(E)-5-Benzyl-1-methyl-N-nitro-1,3,5-triazinan-2-imine

Xu, L.-Z.; Yin, R.-F.; Li, H.-X.

doi:10.1107/S1600536810009426

organic compounds

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Volume 66| Part 4| April 2010| Page o867

doi:10.1107/S1600536810009426

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(E)-5-Benzyl-1-methyl-N-nitro-1,3,5-triazinan-2-imine

Liang-Zhong Xu,^a ^* Rui-Feng Yin ^a and Hong-Xin Li ^a

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: qknhs@yahoo.com.cn

(Received 10 March 2010; accepted 12 March 2010; online 20 March 2010)

In the title compound, C₁₁H₁₅N₅O₂, the 1,3,5-triazine ring exhibits a half-chair conformation. An intramolecular N—H⋯O interaction occurs. In the crystal structure, molecules are connected by intermolecular C—H⋯O and N—H⋯N hydrogen bonds, forming a zigzag chain along the b axis.

Related literature

For the synthesis of the title compound, see: Ebihara et al. (1998 ). For related structures, see: Hu et al. (2008 ); Zhao et al. (2008 ).

Experimental

Crystal data

C₁₁H₁₅N₅O₂
M_r = 249.28
Monoclinic, P 2₁ /c
a = 12.293 (3) Å
b = 6.7769 (14) Å
c = 14.858 (3) Å
β = 107.36 (3)°
V = 1181.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.45 × 0.13 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.956, T_max = 0.990
10812 measured reflections
2697 independent reflections
2215 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.141
S = 1.15
2697 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.86	2.27	3.093 (2)	162
C3—H3A⋯O2ⁱⁱ	0.97	2.59	3.305 (2)	131
N1—H1A⋯O1	0.86	2.33	2.730 (2)	109
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009426/is2529sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009426/is2529Isup2.hkl

checkCIF report

Comment top

The title compound was synthesized as an intermediate for the synthesis of clothianidin (Ebihara et al., 1998). We report here the crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Hu et al., 2008). The 1,3,5-triazine ring (C1/C3/C4/N1—N3) exhibits a half-chair conformation. The crystal structure is stabilized by intermolecular C–H···O and N–H···N hydrogen bonds.

Related literature top

For the synthesis of the title compound, see: Ebihara et al. (1998). For related structures, see: Hu et al. (2008); Zhao et al. (2008).

Experimental top

1-Methyl-2-nitroguanidine 1.18 g (10 mmol) and 2.5 g formaldehyde (concentration 36%, 30 mmol) was dissolved in 20 ml ethanol, then phenylmethanamine (10 mmol) was added dropwise during 30 min at 30-40 °C. After this addition, the reaction mixture was heated with stirring for three hours at 30-40 °C. The mixture was cooled to room temperature and filtered to afford title compound 2.39 g (yield 96%). Single crystals suitable for X-ray diffraction were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

(E)-5-Benzyl-1-methyl-N-nitro-1,3,5-triazinan-2-imine top

Crystal data top

C₁₁H₁₅N₅O₂	F(000) = 528
M_r = 249.28	D_x = 1.401 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2501 reflections
a = 12.293 (3) Å	θ = 2.3–25.1°
b = 6.7769 (14) Å	µ = 0.10 mm⁻¹
c = 14.858 (3) Å	T = 293 K
β = 107.36 (3)°	Needle, colorless
V = 1181.5 (4) Å³	0.45 × 0.13 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2697 independent reflections
Radiation source: Rotating Anode	2215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.956, T_max = 0.990	k = −8→8
10812 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0641P)² + 0.4408P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
2697 reflections	Δρ_max = 0.33 e Å⁻³
164 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (5)

Crystal data top

C₁₁H₁₅N₅O₂	V = 1181.5 (4) Å³
M_r = 249.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.293 (3) Å	µ = 0.10 mm⁻¹
b = 6.7769 (14) Å	T = 293 K
c = 14.858 (3) Å	0.45 × 0.13 × 0.10 mm
β = 107.36 (3)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2697 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2215 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.990	R_int = 0.026
10812 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.15	Δρ_max = 0.33 e Å⁻³
2697 reflections	Δρ_min = −0.28 e Å⁻³
164 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	−0.08476 (12)	0.2664 (2)	0.32912 (13)	0.0648 (5)
O2	−0.20472 (10)	0.4688 (2)	0.23990 (9)	0.0491 (4)
N1	0.13187 (12)	0.3877 (2)	0.34487 (10)	0.0396 (4)
H1A	0.0946	0.2966	0.3081	0.048*
N2	0.13204 (11)	0.69132 (19)	0.41305 (9)	0.0337 (3)
N3	0.29652 (11)	0.4822 (2)	0.47169 (9)	0.0324 (3)
N4	−0.03718 (11)	0.5836 (2)	0.31457 (11)	0.0399 (4)
N5	−0.10875 (11)	0.4321 (2)	0.29433 (9)	0.0342 (3)
C1	0.07548 (13)	0.5462 (2)	0.35840 (10)	0.0320 (3)
C2	0.07568 (15)	0.8650 (3)	0.43518 (14)	0.0446 (4)
H2A	−0.0053	0.8513	0.4084	0.067*
H2B	0.1011	0.9799	0.4094	0.067*
H2C	0.0940	0.8786	0.5024	0.067*
C3	0.25803 (13)	0.6801 (2)	0.44754 (12)	0.0379 (4)
H3A	0.2893	0.7288	0.3991	0.046*
H3B	0.2858	0.7639	0.5025	0.046*
C4	0.25463 (13)	0.3596 (3)	0.38930 (11)	0.0354 (4)
H4B	0.2694	0.2222	0.4071	0.043*
H4C	0.2951	0.3913	0.3443	0.043*
C5	0.26964 (14)	0.4064 (3)	0.55497 (11)	0.0370 (4)
H5A	0.1889	0.3765	0.5381	0.044*
H5B	0.2855	0.5083	0.6030	0.044*
C6	0.33636 (12)	0.2241 (2)	0.59520 (10)	0.0305 (3)
C7	0.29232 (14)	0.0894 (3)	0.64553 (11)	0.0366 (4)
H7A	0.2200	0.1099	0.6516	0.044*
C8	0.35422 (16)	−0.0750 (3)	0.68681 (12)	0.0420 (4)
H8A	0.3239	−0.1632	0.7209	0.050*
C9	0.46112 (16)	−0.1076 (3)	0.67726 (12)	0.0426 (4)
H9A	0.5029	−0.2181	0.7046	0.051*
C10	0.50547 (14)	0.0239 (3)	0.62723 (12)	0.0426 (4)
H10A	0.5775	0.0018	0.6209	0.051*
C11	0.44426 (13)	0.1892 (3)	0.58611 (11)	0.0376 (4)
H11A	0.4753	0.2770	0.5524	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0479 (8)	0.0396 (8)	0.1065 (13)	−0.0004 (6)	0.0227 (8)	0.0232 (8)
O2	0.0311 (6)	0.0622 (9)	0.0465 (7)	−0.0060 (6)	0.0002 (5)	−0.0005 (6)
N1	0.0354 (7)	0.0328 (7)	0.0410 (8)	0.0066 (6)	−0.0033 (6)	−0.0094 (6)
N2	0.0310 (7)	0.0272 (7)	0.0375 (7)	0.0028 (5)	0.0022 (5)	−0.0029 (5)
N3	0.0301 (6)	0.0355 (7)	0.0283 (6)	0.0030 (5)	0.0038 (5)	0.0022 (5)
N4	0.0302 (7)	0.0320 (7)	0.0485 (8)	−0.0010 (6)	−0.0020 (6)	0.0041 (6)
N5	0.0324 (7)	0.0367 (7)	0.0341 (7)	−0.0014 (6)	0.0106 (5)	0.0000 (5)
C1	0.0325 (7)	0.0290 (7)	0.0297 (7)	0.0025 (6)	0.0019 (6)	0.0016 (6)
C2	0.0442 (9)	0.0344 (9)	0.0510 (10)	0.0073 (7)	0.0079 (8)	−0.0097 (7)
C3	0.0306 (8)	0.0341 (8)	0.0423 (9)	−0.0016 (6)	0.0005 (6)	0.0018 (7)
C4	0.0336 (8)	0.0413 (9)	0.0296 (7)	0.0088 (7)	0.0065 (6)	−0.0003 (6)
C5	0.0372 (8)	0.0441 (9)	0.0301 (8)	0.0096 (7)	0.0105 (6)	0.0018 (7)
C6	0.0297 (7)	0.0363 (8)	0.0231 (6)	0.0011 (6)	0.0042 (5)	−0.0020 (6)
C7	0.0329 (7)	0.0467 (9)	0.0296 (7)	−0.0024 (7)	0.0086 (6)	−0.0020 (7)
C8	0.0502 (10)	0.0419 (9)	0.0324 (8)	−0.0064 (8)	0.0101 (7)	0.0030 (7)
C9	0.0486 (10)	0.0378 (9)	0.0346 (8)	0.0066 (8)	0.0021 (7)	0.0045 (7)
C10	0.0339 (8)	0.0483 (10)	0.0442 (9)	0.0103 (7)	0.0094 (7)	0.0042 (8)
C11	0.0326 (8)	0.0449 (9)	0.0357 (8)	0.0022 (7)	0.0109 (6)	0.0071 (7)

Geometric parameters (Å, º) top

O1—N5	1.2350 (19)	C3—H3B	0.9700
O2—N5	1.2404 (18)	C4—H4B	0.9700
N1—C1	1.326 (2)	C4—H4C	0.9700
N1—C4	1.468 (2)	C5—C6	1.505 (2)
N1—H1A	0.8600	C5—H5A	0.9700
N2—C1	1.332 (2)	C5—H5B	0.9700
N2—C2	1.452 (2)	C6—C7	1.388 (2)
N2—C3	1.4811 (19)	C6—C11	1.393 (2)
N3—C3	1.431 (2)	C7—C8	1.385 (2)
N3—C4	1.442 (2)	C7—H7A	0.9300
N3—C5	1.466 (2)	C8—C9	1.381 (3)
N4—N5	1.3269 (19)	C8—H8A	0.9300
N4—C1	1.367 (2)	C9—C10	1.373 (3)
C2—H2A	0.9600	C9—H9A	0.9300
C2—H2B	0.9600	C10—C11	1.385 (2)
C2—H2C	0.9600	C10—H10A	0.9300
C3—H3A	0.9700	C11—H11A	0.9300

C1—N1—C4	123.43 (14)	N3—C4—H4B	109.3
C1—N1—H1A	118.3	N1—C4—H4B	109.3
C4—N1—H1A	118.3	N3—C4—H4C	109.3
C1—N2—C2	122.62 (13)	N1—C4—H4C	109.3
C1—N2—C3	118.34 (13)	H4B—C4—H4C	108.0
C2—N2—C3	118.93 (13)	N3—C5—C6	112.94 (12)
C3—N3—C4	108.64 (12)	N3—C5—H5A	109.0
C3—N3—C5	113.51 (13)	C6—C5—H5A	109.0
C4—N3—C5	113.66 (14)	N3—C5—H5B	109.0
N5—N4—C1	118.25 (13)	C6—C5—H5B	109.0
O1—N5—O2	121.13 (14)	H5A—C5—H5B	107.8
O1—N5—N4	123.34 (14)	C7—C6—C11	118.43 (15)
O2—N5—N4	115.48 (14)	C7—C6—C5	120.00 (14)
N1—C1—N2	119.30 (14)	C11—C6—C5	121.53 (14)
N1—C1—N4	125.42 (14)	C8—C7—C6	121.10 (15)
N2—C1—N4	115.07 (14)	C8—C7—H7A	119.5
N2—C2—H2A	109.5	C6—C7—H7A	119.5
N2—C2—H2B	109.5	C9—C8—C7	119.81 (16)
H2A—C2—H2B	109.5	C9—C8—H8A	120.1
N2—C2—H2C	109.5	C7—C8—H8A	120.1
H2A—C2—H2C	109.5	C10—C9—C8	119.68 (16)
H2B—C2—H2C	109.5	C10—C9—H9A	120.2
N3—C3—N2	111.61 (13)	C8—C9—H9A	120.2
N3—C3—H3A	109.3	C9—C10—C11	120.81 (16)
N2—C3—H3A	109.3	C9—C10—H10A	119.6
N3—C3—H3B	109.3	C11—C10—H10A	119.6
N2—C3—H3B	109.3	C10—C11—C6	120.15 (15)
H3A—C3—H3B	108.0	C10—C11—H11A	119.9
N3—C4—N1	111.46 (13)	C6—C11—H11A	119.9

C1—N4—N5—O1	15.3 (2)	C5—N3—C4—N1	77.68 (17)
C1—N4—N5—O2	−167.27 (14)	C1—N1—C4—N3	20.6 (2)
C4—N1—C1—N2	1.7 (2)	C3—N3—C5—C6	−164.43 (13)
C4—N1—C1—N4	176.15 (15)	C4—N3—C5—C6	70.73 (17)
C2—N2—C1—N1	−176.81 (16)	N3—C5—C6—C7	−153.33 (14)
C3—N2—C1—N1	7.1 (2)	N3—C5—C6—C11	28.9 (2)
C2—N2—C1—N4	8.2 (2)	C11—C6—C7—C8	0.7 (2)
C3—N2—C1—N4	−167.92 (14)	C5—C6—C7—C8	−177.09 (14)
N5—N4—C1—N1	34.1 (2)	C6—C7—C8—C9	−0.7 (3)
N5—N4—C1—N2	−151.22 (15)	C7—C8—C9—C10	0.3 (3)
C4—N3—C3—N2	59.01 (17)	C8—C9—C10—C11	0.0 (3)
C5—N3—C3—N2	−68.49 (17)	C9—C10—C11—C6	0.1 (3)
C1—N2—C3—N3	−38.5 (2)	C7—C6—C11—C10	−0.4 (2)
C2—N2—C3—N3	145.25 (15)	C5—C6—C11—C10	177.37 (15)
C3—N3—C4—N1	−49.73 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.27	3.093 (2)	162
C3—H3A···O2ⁱⁱ	0.97	2.59	3.305 (2)	131
N1—H1A···O1	0.86	2.33	2.730 (2)	109

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₅O₂
M_r	249.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.293 (3), 6.7769 (14), 14.858 (3)
β (°)	107.36 (3)
V (Å³)	1181.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.45 × 0.13 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.956, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	10812, 2697, 2215
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.141, 1.15
No. of reflections	2697
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.27	3.093 (2)	162
C3—H3A···O2ⁱⁱ	0.97	2.59	3.305 (2)	131
N1—H1A···O1	0.86	2.33	2.730 (2)	109

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

References

Ebihara, K., Ura, D., Miyamoto, M. & Kaiho, T. (1998). EP Patent No. 0869120. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hu, Z.-Q., Yang, X.-D., An, G.-W., Yang, Z. & Xu, L.-Z. (2008). Acta Cryst. E64, o121. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, C., Yang, W., Hu, Y., Shen, L. & Lu, X. (2008). Acta Cryst. E64, o1515. Web of Science CSD CrossRef IUCr Journals Google Scholar

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