1,5-Dimethyl-2-nitrimino-1,2-dihydro­pyridine

Methyl­ation of 5-methyl-2-nitramino­pyridine provides the title compound, C₇H₉N₃O₂, as the only product. The mol­ecule consists of two planar fragments, viz. an aromatic ring and a nitrimino substituent. The NNO₂ group is twisted by 17 (2)° out of the plane of the pyridine ring. Despite a small torsion angle between these fragments, the geometry of the mol­ecule indicates the participation of the π-electrons in the C—N bond. The hydrogen bonds in the crystal structure seem to be too weak to generate any deformations observed in the mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 85 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.037
• wR factor = 0.090
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

1,5-Dimethyl-2-nitrimino-1,2-dihydropyridine

Crystal data

C7H9N3O2	F(000) = 704
Mr = 167.17	Dx = 1.409 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1868 reflections
a = 14.3053 (17) Å	θ = 2.8–28.0°
b = 7.6741 (10) Å	µ = 0.11 mm^−1
c = 15.790 (2) Å	T = 85 K
β = 114.586 (12)°	Plate, colourless
V = 1576.3 (4) Å^3	0.15 × 0.15 × 0.10 mm
Z = 8

Data collection

Oxford Diffraction Xcalibur diffractometer	1456 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 27.0°, θmin = 2.8°
ω scans	h = −16→18
5421 measured reflections	k = −9→9
1713 independent reflections	l = −20→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0333P)^2 + 1.7281P] where P = (Fo^2 + 2Fc^2)/3
1713 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. ¹H NMR (DMSO-d₆, δ, p.p.m.): 8.23 (dd, ³J = 9.4 Hz, ⁴J = 2.3 Hz, ¹H, H4), 8.11 (d, ₄J = 2.3 Hz, ¹H, C6), 7.90 (d, ³J = 9.4 Hz, 1H, H3), 3.79 (s, 3H, N-methyl group), 2.24 (s, 3H, Ar-methyl group); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 155.1 (C2), 144.0 (C6), 140.5 (C4), 124.6 (C5), 117.6 (C3), 42.4 (N-methyl group), 16.7 (Ar-methyl group); IR (KBr, ν, cm^-1): 1412, 1257 (N-nitro group).

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.20349 (8)	0.50738 (14)	0.40361 (7)	0.0129 (2)
H1A	0.0483 (13)	0.498 (2)	0.3406 (11)	0.023 (4)*
H1B	0.1011 (13)	0.367 (2)	0.4306 (13)	0.032 (5)*
H1C	0.0988 (12)	0.319 (2)	0.3308 (11)	0.020 (4)*
C2	0.22804 (9)	0.58983 (16)	0.33769 (8)	0.0127 (3)
C3	0.32343 (9)	0.68028 (17)	0.37076 (9)	0.0154 (3)
H3	0.3409 (12)	0.744 (2)	0.3262 (11)	0.019 (4)*
C4	0.38919 (10)	0.67736 (17)	0.46401 (9)	0.0160 (3)
H4	0.4547 (12)	0.742 (2)	0.4859 (11)	0.020 (4)*
C5	0.36389 (9)	0.58534 (16)	0.52921 (8)	0.0147 (3)
H5A	0.4002 (14)	0.543 (2)	0.6696 (13)	0.034 (5)*
H5B	0.4902 (15)	0.488 (3)	0.6468 (13)	0.037 (5)*
H5C	0.4703 (13)	0.690 (2)	0.6572 (11)	0.027 (4)*
C6	0.26911 (9)	0.50436 (16)	0.49565 (8)	0.0137 (3)
H6	0.2448 (11)	0.444 (2)	0.5348 (10)	0.013 (4)*
C11	0.10337 (10)	0.41482 (18)	0.37451 (9)	0.0163 (3)
C15	0.43599 (10)	0.57605 (18)	0.63121 (9)	0.0177 (3)
N11	0.15013 (8)	0.57819 (14)	0.25006 (7)	0.0153 (2)
N12	0.17194 (8)	0.61738 (14)	0.17783 (7)	0.0146 (2)
O13	0.09775 (7)	0.61441 (14)	0.09939 (6)	0.0237 (2)
O14	0.26038 (8)	0.64818 (17)	0.18476 (7)	0.0324 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0123 (5)	0.0155 (5)	0.0116 (5)	0.0002 (4)	0.0058 (4)	−0.0003 (4)
C2	0.0138 (6)	0.0130 (6)	0.0125 (6)	0.0026 (4)	0.0067 (5)	−0.0002 (5)
C3	0.0159 (6)	0.0165 (6)	0.0149 (6)	−0.0017 (5)	0.0076 (5)	0.0000 (5)
C4	0.0142 (6)	0.0180 (6)	0.0156 (6)	−0.0012 (5)	0.0060 (5)	−0.0023 (5)
C5	0.0164 (6)	0.0156 (6)	0.0110 (6)	0.0027 (5)	0.0044 (5)	−0.0015 (5)
C6	0.0164 (6)	0.0153 (6)	0.0110 (6)	0.0024 (5)	0.0071 (5)	0.0007 (5)
C11	0.0133 (6)	0.0223 (7)	0.0142 (6)	−0.0032 (5)	0.0067 (5)	0.0007 (5)
C15	0.0183 (6)	0.0207 (7)	0.0110 (6)	0.0006 (5)	0.0029 (5)	−0.0004 (5)
N11	0.0138 (5)	0.0221 (6)	0.0108 (5)	0.0003 (4)	0.0060 (4)	0.0018 (4)
N12	0.0174 (5)	0.0150 (5)	0.0126 (5)	0.0005 (4)	0.0073 (4)	−0.0006 (4)
O13	0.0201 (5)	0.0386 (6)	0.0101 (4)	0.0081 (4)	0.0041 (4)	0.0042 (4)
O14	0.0226 (5)	0.0622 (8)	0.0174 (5)	−0.0187 (5)	0.0131 (4)	−0.0106 (5)

Geometric parameters (Å, º)

N1—C6	1.3633 (16)	C6—H6	0.947 (15)
N1—C2	1.3824 (16)	C11—H1A	0.984 (17)
N1—C11	1.4898 (15)	C11—H1B	0.972 (19)
C2—N11	1.3716 (15)	C11—H1C	0.994 (17)
C2—C3	1.4225 (17)	C15—H5A	0.976 (19)
C3—C4	1.3787 (17)	C15—H5B	0.98 (2)
C3—H3	0.970 (16)	C15—H5C	1.000 (18)
C4—C5	1.4141 (18)	N11—N12	1.3359 (15)
C4—H4	0.986 (16)	N12—O14	1.2463 (14)
C5—C6	1.3810 (17)	N12—O13	1.2518 (14)
C5—C15	1.5102 (17)
C6—N1—C2	122.17 (10)	C5—C6—H6	122.6 (9)
C6—N1—C11	117.89 (10)	N1—C11—H1A	107.9 (10)
C2—N1—C11	119.92 (10)	N1—C11—H1B	107.0 (10)
N11—C2—N1	112.04 (10)	H1A—C11—H1B	114.8 (14)
N11—C2—C3	130.91 (11)	N1—C11—H1C	110.2 (9)
N1—C2—C3	116.89 (11)	H1A—C11—H1C	107.4 (13)
C4—C3—C2	120.54 (12)	H1B—C11—H1C	109.5 (14)
C4—C3—H3	121.0 (9)	C5—C15—H5A	111.9 (11)
C2—C3—H3	118.5 (9)	C5—C15—H5B	114.8 (11)
C3—C4—C5	121.20 (12)	H5A—C15—H5B	103.2 (15)
C3—C4—H4	119.5 (9)	C5—C15—H5C	113.4 (10)
C5—C4—H4	119.2 (9)	H5A—C15—H5C	105.6 (14)
C6—C5—C4	116.95 (11)	H5B—C15—H5C	107.1 (14)
C6—C5—C15	120.92 (12)	N12—N11—C2	117.78 (10)
C4—C5—C15	122.13 (11)	O14—N12—O13	120.13 (11)
N1—C6—C5	122.14 (11)	O14—N12—N11	123.84 (11)
N1—C6—H6	115.3 (9)	O13—N12—N11	115.96 (10)
C6—N1—C2—N11	−179.17 (11)	C2—N1—C6—C5	0.82 (18)
C11—N1—C2—N11	2.11 (15)	C11—N1—C6—C5	179.56 (11)
C6—N1—C2—C3	−3.22 (17)	C4—C5—C6—N1	1.97 (18)
C11—N1—C2—C3	178.06 (11)	C15—C5—C6—N1	−178.51 (11)
N11—C2—C3—C4	177.89 (12)	N1—C2—N11—N12	−165.40 (10)
N1—C2—C3—C4	2.86 (18)	C3—C2—N11—N12	19.4 (2)
C2—C3—C4—C5	−0.16 (19)	C2—N11—N12—O14	6.81 (18)
C3—C4—C5—C6	−2.26 (18)	C2—N11—N12—O13	−176.28 (11)
C3—C4—C5—C15	178.22 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H1C···O14^i	0.99 (2)	2.50 (2)	3.2217 (17)	129 (1)
C3—H3···O14	0.97 (2)	2.17 (2)	2.7009 (16)	113 (1)
C4—H4···O13^ii	0.99 (2)	2.36 (2)	3.2738 (16)	154 (1)
C15—H5A···O14^iii	0.98 (2)	2.57 (2)	3.4285 (18)	147 (1)
C6—H6···O14^iii	0.95 (2)	2.39 (2)	3.2576 (16)	152 (1)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) x, −y+1, z+1/2.