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Compounds containing the tricyclic dibenzo[b,e]azepine system have potential activity in the treatment of a number of diseases. Continuing with our studies on the synthesis of new small and potentially bioactive mol­ecules, a synthetic route, involving acid-catalysed intra­molecular Friedel-Crafts cyclization, to the readily separable diastereoisomers of 11-ethyl-6,11-di­hydro-5H-dibenzo[b,e]azepine-6-carboxamide, a potentially useful precursor in the synthesis of analogues of some anti-allergenic, anti­depressant and anti­histaminic drugs currently in use, has been developed starting from 2-allyl­phenyl­amine and methyl 2-bromo-2-phenyl­acetate and proceeding via racemic methyl 2-[(2-allyl­phen­yl)amino]-2-phenyl­acetate (A) and racemic 2-[(2-allyl­phen­yl)amino]-2-phenyl­acetamide (B), to give the two diastereoisomers (I) and (II), C17H18N2O. Isomers (I) and (II), and their precursors (A) and (B), have all been fully characterized spectroscopically. Structure analysis of the minor isomer (I) shows that it has the (6RS,11RS) configuration, and that the azepine ring adopts a conformation inter­mediate between the boat and twist-boat forms, with the carboxamide and ethyl substituents both occupying quasi-equatorial sites. The mol­ecules of (I) are linked by a combination of N-H...O, N-H...[pi](arene) and C-H...[pi](arene) hydrogen bonds to form complex sheets. Comparisons are made with the structures of some related compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616008950/sk3628sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616008950/sk3628Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616008950/sk3628Isup3.cml
Supplementary material

CCDC reference: 1483369

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(6RS,11RS)-11-Ethyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxamide top
Crystal data top
C17H18N2OZ = 2
Mr = 266.33F(000) = 284
Triclinic, P1Dx = 1.288 Mg m3
a = 5.6051 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6411 (3) ÅCell parameters from 3148 reflections
c = 14.3853 (6) Åθ = 2.8–27.5°
α = 86.192 (2)°µ = 0.08 mm1
β = 81.237 (3)°T = 120 K
γ = 87.313 (2)°Block, colourless
V = 686.61 (4) Å30.21 × 0.16 × 0.15 mm
Data collection top
Bruker D8 Venture
diffractometer
3144 independent reflections
Radiation source: high brilliance microfocus sealed tube2352 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.081
φ and ω scansθmax = 27.5°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 77
Tmin = 0.843, Tmax = 0.988k = 1111
19423 measured reflectionsl = 1818
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.177 w = 1/[σ2(Fo2) + (0.0889P)2 + 0.4781P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3144 reflectionsΔρmax = 0.37 e Å3
191 parametersΔρmin = 0.32 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.0174 (4)0.0074 (2)0.19653 (15)0.0229 (4)
H11.07140.01030.13060.028*
C21.1527 (4)0.0790 (2)0.25633 (15)0.0241 (4)
H21.29670.13400.23160.029*
C31.0741 (4)0.0836 (2)0.35252 (15)0.0260 (5)
H31.16260.14390.39420.031*
C40.8674 (4)0.0007 (2)0.38798 (14)0.0242 (4)
H40.81720.00370.45420.029*
C4A0.7291 (4)0.0882 (2)0.32841 (14)0.0210 (4)
N50.5221 (3)0.16428 (19)0.37210 (13)0.0227 (4)
H50.528 (4)0.181 (3)0.4302 (19)0.027*
C60.3736 (4)0.2837 (2)0.32858 (14)0.0205 (4)
H60.27250.23310.28860.025*
C6A0.5271 (3)0.4043 (2)0.26745 (14)0.0206 (4)
C70.5428 (4)0.5549 (2)0.29484 (15)0.0235 (4)
H70.44310.58840.34980.028*
C80.7034 (4)0.6562 (2)0.24215 (16)0.0267 (5)
H80.71220.75900.26070.032*
C90.8504 (4)0.6069 (2)0.16267 (16)0.0275 (5)
H90.96180.67570.12710.033*
C100.8361 (4)0.4573 (2)0.13449 (14)0.0240 (4)
H100.93820.42430.07990.029*
C10A0.6720 (4)0.3548 (2)0.18609 (14)0.0208 (4)
C110.6618 (4)0.1865 (2)0.16240 (14)0.0212 (4)
H110.48950.15720.17970.025*
C11A0.8053 (4)0.0899 (2)0.22988 (14)0.0201 (4)
C610.2072 (4)0.3597 (2)0.40885 (14)0.0230 (4)
O610.2624 (3)0.35691 (18)0.48850 (10)0.0292 (4)
N610.0084 (3)0.4307 (2)0.38410 (14)0.0289 (4)
H61A0.086 (5)0.496 (3)0.423 (2)0.035*
H61B0.022 (5)0.428 (3)0.322 (2)0.035*
C1110.7337 (4)0.1573 (2)0.05796 (14)0.0248 (4)
H1110.89930.19310.03650.030*
H1120.73490.04440.04980.030*
C1120.5612 (4)0.2409 (3)0.00267 (15)0.0309 (5)
H1210.57330.35340.00040.046*
H1220.39530.21160.02140.046*
H1230.60410.21160.06790.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0260 (10)0.0173 (9)0.0238 (10)0.0051 (8)0.0020 (8)0.0005 (7)
C20.0226 (10)0.0169 (9)0.0316 (11)0.0017 (7)0.0001 (8)0.0017 (8)
C30.0303 (11)0.0177 (9)0.0304 (11)0.0008 (8)0.0081 (9)0.0037 (8)
C40.0303 (11)0.0192 (10)0.0219 (10)0.0035 (8)0.0004 (8)0.0023 (8)
C4A0.0238 (10)0.0132 (9)0.0251 (10)0.0053 (7)0.0008 (8)0.0018 (7)
N50.0268 (9)0.0186 (8)0.0209 (9)0.0013 (7)0.0005 (7)0.0030 (7)
C60.0220 (10)0.0159 (9)0.0223 (10)0.0028 (7)0.0002 (8)0.0023 (7)
C6A0.0197 (10)0.0178 (9)0.0240 (10)0.0025 (7)0.0037 (8)0.0037 (7)
C70.0259 (11)0.0169 (9)0.0276 (10)0.0021 (8)0.0034 (8)0.0004 (8)
C80.0286 (11)0.0161 (9)0.0361 (12)0.0035 (8)0.0084 (9)0.0040 (8)
C90.0303 (12)0.0187 (10)0.0322 (11)0.0092 (8)0.0027 (9)0.0087 (8)
C100.0270 (11)0.0203 (10)0.0224 (10)0.0036 (8)0.0015 (8)0.0049 (8)
C10A0.0232 (10)0.0161 (9)0.0232 (10)0.0029 (7)0.0051 (8)0.0042 (7)
C110.0224 (10)0.0182 (9)0.0219 (10)0.0028 (7)0.0002 (8)0.0014 (7)
C11A0.0242 (10)0.0130 (9)0.0224 (10)0.0062 (7)0.0011 (8)0.0030 (7)
C610.0242 (10)0.0167 (9)0.0264 (10)0.0048 (8)0.0014 (8)0.0016 (7)
O610.0348 (9)0.0292 (8)0.0217 (8)0.0044 (6)0.0005 (6)0.0004 (6)
N610.0267 (10)0.0337 (10)0.0260 (10)0.0046 (8)0.0020 (8)0.0065 (8)
C1110.0277 (11)0.0228 (10)0.0227 (10)0.0027 (8)0.0003 (8)0.0003 (8)
C1120.0351 (12)0.0328 (12)0.0242 (11)0.0013 (9)0.0030 (9)0.0005 (9)
Geometric parameters (Å, º) top
C1—C21.390 (3)C8—C91.383 (3)
C1—C11A1.394 (3)C8—H80.9500
C1—H10.9500C9—C101.390 (3)
C2—C31.385 (3)C9—H90.9500
C2—H20.9500C10—C10A1.401 (3)
C3—C41.380 (3)C10—H100.9500
C3—H30.9500C10A—C111.521 (3)
C4—C4A1.409 (3)C11—C1111.530 (3)
C4—H40.9500C11—C11A1.534 (3)
C4A—N51.391 (3)C11—H111.0000
C4A—C11A1.416 (3)C61—O611.230 (3)
N5—C61.463 (3)C61—N611.332 (3)
N5—H50.86 (3)N61—H61A0.92 (3)
C6—C6A1.527 (3)N61—H61B0.93 (3)
C6—C611.533 (3)C111—C1121.525 (3)
C6—H61.0000C111—H1110.9900
C6A—C71.395 (3)C111—H1120.9900
C6A—C10A1.399 (3)C112—H1210.9800
C7—C81.389 (3)C112—H1220.9800
C7—H70.9500C112—H1230.9800
C2—C1—C11A122.37 (19)C10—C9—H9119.8
C2—C1—H1118.8C9—C10—C10A120.38 (19)
C11A—C1—H1118.8C9—C10—H10119.8
C3—C2—C1118.89 (19)C10A—C10—H10119.8
C3—C2—H2120.6C6A—C10A—C10118.96 (18)
C1—C2—H2120.6C6A—C10A—C11118.37 (17)
C4—C3—C2120.19 (19)C10—C10A—C11122.41 (18)
C4—C3—H3119.9C10A—C11—C111114.70 (16)
C2—C3—H3119.9C10A—C11—C11A106.41 (16)
C3—C4—C4A121.63 (19)C111—C11—C11A115.37 (17)
C3—C4—H4119.2C10A—C11—H11106.6
C4A—C4—H4119.2C111—C11—H11106.6
N5—C4A—C4116.43 (18)C11A—C11—H11106.6
N5—C4A—C11A125.18 (18)C1—C11A—C4A118.54 (18)
C4—C4A—C11A118.35 (18)C1—C11A—C11121.27 (18)
C4A—N5—C6126.66 (17)C4A—C11A—C11120.14 (17)
C4A—N5—H5113.1 (17)O61—C61—N61124.2 (2)
C6—N5—H5111.7 (17)O61—C61—C6120.92 (18)
N5—C6—C6A112.01 (16)N61—C61—C6114.81 (18)
N5—C6—C61106.97 (16)C61—N61—H61A121.2 (17)
C6A—C6—C61110.88 (16)C61—N61—H61B119.5 (17)
N5—C6—H6109.0H61A—N61—H61B119 (2)
C6A—C6—H6109.0C112—C111—C11111.97 (17)
C61—C6—H6109.0C112—C111—H111109.2
C7—C6A—C10A120.08 (18)C11—C111—H111109.2
C7—C6A—C6122.16 (18)C112—C111—H112109.2
C10A—C6A—C6117.49 (17)C11—C111—H112109.2
C8—C7—C6A120.4 (2)H111—C111—H112107.9
C8—C7—H7119.8C111—C112—H121109.5
C6A—C7—H7119.8C111—C112—H122109.5
C9—C8—C7119.81 (19)H121—C112—H122109.5
C9—C8—H8120.1C111—C112—H123109.5
C7—C8—H8120.1H121—C112—H123109.5
C8—C9—C10120.39 (19)H122—C112—H123109.5
C8—C9—H9119.8
C11A—C1—C2—C30.1 (3)C9—C10—C10A—C6A1.5 (3)
C1—C2—C3—C41.4 (3)C9—C10—C10A—C11175.49 (19)
C2—C3—C4—C4A1.0 (3)C6A—C10A—C11—C111155.46 (18)
C3—C4—C4A—N5178.80 (18)C10—C10A—C11—C11130.5 (3)
C3—C4—C4A—C11A0.7 (3)C6A—C10A—C11—C11A75.7 (2)
C4—C4A—N5—C6168.43 (18)C10—C10A—C11—C11A98.4 (2)
C11A—C4A—N5—C613.6 (3)C2—C1—C11A—C4A1.6 (3)
C4A—N5—C6—C6A44.4 (3)C2—C1—C11A—C11178.97 (17)
C4A—N5—C6—C61166.12 (18)N5—C4A—C11A—C1179.84 (18)
N5—C6—C6A—C7107.6 (2)C4—C4A—C11A—C11.9 (3)
C61—C6—C6A—C711.8 (3)N5—C4A—C11A—C112.7 (3)
N5—C6—C6A—C10A66.4 (2)C4—C4A—C11A—C11179.35 (17)
C61—C6—C6A—C10A174.19 (17)C10A—C11—C11A—C1115.44 (19)
C10A—C6A—C7—C80.5 (3)C111—C11—C11A—C113.0 (3)
C6—C6A—C7—C8173.28 (18)C10A—C11—C11A—C4A61.9 (2)
C6A—C7—C8—C90.7 (3)C111—C11—C11A—C4A169.61 (17)
C7—C8—C9—C100.9 (3)N5—C6—C61—O6124.0 (2)
C8—C9—C10—C10A0.2 (3)C6A—C6—C61—O6198.4 (2)
C7—C6A—C10A—C101.6 (3)N5—C6—C61—N61158.00 (17)
C6—C6A—C10A—C10172.48 (18)C6A—C6—C61—N6179.6 (2)
C7—C6A—C10A—C11175.88 (18)C10A—C11—C111—C11263.5 (2)
C6—C6A—C10A—C111.8 (3)C11A—C11—C111—C112172.27 (17)
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 represent the centroids of the C1–C4/C4A/C11A and C6A/C7–C10/C10A rings, respectively
D—H···AD—HH···AD···AD—H···A
N5—H5···O610.86 (3)2.19 (3)2.663 (2)114 (2)
N61—H61A···O61i0.92 (3)1.98 (3)2.893 (2)175 (2)
N61—H61B···Cg2ii0.93 (3)2.45 (3)3.254 (2)144 (2)
C6—H6···Cg1ii1.002.773.622 (2)143
C8—H8···Cg1iii0.952.623.501 (2)154
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z; (iii) x, y+1, z.
 

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