Redetermination of cyclo-trimethyl-ene-trinitramine.

The redetermined structure of 1,3,5-trinitro-1,3,5-triaza-cyclo-hexane, C(3)H(6)N(6)O(6), at 90 (2) K has ortho-rhom-bic (Pbca) symmetry. It is of inter-est with respect to energetic compounds. The structure was originally investigated through X-ray diffraction by Hultgren [(1936). J. Chem. Phys.4, 84]. Later X-ray investigations were completed by McCrone [(1950). Anal. Chem.22, 954-955] and Harris, Reed & Gluyas [(1959). AFOSR-TR-59-165 Ohio State University Research Foundation, Columbus, Ohio, USA]. A single-crystal neutron diffraction study was performed by Choi & Prince [(1972). Acta Cryst. B28, 2857-2862] to ascertain the H-atom positions, which had not been defined by the earlier X-ray diffraction studies. All previous studies were performed at or near room temperature. The structure provided is the α polymorph of the title compound. The ring atoms are arranged in the chair conformation with two nitro groups occupying pseudo-equatorial positions and the remaining nitro group is axial. The crystal packing is stabilized by close intramolecular interactions from one H atom in each methylene group to O atoms of adjacent nitro groups, ranging from 2.251 to 2.593 Å.

Related literature

For related literature, see: Akhavan (2004 ▶); Bachmann & Sheehan (1949 ▶); Brockman et al. (1949 ▶); Choi & Prince (1972 ▶); Ciezak et al. (2007 ▶); Davidson et al. (2008 ▶); Harris et al. (1959 ▶); Henning (1899 ▶); von Herz et al. (1920 ▶); Hultgren (1936 ▶); McCrone (1950 ▶); Yi & Cai (2008 ▶).

Experimental

Crystal data

C3H6N6O6

M = 222.14

Orthorhombic,

a = 11.4195 (8) Å

b = 10.5861 (7) Å

c = 13.1401 (9) Å

V = 1588.48 (19) Å3

Z = 8

Mo Kα radiation

μ = 0.18 mm−1

T = 90 (2) K

0.34 × 0.20 × 0.20 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶)T min = 0.943, T max = 0.966

15555 measured reflections

1973 independent reflections

1783 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.082

S = 1.05

1973 reflections

160 parameters

All H-atom parameters refined

Δρmax = 0.34 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019727/lh2649sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019727/lh2649Isup2.hkl

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

C3H6N6O6	F000 = 912
Mr = 222.14	Dx = 1.858 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P2ac2ab	Cell parameters from 4268 reflections
a = 11.4195 (8) Å	θ = 3.1–28.2º
b = 10.5861 (7) Å	µ = 0.18 mm−1
c = 13.1401 (9) Å	T = 90 (2) K
V = 1588.48 (19) Å3	Block, colorless
Z = 8	0.34 × 0.20 × 0.20 mm

Bruker APEX CCD area-detector diffractometer	1973 independent reflections
Monochromator: graphite	1783 reflections with I > 2σ(I)
Detector resolution: 512 pixels mm-1	Rint = 0.028
T = 90(2) K	θmax = 28.3º
φ and ω scans	θmin = 3.1º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −15→15
Tmin = 0.943, Tmax = 0.966	k = −14→14
15555 measured reflections	l = −17→17

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)] = 0.032	All H-atom parameters refined
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0397P)2 + 0.7623P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
1973 reflections	Δρmax = 0.34 e Å−3
160 parameters	Δρmin = −0.19 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
O1	0.96483 (8)	0.36616 (9)	1.02694 (7)	0.0224 (2)
O2	0.85097 (8)	0.24565 (9)	1.11679 (6)	0.0206 (2)
O3	0.81846 (8)	−0.03257 (8)	1.07225 (7)	0.0208 (2)
O4	0.93294 (8)	−0.10398 (8)	0.95344 (7)	0.0213 (2)
O5	1.06779 (7)	0.06532 (8)	0.73282 (6)	0.01755 (19)
O6	1.09321 (8)	0.26371 (8)	0.77072 (7)	0.0205 (2)
N1	0.81806 (8)	0.26489 (9)	0.94911 (7)	0.0121 (2)
N2	0.79657 (8)	0.04040 (9)	0.91362 (7)	0.0127 (2)
N3	0.93467 (8)	0.16430 (9)	0.82559 (7)	0.0134 (2)
N4	0.88448 (9)	0.29180 (9)	1.03687 (7)	0.0144 (2)
N5	0.85527 (9)	−0.03513 (9)	0.98530 (8)	0.0151 (2)
N6	1.03699 (9)	0.16474 (10)	0.77253 (7)	0.0138 (2)
C1	0.74033 (10)	0.15500 (11)	0.95281 (8)	0.0126 (2)
C2	0.87808 (10)	0.28363 (10)	0.85261 (9)	0.0135 (2)
C3	0.85587 (10)	0.05633 (11)	0.81621 (9)	0.0140 (2)
H1A	0.6771 (13)	0.1709 (13)	0.9097 (11)	0.012 (3)*
H1B	0.7145 (13)	0.1409 (13)	1.0185 (11)	0.012 (3)*
H2A	0.8192 (12)	0.3030 (13)	0.8023 (11)	0.010 (3)*
H2B	0.9329 (13)	0.3488 (14)	0.8585 (11)	0.016 (4)*
H3A	0.7972 (13)	0.0760 (14)	0.7669 (12)	0.020 (4)*
H3B	0.8988 (13)	−0.0155 (14)	0.8005 (11)	0.014 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0196 (4)	0.0205 (5)	0.0271 (5)	−0.0051 (4)	−0.0064 (4)	−0.0029 (4)
O2	0.0257 (5)	0.0252 (5)	0.0110 (4)	0.0027 (4)	−0.0017 (3)	−0.0004 (3)
O3	0.0261 (5)	0.0210 (4)	0.0152 (4)	−0.0046 (4)	−0.0036 (4)	0.0046 (3)
O4	0.0172 (4)	0.0146 (4)	0.0320 (5)	0.0030 (3)	−0.0054 (4)	−0.0011 (4)
O5	0.0170 (4)	0.0202 (4)	0.0154 (4)	0.0052 (3)	0.0031 (3)	−0.0015 (3)
O6	0.0166 (4)	0.0196 (4)	0.0255 (5)	−0.0036 (3)	0.0044 (4)	0.0044 (3)
N1	0.0128 (4)	0.0137 (4)	0.0099 (4)	0.0002 (4)	−0.0010 (3)	−0.0014 (3)
N2	0.0120 (4)	0.0129 (4)	0.0133 (5)	0.0004 (3)	−0.0002 (3)	0.0017 (3)
N3	0.0128 (5)	0.0122 (4)	0.0152 (4)	0.0001 (3)	0.0041 (4)	−0.0003 (4)
N4	0.0148 (5)	0.0140 (5)	0.0143 (5)	0.0040 (4)	−0.0031 (4)	−0.0030 (4)
N5	0.0140 (5)	0.0116 (4)	0.0197 (5)	−0.0033 (4)	−0.0050 (4)	0.0019 (4)
N6	0.0125 (4)	0.0181 (5)	0.0109 (4)	0.0011 (4)	0.0003 (3)	0.0033 (4)
C1	0.0101 (5)	0.0152 (5)	0.0126 (5)	0.0005 (4)	0.0010 (4)	−0.0002 (4)
C2	0.0158 (5)	0.0114 (5)	0.0132 (5)	0.0018 (4)	0.0022 (4)	0.0008 (4)
C3	0.0151 (5)	0.0131 (5)	0.0139 (5)	−0.0010 (4)	0.0021 (4)	−0.0019 (4)

O1—N4	1.2159 (13)	N2—C1	1.4660 (14)
O2—N4	1.2199 (13)	N3—N6	1.3606 (13)
O3—N5	1.2177 (14)	N3—C3	1.4600 (14)
O4—N5	1.2219 (14)	N3—C2	1.4626 (14)
O5—N6	1.2263 (13)	C1—H1A	0.934 (15)
O6—N6	1.2290 (13)	C1—H1B	0.925 (14)
N1—N4	1.4093 (13)	C2—H2A	0.964 (15)
N1—C2	1.4551 (14)	C2—H2B	0.934 (15)
N1—C1	1.4641 (14)	C3—H3A	0.956 (16)
N2—N5	1.4056 (13)	C3—H3B	0.928 (15)
N2—C3	1.4579 (14)
N4—N1—C2	115.59 (9)	N1—C1—N2	112.35 (9)
N4—N1—C1	117.37 (9)	N1—C1—H1A	107.8 (9)
C2—N1—C1	115.01 (9)	N2—C1—H1A	105.9 (9)
N5—N2—C3	115.63 (9)	N1—C1—H1B	110.7 (9)
N5—N2—C1	116.38 (9)	N2—C1—H1B	109.5 (9)
C3—N2—C1	114.59 (9)	H1A—C1—H1B	110.4 (13)
N6—N3—C3	119.26 (9)	N1—C2—N3	107.57 (9)
N6—N3—C2	120.05 (9)	N1—C2—H2A	107.3 (8)
C3—N3—C2	115.10 (9)	N3—C2—H2A	109.0 (8)
O1—N4—O2	126.04 (10)	N1—C2—H2B	110.1 (9)
O1—N4—N1	116.69 (10)	N3—C2—H2B	111.2 (9)
O2—N4—N1	117.04 (10)	H2A—C2—H2B	111.5 (12)
O3—N5—O4	125.82 (10)	N2—C3—N3	107.62 (9)
O3—N5—N2	116.84 (10)	N2—C3—H3A	107.2 (9)
O4—N5—N2	117.12 (10)	N3—C3—H3A	108.6 (9)
O5—N6—O6	125.00 (10)	N2—C3—H3B	110.2 (9)
O5—N6—N3	117.48 (10)	N3—C3—H3B	109.5 (9)
O6—N6—N3	117.48 (10)	H3A—C3—H3B	113.5 (13)
C2—N1—N4—O1	24.84 (13)	N4—N1—C1—N2	−93.07 (11)
C1—N1—N4—O1	165.72 (10)	C2—N1—C1—N2	48.04 (12)
C2—N1—N4—O2	−160.30 (10)	N5—N2—C1—N1	91.11 (11)
C1—N1—N4—O2	−19.42 (14)	C3—N2—C1—N1	−48.17 (12)
C3—N2—N5—O3	167.78 (10)	N4—N1—C2—N3	90.33 (11)
C1—N2—N5—O3	28.92 (13)	C1—N1—C2—N3	−51.49 (12)
C3—N2—N5—O4	−17.30 (14)	N6—N3—C2—N1	−148.08 (10)
C1—N2—N5—O4	−156.16 (10)	C3—N3—C2—N1	58.46 (12)
C3—N3—N6—O5	−12.18 (14)	N5—N2—C3—N3	−87.58 (11)
C2—N3—N6—O5	−164.56 (10)	C1—N2—C3—N3	52.01 (12)
C3—N3—N6—O6	170.00 (10)	N6—N3—C3—N2	147.49 (9)
C2—N3—N6—O6	17.63 (15)	C2—N3—C3—N2	−58.82 (12)