2,8-Dimethyl-1,9-dinitro-6H,12H-5,11-methano­dibenzo[b,f][1,5]diazo­cine

In the mol­ecule of the title compound, C₁₇H₁₆N₄O₄, the 2,8-dimethyl-1,9-dinitro analogue of Tröger's base, the diazo­cine bridge imparts a twist such that the two aryl rings are offset with respect to one another. The dihedral angle between the two benzene rings is 94.75 (4)°.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.036
• wR factor = 0.106
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact  O1'    ..  O1'     ..       2.31 Ang.

Author Response: This arises due to disorder of the nitro group. O1' has only 0.1 occupancy and therefore when the oxygen atom is in the O1' position the oxygen atom of the adjacent symmetry related nitro group will be in the O1 position which has 0.9 occupancy.

Alert level C
PLAT301_ALERT_3_C Main Residue  Disorder .........................      11.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C4     -   C6     ...       1.39 Ang.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C6     -   C7     ...       1.39 Ang.

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: ModiCIFer (Guzei, 2005).

2,8-Dimethyl-1,9-dinitro-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine

Crystal data

C17H16N4O4	Z = 2
Mr = 340.34	F(000) = 356
Triclinic, P1	Dx = 1.491 Mg m^−3
Hall symbol: -P 1	Melting point = 515–517 K
a = 7.526 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.057 (2) Å	Cell parameters from 6244 reflections
c = 13.932 (3) Å	θ = 2.8–28.2°
α = 92.944 (3)°	µ = 0.11 mm^−1
β = 92.930 (3)°	T = 150 K
γ = 115.649 (2)°	Plate, yellow
V = 758.0 (3) Å^3	0.53 × 0.48 × 0.18 mm

Data collection

Bruker SMART CCD-1000 area-detector diffractometer	3584 independent reflections
Radiation source: fine-focus sealed tube	3150 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.939, Tmax = 0.981	k = −10→10
10018 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 0.236P] where P = (Fo^2 + 2Fc^2)/3
3584 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.36 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	−0.01103 (15)	−0.1972 (2)	0.02878 (8)	0.0384 (3)	0.90
O1'	0.0147 (18)	−0.1124 (18)	0.0433 (9)	0.043 (3)*	0.10
O2	−0.01913 (15)	−0.19894 (18)	0.18330 (9)	0.0419 (3)	0.90
O2'	−0.0038 (16)	−0.2738 (15)	0.1587 (8)	0.037 (2)*	0.10
O3	0.06708 (13)	0.19032 (13)	0.56714 (7)	0.0345 (2)
O4	0.20369 (14)	0.03922 (14)	0.63945 (7)	0.0380 (2)
N1	0.70888 (13)	0.36496 (13)	0.21301 (7)	0.0240 (2)
N2	0.40949 (13)	0.36717 (12)	0.26833 (7)	0.0224 (2)
N3	0.0688 (2)	−0.1660 (6)	0.1102 (3)	0.0237 (3)	0.90
N3'	0.099 (2)	−0.154 (6)	0.109 (3)	0.0237 (3)	0.10
N4	0.20196 (14)	0.14444 (13)	0.57911 (7)	0.0252 (2)
C1	0.59338 (15)	0.17717 (15)	0.17533 (8)	0.0215 (2)
C2	0.69120 (16)	0.07322 (16)	0.14480 (8)	0.0249 (2)
H2	0.8316	0.1266	0.1523	0.030*
C3	0.58740 (17)	−0.10570 (16)	0.10391 (8)	0.0255 (2)
H3	0.6576	−0.1740	0.0849	0.031*
C4	0.38173 (16)	−0.18797 (15)	0.08993 (8)	0.0230 (2)
C5	0.26787 (18)	−0.38294 (16)	0.04515 (9)	0.0292 (3)
H5A	0.1697	−0.4558	0.0884	0.044*
H5B	0.3593	−0.4381	0.0346	0.044*
H5C	0.2006	−0.3817	−0.0167	0.044*
C6	0.28955 (15)	−0.08134 (15)	0.12190 (8)	0.0213 (2)
C7	0.38622 (15)	0.09758 (14)	0.16637 (7)	0.0203 (2)
C8	0.27549 (15)	0.20231 (15)	0.20629 (8)	0.0225 (2)
H8A	0.2143	0.2399	0.1522	0.027*
H8B	0.1684	0.1202	0.2439	0.027*
C9	0.58701 (17)	0.46544 (15)	0.21747 (8)	0.0258 (2)
H9A	0.5472	0.4819	0.1512	0.031*
H9B	0.6660	0.5895	0.2510	0.031*
C10	0.46148 (15)	0.32154 (14)	0.36063 (8)	0.0208 (2)
C11	0.31933 (15)	0.26169 (14)	0.42707 (8)	0.0218 (2)
H11	0.1909	0.2525	0.4114	0.026*
C12	0.36602 (15)	0.21547 (14)	0.51619 (8)	0.0218 (2)
C13	0.55474 (16)	0.23297 (14)	0.54602 (8)	0.0221 (2)
C14	0.61572 (17)	0.19382 (17)	0.64373 (8)	0.0279 (2)
H14A	0.7589	0.2334	0.6496	0.042*
H14B	0.5470	0.0610	0.6511	0.042*
H14C	0.5809	0.2616	0.6940	0.042*
C15	0.69320 (16)	0.29458 (15)	0.47751 (8)	0.0229 (2)
H15	0.8237	0.3102	0.4945	0.028*
C16	0.65032 (15)	0.33442 (14)	0.38539 (8)	0.0217 (2)
C17	0.80153 (16)	0.38085 (16)	0.31091 (8)	0.0252 (2)
H17A	0.9057	0.5084	0.3264	0.030*
H17B	0.8649	0.2959	0.3133	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0252 (5)	0.0526 (8)	0.0350 (6)	0.0170 (5)	−0.0092 (4)	−0.0066 (5)
O2	0.0241 (5)	0.0496 (7)	0.0394 (6)	0.0031 (5)	0.0118 (4)	0.0059 (5)
O3	0.0274 (4)	0.0457 (5)	0.0374 (5)	0.0216 (4)	0.0082 (4)	0.0054 (4)
O4	0.0343 (5)	0.0493 (6)	0.0346 (5)	0.0196 (4)	0.0105 (4)	0.0190 (4)
N1	0.0194 (4)	0.0243 (5)	0.0250 (5)	0.0062 (4)	0.0025 (3)	0.0038 (4)
N2	0.0219 (4)	0.0208 (4)	0.0244 (5)	0.0089 (4)	0.0021 (3)	0.0040 (3)
N3	0.0174 (7)	0.0210 (8)	0.0309 (5)	0.0068 (9)	0.0010 (8)	0.0019 (4)
N3'	0.0174 (7)	0.0210 (8)	0.0309 (5)	0.0068 (9)	0.0010 (8)	0.0019 (4)
N4	0.0226 (5)	0.0289 (5)	0.0239 (5)	0.0111 (4)	0.0031 (4)	0.0003 (4)
C1	0.0191 (5)	0.0245 (5)	0.0196 (5)	0.0080 (4)	0.0026 (4)	0.0045 (4)
C2	0.0189 (5)	0.0326 (6)	0.0241 (5)	0.0117 (4)	0.0033 (4)	0.0055 (4)
C3	0.0258 (5)	0.0314 (6)	0.0246 (5)	0.0171 (5)	0.0039 (4)	0.0046 (4)
C4	0.0256 (5)	0.0246 (5)	0.0205 (5)	0.0121 (4)	0.0022 (4)	0.0048 (4)
C5	0.0325 (6)	0.0252 (6)	0.0315 (6)	0.0142 (5)	0.0006 (5)	0.0014 (4)
C6	0.0187 (5)	0.0245 (5)	0.0202 (5)	0.0088 (4)	0.0012 (4)	0.0052 (4)
C7	0.0185 (5)	0.0236 (5)	0.0193 (5)	0.0093 (4)	0.0020 (4)	0.0045 (4)
C8	0.0185 (5)	0.0246 (5)	0.0250 (5)	0.0102 (4)	0.0002 (4)	0.0022 (4)
C9	0.0256 (5)	0.0222 (5)	0.0282 (6)	0.0084 (4)	0.0048 (4)	0.0067 (4)
C10	0.0208 (5)	0.0164 (4)	0.0245 (5)	0.0076 (4)	0.0010 (4)	0.0008 (4)
C11	0.0196 (5)	0.0203 (5)	0.0260 (5)	0.0096 (4)	0.0013 (4)	0.0002 (4)
C12	0.0205 (5)	0.0199 (5)	0.0241 (5)	0.0081 (4)	0.0037 (4)	0.0001 (4)
C13	0.0230 (5)	0.0193 (5)	0.0235 (5)	0.0091 (4)	0.0004 (4)	−0.0004 (4)
C14	0.0262 (5)	0.0323 (6)	0.0249 (6)	0.0127 (5)	−0.0002 (4)	0.0030 (4)
C15	0.0185 (5)	0.0218 (5)	0.0263 (5)	0.0073 (4)	−0.0008 (4)	−0.0008 (4)
C16	0.0187 (5)	0.0188 (5)	0.0251 (5)	0.0061 (4)	0.0020 (4)	−0.0003 (4)
C17	0.0168 (5)	0.0277 (5)	0.0258 (5)	0.0050 (4)	0.0013 (4)	0.0018 (4)

Geometric parameters (Å, º)

O1—N3	1.217 (3)	C5—H5B	0.9800
O1'—N3'	1.224 (5)	C5—H5C	0.9800
O2—N3	1.221 (3)	C6—C7	1.3948 (15)
O2'—N3'	1.224 (5)	C7—C8	1.5243 (15)
O3—N4	1.2283 (13)	C8—H8A	0.9900
O4—N4	1.2277 (13)	C8—H8B	0.9900
N1—C1	1.4330 (14)	C9—H9A	0.9900
N1—C9	1.4642 (15)	C9—H9B	0.9900
N1—C17	1.4733 (15)	C10—C11	1.3908 (15)
N2—C10	1.4365 (14)	C10—C16	1.4029 (15)
N2—C9	1.4672 (14)	C11—C12	1.3856 (15)
N2—C8	1.4703 (14)	C11—H11	0.9500
N3—C6	1.4936 (18)	C12—C13	1.4036 (15)
N3'—C6	1.291 (16)	C13—C15	1.3949 (15)
N4—C12	1.4734 (14)	C13—C14	1.5063 (15)
C1—C2	1.3976 (15)	C14—H14A	0.9800
C1—C7	1.4014 (15)	C14—H14B	0.9800
C2—C3	1.3814 (17)	C14—H14C	0.9800
C2—H2	0.9500	C15—C16	1.3943 (16)
C3—C4	1.3931 (16)	C15—H15	0.9500
C3—H3	0.9500	C16—C17	1.5179 (15)
C4—C6	1.3878 (16)	C17—H17A	0.9900
C4—C5	1.5068 (16)	C17—H17B	0.9900
C5—H5A	0.9800
C1—N1—C9	110.99 (9)	N2—C8—H8A	109.4
C1—N1—C17	112.92 (9)	C7—C8—H8A	109.4
C9—N1—C17	107.26 (9)	N2—C8—H8B	109.4
C10—N2—C9	110.57 (9)	C7—C8—H8B	109.4
C10—N2—C8	112.21 (8)	H8A—C8—H8B	108.0
C9—N2—C8	107.91 (9)	N1—C9—N2	111.65 (9)
O1—N3—O2	124.47 (14)	N1—C9—H9A	109.3
O1—N3—C6	118.0 (2)	N2—C9—H9A	109.3
O2—N3—C6	117.6 (2)	N1—C9—H9B	109.3
O2'—N3'—O1'	117.4 (15)	N2—C9—H9B	109.3
O2'—N3'—C6	120.7 (11)	H9A—C9—H9B	108.0
O1'—N3'—C6	121.9 (11)	C11—C10—C16	119.18 (10)
O4—N4—O3	122.98 (10)	C11—C10—N2	118.77 (9)
O4—N4—C12	118.80 (9)	C16—C10—N2	122.05 (9)
O3—N4—C12	118.20 (9)	C12—C11—C10	119.66 (10)
C2—C1—C7	119.59 (10)	C12—C11—H11	120.2
C2—C1—N1	118.73 (10)	C10—C11—H11	120.2
C7—C1—N1	121.66 (10)	C11—C12—C13	123.43 (10)
C3—C2—C1	121.17 (10)	C11—C12—N4	115.27 (9)
C3—C2—H2	119.4	C13—C12—N4	121.30 (10)
C1—C2—H2	119.4	C15—C13—C12	115.02 (10)
C2—C3—C4	121.27 (10)	C15—C13—C14	119.48 (10)
C2—C3—H3	119.4	C12—C13—C14	125.49 (10)
C4—C3—H3	119.4	C13—C14—H14A	109.5
C6—C4—C3	115.96 (10)	C13—C14—H14B	109.5
C6—C4—C5	122.55 (10)	H14A—C14—H14B	109.5
C3—C4—C5	121.47 (10)	C13—C14—H14C	109.5
C4—C5—H5A	109.5	H14A—C14—H14C	109.5
C4—C5—H5B	109.5	H14B—C14—H14C	109.5
H5A—C5—H5B	109.5	C16—C15—C13	123.50 (10)
C4—C5—H5C	109.5	C16—C15—H15	118.2
H5A—C5—H5C	109.5	C13—C15—H15	118.2
H5B—C5—H5C	109.5	C15—C16—C10	119.09 (10)
N3'—C6—C4	117 (2)	C15—C16—C17	120.62 (10)
N3'—C6—C7	118 (2)	C10—C16—C17	120.20 (10)
C4—C6—C7	125.25 (10)	N1—C17—C16	111.28 (9)
C4—C6—N3	117.6 (2)	N1—C17—H17A	109.4
C7—C6—N3	117.1 (2)	C16—C17—H17A	109.4
C6—C7—C1	116.67 (10)	N1—C17—H17B	109.4
C6—C7—C8	122.64 (9)	C16—C17—H17B	109.4
C1—C7—C8	120.67 (9)	H17A—C17—H17B	108.0
N2—C8—C7	111.04 (9)
C9—N1—C1—C2	165.17 (10)	C6—C7—C8—N2	166.76 (9)
C17—N1—C1—C2	−74.35 (12)	C1—C7—C8—N2	−11.55 (14)
C9—N1—C1—C7	−13.29 (14)	C1—N1—C9—N2	52.07 (12)
C17—N1—C1—C7	107.20 (11)	C17—N1—C9—N2	−71.71 (11)
C7—C1—C2—C3	1.42 (16)	C10—N2—C9—N1	52.05 (12)
N1—C1—C2—C3	−177.07 (10)	C8—N2—C9—N1	−71.01 (11)
C1—C2—C3—C4	1.21 (17)	C9—N2—C10—C11	167.29 (9)
C2—C3—C4—C6	−1.73 (16)	C8—N2—C10—C11	−72.18 (12)
C2—C3—C4—C5	179.86 (10)	C9—N2—C10—C16	−13.11 (13)
O2'—N3'—C6—C4	75 (5)	C8—N2—C10—C16	107.41 (11)
O1'—N3'—C6—C4	−102 (5)	C16—C10—C11—C12	−0.16 (15)
O2'—N3'—C6—C7	−106 (4)	N2—C10—C11—C12	179.44 (9)
O1'—N3'—C6—C7	78 (5)	C10—C11—C12—C13	2.84 (16)
C3—C4—C6—N3'	179.1 (8)	C10—C11—C12—N4	−176.89 (9)
C5—C4—C6—N3'	−2.5 (8)	O4—N4—C12—C11	152.85 (11)
C3—C4—C6—C7	−0.35 (16)	O3—N4—C12—C11	−25.54 (14)
C5—C4—C6—C7	178.05 (10)	O4—N4—C12—C13	−26.89 (15)
C3—C4—C6—N3	−178.68 (12)	O3—N4—C12—C13	154.72 (11)
C5—C4—C6—N3	−0.29 (17)	C11—C12—C13—C15	−2.33 (15)
O1—N3—C6—C4	−68.0 (3)	N4—C12—C13—C15	177.38 (9)
O2—N3—C6—C4	112.1 (4)	C11—C12—C13—C14	176.75 (10)
O1—N3—C6—C7	113.5 (4)	N4—C12—C13—C14	−3.53 (16)
O2—N3—C6—C7	−66.4 (3)	C12—C13—C15—C16	−0.79 (15)
N3'—C6—C7—C1	−176.6 (9)	C14—C13—C15—C16	−179.93 (10)
C4—C6—C7—C1	2.85 (16)	C13—C15—C16—C10	3.32 (16)
N3—C6—C7—C1	−178.81 (11)	C13—C15—C16—C17	−173.33 (10)
N3'—C6—C7—C8	5.0 (9)	C11—C10—C16—C15	−2.76 (15)
C4—C6—C7—C8	−175.53 (10)	N2—C10—C16—C15	177.64 (9)
N3—C6—C7—C8	2.81 (16)	C11—C10—C16—C17	173.90 (9)
C2—C1—C7—C6	−3.28 (15)	N2—C10—C16—C17	−5.69 (15)
N1—C1—C7—C6	175.16 (9)	C1—N1—C17—C16	−73.89 (11)
C2—C1—C7—C8	175.13 (9)	C9—N1—C17—C16	48.70 (11)
N1—C1—C7—C8	−6.43 (15)	C15—C16—C17—N1	163.52 (10)
C10—N2—C8—C7	−74.82 (11)	C10—C16—C17—N1	−13.10 (14)
C9—N2—C8—C7	47.23 (11)