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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1515.
Published online 2008 July 16. doi:  10.1107/S1600536808021533
PMCID: PMC2962141

1,5-Dimethyl-2-nitro­imino-1,3,5-tri­azinane

Abstract

The asymmetric unit of the title compound, C5H11N5O2, contains two independent mol­ecules. The two triazine rings adopt envelope conformations. Intra­molecular C—H(...)N and N—H(...)O hydrogen bonds result in the formation of two five- and two six-membered rings which are nearly planar; in addition, they are also nearly coplanar. In the crystal structure, inter­molecular N—H(...)N, C—H(...)N and C—H(...)O hydrogen bonds link the mol­ecules.

Related literature

For general background, see: Wakita et al. (2003 [triangle]). For related literature, see: Shiokawa et al. (1991 [triangle]).

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Object name is e-64-o1515-scheme1.jpg

Experimental

Crystal data

  • C5H11N5O2
  • M r = 173.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1515-efi1.jpg
  • a = 6.6490 (13) Å
  • b = 30.103 (6) Å
  • c = 8.2940 (17) Å
  • β = 104.19 (3)°
  • V = 1609.4 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 294 (2) K
  • 0.30 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.967, T max = 0.989
  • 3126 measured reflections
  • 2873 independent reflections
  • 1979 reflections with I > 2σ(I)
  • R int = 0.037
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.072
  • wR(F 2) = 0.194
  • S = 1.00
  • 2873 reflections
  • 217 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021533/hk2491sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021533/hk2491Isup2.hkl

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

supplementary crystallographic information

Comment

Nitroguanidine derivatives have a high insecticidal activity and a wide spectrum (Wakita et al., 2003). As part of our ongoing studies in this area, we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains two independent molecules, in which the bond lengths and angles are generally within normal ranges. Rings A (N1-N3/C3-C5) and B (N6-N8/C8-C10) have envelope conformations, with N3 and N6 atoms displaced by -0.652 (2) and -0.645 (3) Å, respectively, from the plane of the other rings atoms. The intramolecular C-H···N and N-H···O hydrogen bonds (Table 1) result in the formation of nearly planar two five- and two six-membered rings: C (N1/N4/C2/C3/H2B), D (O1/N2/N4/N5/C3/H2A) and E (N8/N9/C7/C10/H7B), F (O3/N7/N9/N10/C10/H7A). The dihedral angles between the rings are C/D = 1.63 (3)° and E/F = 3.43 (3)°. So, rings C, D and E, F are nearly coplanar.

In the crystal structure, intermolecular N-H···N, C-H···N and C-H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Experimental

The title compound was synthesized according to the literature method (Shiokawa et al., 1991). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.97 and 0.96 Å for methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.

Crystal data

C5H11N5O2F000 = 736
Mr = 173.19Dx = 1.430 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.6490 (13) Åθ = 9–12º
b = 30.103 (6) ŵ = 0.11 mm1
c = 8.2940 (17) ÅT = 294 (2) K
β = 104.19 (3)ºBlock, colorless
V = 1609.4 (6) Å30.30 × 0.10 × 0.10 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.037
Radiation source: fine-focus sealed tubeθmax = 25.2º
Monochromator: graphiteθmin = 1.4º
T = 294(2) Kh = −7→7
ω/2θ scansk = 0→36
Absorption correction: ψ scan(North et al., 1968)l = 0→9
Tmin = 0.967, Tmax = 0.9893 standard reflections
3126 measured reflections every 120 min
2873 independent reflections intensity decay: none
1979 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.194  w = 1/[σ2(Fo2) + (0.06P)2 + 4P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2873 reflectionsΔρmax = 0.36 e Å3
217 parametersΔρmin = −0.37 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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 > 2sigma(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)

xyzUiso*/Ueq
O10.4157 (7)0.16494 (15)0.6298 (4)0.0982 (15)
O20.2294 (5)0.22215 (11)0.5490 (4)0.0699 (10)
N10.3763 (5)0.19429 (11)1.0927 (4)0.0447 (8)
N20.4955 (5)0.14315 (11)0.9359 (4)0.0466 (8)
H2A0.50270.13340.84000.056*
N30.6537 (5)0.14525 (12)1.2299 (4)0.0501 (9)
N40.3096 (5)0.20872 (11)0.8150 (4)0.0469 (8)
N50.3202 (5)0.19792 (13)0.6628 (4)0.0549 (10)
C10.8312 (7)0.17403 (17)1.2213 (7)0.0731 (15)
H1A0.86660.19251.31840.110*
H1B0.79390.19241.12380.110*
H1C0.94810.15591.21600.110*
C20.2708 (8)0.23592 (15)1.1160 (6)0.0616 (12)
H2B0.21300.24931.00970.092*
H2C0.36880.25591.18350.092*
H2D0.16170.22971.17010.092*
C30.3970 (6)0.18117 (13)0.9446 (5)0.0442 (9)
C40.5922 (7)0.11728 (14)1.0841 (5)0.0500 (10)
H4B0.49510.09501.10290.060*
H4C0.71320.10201.06570.060*
C50.4757 (8)0.16943 (17)1.2470 (5)0.0621 (13)
H5A0.51620.19021.33870.075*
H5B0.37570.14891.27340.075*
O30.0455 (5)0.07427 (13)0.2450 (4)0.0804 (12)
O40.3371 (5)0.04202 (11)0.2690 (4)0.0640 (9)
N6−0.1841 (5)0.09106 (11)0.7596 (4)0.0466 (8)
N7−0.1239 (4)0.07164 (11)0.4938 (4)0.0421 (8)
H7A−0.15080.07880.39040.051*
N80.0994 (5)0.04358 (11)0.7263 (4)0.0429 (8)
N90.2160 (5)0.04411 (11)0.4922 (4)0.0424 (8)
N100.1942 (5)0.05374 (11)0.3332 (4)0.0426 (8)
C6−0.0729 (8)0.13372 (16)0.7715 (7)0.0729 (15)
H6A−0.01360.14070.88630.109*
H6B−0.16800.15670.72210.109*
H6C0.03550.13160.71380.109*
C70.2916 (7)0.02129 (16)0.8125 (5)0.0579 (12)
H7B0.37450.01540.73510.087*
H7C0.2587−0.00620.85890.087*
H7D0.36740.04010.90010.087*
C8−0.0443 (6)0.05545 (15)0.8268 (5)0.0486 (10)
H8A−0.12530.02940.83910.058*
H8B0.03520.06390.93690.058*
C9−0.2774 (6)0.07940 (15)0.5863 (5)0.0481 (10)
H9B−0.36120.05290.58300.058*
H9C−0.36820.10330.53420.058*
C100.0585 (5)0.05359 (12)0.5651 (4)0.0371 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.131 (3)0.121 (3)0.0415 (19)0.080 (3)0.019 (2)0.023 (2)
O20.085 (2)0.070 (2)0.0385 (16)0.0103 (18)−0.0163 (15)0.0154 (15)
N10.0489 (19)0.050 (2)0.0296 (16)0.0062 (15)−0.0016 (14)0.0029 (14)
N20.053 (2)0.050 (2)0.0286 (16)0.0079 (16)−0.0075 (14)0.0035 (14)
N30.054 (2)0.054 (2)0.0308 (17)0.0081 (17)−0.0110 (14)0.0006 (15)
N40.050 (2)0.051 (2)0.0281 (17)−0.0018 (16)−0.0123 (14)0.0093 (14)
N50.049 (2)0.059 (2)0.043 (2)0.0020 (18)−0.0152 (16)0.0148 (18)
C10.056 (3)0.058 (3)0.082 (4)−0.009 (2)−0.026 (3)−0.001 (3)
C20.068 (3)0.058 (3)0.055 (3)0.011 (2)0.007 (2)0.002 (2)
C30.039 (2)0.043 (2)0.039 (2)−0.0049 (17)−0.0137 (16)0.0054 (17)
C40.059 (3)0.044 (2)0.036 (2)−0.0027 (19)−0.0087 (18)0.0081 (18)
C50.075 (3)0.070 (3)0.033 (2)0.017 (3)−0.004 (2)0.010 (2)
O30.080 (2)0.117 (3)0.0414 (17)0.052 (2)0.0087 (16)0.0229 (18)
O40.0575 (19)0.079 (2)0.0566 (19)0.0107 (17)0.0153 (15)0.0055 (16)
N60.0420 (18)0.051 (2)0.0409 (18)−0.0008 (15)−0.0012 (14)−0.0055 (16)
N70.0349 (17)0.059 (2)0.0275 (16)0.0067 (15)−0.0026 (13)0.0045 (14)
N80.0411 (18)0.053 (2)0.0274 (16)0.0113 (15)−0.0043 (13)0.0025 (14)
N90.0380 (17)0.050 (2)0.0326 (17)0.0027 (14)−0.0036 (13)0.0066 (14)
N100.0430 (18)0.045 (2)0.0373 (17)0.0064 (15)0.0054 (14)0.0010 (14)
C60.065 (3)0.057 (3)0.094 (4)−0.012 (2)0.015 (3)−0.022 (3)
C70.054 (3)0.072 (3)0.038 (2)0.016 (2)−0.0067 (19)0.012 (2)
C80.050 (2)0.061 (3)0.031 (2)0.001 (2)0.0023 (17)0.0038 (18)
C90.036 (2)0.064 (3)0.040 (2)0.0028 (19)0.0014 (16)0.0006 (19)
C100.0341 (19)0.035 (2)0.0353 (19)−0.0013 (15)−0.0040 (15)−0.0016 (15)

Geometric parameters (Å, °)

O1—N51.245 (5)O3—N101.241 (4)
O2—N51.228 (4)O4—N101.249 (4)
N1—C31.329 (5)N6—C81.439 (5)
N1—C21.472 (5)N6—C91.461 (5)
N1—C51.490 (5)N6—C61.473 (6)
N2—C31.329 (5)N7—C101.328 (4)
N2—C41.464 (5)N7—C91.438 (5)
N2—H2A0.8600N7—H7A0.8600
N3—C51.426 (6)N8—C101.332 (5)
N3—C41.448 (5)N8—C81.458 (5)
N3—C11.480 (6)N8—C71.465 (5)
N4—N51.322 (5)N9—N101.323 (4)
N4—C31.369 (5)N9—C101.362 (5)
C1—H1A0.9600C6—H6A0.9600
C1—H1B0.9600C6—H6B0.9600
C1—H1C0.9600C6—H6C0.9600
C2—H2B0.9600C7—H7B0.9600
C2—H2C0.9600C7—H7C0.9600
C2—H2D0.9600C7—H7D0.9600
C4—H4B0.9700C8—H8A0.9700
C4—H4C0.9700C8—H8B0.9700
C5—H5A0.9700C9—H9B0.9700
C5—H5B0.9700C9—H9C0.9700
C3—N1—C2122.4 (3)C8—N6—C9106.3 (3)
C3—N1—C5121.3 (3)C8—N6—C6110.9 (3)
C2—N1—C5116.1 (3)C9—N6—C6111.1 (4)
C3—N2—C4122.3 (3)C10—N7—C9121.2 (3)
C3—N2—H2A118.9C10—N7—H7A119.4
C4—N2—H2A118.9C9—N7—H7A119.4
C5—N3—C4108.0 (3)C10—N8—C8121.2 (3)
C5—N3—C1113.4 (4)C10—N8—C7122.2 (3)
C4—N3—C1111.4 (4)C8—N8—C7116.6 (3)
N5—N4—C3119.3 (4)N10—N9—C10119.2 (3)
O2—N5—O1119.1 (4)O3—N10—O4118.0 (3)
O2—N5—N4117.2 (4)O3—N10—N9125.0 (3)
O1—N5—N4123.7 (3)O4—N10—N9117.0 (3)
N3—C1—H1A109.5N6—C6—H6A109.5
N3—C1—H1B109.5N6—C6—H6B109.5
H1A—C1—H1B109.5H6A—C6—H6B109.5
N3—C1—H1C109.5N6—C6—H6C109.5
H1A—C1—H1C109.5H6A—C6—H6C109.5
H1B—C1—H1C109.5H6B—C6—H6C109.5
N1—C2—H2B109.5N8—C7—H7B109.5
N1—C2—H2C109.5N8—C7—H7C109.5
H2B—C2—H2C109.5H7B—C7—H7C109.5
N1—C2—H2D109.5N8—C7—H7D109.5
H2B—C2—H2D109.5H7B—C7—H7D109.5
H2C—C2—H2D109.5H7C—C7—H7D109.5
N1—C3—N2118.0 (3)N6—C8—N8114.4 (3)
N1—C3—N4115.2 (4)N6—C8—H8A108.7
N2—C3—N4126.8 (4)N8—C8—H8A108.7
N3—C4—N2111.6 (3)N6—C8—H8B108.7
N3—C4—H4B109.3N8—C8—H8B108.7
N2—C4—H4B109.3H8A—C8—H8B107.6
N3—C4—H4C109.3N7—C9—N6112.2 (3)
N2—C4—H4C109.3N7—C9—H9B109.2
H4B—C4—H4C108.0N6—C9—H9B109.2
N3—C5—N1112.0 (4)N7—C9—H9C109.2
N3—C5—H5A109.2N6—C9—H9C109.2
N1—C5—H5A109.2H9B—C9—H9C107.9
N3—C5—H5B109.2N7—C10—N8118.6 (3)
N1—C5—H5B109.2N7—C10—N9127.3 (3)
H5A—C5—H5B107.9N8—C10—N9114.1 (3)
C3—N4—N5—O2175.8 (4)C10—N9—N10—O35.9 (6)
C3—N4—N5—O1−4.1 (6)C10—N9—N10—O4−175.7 (3)
C2—N1—C3—N2179.7 (4)C9—N6—C8—N850.4 (4)
C5—N1—C3—N25.2 (6)C6—N6—C8—N8−70.5 (5)
C2—N1—C3—N4−1.2 (6)C10—N8—C8—N6−21.6 (5)
C5—N1—C3—N4−175.7 (4)C7—N8—C8—N6156.9 (4)
C4—N2—C3—N1−4.1 (6)C10—N7—C9—N633.9 (5)
C4—N2—C3—N4176.9 (4)C8—N6—C9—N7−56.1 (4)
N5—N4—C3—N1−179.0 (3)C6—N6—C9—N764.7 (5)
N5—N4—C3—N20.0 (6)C9—N7—C10—N8−1.5 (5)
C5—N3—C4—N255.1 (5)C9—N7—C10—N9179.4 (4)
C1—N3—C4—N2−70.1 (4)C8—N8—C10—N7−5.1 (5)
C3—N2—C4—N3−27.1 (5)C7—N8—C10—N7176.4 (4)
C4—N3—C5—N1−54.2 (5)C8—N8—C10—N9174.1 (3)
C1—N3—C5—N169.8 (5)C7—N8—C10—N9−4.3 (5)
C3—N1—C5—N325.4 (6)N10—N9—C10—N70.9 (6)
C2—N1—C5—N3−149.4 (4)N10—N9—C10—N8−178.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.942.549 (5)126
N7—H7A···O30.861.992.583 (5)126
N7—H7A···N3i0.862.573.210 (5)132
C1—H1C···O3ii0.962.543.309 (6)137
C2—H2B···N40.962.242.699 (6)108
C4—H4B···O4iii0.972.503.411 (6)156
C4—H4C···O3ii0.972.493.251 (6)136
C7—H7B···N90.962.212.670 (5)108
C7—H7B···O4iv0.962.593.317 (6)133
C8—H8B···O3iii0.972.563.420 (5)148
C9—H9C···O1v0.972.593.359 (6)137

Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z+1; (iii) x, y, z+1; (iv) −x+1, −y, −z+1; (v) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2491).

References

  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shiokawa, K., Tsuboi, S., Moriya, K., Hattori, Y., Honda, I. & Shibuya, K. (1991). PCT Int. Appl. US 5032589.
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Wakita, T., Kinoshita, K., Yamada, E., Yasui, N., Kawahara, N., Naoi, A., Nakaya, M., Ebihara, K., Matsuno, H. & Kodaka, K. (2003). Pest Manag. Sci.59, 1016–1022. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography