Diethyl 6H,12H-5,11-methano-dibenzo[b,f][1,5]diazo-cine-1,7-dicarboxyl-ate.

In the mol-ecule of the title compound, C(21)H(22)N(2)O(4), the 1,7-diethyl ester analogue of Tröger's base, the dihedral angle between the two benzene rings is 93.16 (3)°; the mol-ecule is C(2) symmetric.

Related literature

For background to the synthesis of Tröger’s base products, see: Hansson et al. (2003 ▶); Solano et al. (2005 ▶); Bhuiyan et al. (2007 ▶); Didier & Sergeyev (2007 ▶); Zhu et al. (2008 ▶); Vande Velde et al. (2008 ▶). For related structures, see: Faroughi et al. (2006 ▶); Bhuiyan et al. (2006 ▶).

Experimental

Crystal data

C21H22N2O4

M = 366.41

Monoclinic,

a = 14.306 (3) Å

b = 9.251 (2) Å

c = 15.081 (4) Å

β = 118.149 (4)°

V = 1759.8 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 150 (2) K

0.47 × 0.30 × 0.19 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.856, T max = 0.980

8475 measured reflections

2135 independent reflections

1925 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.099

S = 1.04

2135 reflections

124 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Siemens, 1995 ▶); cell refinement: SAINT (Siemens, 1995 ▶); data reduction: SAINT and XPREP (Siemens, 1995 ▶); program(s) used to solve structure: SIR97 (Altomare et al. 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and WinGX32 (Farrugia, 1999 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042967/zl2169sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042967/zl2169Isup2.hkl

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

C21H22N2O4	F(000) = 776
Mr = 366.41	Dx = 1.383 Mg m−3
Monoclinic, C2/c	Melting point: 441 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 14.306 (3) Å	Cell parameters from 5209 reflections
b = 9.251 (2) Å	θ = 2.7–28.5°
c = 15.081 (4) Å	µ = 0.10 mm−1
β = 118.149 (4)°	T = 150 K
V = 1759.8 (7) Å3	Shard, colourless
Z = 4	0.47 × 0.30 × 0.19 mm

Bruker SMART 1000 CCD diffractometer	2135 independent reflections
Radiation source: sealed tube	1925 reflections with I > 2σ(I)
graphite	Rint = 0.020
ω scans	θmax = 28.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
Tmin = 0.856, Tmax = 0.980	k = −12→11
8475 measured reflections	l = −20→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0513P)2 + 1.146P] where P = (Fo2 + 2Fc2)/3
2135 reflections	(Δ/σ)max = 0.001
124 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Experimental. The crystal was coated in Exxon Paratone N hydrocarbon oil and mounted on a thin mohair fibre attached to a copper pin. Upon mounting on the diffractometer, the crystal was quenched to 150(K) under a cold nitrogen gas stream supplied by an Oxford Cryosystems Cryostream and data were collected at this temperature.

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	Occ. (<1)
C1	0.83967 (10)	0.37215 (14)	1.11492 (10)	0.0346 (3)
H1A	0.7669	0.4024	1.0692	0.052*
H1B	0.8563	0.3944	1.1844	0.052*
H1C	0.8465	0.2679	1.1081	0.052*
C2	0.91539 (9)	0.45165 (12)	1.08889 (8)	0.0291 (2)
H2A	0.9125	0.5564	1.1007	0.035*
H2B	0.9886	0.4177	1.1328	0.035*
C3	0.92507 (8)	0.30443 (11)	0.96454 (8)	0.0217 (2)
C4	0.88028 (8)	0.27735 (11)	0.85453 (8)	0.0205 (2)
C5	0.92893 (8)	0.17644 (10)	0.81900 (8)	0.0194 (2)
C6	0.87857 (8)	0.14597 (11)	0.71558 (8)	0.0201 (2)
C7	0.78414 (8)	0.21655 (12)	0.65048 (8)	0.0238 (2)
H7	0.7503	0.1941	0.5808	0.029*
C8	0.73945 (8)	0.31834 (12)	0.68617 (8)	0.0262 (2)
H8	0.6764	0.3673	0.6411	0.031*
C9	0.78727 (8)	0.34861 (12)	0.78832 (8)	0.0242 (2)
H9	0.7566	0.4180	0.8133	0.029*
C10	1.03523 (8)	0.10512 (11)	0.88716 (8)	0.0211 (2)
H10A	1.0846	0.1783	0.9335	0.025*
H10B	1.0250	0.0294	0.9282	0.025*
C11	1.0000	−0.05009 (15)	0.7500	0.0236 (3)
H11A	0.9674	−0.1129	0.7810	0.028*	0.50
H11B	1.0326	−0.1129	0.7190	0.028*	0.50
N1	0.91816 (7)	0.03970 (9)	0.67236 (6)	0.0214 (2)
O1	0.88792 (6)	0.42718 (8)	0.98415 (6)	0.02669 (19)
O2	0.98621 (6)	0.22448 (9)	1.02960 (6)	0.0285 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0422 (7)	0.0347 (6)	0.0350 (6)	−0.0024 (5)	0.0249 (5)	−0.0045 (5)
C2	0.0339 (6)	0.0266 (5)	0.0284 (5)	−0.0023 (4)	0.0161 (5)	−0.0066 (4)
C3	0.0205 (5)	0.0209 (5)	0.0272 (5)	−0.0007 (4)	0.0142 (4)	0.0015 (4)
C4	0.0195 (5)	0.0198 (5)	0.0247 (5)	−0.0003 (4)	0.0124 (4)	0.0025 (4)
C5	0.0178 (4)	0.0174 (4)	0.0246 (5)	−0.0002 (3)	0.0113 (4)	0.0032 (4)
C6	0.0186 (4)	0.0182 (4)	0.0256 (5)	−0.0032 (4)	0.0121 (4)	0.0005 (4)
C7	0.0192 (5)	0.0274 (5)	0.0234 (5)	−0.0028 (4)	0.0090 (4)	0.0014 (4)
C8	0.0182 (5)	0.0294 (5)	0.0293 (5)	0.0037 (4)	0.0097 (4)	0.0062 (4)
C9	0.0210 (5)	0.0240 (5)	0.0305 (5)	0.0039 (4)	0.0146 (4)	0.0033 (4)
C10	0.0208 (5)	0.0206 (5)	0.0230 (5)	0.0031 (4)	0.0113 (4)	0.0027 (4)
C11	0.0254 (7)	0.0177 (6)	0.0296 (7)	0.000	0.0145 (6)	0.000
N1	0.0215 (4)	0.0191 (4)	0.0257 (4)	−0.0021 (3)	0.0128 (4)	−0.0009 (3)
O1	0.0322 (4)	0.0230 (4)	0.0277 (4)	0.0043 (3)	0.0165 (3)	0.0007 (3)
O2	0.0307 (4)	0.0292 (4)	0.0258 (4)	0.0078 (3)	0.0135 (3)	0.0048 (3)

C1—C2	1.5065 (17)	C6—C7	1.4014 (14)
C1—H1A	0.9800	C6—N1	1.4354 (13)
C1—H1B	0.9800	C7—C8	1.3820 (16)
C1—H1C	0.9800	C7—H7	0.9500
C2—O1	1.4544 (13)	C8—C9	1.3876 (16)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C9—H9	0.9500
C3—O2	1.2103 (13)	C10—N1i	1.4770 (13)
C3—O1	1.3445 (13)	C10—H10A	0.9900
C3—C4	1.4909 (15)	C10—H10B	0.9900
C4—C9	1.3959 (14)	C11—N1	1.4623 (12)
C4—C5	1.4124 (14)	C11—H11A	0.9900
C5—C6	1.4039 (15)	C11—H11B	0.9900
C5—C10	1.5262 (13)
C2—C1—H1A	109.5	C8—C7—H7	119.5
C2—C1—H1B	109.5	C6—C7—H7	119.5
H1A—C1—H1B	109.5	C7—C8—C9	119.58 (10)
C2—C1—H1C	109.5	C7—C8—H8	120.2
H1A—C1—H1C	109.5	C9—C8—H8	120.2
H1B—C1—H1C	109.5	C8—C9—C4	120.20 (10)
O1—C2—C1	110.36 (9)	C8—C9—H9	119.9
O1—C2—H2A	109.6	C4—C9—H9	119.9
C1—C2—H2A	109.6	N1i—C10—C5	111.09 (8)
O1—C2—H2B	109.6	N1i—C10—H10A	109.4
C1—C2—H2B	109.6	C5—C10—H10A	109.4
H2A—C2—H2B	108.1	N1i—C10—H10B	109.4
O2—C3—O1	123.18 (10)	C5—C10—H10B	109.4
O2—C3—C4	124.49 (10)	H10A—C10—H10B	108.0
O1—C3—C4	112.31 (9)	N1i—C11—N1	110.77 (11)
C9—C4—C5	120.99 (10)	N1i—C11—H11A	109.5
C9—C4—C3	118.74 (9)	N1—C11—H11A	109.5
C5—C4—C3	120.21 (9)	N1i—C11—H11B	109.5
C6—C5—C4	117.88 (9)	N1—C11—H11B	109.5
C6—C5—C10	119.18 (9)	H11A—C11—H11B	108.1
C4—C5—C10	122.88 (9)	C6—N1—C11	111.33 (8)
C7—C6—C5	120.31 (9)	C6—N1—C10i	112.54 (8)
C7—C6—N1	117.22 (9)	C11—N1—C10i	107.39 (7)
C5—C6—N1	122.43 (9)	C3—O1—C2	115.98 (8)
C8—C7—C6	120.98 (10)
O2—C3—C4—C9	159.42 (10)	C7—C8—C9—C4	0.40 (16)
O1—C3—C4—C9	−19.11 (13)	C5—C4—C9—C8	1.66 (16)
O2—C3—C4—C5	−17.78 (16)	C3—C4—C9—C8	−175.52 (10)
O1—C3—C4—C5	163.70 (9)	C6—C5—C10—N1i	13.93 (12)
C9—C4—C5—C6	−2.43 (14)	C4—C5—C10—N1i	−163.33 (9)
C3—C4—C5—C6	174.70 (9)	C7—C6—N1—C11	−165.60 (8)
C9—C4—C5—C10	174.85 (9)	C5—C6—N1—C11	12.31 (12)
C3—C4—C5—C10	−8.01 (14)	C7—C6—N1—C10i	73.76 (11)
C4—C5—C6—C7	1.21 (14)	C5—C6—N1—C10i	−108.32 (10)
C10—C5—C6—C7	−176.18 (9)	N1i—C11—N1—C6	−51.41 (6)
C4—C5—C6—N1	−176.64 (8)	N1i—C11—N1—C10i	72.21 (6)
C10—C5—C6—N1	5.97 (14)	O2—C3—O1—C2	−7.03 (15)
C5—C6—C7—C8	0.80 (15)	C4—C3—O1—C2	171.51 (8)
N1—C6—C7—C8	178.76 (9)	C1—C2—O1—C3	−83.19 (12)
C6—C7—C8—C9	−1.62 (16)