(2RS,4RS)-7-Fluoro-2-(2-phenyl­eth­yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine and (2RS,4RS)-7-chloro-2-(2-phenyl­eth­yl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine are isomorphous but not strictly isostructural

(2RS,4RS)-7-Fluoro-2-(2-phenyl­ethyl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₈H₁₈FNO, (I), and (2RS,4RS)-7-chloro-2-(2-phenyl­ethyl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₈H₁₈ClNO, (II), are isomorphous but not strictly isostructural, as the slight differences in the unit-cell dimensions and mol­ecular conformations are sufficient to preclude, in the structure of (I), the direction-specific inter­molecular inter­actions present in the structure of (II), where the mol­ecules are linked into sheets by a combination of C-H...N and C-H...[pi](arene) hydrogen bonds.

S1. Comment

We report here the structures of the two title compounds, (I) and (II) (Figs. 1 and 2), which we compare with their 2-styryl analogues (Acosta et al., 2008). The present work forms part of a continuing study of the structures of substituted tetrahydro-1,4-epoxy-1-benzazepines (Acosta et al., 2008, 2010a,b; Blanco et al., 2008, 2009, 2012; Gómez et al., 2008, 2009, 2010; Palma et al., 2009; Sanabria et al., 2010). Compounds (I) and (II) were prepared by appropriate modification of the method previously reported (Acosta et al., 2008). The importance of compounds of this general type arises from their high potential value as anti-Chagasic and anti-leishmanicidal agents (Gómez-Ayala et al., 2010).

Compounds (I) and (II) are isomorphous, although with modest differences between the corresponding pairs of unit-cell dimensions. Thus, for example, the a repeat distance is greater in (II) than in (I) by ca 4.8%, while the b repeat distance is smaller in (II) by ca 2.7%. Both compounds crystallize as true racemates in space group P2₁/c and they are approximately isostructural, in that each structure can be refined using the atomic coordinates of the other as the starting point, provided that due allowance is made for the presence in (I) of a 7-fluoro substituent as opposed to a 7-chloro substituent in (II).

There are, however, some detailed differences between the molecular conformations of (I) and (II), in particular the conformation of the 2-phenylethyl side chain and its orientation relative to the rest of the molecule, as indicated by the values of the torsion angles C2—C21—C22—C221 and C21—C22—C221—C222 (Table 1; Figs. 1 and 2). On the other hand, the conformations of the heterobicyclic ring systems, as shown by the values (Table 1) of the ring-puckering parameters (Cremer & Pople, 1975), are very similar. In each of (I) and (II), the five-membered ring adopts the half-chair conformation, for which the ideal value of the puckering angle ϕ₂ is (36k + 18)°, where k represents an integer. The conformations of the six-membered rings are intermediate between the envelope form, for which the idealized puckering angles are θ = 54.7° and ϕ = (60k)°, and the half-chair form, where the idealized puckering angles are θ = 50.8° and ϕ = (60k + 30)°, where k again represents an integer.

The crystallization behaviour of (I) and (II) may be contrasted with that of the 2-styryl analogues (Acosta et al., 2008), the molecular constitutions of which differ from those of (I) and (II) only by having two fewer H atoms in the hydrocarbyl side chain. The 2-styryl compounds crystallize in different crystal systems, both in Sohnke space groups and neither of them as a true racemate, although their method of synthesis is expected to lead to the formation of racemic mixtures (Acosta et al., 2008). The 2-styryl analogue of (I) crystallizes as a single enantiomorph in space group P2₁, i.e. as a conglomerate, while the 2-styryl analogue of (II) crystallizes as an inversion twin in space group P2₁2₁2₁. Hence, these two styryl compounds are neither isomorphous with one another nor with their 2-phenylethyl analogues.

In the crystal structure of (II), the molecules are linked into sheets by a combination of C—H···N and C—H···π(arene) hydrogen bonds (Table 2), and the formation of this hydrogen-bonded sheet can be readily analysed in terms of two substructures (Ferguson et al., 1998a,b; Gregson et al., 2000), each in the form of a simple chain. Molecules of (II) related by the 2₁ axis along (1, y, 1/4) are linked by C—H···N hydrogen bonds to form a C(9) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 3). In addition, molecules related by translation along [100] are linked by a C—H···π(arene) to form a second chain motif, and the combination of chains along [100] and [010] leads to the formation of a sheet lying parallel to (001) in the form of (4,4) net containing just one type of ring (Fig. 3).

The geometric parameters (Table 2) for the intermolecular contacts in the structure of (I) which correspond to hydrogen bonds in the structure of (II) show some significantly longer distances, particularly for the H···A contacts. Thus, for example, while the H···N distance in the C—H···N hydrogen bond in (II) is well below the sum of the van der Waals radii for H and N (2.64 Å; Bondi, 1964; Rowland & Taylor, 1996), the corresponding distance in (I) is markedly greater than this van der Waals sum. At the same time, the C—H···N angle in (I) is ca 40° smaller than that in (II) and this angle in itself would be sufficient to raise doubts about the structural significance of this contact (cf. Wood et al., 2009), irrespective of the H···A distance. In a similar way, the H···A and D···A distances for the C—H···π(arene) contact are much longer for (I) than for (II). Hence, the modest differences in unit-cell dimensions and atomic coordinates between (I) and (II) are sufficient to render the contacts in (I), which correspond to the hydrogen bonds in (II), far too long to be regarded as hydrogen bonds or as structurally significant. It is for this reason that the isomorphous compounds (I) and (II) are not strictly isostructural, but only approximately so.

We have recently reported a similar phenomenon in a series of isomorphous 4-hydroxy-2-vinyl-2,3,4,5–1-benzazepines, (III)–(V) (Acosta et al., 2009), where modest but monotonic changes in all of the unit-cell dimensions from (III) via (IV) to (V) are sufficient to preclude, in the structure of (V), the occurrence of one of the hydrogen bonds present in the structures of (III) and (IV).

Related literature

For related literature, see: Acosta et al. (2008, 2009, 2010a, 2010b); Bernstein et al. (1995); Blanco et al. (2008, 2009, 2012); Bondi (1964); Cremer & Pople (1975); Ferguson et al. (1998a, 1998b); Gómez et al. (2008, 2009, 2010); Gómez-Ayala, Castrillón, Palma, Leal, Escobar & Bahsas (2010); Gregson et al. (2000); Palma et al. (2009); Rowland & Taylor (1996); Sanabria et al. (2010); Wood et al. (2009).

S2. Experimental

For the synthesis of (I) and (II), sodium tungstate dihydrate (10 mol% Na₂WO₄.2H₂O), followed by 30% aqueous hydrogen peroxide solution (12 mmol), were added to a stirred and cooled (ice-bath) solution of the appropriate substituted 2-allyl-N-(3-phenylpropyl)aniline (4 mmol) in methanol (30 ml). The resulting mixtures were stirred at 273 K for 2–8 h, and then at ambient temperature for an additional 12–20 h (the progress of the reactions was monitored by thin-layer chromatography). Each mixture was filtered and then extracted with ethyl acetate (2 × 50 ml) and, for each, the combined extracts were dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and toluene (30 ml) was added to the organic residue. The resulting solution was heated under reflux for 6–8 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude products were purified by column chromatography on silica gel using heptane–ethyl acetate (compositions 50:1 to 10:1 v/v) as eluant. Crystallization from heptane or heptane–ethyl acetate [Solvent ratio?], at ambient temperature and exposed to air, gave colourless crystals suitable for single-crystal X-ray diffraction. Compound (I): yield 42%, m.p. 371 K; MS (70 eV) m/z (%) = 283 (M⁺, 15), 266 (2), 253 (1), 148 (18), 136 (100), 122 (18), 91 (48). Compound (II), yield 32%, m.p. 374 K; MS (70 eV) m/z (%) = 299 (M⁺, ³⁵Cl, 15), 282 (3), 269 (1), 164 (12), 152 (100), 138 (15), 91 (67).

S3. Refinement

All H atoms were located in difference maps and then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.99 (CH₂) or 1.00 Å (aliphatic CH), and with U_iso(H) = 1.2U_eq(C). In each compound, the reference molecule was selected to have the R configuration at atom C4, and on this basis the configuration at atom C2 is S [R?]. The centrosymmetric space group thus accommodates equal numbers of the (2R,4R) and (2S,4S) enantiomers in each unit cell.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the (2R,4R) enantiomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of the (2R,4R) enantiomer of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded (dashed lines) sheet parallel to (001). For the sake of clarity, H atoms bonded to C atoms which are not involved in the motifs shown have been omitted.

(I) (2RS,4RS)-7-Fluoro-2-(2-phenylethyl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C18H18FNO	F(000) = 600
Mr = 283.33	Dx = 1.299 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3324 reflections
a = 9.6285 (4) Å	θ = 2.8–27.5°
b = 11.2875 (5) Å	µ = 0.09 mm^−1
c = 13.5147 (6) Å	T = 120 K
β = 99.565 (3)°	Block, colourless
V = 1448.38 (11) Å^3	0.45 × 0.31 × 0.16 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3324 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2004 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.961, Tmax = 0.986	l = −17→17
20017 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0427P)^2 + 0.4791P] where P = (Fo^2 + 2Fc^2)/3
3324 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.59693 (15)	0.58170 (13)	0.32908 (10)	0.0235 (4)
C2	0.59285 (19)	0.46297 (15)	0.37747 (13)	0.0235 (4)
H2	0.5985	0.4722	0.4516	0.028*
C3	0.44774 (19)	0.41139 (16)	0.33073 (13)	0.0257 (4)
H3A	0.4572	0.3294	0.3067	0.031*
H3B	0.3821	0.4116	0.3798	0.031*
C4	0.39692 (19)	0.49517 (16)	0.24318 (13)	0.0260 (4)
H4	0.3564	0.4495	0.1817	0.031*
C5	0.29254 (19)	0.58747 (16)	0.26785 (13)	0.0270 (4)
H5A	0.2527	0.6316	0.2064	0.032*
H5B	0.2142	0.5479	0.2938	0.032*
C5a	0.36658 (19)	0.67200 (15)	0.34554 (13)	0.0233 (4)
C6	0.2928 (2)	0.75762 (16)	0.39015 (13)	0.0266 (4)
H6	0.1936	0.7645	0.3717	0.032*
C7	0.3655 (2)	0.83210 (16)	0.46127 (13)	0.0271 (4)
F7	0.29029 (12)	0.91484 (9)	0.50416 (8)	0.0378 (3)
C8	0.5089 (2)	0.82680 (16)	0.49151 (13)	0.0268 (4)
H8	0.5556	0.8785	0.5418	0.032*
C9	0.5830 (2)	0.74319 (15)	0.44597 (13)	0.0245 (4)
H9	0.6825	0.7380	0.4643	0.029*
C9a	0.51255 (19)	0.66690 (15)	0.37359 (13)	0.0223 (4)
O14	0.52379 (13)	0.55798 (11)	0.22789 (8)	0.0281 (3)
C21	0.71349 (19)	0.38671 (16)	0.35503 (13)	0.0266 (4)
H21A	0.7095	0.3843	0.2814	0.032*
H21B	0.6985	0.3049	0.3774	0.032*
C22	0.86159 (19)	0.42607 (17)	0.40323 (14)	0.0310 (5)
H22A	0.8815	0.5057	0.3782	0.037*
H22B	0.8675	0.4308	0.4770	0.037*
C221	0.96877 (18)	0.33860 (17)	0.37783 (14)	0.0287 (4)
C222	1.0046 (2)	0.23890 (18)	0.43690 (15)	0.0337 (5)
H222	0.9673	0.2296	0.4972	0.040*
C223	1.0936 (2)	0.15280 (19)	0.40971 (17)	0.0413 (5)
H223	1.1160	0.0851	0.4510	0.050*
C224	1.1497 (2)	0.1651 (2)	0.32291 (18)	0.0453 (6)
H224	1.2113	0.1064	0.3043	0.054*
C225	1.1156 (2)	0.2635 (2)	0.26324 (17)	0.0436 (6)
H225	1.1540	0.2725	0.2033	0.052*
C226	1.0259 (2)	0.34936 (18)	0.29000 (15)	0.0357 (5)
H226	1.0030	0.4164	0.2480	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0292 (9)	0.0230 (8)	0.0181 (7)	−0.0009 (7)	0.0034 (6)	−0.0020 (6)
C2	0.0280 (10)	0.0223 (9)	0.0205 (9)	0.0007 (8)	0.0050 (8)	0.0007 (7)
C3	0.0291 (10)	0.0219 (9)	0.0270 (10)	0.0010 (9)	0.0073 (8)	0.0004 (8)
C4	0.0295 (11)	0.0243 (10)	0.0240 (9)	−0.0054 (9)	0.0033 (8)	−0.0018 (8)
C5	0.0274 (10)	0.0263 (10)	0.0261 (10)	−0.0015 (9)	0.0003 (8)	0.0024 (8)
C5a	0.0263 (10)	0.0214 (9)	0.0218 (9)	0.0007 (8)	0.0031 (8)	0.0049 (8)
C6	0.0249 (10)	0.0274 (10)	0.0275 (10)	0.0039 (9)	0.0040 (8)	0.0068 (8)
C7	0.0358 (11)	0.0217 (10)	0.0256 (10)	0.0080 (9)	0.0105 (9)	0.0025 (8)
F7	0.0437 (7)	0.0322 (6)	0.0388 (6)	0.0124 (6)	0.0108 (5)	−0.0047 (5)
C8	0.0331 (11)	0.0223 (10)	0.0245 (9)	−0.0008 (9)	0.0036 (8)	0.0013 (8)
C9	0.0248 (10)	0.0223 (10)	0.0261 (10)	−0.0015 (8)	0.0034 (8)	0.0028 (8)
C9a	0.0265 (10)	0.0195 (9)	0.0216 (9)	0.0012 (8)	0.0055 (8)	0.0049 (8)
O14	0.0329 (8)	0.0329 (7)	0.0188 (6)	−0.0055 (6)	0.0050 (5)	−0.0002 (6)
C21	0.0282 (10)	0.0249 (10)	0.0274 (10)	0.0009 (9)	0.0065 (8)	−0.0025 (8)
C22	0.0303 (11)	0.0282 (10)	0.0332 (11)	0.0016 (9)	0.0017 (9)	−0.0040 (9)
C221	0.0204 (10)	0.0301 (11)	0.0347 (11)	−0.0024 (9)	0.0014 (8)	−0.0084 (9)
C222	0.0245 (11)	0.0376 (12)	0.0381 (11)	0.0033 (9)	0.0023 (9)	−0.0026 (10)
C223	0.0283 (11)	0.0359 (12)	0.0568 (14)	0.0064 (10)	−0.0020 (10)	−0.0069 (11)
C224	0.0204 (11)	0.0532 (15)	0.0607 (15)	0.0033 (11)	0.0022 (10)	−0.0286 (13)
C225	0.0280 (11)	0.0599 (16)	0.0443 (13)	−0.0085 (12)	0.0103 (10)	−0.0164 (12)
C226	0.0276 (11)	0.0401 (12)	0.0393 (12)	−0.0069 (10)	0.0049 (9)	−0.0063 (10)

Geometric parameters (Å, º)

N1—C9a	1.452 (2)	C8—C9	1.387 (2)
N1—O14	1.4553 (17)	C8—H8	0.9500
N1—C2	1.495 (2)	C9—C9a	1.392 (2)
C2—C21	1.516 (2)	C9—H9	0.9500
C2—C3	1.548 (2)	C21—C22	1.532 (3)
C2—H2	1.0000	C21—H21A	0.9900
C3—C4	1.530 (2)	C21—H21B	0.9900
C3—H3A	0.9900	C22—C221	1.509 (3)
C3—H3B	0.9900	C22—H22A	0.9900
C4—O14	1.457 (2)	C22—H22B	0.9900
C4—C5	1.522 (2)	C221—C222	1.390 (3)
C4—H4	1.0000	C221—C226	1.394 (3)
C5—C5a	1.507 (2)	C222—C223	1.385 (3)
C5—H5A	0.9900	C222—H222	0.9500
C5—H5B	0.9900	C223—C224	1.378 (3)
C5a—C6	1.394 (2)	C223—H223	0.9500
C5a—C9a	1.395 (2)	C224—C225	1.380 (3)
C6—C7	1.377 (3)	C224—H224	0.9500
C6—H6	0.9500	C225—C226	1.386 (3)
C7—F7	1.368 (2)	C225—H225	0.9500
C7—C8	1.375 (3)	C226—H226	0.9500
C9a—N1—O14	107.12 (13)	C9—C8—H8	121.2
C9a—N1—C2	110.82 (13)	C8—C9—C9a	120.38 (17)
O14—N1—C2	101.67 (12)	C8—C9—H9	119.8
N1—C2—C21	110.17 (14)	C9a—C9—H9	119.8
N1—C2—C3	104.26 (14)	C9—C9a—C5a	121.13 (16)
C21—C2—C3	111.98 (14)	C9—C9a—N1	117.36 (15)
N1—C2—H2	110.1	C5a—C9a—N1	121.51 (16)
C21—C2—H2	110.1	N1—O14—C4	104.04 (11)
C3—C2—H2	110.1	C2—C21—C22	116.12 (15)
C4—C3—C2	103.53 (14)	C2—C21—H21A	108.3
C4—C3—H3A	111.1	C22—C21—H21A	108.3
C2—C3—H3A	111.1	C2—C21—H21B	108.3
C4—C3—H3B	111.1	C22—C21—H21B	108.3
C2—C3—H3B	111.1	H21A—C21—H21B	107.4
H3A—C3—H3B	109.0	C221—C22—C21	109.70 (15)
O14—C4—C5	107.32 (14)	C221—C22—H22A	109.7
O14—C4—C3	104.04 (14)	C21—C22—H22A	109.7
C5—C4—C3	113.05 (14)	C221—C22—H22B	109.7
O14—C4—H4	110.7	C21—C22—H22B	109.7
C5—C4—H4	110.7	H22A—C22—H22B	108.2
C3—C4—H4	110.7	C222—C221—C226	117.66 (18)
C5a—C5—C4	109.43 (15)	C222—C221—C22	120.88 (17)
C5a—C5—H5A	109.8	C226—C221—C22	121.23 (18)
C4—C5—H5A	109.8	C223—C222—C221	121.4 (2)
C5a—C5—H5B	109.8	C223—C222—H222	119.3
C4—C5—H5B	109.8	C221—C222—H222	119.3
H5A—C5—H5B	108.2	C224—C223—C222	120.2 (2)
C6—C5a—C9a	118.27 (17)	C224—C223—H223	119.9
C6—C5a—C5	121.61 (16)	C222—C223—H223	119.9
C9a—C5a—C5	120.12 (16)	C223—C224—C225	119.3 (2)
C7—C6—C5a	119.28 (17)	C223—C224—H224	120.4
C7—C6—H6	120.4	C225—C224—H224	120.4
C5a—C6—H6	120.4	C224—C225—C226	120.6 (2)
F7—C7—C8	118.67 (16)	C224—C225—H225	119.7
F7—C7—C6	118.01 (16)	C226—C225—H225	119.7
C8—C7—C6	123.32 (17)	C225—C226—C221	120.9 (2)
C7—C8—C9	117.60 (17)	C225—C226—H226	119.6
C7—C8—H8	121.2	C221—C226—H226	119.6
C9a—N1—C2—C21	−162.34 (14)	C6—C5a—C9a—N1	−178.82 (15)
O14—N1—C2—C21	84.07 (16)	C5—C5a—C9a—N1	0.4 (2)
C9a—N1—C2—C3	77.34 (16)	O14—N1—C9a—C9	−150.96 (14)
O14—N1—C2—C3	−36.25 (15)	C2—N1—C9a—C9	98.94 (17)
N1—C2—C3—C4	11.95 (16)	O14—N1—C9a—C5a	29.4 (2)
C21—C2—C3—C4	−107.15 (16)	C2—N1—C9a—C5a	−80.73 (19)
C2—C3—C4—O14	16.74 (16)	C9a—N1—O14—C4	−67.96 (15)
C2—C3—C4—C5	−99.36 (16)	C2—N1—O14—C4	48.36 (15)
O14—C4—C5—C5a	−46.56 (18)	C5—C4—O14—N1	79.43 (15)
C3—C4—C5—C5a	67.57 (19)	C3—C4—O14—N1	−40.62 (15)
C4—C5—C5a—C6	−172.79 (15)	N1—C2—C21—C22	68.0 (2)
C4—C5—C5a—C9a	8.1 (2)	C3—C2—C21—C22	−176.49 (15)
C9a—C5a—C6—C7	−1.3 (2)	C2—C21—C22—C221	177.41 (15)
C5—C5a—C6—C7	179.53 (16)	C21—C22—C221—C222	−87.2 (2)
C5a—C6—C7—F7	−179.67 (15)	C21—C22—C221—C226	87.1 (2)
C5a—C6—C7—C8	−0.1 (3)	C226—C221—C222—C223	−0.2 (3)
F7—C7—C8—C9	−179.17 (15)	C22—C221—C222—C223	174.38 (18)
C6—C7—C8—C9	1.3 (3)	C221—C222—C223—C224	0.5 (3)
C7—C8—C9—C9a	−1.0 (3)	C222—C223—C224—C225	−0.4 (3)
C8—C9—C9a—C5a	−0.4 (3)	C223—C224—C225—C226	0.0 (3)
C8—C9—C9a—N1	179.97 (15)	C224—C225—C226—C221	0.4 (3)
C6—C5a—C9a—C9	1.5 (2)	C222—C221—C226—C225	−0.3 (3)
C5—C5a—C9a—C9	−179.29 (16)	C22—C221—C226—C225	−174.79 (18)

(II) (2RS,4RS)-7-chloro-2-(2-phenylethyl)-2,3,4,5-tetrahydro- 1H-1,4-epoxy-1-benzazepine

Crystal data

C18H18ClNO	F(000) = 632
Mr = 299.78	Dx = 1.304 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3506 reflections
a = 10.0891 (10) Å	θ = 2.7–27.5°
b = 10.981 (2) Å	µ = 0.25 mm^−1
c = 13.7952 (18) Å	T = 120 K
β = 92.771 (11)°	Block, colourless
V = 1526.6 (4) Å^3	0.32 × 0.26 × 0.20 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3506 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2409 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
ϕ and ω scans	h = −12→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.925, Tmax = 0.952	l = −17→17
22115 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.7043P] where P = (Fo^2 + 2Fc^2)/3
3506 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.57949 (15)	0.59495 (14)	0.32933 (10)	0.0227 (4)
C2	0.58623 (17)	0.47172 (16)	0.37488 (13)	0.0219 (4)
H2	0.5879	0.4793	0.4472	0.026*
C3	0.45627 (18)	0.40941 (17)	0.33744 (13)	0.0248 (4)
H3A	0.4737	0.3264	0.3132	0.030*
H3B	0.3919	0.4043	0.3893	0.030*
C4	0.40463 (18)	0.49283 (17)	0.25492 (13)	0.0248 (4)
H4	0.3745	0.4440	0.1968	0.030*
C5	0.29577 (19)	0.57919 (17)	0.28453 (14)	0.0265 (4)
H5A	0.2570	0.6215	0.2265	0.032*
H5B	0.2244	0.5324	0.3144	0.032*
C5a	0.35249 (18)	0.67128 (17)	0.35597 (13)	0.0222 (4)
C6	0.27197 (19)	0.75463 (17)	0.40087 (13)	0.0246 (4)
H6	0.1790	0.7549	0.3861	0.029*
C7	0.32673 (19)	0.83715 (17)	0.46696 (13)	0.0257 (4)
Cl7	0.22206 (5)	0.94235 (5)	0.51950 (4)	0.03639 (16)
C8	0.46189 (19)	0.83834 (17)	0.49189 (13)	0.0266 (4)
H8	0.4978	0.8932	0.5395	0.032*
C9	0.54282 (19)	0.75730 (17)	0.44536 (13)	0.0242 (4)
H9	0.6358	0.7580	0.4600	0.029*
C9a	0.48956 (18)	0.67498 (16)	0.37753 (13)	0.0212 (4)
O14	0.51930 (12)	0.56742 (12)	0.23372 (9)	0.0264 (3)
C21	0.70888 (17)	0.40527 (17)	0.34434 (13)	0.0240 (4)
H21A	0.7086	0.4047	0.2726	0.029*
H21B	0.7038	0.3196	0.3662	0.029*
C22	0.84035 (18)	0.45963 (18)	0.38382 (14)	0.0268 (4)
H22A	0.8455	0.5461	0.3641	0.032*
H22B	0.8442	0.4563	0.4556	0.032*
C221	0.95691 (18)	0.39081 (17)	0.34607 (14)	0.0262 (4)
C222	1.0290 (2)	0.30931 (19)	0.40455 (17)	0.0365 (5)
H222	1.0088	0.3001	0.4707	0.044*
C223	1.1310 (2)	0.2409 (2)	0.3669 (2)	0.0504 (7)
H223	1.1798	0.1853	0.4075	0.061*
C224	1.1614 (2)	0.2534 (2)	0.2708 (2)	0.0525 (7)
H224	1.2310	0.2069	0.2453	0.063*
C225	1.0898 (2)	0.3343 (2)	0.21217 (18)	0.0447 (6)
H225	1.1099	0.3428	0.1459	0.054*
C226	0.9888 (2)	0.40310 (19)	0.24932 (16)	0.0332 (5)
H226	0.9409	0.4591	0.2085	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0241 (8)	0.0244 (8)	0.0196 (8)	−0.0016 (7)	0.0021 (6)	0.0009 (6)
C2	0.0216 (9)	0.0215 (10)	0.0227 (9)	−0.0013 (8)	0.0035 (7)	0.0026 (7)
C3	0.0244 (10)	0.0225 (10)	0.0276 (10)	−0.0011 (8)	0.0034 (8)	−0.0005 (8)
C4	0.0254 (10)	0.0252 (10)	0.0235 (10)	−0.0028 (8)	0.0001 (8)	−0.0030 (8)
C5	0.0252 (10)	0.0285 (11)	0.0253 (10)	0.0000 (9)	−0.0027 (8)	−0.0026 (8)
C5a	0.0235 (10)	0.0228 (10)	0.0201 (9)	−0.0006 (8)	0.0002 (7)	0.0043 (8)
C6	0.0256 (10)	0.0257 (10)	0.0222 (9)	0.0025 (8)	−0.0005 (8)	0.0042 (8)
C7	0.0344 (11)	0.0205 (10)	0.0225 (10)	0.0049 (9)	0.0045 (8)	0.0029 (8)
Cl7	0.0451 (3)	0.0320 (3)	0.0321 (3)	0.0120 (2)	0.0022 (2)	−0.0059 (2)
C8	0.0362 (12)	0.0202 (10)	0.0230 (10)	−0.0030 (9)	−0.0013 (8)	−0.0011 (8)
C9	0.0242 (10)	0.0215 (10)	0.0265 (10)	−0.0039 (8)	−0.0029 (8)	0.0039 (8)
C9a	0.0239 (10)	0.0194 (9)	0.0205 (9)	−0.0013 (8)	0.0036 (7)	0.0040 (7)
O14	0.0296 (7)	0.0308 (7)	0.0189 (7)	−0.0021 (6)	0.0025 (5)	−0.0002 (6)
C21	0.0238 (10)	0.0228 (10)	0.0256 (10)	−0.0009 (8)	0.0026 (8)	−0.0010 (8)
C22	0.0248 (10)	0.0279 (11)	0.0278 (10)	0.0018 (8)	0.0012 (8)	−0.0019 (8)
C221	0.0189 (9)	0.0237 (10)	0.0360 (11)	−0.0045 (8)	0.0013 (8)	−0.0063 (9)
C222	0.0281 (11)	0.0333 (12)	0.0472 (14)	0.0021 (10)	−0.0064 (10)	0.0000 (10)
C223	0.0267 (12)	0.0312 (13)	0.091 (2)	0.0061 (10)	−0.0162 (13)	−0.0099 (14)
C224	0.0220 (12)	0.0429 (15)	0.093 (2)	−0.0038 (11)	0.0085 (13)	−0.0365 (15)
C225	0.0282 (12)	0.0521 (15)	0.0550 (15)	−0.0150 (11)	0.0146 (11)	−0.0261 (12)
C226	0.0272 (11)	0.0346 (12)	0.0382 (12)	−0.0085 (9)	0.0040 (9)	−0.0059 (10)

Geometric parameters (Å, º)

N1—C9a	1.448 (2)	C8—C9	1.386 (3)
N1—O14	1.4568 (18)	C8—H8	0.9500
N1—C2	1.492 (2)	C9—C9a	1.390 (3)
C2—C21	1.514 (2)	C9—H9	0.9500
C2—C3	1.546 (3)	C21—C22	1.531 (3)
C2—H2	1.0000	C21—H21A	0.9900
C3—C4	1.533 (3)	C21—H21B	0.9900
C3—H3A	0.9900	C22—C221	1.511 (3)
C3—H3B	0.9900	C22—H22A	0.9900
C4—O14	1.459 (2)	C22—H22B	0.9900
C4—C5	1.522 (3)	C221—C222	1.387 (3)
C4—H4	1.0000	C221—C226	1.394 (3)
C5—C5a	1.506 (3)	C222—C223	1.395 (3)
C5—H5A	0.9900	C222—H222	0.9500
C5—H5B	0.9900	C223—C224	1.381 (4)
C5a—C6	1.389 (2)	C223—H223	0.9500
C5a—C9a	1.401 (3)	C224—C225	1.381 (4)
C6—C7	1.382 (3)	C224—H224	0.9500
C6—H6	0.9500	C225—C226	1.387 (3)
C7—C8	1.390 (3)	C225—H225	0.9500
C7—Cl7	1.7462 (19)	C226—H226	0.9500
C9a—N1—O14	107.38 (13)	C7—C8—H8	120.9
C9a—N1—C2	111.96 (13)	C8—C9—C9a	120.79 (17)
O14—N1—C2	101.63 (13)	C8—C9—H9	119.6
N1—C2—C21	109.95 (14)	C9a—C9—H9	119.6
N1—C2—C3	103.89 (14)	C9—C9a—C5a	120.48 (17)
C21—C2—C3	112.66 (15)	C9—C9a—N1	118.26 (16)
N1—C2—H2	110.1	C5a—C9a—N1	121.26 (16)
C21—C2—H2	110.1	N1—O14—C4	103.59 (12)
C3—C2—H2	110.1	C2—C21—C22	114.77 (15)
C4—C3—C2	103.65 (14)	C2—C21—H21A	108.6
C4—C3—H3A	111.0	C22—C21—H21A	108.6
C2—C3—H3A	111.0	C2—C21—H21B	108.6
C4—C3—H3B	111.0	C22—C21—H21B	108.6
C2—C3—H3B	111.0	H21A—C21—H21B	107.6
H3A—C3—H3B	109.0	C221—C22—C21	110.96 (15)
O14—C4—C5	107.07 (15)	C221—C22—H22A	109.4
O14—C4—C3	103.90 (14)	C21—C22—H22A	109.4
C5—C4—C3	113.38 (15)	C221—C22—H22B	109.4
O14—C4—H4	110.7	C21—C22—H22B	109.4
C5—C4—H4	110.7	H22A—C22—H22B	108.0
C3—C4—H4	110.7	C222—C221—C226	118.71 (19)
C5a—C5—C4	109.74 (15)	C222—C221—C22	121.14 (18)
C5a—C5—H5A	109.7	C226—C221—C22	120.04 (18)
C4—C5—H5A	109.7	C221—C222—C223	120.4 (2)
C5a—C5—H5B	109.7	C221—C222—H222	119.8
C4—C5—H5B	109.7	C223—C222—H222	119.8
H5A—C5—H5B	108.2	C224—C223—C222	120.4 (2)
C6—C5a—C9a	118.60 (17)	C224—C223—H223	119.8
C6—C5a—C5	121.49 (16)	C222—C223—H223	119.8
C9a—C5a—C5	119.90 (16)	C223—C224—C225	119.5 (2)
C7—C6—C5a	120.16 (18)	C223—C224—H224	120.3
C7—C6—H6	119.9	C225—C224—H224	120.3
C5a—C6—H6	119.9	C224—C225—C226	120.4 (2)
C6—C7—C8	121.71 (17)	C224—C225—H225	119.8
C6—C7—Cl7	118.50 (15)	C226—C225—H225	119.8
C8—C7—Cl7	119.79 (15)	C225—C226—C221	120.6 (2)
C9—C8—C7	118.18 (17)	C225—C226—H226	119.7
C9—C8—H8	120.9	C221—C226—H226	119.7
C9a—N1—C2—C21	−162.56 (15)	C6—C5a—C9a—N1	−176.68 (16)
O14—N1—C2—C21	83.12 (16)	C5—C5a—C9a—N1	2.6 (3)
C9a—N1—C2—C3	76.65 (17)	O14—N1—C9a—C9	−150.75 (15)
O14—N1—C2—C3	−37.67 (15)	C2—N1—C9a—C9	98.51 (18)
N1—C2—C3—C4	13.20 (17)	O14—N1—C9a—C5a	28.4 (2)
C21—C2—C3—C4	−105.76 (17)	C2—N1—C9a—C5a	−82.3 (2)
C2—C3—C4—O14	16.04 (17)	C9a—N1—O14—C4	−68.36 (16)
C2—C3—C4—C5	−99.84 (17)	C2—N1—O14—C4	49.31 (15)
O14—C4—C5—C5a	−45.98 (19)	C5—C4—O14—N1	79.67 (16)
C3—C4—C5—C5a	68.0 (2)	C3—C4—O14—N1	−40.57 (16)
C4—C5—C5a—C6	−174.54 (16)	N1—C2—C21—C22	67.6 (2)
C4—C5—C5a—C9a	6.2 (2)	C3—C2—C21—C22	−177.07 (15)
C9a—C5a—C6—C7	−1.5 (3)	C2—C21—C22—C221	−177.52 (16)
C5—C5a—C6—C7	179.26 (17)	C21—C22—C221—C222	−103.9 (2)
C5a—C6—C7—C8	−1.2 (3)	C21—C22—C221—C226	72.3 (2)
C5a—C6—C7—Cl7	178.59 (14)	C226—C221—C222—C223	−0.2 (3)
C6—C7—C8—C9	2.7 (3)	C22—C221—C222—C223	175.96 (19)
Cl7—C7—C8—C9	−177.02 (14)	C221—C222—C223—C224	0.0 (3)
C7—C8—C9—C9a	−1.7 (3)	C222—C223—C224—C225	−0.1 (3)
C8—C9—C9a—C5a	−0.9 (3)	C223—C224—C225—C226	0.5 (3)
C8—C9—C9a—N1	178.28 (16)	C224—C225—C226—C221	−0.7 (3)
C6—C5a—C9a—C9	2.5 (3)	C222—C221—C226—C225	0.6 (3)
C5—C5a—C9a—C9	−178.21 (16)	C22—C221—C226—C225	−175.64 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···Cg^i	0.99	2.85	3.721 (2)	148
C224—H224···N1^ii	0.95	2.53	3.481 (3)	176

Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z+1/2.