(3,5-Dinitro-1,3,5-triazinan-1-yl)methanone

Zhang, Q.-L.; Qu, X.-F.; Wang, J.-L.

doi:10.1107/S1600536809041531

organic compounds

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Volume 65| Part 11| November 2009| Page o2749

https://doi.org/10.1107/S1600536809041531

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(3,5-Dinitro-1,3,5-triazinan-1-yl)methanone

Qiao-Ling Zhang,^a Xiao-Feng Qu ^a and Jian-Long Wang ^a ^*

^aSchool of Chemical Engineering and Environment, North University of China, Taiyuan, People's Republic of China
^*Correspondence e-mail: wangjianlong@nuc.edu.cn

(Received 2 October 2009; accepted 12 October 2009; online 17 October 2009)

In the title compound, C₅H₉N₅O₅, prepared from hexamine by acetylation and nitration, the triazine ring adopts a chair conformation with all three substituent groups lying on the same side of the ring.

Related literature

For the Bachmann process, see: Bachmann & Sheehan (1949 ). For the synthesis, see: Warman et al. (1973 ). For a related structure, see: Choi et al. (1975 ).

Experimental

Crystal data

C₅H₉N₅O₅
M_r = 219.17
Monoclinic, P 2₁ /n
a = 8.8972 (18) Å
b = 10.061 (2) Å
c = 9.890 (2) Å
β = 100.42 (3)°
V = 870.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.50 × 0.50 × 0.40 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.929, T_max = 0.943
3599 measured reflections
1988 independent reflections
1419 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.142
S = 1.03
1988 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2000 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2000 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809041531/zs2012sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041531/zs2012Isup2.hkl

checkCIF report

Comment top

1-Acetyl-3,5-dinitro-1,3,5-triazinane (1-acetylhexahydro-3,5-dinitro-1,3,5-triazine) (I) is obtained as a by-product in the synthesis of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from 1,3,5,7 -tetraazaadamantane (hexamine) by the Bachmann process (Bachmann & Sheehan, 1949). As part of our search for the reaction mechanism involved in the nitrolysis of hexamine, we synthesized the title compound, and describe its structure here.

In (I), the hexahydrotriazine ring adopts a chair conformation with all three substituent groups lying on the same side of the triazine ring.The ring bond distances and angles are almost identical (the maximum deviation from the average C—N bond distance [1.44 (8) Å] is 0.01Å and the maximum deviation from the average bond angle [112 (3)°] is 3°). The three ring N atoms are equally distant from the plane through the C atoms (C1, C2 and C3) (0.40±0.06 (2) Å). This deviation is slightly larger than that found in hexahydro-1,3,5-triacetyl-1,3,5-triazine (TRAT) (Choi et al., 1975), due to the three different substituent groups on the hexahydrotriazine ring in (I), whereas in TRAT, the three groups are the same. In (I) the three substituent groups are essentially planar with maximum deviations from the mean plane of these groups for atoms N1, N2 and N3 of 0.02 (4), 0.09 (6) and 0.10 (3) Å respectively.

Related literature top

For the Bachmann process, see: Bachmann & Sheehan (1949). For the synthesis, see: Warman et al. (1973). For a related structure, see: Choi et al. (1975).

Experimental top

The title compound was prepared from hexamine according to a literature method (Warman et al., 1973). Crystals suitable for X-ray analysis were obtained by slow evaporation of an nitromethane solution at room temperature.

Structure description top

For the Bachmann process, see: Bachmann & Sheehan (1949). For the synthesis, see: Warman et al. (1973). For a related structure, see: Choi et al. (1975).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2000); cell refinement: RAPID-AUTO (Rigaku, 2000); data reduction: CrystalStructure (Rigaku/MSC, 2000); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure and atom numbering scheme for the title compound (I). Non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 2. The packing of the title compound, viewed down the c axis of the unit cell.

(3,5-Dinitro-1,3,5-triazinan-1-yl)methanone top

Crystal data top

C₅H₉N₅O₅	F(000) = 456
M_r = 219.17	D_x = 1.672 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 431(2) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.8972 (18) Å	Cell parameters from 3599 reflections
b = 10.061 (2) Å	θ = 2.8–27.5°
c = 9.890 (2) Å	µ = 0.15 mm⁻¹
β = 100.42 (3)°	T = 293 K
V = 870.7 (3) Å³	Block, colorless
Z = 4	0.50 × 0.50 × 0.40 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1988 independent reflections
Radiation source: fine-focus sealed tube	1419 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
T_min = 0.929, T_max = 0.943	l = −12→12
3599 measured reflections

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.09P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
1988 reflections	Δρ_max = 0.28 e Å⁻³
138 parameters	Δρ_min = −0.26 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: 0.242 (16)

Crystal data top

C₅H₉N₅O₅	V = 870.7 (3) Å³
M_r = 219.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8972 (18) Å	µ = 0.15 mm⁻¹
b = 10.061 (2) Å	T = 293 K
c = 9.890 (2) Å	0.50 × 0.50 × 0.40 mm
β = 100.42 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1988 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1419 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.943	R_int = 0.028
3599 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
1988 reflections	Δρ_min = −0.26 e Å⁻³
138 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.47469 (19)	0.41301 (16)	0.32195 (16)	0.0389 (4)
H1A	0.5005	0.3837	0.4168	0.047*
H1B	0.4000	0.4839	0.3170	0.047*
C2	0.72467 (19)	0.35894 (19)	0.26987 (18)	0.0456 (4)
H2A	0.8044	0.3941	0.2248	0.055*
H2B	0.7713	0.3329	0.3624	0.055*
C3	0.51659 (19)	0.19589 (16)	0.23350 (19)	0.0429 (4)
H3A	0.4708	0.1292	0.1680	0.052*
H3B	0.5392	0.1547	0.3236	0.052*
C4	0.26587 (18)	0.29469 (17)	0.16314 (15)	0.0385 (4)
C5	0.1604 (2)	0.4079 (2)	0.1715 (2)	0.0531 (5)
H5A	0.0627	0.3892	0.1158	0.080*
H5B	0.2020	0.4873	0.1390	0.080*
H5C	0.1485	0.4201	0.2653	0.080*
N1	0.41055 (15)	0.30361 (13)	0.23592 (13)	0.0357 (3)
N2	0.61111 (16)	0.46206 (14)	0.27642 (13)	0.0405 (4)
N3	0.65682 (16)	0.24375 (17)	0.19558 (16)	0.0491 (4)
N4	0.5835 (2)	0.54679 (16)	0.16262 (16)	0.0550 (5)
N5	0.69287 (18)	0.21008 (15)	0.07159 (15)	0.0468 (4)
O1	0.6820 (2)	0.55437 (17)	0.09159 (16)	0.0839 (6)
O2	0.22571 (14)	0.19538 (13)	0.09572 (13)	0.0525 (4)
O3	0.6163 (2)	0.12455 (17)	0.00671 (15)	0.0723 (5)
O4	0.80447 (17)	0.26203 (18)	0.03929 (15)	0.0685 (5)
O5	0.4676 (2)	0.61206 (16)	0.14783 (19)	0.0819 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0417 (9)	0.0443 (9)	0.0292 (7)	−0.0021 (7)	0.0023 (6)	−0.0039 (6)
C2	0.0363 (9)	0.0593 (11)	0.0390 (9)	−0.0075 (8)	0.0013 (7)	−0.0027 (8)
C3	0.0415 (9)	0.0399 (9)	0.0479 (9)	−0.0033 (7)	0.0094 (7)	0.0018 (7)
C4	0.0371 (8)	0.0507 (9)	0.0274 (7)	−0.0073 (7)	0.0055 (6)	0.0032 (7)
C5	0.0363 (9)	0.0751 (13)	0.0465 (10)	0.0059 (9)	0.0041 (7)	0.0011 (9)
N1	0.0341 (7)	0.0390 (7)	0.0327 (7)	−0.0025 (5)	0.0024 (5)	−0.0012 (5)
N2	0.0441 (8)	0.0439 (8)	0.0297 (7)	−0.0106 (6)	−0.0034 (6)	0.0009 (6)
N3	0.0420 (8)	0.0595 (9)	0.0480 (9)	−0.0067 (7)	0.0141 (6)	−0.0122 (7)
N4	0.0761 (11)	0.0453 (9)	0.0368 (8)	−0.0260 (8)	−0.0076 (8)	0.0032 (7)
N5	0.0487 (9)	0.0542 (9)	0.0368 (8)	0.0130 (7)	0.0059 (7)	0.0037 (7)
O1	0.1182 (14)	0.0832 (12)	0.0533 (9)	−0.0413 (11)	0.0236 (10)	0.0118 (8)
O2	0.0479 (7)	0.0615 (8)	0.0450 (7)	−0.0159 (6)	0.0006 (6)	−0.0099 (6)
O3	0.1003 (13)	0.0668 (9)	0.0496 (8)	−0.0102 (9)	0.0129 (8)	−0.0185 (7)
O4	0.0577 (9)	0.0945 (11)	0.0598 (9)	0.0010 (9)	0.0281 (7)	−0.0005 (8)
O5	0.0946 (13)	0.0625 (10)	0.0768 (12)	0.0044 (9)	−0.0163 (9)	0.0260 (9)

Geometric parameters (Å, º) top

C1—N1	1.4440 (19)	C4—O2	1.2184 (19)
C1—N2	1.455 (2)	C4—N1	1.359 (2)
C1—H1A	0.9700	C4—C5	1.487 (2)
C1—H1B	0.9700	C5—H5A	0.9600
C2—N3	1.445 (2)	C5—H5B	0.9600
C2—N2	1.458 (2)	C5—H5C	0.9600
C2—H2A	0.9700	N2—N4	1.398 (2)
C2—H2B	0.9700	N3—N5	1.365 (2)
C3—N1	1.440 (2)	N4—O5	1.209 (2)
C3—N3	1.449 (2)	N4—O1	1.220 (2)
C3—H3A	0.9700	N5—O3	1.208 (2)
C3—H3B	0.9700	N5—O4	1.215 (2)

N1—C1—N2	109.82 (13)	C4—C5—H5A	109.5
N1—C1—H1A	109.7	C4—C5—H5B	109.5
N2—C1—H1A	109.7	H5A—C5—H5B	109.5
N1—C1—H1B	109.7	C4—C5—H5C	109.5
N2—C1—H1B	109.7	H5A—C5—H5C	109.5
H1A—C1—H1B	108.2	H5B—C5—H5C	109.5
N3—C2—N2	111.37 (13)	C4—N1—C3	120.14 (13)
N3—C2—H2A	109.4	C4—N1—C1	126.71 (14)
N2—C2—H2A	109.4	C3—N1—C1	113.15 (13)
N3—C2—H2B	109.4	N4—N2—C1	114.91 (14)
N2—C2—H2B	109.4	N4—N2—C2	114.86 (15)
H2A—C2—H2B	108.0	C1—N2—C2	113.33 (13)
N1—C3—N3	110.59 (14)	N5—N3—C2	120.76 (15)
N1—C3—H3A	109.5	N5—N3—C3	120.23 (15)
N3—C3—H3A	109.5	C2—N3—C3	115.80 (14)
N1—C3—H3B	109.5	O5—N4—O1	125.60 (18)
N3—C3—H3B	109.5	O5—N4—N2	116.75 (17)
H3A—C3—H3B	108.1	O1—N4—N2	117.51 (19)
O2—C4—N1	119.99 (16)	O3—N5—O4	125.20 (17)
O2—C4—C5	122.20 (16)	O3—N5—N3	116.89 (16)
N1—C4—C5	117.81 (15)	O4—N5—N3	117.74 (16)

O2—C4—N1—C3	0.0 (2)	N2—C2—N3—N5	112.60 (17)
C5—C4—N1—C3	178.88 (14)	N2—C2—N3—C3	−47.2 (2)
O2—C4—N1—C1	−179.01 (15)	N1—C3—N3—N5	−110.68 (18)
C5—C4—N1—C1	−0.2 (2)	N1—C3—N3—C2	49.2 (2)
N3—C3—N1—C4	126.86 (15)	C1—N2—N4—O5	28.9 (2)
N3—C3—N1—C1	−53.98 (18)	C2—N2—N4—O5	163.00 (15)
N2—C1—N1—C4	−123.74 (16)	C1—N2—N4—O1	−155.26 (16)
N2—C1—N1—C3	57.17 (17)	C2—N2—N4—O1	−21.1 (2)
N1—C1—N2—N4	80.18 (16)	C2—N3—N5—O3	−169.79 (16)
N1—C1—N2—C2	−54.65 (17)	C3—N3—N5—O3	−10.9 (2)
N3—C2—N2—N4	−85.27 (16)	C2—N3—N5—O4	14.7 (2)
N3—C2—N2—C1	49.60 (18)	C3—N3—N5—O4	173.59 (16)

Experimental details

Crystal data
Chemical formula	C₅H₉N₅O₅
M_r	219.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.8972 (18), 10.061 (2), 9.890 (2)
β (°)	100.42 (3)
V (Å³)	870.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.50 × 0.50 × 0.40

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.929, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	3599, 1988, 1419
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.142, 1.03
No. of reflections	1988
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.26

Computer programs: RAPID-AUTO (Rigaku, 2000), CrystalStructure (Rigaku/MSC, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank China North Industries Group Corporation for financial support.

References

Bachmann, W. E. & Sheehan, J. C. (1949). J. Am. Chem. Soc. 71, 1482–1485. Google Scholar
Choi, C. S., Santoro, A. & Marinkas, P. L. (1975). Acta Cryst. B31, 2934–2937. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2000). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2000). CrystalStructure. Molecular Structure Corporation, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Warman, M., Siele, V. I. & Gilbert, E. E. (1973). J. Heterocycl. Chem. 10, 97–98. CAS Google Scholar