Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The conformation and density were determined for the title compound, C7H10N6O8. As expected, the bicyclic nine-membered ring has two chair-shaped aza­cyclo­hexane rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017780/om6062sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017780/om6062Isup2.hkl
Contains datablock I

CCDC reference: 176036

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • Disorder in main residue
  • R factor = 0.056
  • wR factor = 0.147
  • Data-to-parameter ratio = 12.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.05 From the CIF: _reflns_number_total 2971 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3195 Completeness (_total/calc) 92.99% Alert C: < 95% complete PLAT_301 Alert C Main Residue Disorder ........................ 8.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

A key thrust of much current research in energetic materials is the development of higher performance materials to defeat increasingly hardened targets. Important goals are new crystalline explosive fillers with energy density exceeding HMX (1,3,5,7-tetranitro-1,3,5,7- tetrazacyclooctane), as well as new nitramines capable of replacing ammonium perchlorate as the mainstay of many present missile propellants. The title compound, (I), is a variant similar to HMX in that it contains four nitro groups, but only two are nitramines (four in HMX) and the other two are C-nitro groupings that are considered less sensitive than nitramines. However the density is 10% less than HMX (Cady et al., 1963), which lowers its efficacy as an energetic material. Although there could be a vertical twofold axis passing through C9, and this is roughly so for the ring system (two chair-shaped azacyclohexane rings), there is no crystallographic symmetry, and corresponding nitro groups, especially those on N3 and N7, deviate from each other in their orientation (Fig. 2).

Experimental top

The nitrolysis of 3,7-Di-tert-butyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane (Authors? Reference no? Acta E, submitted) was carried out in 100% nitric acid to afford the title compound in 52% yield.

Refinement top

One of the nitro groups, on N1, is disordered over three sites with occupancies of 0.54, 0.24 and 0.22; the other three nitro groups are well ordered.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of 3,7-Di-tert-butyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane with 30% probability ellipsoids.
[Figure 2] Fig. 2. The molecule "fitted" to itself by performing a twofold around C9 showing the slight differences in orientation of the nitro groups and the disordered nitro group on N1.
(I) top
Crystal data top
C7H10N6O8F(000) = 632
Mr = 306.21Dx = 1.704 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.5750 (8) ÅCell parameters from 5710 reflections
b = 7.9570 (4) Åθ = 4.6–56.6°
c = 11.0684 (6) ŵ = 0.16 mm1
β = 93.436 (1)°T = 293 K
V = 1193.42 (11) Å3Prism, colorless
Z = 40.66 × 0.66 × 0.23 mm
Data collection top
CCD area-detector
diffractometer
2971 independent reflections
Radiation source: normal-focus sealed tube2466 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 0.73 pixels mm-1θmax = 29.1°, θmin = 3.0°
phi and ω scansh = 1817
Absorption correction: multi-scan
(Sheldrick, 2001)
k = 410
Tmin = 0.89, Tmax = 0.96l = 1413
8750 measured reflections
Refinement top
Refinement on F2Secondary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: calc
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.147 w = 1/[σ2(Fo2) + (0.067P)2 + 0.5997P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.003
2971 reflectionsΔρmax = 0.39 e Å3
230 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.035 (4)
Crystal data top
C7H10N6O8V = 1193.42 (11) Å3
Mr = 306.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.5750 (8) ŵ = 0.16 mm1
b = 7.9570 (4) ÅT = 293 K
c = 11.0684 (6) Å0.66 × 0.66 × 0.23 mm
β = 93.436 (1)°
Data collection top
CCD area-detector
diffractometer
2971 independent reflections
Absorption correction: multi-scan
(Sheldrick, 2001)
2466 reflections with I > 2σ(I)
Tmin = 0.89, Tmax = 0.96Rint = 0.031
8750 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.10Δρmax = 0.39 e Å3
2971 reflectionsΔρmin = 0.23 e Å3
230 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.

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
xyzUiso*/UeqOcc. (<1)
C10.33494 (12)0.0635 (2)0.83763 (16)0.0257 (4)
N10.43303 (12)0.1355 (2)0.80170 (18)0.0421 (5)
O1A0.4365 (5)0.198 (3)0.7016 (11)0.057 (3)0.54 (3)
O1B0.5017 (6)0.123 (2)0.8737 (9)0.044 (2)0.54 (3)
O1A10.4300 (11)0.267 (3)0.743 (2)0.057 (4)0.24 (2)
O1B10.5100 (14)0.072 (3)0.844 (2)0.054 (4)0.24 (2)
O1A20.4478 (17)0.125 (4)0.6898 (19)0.066 (5)0.22 (2)
O1B20.4910 (17)0.189 (4)0.8863 (18)0.061 (5)0.22 (2)
C20.35097 (13)0.1261 (2)0.8510 (2)0.0317 (4)
H2A0.40110.14930.91490.038*
H2B0.37220.17340.77610.038*
N30.25659 (11)0.19864 (17)0.88066 (15)0.0292 (4)
N3A0.26203 (14)0.3584 (2)0.92798 (19)0.0422 (5)
O3A0.34280 (14)0.4095 (2)0.9653 (2)0.0679 (6)
O3B0.18524 (14)0.4362 (2)0.9338 (2)0.0640 (6)
C40.16666 (14)0.1608 (2)0.80566 (19)0.0308 (4)
H4A0.16810.21860.72860.037*
H4B0.10920.19920.84590.037*
C50.16023 (12)0.0292 (2)0.78487 (16)0.0245 (4)
N50.07644 (12)0.0604 (2)0.68953 (15)0.0350 (4)
O5A0.01917 (15)0.0519 (3)0.6662 (2)0.0820 (8)
O5B0.07125 (12)0.1982 (2)0.64403 (16)0.0525 (5)
C60.13347 (14)0.1297 (2)0.89680 (17)0.0286 (4)
H6A0.07250.08720.92650.034*
H6B0.12400.24710.87560.034*
N70.21284 (12)0.11332 (19)0.99003 (14)0.0293 (4)
N7A0.20085 (13)0.0021 (2)1.08030 (15)0.0342 (4)
O7A0.27214 (13)0.0302 (2)1.15008 (15)0.0523 (5)
O7B0.11930 (12)0.0642 (2)1.08749 (16)0.0487 (4)
C80.31272 (14)0.1515 (2)0.95676 (18)0.0311 (4)
H8A0.31990.27210.94750.037*
H8B0.35970.11471.02070.037*
C90.25533 (13)0.0999 (2)0.73855 (17)0.0283 (4)
H9A0.24930.21980.72440.034*
H9B0.27070.04540.66350.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0207 (8)0.0248 (8)0.0317 (9)0.0025 (6)0.0013 (7)0.0052 (7)
N10.0259 (8)0.0501 (11)0.0499 (11)0.0082 (8)0.0007 (8)0.0149 (9)
O1A0.037 (3)0.079 (7)0.055 (5)0.015 (4)0.007 (3)0.031 (5)
O1B0.024 (3)0.055 (6)0.051 (4)0.007 (4)0.005 (2)0.001 (4)
O1A10.045 (4)0.050 (7)0.075 (8)0.009 (4)0.010 (5)0.028 (6)
O1B10.030 (4)0.053 (8)0.078 (9)0.000 (5)0.001 (6)0.013 (6)
O1A20.058 (7)0.080 (10)0.064 (6)0.020 (7)0.026 (5)0.004 (7)
O1B20.043 (6)0.068 (9)0.074 (7)0.028 (7)0.005 (5)0.021 (7)
C20.0244 (9)0.0254 (9)0.0454 (11)0.0036 (7)0.0022 (8)0.0003 (8)
N30.0297 (8)0.0160 (7)0.0418 (9)0.0013 (6)0.0004 (7)0.0014 (6)
N3A0.0492 (11)0.0204 (8)0.0563 (12)0.0017 (7)0.0013 (9)0.0063 (7)
O3A0.0560 (11)0.0368 (9)0.1086 (17)0.0091 (8)0.0136 (11)0.0282 (10)
O3B0.0574 (11)0.0333 (8)0.1005 (16)0.0143 (8)0.0010 (10)0.0207 (9)
C40.0293 (9)0.0224 (8)0.0399 (10)0.0021 (7)0.0042 (8)0.0039 (7)
C50.0228 (8)0.0242 (8)0.0261 (8)0.0003 (6)0.0010 (6)0.0027 (6)
N50.0272 (8)0.0439 (10)0.0334 (9)0.0003 (7)0.0030 (7)0.0062 (7)
O5A0.0585 (12)0.0721 (14)0.1088 (18)0.0288 (10)0.0498 (12)0.0272 (12)
O5B0.0435 (9)0.0549 (10)0.0573 (10)0.0030 (8)0.0114 (7)0.0250 (8)
C60.0292 (9)0.0243 (8)0.0327 (9)0.0078 (7)0.0043 (7)0.0016 (7)
N70.0354 (8)0.0250 (7)0.0276 (8)0.0018 (6)0.0036 (6)0.0010 (6)
N7A0.0437 (10)0.0291 (8)0.0300 (8)0.0013 (7)0.0027 (7)0.0022 (7)
O7A0.0536 (10)0.0583 (10)0.0433 (9)0.0052 (8)0.0110 (7)0.0166 (8)
O7B0.0435 (9)0.0521 (10)0.0511 (10)0.0068 (7)0.0062 (7)0.0174 (7)
C80.0336 (10)0.0238 (8)0.0354 (10)0.0072 (7)0.0021 (8)0.0018 (7)
C90.0260 (9)0.0317 (9)0.0273 (9)0.0014 (7)0.0018 (7)0.0066 (7)
Geometric parameters (Å, º) top
C1—C91.521 (2)N3A—O3B1.217 (2)
C1—N11.524 (2)N3A—O3A1.218 (3)
C1—C21.530 (2)C4—C51.531 (2)
C1—C81.539 (3)C5—C91.525 (2)
N1—O1B1.194 (7)C5—N51.525 (2)
N1—O1A1.217 (7)C5—C61.536 (2)
N1—O1B11.226 (19)N5—O5A1.203 (2)
N1—O1A11.236 (12)N5—O5B1.207 (2)
N1—O1B21.262 (18)C6—N71.452 (2)
N1—O1A21.27 (2)N7—N7A1.374 (2)
C2—N31.460 (2)N7—C81.458 (2)
N3—N3A1.375 (2)N7A—O7B1.219 (2)
N3—C41.466 (2)N7A—O7A1.222 (2)
C9—C1—N1109.55 (14)O3A—N3A—N3117.67 (18)
C9—C1—C2110.37 (15)N3—C4—C5109.04 (14)
N1—C1—C2105.94 (15)C9—C5—N5108.58 (14)
C9—C1—C8111.35 (15)C9—C5—C4111.89 (15)
N1—C1—C8105.76 (15)N5—C5—C4107.37 (14)
C2—C1—C8113.58 (16)C9—C5—C6108.98 (15)
O1B—N1—O1A124.7 (5)N5—C5—C6105.70 (14)
O1B1—N1—O1A1123.4 (11)C4—C5—C6114.00 (15)
O1B2—N1—O1A2128.2 (13)O5A—N5—O5B124.40 (18)
O1B—N1—C1117.0 (4)O5A—N5—C5118.24 (17)
O1A—N1—C1118.2 (3)O5B—N5—C5117.35 (16)
O1B1—N1—C1119.0 (9)N7—C6—C5108.98 (14)
O1A1—N1—C1117.1 (7)N7A—N7—C6117.47 (15)
O1B2—N1—C1116.7 (9)N7A—N7—C8118.39 (15)
O1A2—N1—C1114.9 (9)C6—N7—C8117.60 (15)
N3—C2—C1106.85 (14)O7B—N7A—O7A124.92 (17)
N3A—N3—C2115.03 (15)O7B—N7A—N7117.77 (16)
N3A—N3—C4115.44 (15)O7A—N7A—N7117.26 (17)
C2—N3—C4120.23 (16)N7—C8—C1110.76 (14)
O3B—N3A—O3A124.65 (18)C1—C9—C5105.48 (14)
O3B—N3A—N3117.62 (18)

Experimental details

Crystal data
Chemical formulaC7H10N6O8
Mr306.21
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.5750 (8), 7.9570 (4), 11.0684 (6)
β (°) 93.436 (1)
V3)1193.42 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.66 × 0.66 × 0.23
Data collection
DiffractometerCCD area-detector
diffractometer
Absorption correctionMulti-scan
(Sheldrick, 2001)
Tmin, Tmax0.89, 0.96
No. of measured, independent and
observed [I > 2σ(I)] reflections
8750, 2971, 2466
Rint0.031
(sin θ/λ)max1)0.683
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.147, 1.10
No. of reflections2971
No. of parameters230
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.23

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXTL (Sheldrick, 1997), SHELXTL.

 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds