	0.0872	0.8945	0.2918	0.021*
C6	0.10220 (12)	0.83451 (17)	0.18541 (17)	0.0155 (4)
C7	0.14051 (13)	0.63366 (18)	0.21973 (17)	0.0180 (4)
C8	0.19130 (13)	0.64237 (19)	0.18564 (18)	0.0191 (4)
H8A	0.2184	0.5700	0.1991	0.023*
H8B	0.2364	0.6978	0.2347	0.023*
C9	0.13798 (13)	0.67632 (17)	0.05830 (17)	0.0165 (4)
C10	0.05645 (14)	0.60604 (19)	−0.02308 (18)	0.0216 (4)
H10A	0.0269	0.6260	−0.1015	0.032*
H10B	0.0200	0.6207	−0.0077	0.032*
H10C	0.0710	0.5271	−0.0113	0.032*
C11	0.19389 (15)	0.6604 (2)	0.0295 (2)	0.0234 (5)
H11A	0.1627	0.6841	−0.0485	0.035*
H11B	0.2091	0.5821	0.0377	0.035*
H11C	0.2450	0.7051	0.0813	0.035*
C12	0.13540 (15)	0.52362 (18)	0.26078 (19)	0.0222 (4)
H12A	0.0970	0.5305	0.2738	0.033*
H12B	0.1914	0.5028	0.3315	0.033*
H12C	0.1145	0.4665	0.2035	0.033*
H1N1	0.1130 (16)	0.826 (2)	−0.006 (2)	0.016 (6)*
H1N2	0.0798 (19)	0.715 (2)	0.243 (3)	0.030 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0193 (3)	0.0214 (3)	0.0170 (3)	−0.00116 (18)	0.0122 (2)	−0.00003 (18)
O1	0.0328 (9)	0.0283 (9)	0.0249 (8)	−0.0029 (7)	0.0228 (8)	0.0002 (7)
O2	0.0298 (8)	0.0167 (8)	0.0277 (8)	−0.0057 (6)	0.0195 (7)	−0.0039 (6)
O3	0.0230 (8)	0.0219 (8)	0.0289 (9)	0.0046 (6)	0.0162 (7)	0.0013 (7)
O4	0.0169 (7)	0.0350 (9)	0.0147 (8)	−0.0018 (6)	0.0091 (7)	−0.0003 (6)
O5	0.0305 (9)	0.0176 (8)	0.0253 (8)	0.0029 (6)	0.0183 (7)	0.0006 (6)
O6	0.0319 (9)	0.0267 (8)	0.0192 (8)	0.0026 (7)	0.0188 (7)	0.0002 (6)
N1	0.0239 (9)	0.0180 (9)	0.0167 (9)	0.0012 (7)	0.0152 (8)	0.0019 (7)
N2	0.0186 (8)	0.0192 (9)	0.0156 (8)	−0.0018 (7)	0.0118 (7)	0.0008 (7)
N3	0.0185 (8)	0.0213 (9)	0.0169 (8)	0.0015 (7)	0.0113 (7)	−0.0003 (7)
C1	0.0108 (8)	0.0192 (10)	0.0122 (9)	−0.0005 (7)	0.0064 (7)	−0.0002 (7)
C2	0.0147 (9)	0.0202 (10)	0.0134 (9)	−0.0019 (8)	0.0088 (8)	0.0006 (7)
C3	0.0132 (9)	0.0174 (10)	0.0136 (9)	−0.0013 (7)	0.0067 (8)	0.0001 (7)
C4	0.0146 (9)	0.0204 (10)	0.0141 (9)	0.0014 (8)	0.0087 (8)	−0.0008 (8)
C5	0.0144 (9)	0.0234 (10)	0.0127 (9)	0.0004 (8)	0.0086 (8)	0.0012 (8)
C6	0.0128 (9)	0.0179 (10)	0.0138 (9)	−0.0011 (7)	0.0082 (8)	0.0003 (7)
C7	0.0164 (9)	0.0205 (10)	0.0113 (9)	−0.0025 (8)	0.0069 (8)	0.0003 (7)
C8	0.0159 (9)	0.0220 (10)	0.0172 (10)	0.0016 (8)	0.0102 (8)	0.0027 (8)
C9	0.0162 (9)	0.0164 (9)	0.0174 (10)	0.0013 (8)	0.0115 (8)	0.0018 (8)
C10	0.0209 (10)	0.0231 (11)	0.0182 (10)	−0.0032 (8)	0.0121 (9)	−0.0019 (8)
C11	0.0254 (11)	0.0241 (11)	0.0289 (12)	0.0026 (9)	0.0215 (10)	0.0029 (9)
C12	0.0278 (11)	0.0181 (10)	0.0207 (10)	−0.0013 (9)	0.0163 (9)	0.0017 (8)

Cl1—O1	1.4310 (16)	C4—C5	1.374 (3)
Cl1—O4	1.4538 (16)	C5—C6	1.387 (3)
Cl1—O2	1.4941 (16)	C5—H5A	0.9300
Cl1—O3	1.5388 (17)	C7—C8	1.484 (3)
O5—N3	1.229 (2)	C7—C12	1.486 (3)
O6—N3	1.246 (2)	C8—C9	1.544 (3)
N1—C1	1.345 (3)	C8—H8A	0.9700
N1—C9	1.460 (3)	C8—H8B	0.9700
N1—H1N1	0.79 (3)	C9—C10	1.524 (3)
N2—C7	1.288 (3)	C9—C11	1.528 (3)
N2—C6	1.424 (3)	C10—H10A	0.9600
N2—H1N2	0.81 (3)	C10—H10B	0.9600
N3—C4	1.436 (3)	C10—H10C	0.9600
C1—C6	1.425 (3)	C11—H11A	0.9600
C1—C2	1.425 (3)	C11—H11B	0.9600
C2—C3	1.364 (3)	C11—H11C	0.9600
C2—H2A	0.9300	C12—H12A	0.9600
C3—C4	1.398 (3)	C12—H12B	0.9600
C3—H3A	0.9300	C12—H12C	0.9600
O1—Cl1—O4	114.06 (10)	N2—C7—C8	120.61 (19)
O1—Cl1—O2	110.86 (10)	N2—C7—C12	119.75 (19)
O4—Cl1—O2	110.46 (10)	C8—C7—C12	119.63 (19)
O1—Cl1—O3	107.10 (10)	C7—C8—C9	113.96 (17)
O4—Cl1—O3	108.27 (10)	C7—C8—H8A	108.8
O2—Cl1—O3	105.65 (10)	C9—C8—H8A	108.8
C1—N1—C9	130.62 (18)	C7—C8—H8B	108.8
C1—N1—H1N1	115.8 (19)	C9—C8—H8B	108.8
C9—N1—H1N1	113.4 (19)	H8A—C8—H8B	107.7
C7—N2—C6	128.90 (19)	N1—C9—C10	110.47 (17)
C7—N2—H1N2	118 (2)	N1—C9—C11	106.44 (17)
C6—N2—H1N2	113 (2)	C10—C9—C11	110.21 (18)
O5—N3—O6	122.75 (18)	N1—C9—C8	109.64 (17)
O5—N3—C4	119.30 (18)	C10—C9—C8	111.79 (17)
O6—N3—C4	117.94 (18)	C11—C9—C8	108.13 (17)
N1—C1—C6	127.01 (19)	C9—C10—H10A	109.5
N1—C1—C2	116.50 (18)	C9—C10—H10B	109.5
C6—C1—C2	116.48 (18)	H10A—C10—H10B	109.5
C3—C2—C1	122.82 (19)	C9—C10—H10C	109.5
C3—C2—H2A	118.6	H10A—C10—H10C	109.5
C1—C2—H2A	118.6	H10B—C10—H10C	109.5
C2—C3—C4	118.43 (19)	C9—C11—H11A	109.5
C2—C3—H3A	120.8	C9—C11—H11B	109.5
C4—C3—H3A	120.8	H11A—C11—H11B	109.5
C5—C4—C3	121.52 (19)	C9—C11—H11C	109.5
C5—C4—N3	118.88 (18)	H11A—C11—H11C	109.5
C3—C4—N3	119.55 (19)	H11B—C11—H11C	109.5
C4—C5—C6	120.17 (19)	C7—C12—H12A	109.5
C4—C5—H5A	119.9	C7—C12—H12B	109.5
C6—C5—H5A	119.9	H12A—C12—H12B	109.5
C5—C6—N2	114.60 (18)	C7—C12—H12C	109.5
C5—C6—C1	120.55 (19)	H12A—C12—H12C	109.5
N2—C6—C1	124.83 (18)	H12B—C12—H12C	109.5
C9—N1—C1—C6	−14.5 (3)	C7—N2—C6—C1	31.3 (3)
C9—N1—C1—C2	166.30 (19)	N1—C1—C6—C5	−178.74 (19)
N1—C1—C2—C3	178.87 (18)	C2—C1—C6—C5	0.5 (3)
C6—C1—C2—C3	−0.5 (3)	N1—C1—C6—N2	0.2 (3)
C1—C2—C3—C4	1.0 (3)	C2—C1—C6—N2	179.44 (18)
C2—C3—C4—C5	−1.6 (3)	C6—N2—C7—C8	−2.4 (3)
C2—C3—C4—N3	175.77 (18)	C6—N2—C7—C12	176.47 (19)
O5—N3—C4—C5	−175.37 (19)	N2—C7—C8—C9	−62.3 (3)
O6—N3—C4—C5	6.1 (3)	C12—C7—C8—C9	118.8 (2)
O5—N3—C4—C3	7.1 (3)	C1—N1—C9—C10	97.6 (2)
O6—N3—C4—C3	−171.40 (18)	C1—N1—C9—C11	−142.8 (2)
C3—C4—C5—C6	1.7 (3)	C1—N1—C9—C8	−26.1 (3)
N3—C4—C5—C6	−175.70 (18)	C7—C8—C9—N1	74.8 (2)
C4—C5—C6—N2	179.81 (18)	C7—C8—C9—C10	−48.0 (2)
C4—C5—C6—C1	−1.2 (3)	C7—C8—C9—C11	−169.51 (18)
C7—N2—C6—C5	−149.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O6i	0.80 (3)	2.15 (3)	2.941 (3)	173 (3)
N2—H1N2···O4	0.82 (5)	2.09 (4)	2.864 (4)	156 (4)
N2—H1N2···O4ii	0.82 (5)	2.46 (5)	3.000 (4)	124 (3)
C3—H3A···O1i	0.93	2.51	3.373 (3)	155
C11—H11A···O5i	0.96	2.58	3.524 (3)	169
C11—H11B···O3iii	0.96	2.45	3.396 (3)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O6i	0.80 (3)	2.15 (3)	2.941 (3)	173 (3)
N2—H1N2⋯O4	0.82 (5)	2.09 (4)	2.864 (4)	156 (4)
N2—H1N2⋯O4ii	0.82 (5)	2.46 (5)	3.000 (4)	124 (3)
C3—H3A⋯O1i	0.93	2.51	3.373 (3)	155
C11—H11A⋯O5i	0.96	2.58	3.524 (3)	169
C11—H11B⋯O3iii	0.96	2.45	3.396 (3)	168

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