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4-Hydr­oxy-2-vinyl-2,3,4,5-tetra­hydro-1-benzazepine, C12H15NO, (I), and its 7-fluoro and 7-chloro analogues, namely 7-fluoro-4-hydr­oxy-2-vinyl-2,3,4,5-tetra­hydro-1-benzazepine, C12H14FNO, (II), and 7-chloro-4-hydr­oxy-2-vinyl-2,3,4,5-tetra­hydro-1-benz­azepine, C12H14ClNO, (III), are isomorphous, but with variations in the unit-cell dimensions which preclude in compound (III) one of the weaker inter­molecular inter­actions found in compounds (I) and (II). Thus the compounds are not strictly isostructural in terms of the structurally significant inter­molecular inter­actions, although the corresponding atomic coordinates are very similar. The azepine rings adopt chair conformations. The mol­ecules are linked by a combination of N—H...O and O—H...N hydrogen bonds into chains of edge-fused R33(10) rings, which in compounds (I) and (II) are further linked into sheets by a single C—H...π(arene) hydrogen bond. The significance of this study lies in its observation of isomorphism in compounds (I)–(III), and its observation of a sufficient variation in one of the cell dimensions effectively to alter the range of significant hydrogen bonds present in the crystal structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109003370/gg3188sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109003370/gg3188Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109003370/gg3188IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109003370/gg3188IIIsup4.hkl
Contains datablock III

CCDC references: 728210; 728211; 728212

Comment top

In our investigation of the use of the tetrahydro-1-benzazepine system as a scaffold for the elaboration of novel antiparasitic compounds exhibiting new modes of action to combat both Trypanosoma cruzi and Leishmania chagasi parasites, we have recently reported a simple and efficient synthetic pathway to obtain novel cis-2-aryl-4-hydroxytetrahydro-1-benzazepines and cis-2-aryl-4-hydroxytetrahydronaphtho[1,2-b]azepines from readily available ortho-allyl-N-benzyl-substituted anilines (Gómez et al., 2006; Yépez et al., 2006). These compounds appear to be promising as anti-Trypanosoma cruzi and anti-Leishmania chagasi agents (Palma et al., 2008). As a part of this study, we have now developed a stereoselective synthesis of cis-4-hydroxy-2-vinyltetrahydro-1-benzazepines, and here we present the molecular and supramolecular structures of the three title compounds, (I)–(III), which belong to this class. Compounds (I)–(III) were obtained via the reductive cleavage of the N—O bond in the corresponding 1,4-epoxy-2-exo-vinyl-2,3,4,5-tetrahydro-1-benzazepines, which were themselves prepared using a method exactly analogous to that for the 2-exo-styryl analogues (Acosta et al., 2008). The reduction was effected using an excess of zinc powder in 80% acetic acid solution.

Compounds (I)–(III) (Figs. 1–3) are isomorphous and the corresponding atomic coordinates are very similar. The unit-cell dimensions show some interesting variations as the 7-substituent X is altered from X = H to F to Cl. The unit-cell dimension b decreases slightly along this series, while the dimension c shows a rather modest increase: however, the dimension a shows the largest increase, of some 1.73% from X = H to X = F, and a further 5.31% from X = F to X = Cl. The dominant effect on the dimension a of the change in substituent is readily understood in terms of the direction of the C7—X7 bonds, which are inclined at only ca 15° to the a direction. Hence as X is varied from H to F to Cl with a concomitant increase in the C—X bond distance, this effects a corresponding increase in the unit-cell dimensions, predominantly in the a repeat distance. This in turn influences the longer and weaker of the direction-specific intermolecular interactions, as discussed below.

There are two stereogenic centres in each molecule, and for the selected reference molecule in each structure the configuration is (2S,4R). However, the centrosymmetric space groups mean that the compounds are all racemic, with configuration (2SR,4RS). The overall molecular conformations are defined by the shape of the azepine ring and by the orientation of the vinyl substituent relative to this ring. The ring-puckering parameters (Cremer & Pople, 1975) are very similar for compounds (I)–(III), as are the torsion angles defining the orientation of the vinyl substituent (Table 1), and for each compound, the best description of the azepine ring is a chair conformation, with the hydroxyl and vinyl substituents both occupying equatorial sites. The bond distances show no unexpected values.

The supramolecular aggregation is simpler in (III) than in (I) and (II), and the hydrogen-bonded structure in (III) can in fact be identified as a sub-structure in the isostructural pair of compounds (I) and (II); accordingly we discuss (III) first. In (III), the aggregation is determined by the combination of two hydrogen bonds, one each of N—H···O and O—H···N types (Table 2). Amine atom N1 in the molecule at (x, y, z) acts a hydrogen-bond donor to hydroxyl atom O41 in the molecule at (x, 1 + y, z), so forming by translation a C(6) (Bernstein et al., 1995) chain running parallel to the [010] direction. Pairs of such chains, related by the 21 screw axis along (1/4, y, 1/4), are linked by the O—H···N hydrogen bonds to form a chain of edge-fused R33(10) rings running parallel to the [010] direction (Fig. 4). The only additional hydrogen bond in (III) is a C—H···O contact, which is probably too long and too weak to be structurally significant and which, in any event, lies within the chain of rings generated by the N—H···O and O—H···N hydrogen bonds.

Precisely the same type of chain of rings is generated in each of compounds (I) and (II) by exactly the same combination of hydrogen bonds (Table 2), although the C—H···O contact distances are even longer in compounds (I) and (II). However, in these two compounds these chains are linked by a single C—H···π(arene) hydrogen bond to form a sheet parallel to (101) (Fig. 5). A similar type of contact is present in compound (III), but now the H···Cgiv and C···Cgiv distances [symmetry code: (iv) 1 - x, 1 - y, -z] are much larger than in compounds (I) and (II), to the extent that this contact cannot be regarded as structurally significant in (III). The steady elongation of the H···Cgiv and C···Cgiv distances from (I) to (II) (Table 2) is a consequence of the increased offset of the inversion-related molecules involved, itself a direct consequence of the increased unit-cell dimension a which, as noted above, appears to be directly associated with the alignment of the C7—X7 bond (X = H, F or Cl). Accordingly, the series (I)–(III) presents examples of isomorphous compounds whose cell dimensions vary sufficiently between the extreme members of the series to take a weak, but structurally significant, intermolecular interaction outside the range of significance as the critical cell dimension increases.

The structures of only a rather small number of 2,3,4,5-tetrahydro-1-benzazepines carrying a hydroxyl substituent in the azepine ring are recorded in the Cambridge Structural Database (CSD, September 2008 update; Allen, 2002). The majority of these (CSD refcodes DOJJER, RAYYAR, SIJMIH, SIJMON, YUCTOF, YUCVUN [please give original references as well as refcodes]) carry other hydrogen-bonding functional groups on this ring, such as ring carbonyl groups, or pendent acyl or carboxyl groups. However, two 4-hydroxy-1-benzazepines have been reported, viz. compounds (IV) (AFOKUB; Ducray et al., 2001a) and (V) (AFOLAI; Ducray et al., 2001b). Unfortunately, no atom coordinates are available for the 5-hydroxy compound (VI) (FABJAU; Matsubara et al., 2001).

While compound (IV) crystallizes as a single enantiomorph in space group P212121, (V) crystallizes as a racemate in P21/n. In compound (IV), where the configuration at the C atom carrying the hydroxyl substituent is (R) as in compounds (I)-(III), the azepine ring adopts a chair conformation, but folded in the opposite sense to that in compounds (I)–(III), so that the hydroxyl group in (IV) occupies an axial site, as opposed to the equatorial site in each of (I)–(III). However, the SiMe3 group in (IV) occupies an equatorial site. In compound (V), by contrast, the azepine ring has a twist-boat conformation, although with the OH and SiMe3 substituents again in axial and equatorial sites, respectively. In each of (IV) and (V), the molecules are linked into simple chains by a single O—H···N hydrogen bond. In compound (IV), molecules related by translation are linked into C(7) chains, and in (V), molecules related by a 21 screw axis are linked into C(6) chains, but C—H···π(arene) interactions are absent from the structures of both (IV) and (V).

Related literature top

For related literature, see: Acosta et al. (2008); Allen (2002); Bernstein et al. (1995); Ducray et al. (2001a, 2001b); Gómez et al. (2006); Matsubara et al. (2001); Palma et al. (2008); Yépez et al. (2006).

Experimental top

Samples of 1,4-epoxy-2-exo-vinyltetraydro-1-benzazepine and its 7-fluoro and 7-chloro derivatives were prepared using a simple modification of the method recently described (Acosta et al., 2008) for the synthesis of the analogous 2-exo-(E)-styryl compounds. An eightfold molar excess of zinc powder was added to a solution in 80% aqueous acetic acid of 1,4-epoxy-2-exo-vinyltetraydro-1-benzazepine, for (I), or its 7-fluoro and 7-chloro derivatives, for (II) and (III), respectively. The reaction mixtures were stirred at 350–353 K for 8–10 h. The mixtures were then filtered, and the filtrates were neutralized with aqueous ammonia solution to pH 8 and then extracted with ethyl acetate (3 × 50 ml). In each case, the organic phase was then dried over anhydrous sodium sulfate; after removal of the solvent under reduced pressure, the crude product was purified by column chromatography on silica gel using heptane/ethyl acetate (10:1 to 2:1 v/v) as eluant. Crystallization from heptane gave crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, yield 82%, m.p. 376 K; MS (70 eV) m/z (%): 189 (91), 172 (11), 170 (33), 162 (8), 146 (26), 145 (28), 144 (100), 130 (65), 118 (92), 117 (54), 107 (11), 106 (46). For (II), colourless crystals, yield 93%, m.p. 400 K; MS (70 eV) m/z (%): 207 (60), 190 (7), 188 (21), 180 (7), 164 (27), 163 (27), 162 (90), 148 (67), 136 (100), 135 (55), 125 (13), 124 (45). For (III), colourless crystals, yield 87%, m.p. 391 K; MS (70 eV) m/z (%): 223 (M+, 35Cl, 100), 206 (21), 204 (30), 196 (7), 180 (58), 179 (37), 178 (94), 164 (57), 152 (68), 151 (46), 141 (11), 140 (44).

Refinement top

All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to N or O atoms were permitted to ride at the positions deduced from the difference maps, giving N—H distances of 0.88–0.95 Å and O—H of 0.86–1.00 Å, with Uiso(H) set at 1.2Ueq(N) or 1.5Ueq(O). H atoms bonded to C atoms were permitted to ride in geometrically idealized positions with C—H distances of 0.95 (aromatic and vinyl), 0.99 (aliphatic CH2) or 1.00 Å (aliphatic CH), all with Uiso(H) values of 1.2Ueq(C).

Computing details top

For all compounds, data collection: COLLECT (Hooft, 1999). Cell refinement: DIRAX/LSQ (Duisenberg et al., 2000) for (I), (III); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1999) for (II). Data reduction: EVALCCD (Duisenberg et al., 2003) for (I), (III); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1999) for (II). For all compounds, program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain of edge-fused R33(10) rings parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (101). For the sake of clarity, H atoms bonded to C atoms but not involved in the motif shown have been omitted. An entirely equivalent sheet is formed in compound (II).
(I) 4-Hydroxy-2-vinyl-2,3,4,5-tetrahydro-1-benzazepine top
Crystal data top
C12H15NOF(000) = 408
Mr = 189.25Dx = 1.228 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2360 reflections
a = 10.3466 (13) Åθ = 3.1–27.5°
b = 7.488 (3) ŵ = 0.08 mm1
c = 13.227 (9) ÅT = 120 K
β = 92.94 (2)°Plate, colourless
V = 1023.4 (8) Å30.39 × 0.36 × 0.08 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2360 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1626 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ & ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
k = 99
Tmin = 0.978, Tmax = 0.994l = 1717
23550 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0322P)2 + 0.6437P]
where P = (Fo2 + 2Fc2)/3
2360 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C12H15NOV = 1023.4 (8) Å3
Mr = 189.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.3466 (13) ŵ = 0.08 mm1
b = 7.488 (3) ÅT = 120 K
c = 13.227 (9) Å0.39 × 0.36 × 0.08 mm
β = 92.94 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2360 independent reflections
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
1626 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.994Rint = 0.066
23550 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.11Δρmax = 0.27 e Å3
2360 reflectionsΔρmin = 0.25 e Å3
127 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O410.28224 (13)0.19700 (16)0.16073 (9)0.0227 (3)
H410.24510.22310.21900.034*
N10.31988 (14)0.78135 (19)0.13757 (11)0.0164 (3)
H10.30320.90440.12340.020*
C20.24668 (17)0.6723 (2)0.05959 (13)0.0168 (4)
H20.29990.65980.00100.020*
C30.21564 (17)0.4864 (2)0.09936 (13)0.0179 (4)
H310.15680.42660.04860.021*
H320.16780.50080.16180.021*
C40.32985 (17)0.3634 (2)0.12308 (13)0.0177 (4)
H40.37330.33900.05870.021*
C50.43098 (17)0.4385 (2)0.20023 (13)0.0180 (4)
H510.38570.47690.26070.022*
H520.49030.34020.22160.022*
C5A0.51177 (17)0.5928 (2)0.16630 (12)0.0171 (4)
C60.64588 (17)0.5760 (3)0.16766 (13)0.0222 (4)
H60.68410.46340.18350.027*
C70.72502 (19)0.7190 (3)0.14649 (14)0.0276 (5)
H70.81630.70440.14770.033*
C80.66985 (19)0.8834 (3)0.12364 (14)0.0270 (5)
H80.72340.98260.11000.032*
C90.53673 (18)0.9033 (3)0.12056 (13)0.0219 (4)
H90.49931.01640.10460.026*
C9A0.45700 (17)0.7586 (2)0.14075 (12)0.0165 (4)
C210.12223 (17)0.7663 (2)0.02877 (14)0.0211 (4)
H210.07410.81660.08100.025*
C220.07487 (19)0.7844 (3)0.06481 (15)0.0249 (4)
H2210.12010.73610.11920.030*
H2220.00450.84590.07800.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O410.0334 (8)0.0120 (7)0.0233 (7)0.0018 (6)0.0067 (5)0.0002 (5)
N10.0200 (8)0.0110 (7)0.0182 (7)0.0000 (6)0.0007 (6)0.0011 (6)
C20.0182 (9)0.0162 (9)0.0159 (8)0.0001 (7)0.0007 (7)0.0013 (7)
C30.0188 (9)0.0160 (9)0.0187 (9)0.0022 (7)0.0013 (7)0.0014 (7)
C40.0240 (10)0.0124 (9)0.0168 (9)0.0025 (7)0.0028 (7)0.0020 (7)
C50.0230 (10)0.0146 (9)0.0164 (9)0.0043 (8)0.0002 (7)0.0016 (7)
C5A0.0191 (9)0.0203 (10)0.0117 (8)0.0005 (7)0.0013 (6)0.0034 (7)
C60.0216 (10)0.0299 (11)0.0148 (9)0.0037 (8)0.0018 (7)0.0043 (8)
C70.0168 (9)0.0451 (14)0.0207 (9)0.0029 (9)0.0008 (7)0.0066 (9)
C80.0266 (11)0.0342 (12)0.0204 (10)0.0145 (9)0.0021 (8)0.0031 (9)
C90.0276 (11)0.0198 (10)0.0182 (9)0.0058 (8)0.0004 (7)0.0003 (8)
C9A0.0192 (9)0.0187 (9)0.0115 (8)0.0028 (8)0.0006 (6)0.0028 (7)
C210.0203 (9)0.0165 (9)0.0266 (10)0.0008 (8)0.0009 (7)0.0003 (8)
C220.0225 (10)0.0224 (10)0.0291 (11)0.0026 (8)0.0045 (8)0.0058 (8)
Geometric parameters (Å, º) top
N1—C21.491 (2)C6—H60.9500
C2—H21.0000C6—C71.385 (3)
N1—H10.9541C7—H70.9500
C2—C31.528 (2)C7—C81.383 (3)
C3—H310.9900C8—H80.9500
C3—H320.9900C8—C91.384 (3)
C3—C41.518 (2)C9—C9A1.396 (2)
C4—H41.0000C9—H90.9500
C4—O411.438 (2)C9A—N11.427 (2)
O41—H410.90C9A—C5A1.399 (3)
C4—C51.531 (2)C2—C211.505 (2)
C5—C5A1.508 (2)C21—C221.315 (3)
C5—H510.9900C21—H210.9500
C5—H520.9900C22—H2210.9500
C5A—C61.392 (3)C22—H2220.9500
C4—O41—H41106.1C22—C21—H21117.4
C9A—N1—C2115.09 (13)C2—C21—H21117.4
C9A—N1—H1106.9C9—C9A—C5A119.94 (16)
C2—N1—H1108.2C9—C9A—N1119.88 (16)
C4—C3—C2116.66 (15)C5A—C9A—N1120.16 (15)
C4—C3—H31108.1C7—C6—C5A121.77 (19)
C2—C3—H31108.1C7—C6—H6119.1
C4—C3—H32108.1C5A—C6—H6119.1
C2—C3—H32108.1C6—C5A—C9A118.30 (17)
H31—C3—H32107.3C6—C5A—C5119.62 (17)
C5A—C5—C4116.96 (14)C9A—C5A—C5121.88 (16)
C5A—C5—H51108.1C8—C7—C6119.36 (18)
C4—C5—H51108.1C8—C7—H7120.3
C5A—C5—H52108.1C6—C7—H7120.3
C4—C5—H52108.1O41—C4—C3108.69 (14)
H51—C5—H52107.3O41—C4—C5108.77 (14)
N1—C2—C21109.16 (14)C3—C4—C5114.40 (14)
N1—C2—C3111.65 (14)O41—C4—H4108.3
C21—C2—C3109.12 (15)C3—C4—H4108.3
N1—C2—H2109.0C5—C4—H4108.3
C21—C2—H2109.0C7—C8—C9120.10 (18)
C3—C2—H2109.0C7—C8—H8120.0
C8—C9—C9A120.50 (18)C9—C8—H8120.0
C8—C9—H9119.7C21—C22—H221120.0
C9A—C9—H9119.7C21—C22—H222120.0
C22—C21—C2125.14 (18)H221—C22—H222120.0
C9A—N1—C2—C21152.61 (15)N1—C9A—C5A—C6179.46 (15)
C9A—N1—C2—C386.67 (18)C9—C9A—C5A—C5172.92 (15)
C4—C3—C2—N165.95 (19)N1—C9A—C5A—C55.6 (2)
C4—C3—C2—C21173.30 (15)C4—C5—C5A—C6120.92 (18)
N1—C2—C21—C22136.18 (19)C4—C5—C5A—C9A64.2 (2)
C3—C2—C21—C22101.6 (2)C5A—C6—C7—C80.2 (3)
C8—C9—C9A—C5A1.3 (3)C2—C3—C4—O41179.13 (14)
C8—C9—C9A—N1179.83 (16)C2—C3—C4—C557.4 (2)
C2—N1—C9A—C9117.75 (18)C5A—C5—C4—O41168.18 (14)
C2—N1—C9A—C5A63.7 (2)C5A—C5—C4—C370.1 (2)
C7—C6—C5A—C9A1.3 (3)C6—C7—C8—C91.0 (3)
C7—C6—C5A—C5173.76 (16)C9A—C9—C8—C70.2 (3)
C9—C9A—C5A—C62.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O41i0.952.263.154 (3)156
O41—H41···N1ii0.902.092.987 (3)173
C4—H4···Cgiii1.002.793.749 (3)161
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y+1, z.
(II) 7-fluoro-4-hydroxy-2-vinyl-2,3,4,5-tetrahydro-1-benzazepine top
Crystal data top
C12H14FNOF(000) = 440
Mr = 207.24Dx = 1.327 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2365 reflections
a = 10.5258 (13) Åθ = 3.1–27.5°
b = 7.4501 (13) ŵ = 0.10 mm1
c = 13.251 (2) ÅT = 120 K
β = 93.441 (2)°Lath, colourless
V = 1037.2 (3) Å30.10 × 0.07 × 0.02 mm
Z = 4
Data collection top
Bruker-Nonius APEX II CCD camera onκ goniostat
diffractometer
2365 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1850 reflections with I > 2σ(I)
10 cm confocal mirros monochromatorRint = 0.046
Detector resolution: 4096 x 4096 pixels/62 x 62 mm pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ & ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Version 2007.2; Sheldrick, 2007)
k = 99
Tmin = 0.981, Tmax = 0.998l = 1617
11679 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0008P)2 + 1.278P]
where P = (Fo2 + 2Fc2)/3
2365 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C12H14FNOV = 1037.2 (3) Å3
Mr = 207.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.5258 (13) ŵ = 0.10 mm1
b = 7.4501 (13) ÅT = 120 K
c = 13.251 (2) Å0.10 × 0.07 × 0.02 mm
β = 93.441 (2)°
Data collection top
Bruker-Nonius APEX II CCD camera onκ goniostat
diffractometer
2365 independent reflections
Absorption correction: multi-scan
(SADABS; Version 2007.2; Sheldrick, 2007)
1850 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.998Rint = 0.046
11679 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.10Δρmax = 0.25 e Å3
2365 reflectionsΔρmin = 0.24 e Å3
136 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F70.84156 (10)0.69527 (19)0.15258 (10)0.0345 (3)
O410.28026 (13)0.19258 (18)0.16035 (10)0.0228 (3)
H410.24650.21290.21680.034*
N10.31738 (14)0.7790 (2)0.13759 (11)0.0174 (3)
H10.30130.89370.12720.021*
C20.24518 (17)0.6701 (3)0.05849 (14)0.0177 (4)
H20.29770.65790.00150.021*
C30.21483 (18)0.4833 (3)0.09763 (14)0.0196 (4)
H310.16680.49750.15910.023*
H320.15780.42300.04610.023*
C40.32706 (18)0.3597 (3)0.12318 (14)0.0191 (4)
H40.37020.33480.05940.023*
C50.42619 (18)0.4350 (3)0.20080 (14)0.0187 (4)
H510.38160.47410.26070.022*
H520.48430.33620.22280.022*
C5A0.50593 (17)0.5897 (3)0.16735 (13)0.0169 (4)
C60.63804 (18)0.5718 (3)0.17006 (14)0.0212 (4)
H60.67670.45960.18680.025*
C70.71209 (18)0.7175 (3)0.14843 (14)0.0242 (5)
C80.66227 (19)0.8835 (3)0.12478 (15)0.0253 (5)
H80.71580.98240.11150.030*
C90.53062 (19)0.9018 (3)0.12096 (14)0.0228 (4)
H90.49341.01500.10440.027*
C9A0.45218 (17)0.7565 (3)0.14106 (13)0.0171 (4)
C210.12346 (18)0.7653 (3)0.02688 (15)0.0214 (4)
H210.07540.81450.07860.026*
C220.07848 (19)0.7854 (3)0.06717 (16)0.0257 (5)
H2210.12390.73800.12100.031*
H2220.00060.84750.08130.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F70.0146 (6)0.0517 (9)0.0370 (7)0.0034 (6)0.0006 (5)0.0067 (6)
O410.0306 (8)0.0138 (7)0.0243 (7)0.0023 (6)0.0040 (6)0.0014 (6)
N10.0191 (8)0.0124 (7)0.0204 (8)0.0000 (6)0.0006 (6)0.0006 (6)
C20.0187 (9)0.0160 (9)0.0182 (9)0.0004 (7)0.0001 (7)0.0009 (7)
C30.0202 (9)0.0175 (9)0.0207 (9)0.0015 (8)0.0014 (7)0.0009 (8)
C40.0237 (10)0.0142 (9)0.0195 (9)0.0012 (8)0.0025 (7)0.0003 (7)
C50.0206 (9)0.0165 (9)0.0189 (9)0.0017 (8)0.0008 (7)0.0009 (7)
C5A0.0188 (9)0.0189 (9)0.0128 (8)0.0011 (7)0.0004 (7)0.0026 (7)
C60.0203 (9)0.0267 (11)0.0163 (9)0.0030 (8)0.0017 (7)0.0029 (8)
C70.0143 (9)0.0392 (13)0.0192 (10)0.0037 (8)0.0004 (7)0.0065 (9)
C80.0241 (10)0.0315 (12)0.0204 (10)0.0103 (9)0.0017 (8)0.0033 (9)
C90.0255 (10)0.0223 (10)0.0205 (10)0.0045 (8)0.0007 (8)0.0009 (8)
C9A0.0185 (9)0.0187 (9)0.0141 (9)0.0006 (7)0.0009 (7)0.0022 (7)
C210.0187 (9)0.0191 (10)0.0263 (10)0.0014 (8)0.0003 (8)0.0001 (8)
C220.0230 (10)0.0245 (11)0.0289 (11)0.0019 (8)0.0032 (8)0.0056 (9)
Geometric parameters (Å, º) top
F7—C71.371 (2)C5—H510.9900
O41—C41.437 (2)C5—H520.9900
O41—H410.8600C5A—C61.395 (3)
N1—C9A1.427 (2)C5A—C9A1.401 (3)
N1—C21.496 (2)C6—C71.376 (3)
N1—H10.8800C6—H60.9500
C2—C211.502 (3)C7—C81.373 (3)
C2—C31.526 (3)C8—C91.390 (3)
C2—H21.0000C8—H80.9500
C3—C41.520 (3)C9—C9A1.396 (3)
C3—H310.9900C9—H90.9500
C3—H320.9900C21—C221.315 (3)
C4—C51.527 (3)C21—H210.9500
C4—H41.0000C22—H2210.9500
C5—C5A1.508 (3)C22—H2220.9500
C4—O41—H41108.2C4—C5—H52108.1
C9A—N1—C2114.92 (14)H51—C5—H52107.3
C9A—N1—H1107.5C6—C5A—C9A118.56 (18)
C2—N1—H1109.4C6—C5A—C5119.41 (17)
N1—C2—C21109.17 (15)C9A—C5A—C5121.83 (16)
N1—C2—C3111.36 (15)C7—C6—C5A119.71 (19)
C21—C2—C3109.44 (15)C7—C6—H6120.1
N1—C2—H2108.9C5A—C6—H6120.1
C21—C2—H2108.9F7—C7—C8118.89 (18)
C3—C2—H2108.9F7—C7—C6118.09 (19)
C4—C3—C2116.91 (16)C8—C7—C6123.01 (18)
C4—C3—H31108.1C7—C8—C9117.56 (19)
C2—C3—H31108.1C7—C8—H8121.2
C4—C3—H32108.1C9—C8—H8121.2
C2—C3—H32108.1C8—C9—C9A121.12 (19)
H31—C3—H32107.3C8—C9—H9119.4
O41—C4—C3108.88 (15)C9A—C9—H9119.4
O41—C4—C5108.78 (15)C9—C9A—C5A120.02 (17)
C3—C4—C5114.71 (16)C9—C9A—N1120.07 (17)
O41—C4—H4108.1C5A—C9A—N1119.88 (16)
C3—C4—H4108.1C22—C21—C2124.81 (19)
C5—C4—H4108.1C22—C21—H21117.6
C5A—C5—C4116.91 (15)C2—C21—H21117.6
C5A—C5—H51108.1C21—C22—H221120.0
C4—C5—H51108.1C21—C22—H222120.0
C5A—C5—H52108.1H221—C22—H222120.0
C9A—N1—C2—C21151.99 (16)F7—C7—C8—C9179.88 (17)
C9A—N1—C2—C387.06 (19)C6—C7—C8—C91.3 (3)
N1—C2—C3—C465.2 (2)C7—C8—C9—C9A0.4 (3)
C21—C2—C3—C4173.96 (16)C8—C9—C9A—C5A1.1 (3)
C2—C3—C4—O41178.92 (15)C8—C9—C9A—N1179.42 (17)
C2—C3—C4—C556.8 (2)C6—C5A—C9A—C91.7 (3)
O41—C4—C5—C5A167.94 (15)C5—C5A—C9A—C9173.14 (16)
C3—C4—C5—C5A69.9 (2)C6—C5A—C9A—N1179.97 (16)
C4—C5—C5A—C6120.97 (19)C5—C5A—C9A—N15.1 (3)
C4—C5—C5A—C9A64.2 (2)C2—N1—C9A—C9117.03 (19)
C9A—C5A—C6—C70.9 (3)C2—N1—C9A—C5A64.7 (2)
C5—C5A—C6—C7174.14 (17)N1—C2—C21—C22135.5 (2)
C5A—C6—C7—F7179.51 (16)C3—C2—C21—C22102.4 (2)
C5A—C6—C7—C80.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O41i0.882.283.123 (2)159
O41—H41···N1ii0.862.142.995 (2)173
C4—H4···Cgiii1.002.843.905 (2)163
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y+1, z.
(III) 7-chloro-4-hydroxy-2-vinyl-2,3,4,5-tetrahydro-1-benzazepine top
Crystal data top
C12H14ClNOF(000) = 472
Mr = 223.69Dx = 1.347 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2535 reflections
a = 11.0850 (7) Åθ = 3.0–27.5°
b = 7.4214 (10) ŵ = 0.32 mm1
c = 13.4588 (11) ÅT = 120 K
β = 94.721 (8)°Plate, colourless
V = 1103.45 (19) Å30.56 × 0.41 × 0.05 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2535 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1691 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ & ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
k = 99
Tmin = 0.841, Tmax = 0.984l = 1717
25737 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0552P)2 + 1.1726P]
where P = (Fo2 + 2Fc2)/3
2535 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C12H14ClNOV = 1103.45 (19) Å3
Mr = 223.69Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.0850 (7) ŵ = 0.32 mm1
b = 7.4214 (10) ÅT = 120 K
c = 13.4588 (11) Å0.56 × 0.41 × 0.05 mm
β = 94.721 (8)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2535 independent reflections
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
1691 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 0.984Rint = 0.064
25737 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.12Δρmax = 0.40 e Å3
2535 reflectionsΔρmin = 0.35 e Å3
136 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl70.84250 (5)0.68415 (10)0.15093 (5)0.0322 (2)
O410.26775 (15)0.1987 (2)0.16186 (13)0.0239 (4)
H410.24460.23200.22990.036*
N10.31033 (18)0.7875 (3)0.13549 (15)0.0208 (5)
H10.29600.91220.12540.025*
C20.2371 (2)0.6766 (3)0.06001 (17)0.0208 (5)
H20.28520.65690.00120.025*
C30.2049 (2)0.4943 (3)0.10253 (18)0.0227 (5)
H310.14430.43530.05500.027*
H320.16630.51450.16540.027*
C40.3112 (2)0.3660 (3)0.12362 (18)0.0223 (5)
H40.34650.34010.05910.027*
C50.4123 (2)0.4377 (3)0.19703 (18)0.0217 (5)
H510.37530.47610.25810.026*
H520.46750.33630.21590.026*
C5A0.4879 (2)0.5920 (3)0.16376 (17)0.0205 (5)
C60.6133 (2)0.5718 (3)0.16661 (17)0.0213 (5)
H60.64880.45750.18180.026*
C70.6863 (2)0.7160 (4)0.14764 (18)0.0237 (5)
C80.6387 (2)0.8853 (4)0.12576 (19)0.0264 (6)
H80.69000.98430.11410.032*
C90.5136 (2)0.9064 (3)0.12137 (18)0.0237 (5)
H90.47911.02120.10590.028*
C9A0.4380 (2)0.7620 (3)0.13932 (17)0.0202 (5)
C210.1237 (2)0.7777 (3)0.02658 (19)0.0248 (6)
H220.07870.82900.07660.030*
C220.0820 (2)0.8005 (4)0.0672 (2)0.0303 (6)
H2210.12450.75110.11930.036*
H2220.00930.86620.08270.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl70.0205 (3)0.0427 (4)0.0338 (4)0.0030 (3)0.0035 (2)0.0063 (3)
O410.0297 (9)0.0159 (9)0.0260 (9)0.0027 (7)0.0023 (7)0.0012 (7)
N10.0201 (10)0.0175 (11)0.0244 (11)0.0002 (8)0.0003 (8)0.0004 (8)
C20.0216 (11)0.0207 (13)0.0198 (12)0.0008 (10)0.0004 (9)0.0007 (10)
C30.0231 (12)0.0216 (13)0.0229 (12)0.0011 (10)0.0014 (9)0.0002 (10)
C40.0259 (12)0.0190 (12)0.0219 (12)0.0027 (10)0.0017 (10)0.0010 (10)
C50.0224 (12)0.0212 (13)0.0215 (12)0.0023 (10)0.0018 (9)0.0012 (10)
C5A0.0235 (12)0.0209 (13)0.0170 (12)0.0029 (10)0.0005 (9)0.0025 (10)
C60.0231 (12)0.0225 (13)0.0181 (12)0.0011 (10)0.0001 (9)0.0020 (10)
C70.0175 (11)0.0339 (15)0.0198 (12)0.0031 (10)0.0024 (9)0.0048 (11)
C80.0279 (13)0.0277 (14)0.0238 (13)0.0074 (11)0.0029 (10)0.0015 (11)
C90.0261 (13)0.0206 (13)0.0245 (13)0.0019 (10)0.0024 (10)0.0004 (10)
C9A0.0229 (12)0.0218 (12)0.0160 (11)0.0003 (10)0.0013 (9)0.0015 (9)
C210.0211 (12)0.0243 (14)0.0293 (14)0.0023 (10)0.0030 (10)0.0007 (11)
C220.0301 (14)0.0283 (14)0.0311 (14)0.0030 (12)0.0050 (11)0.0036 (12)
Geometric parameters (Å, º) top
Cl7—C71.744 (2)C3—C41.523 (3)
O41—C41.442 (3)C3—H310.9900
O41—H411.00C3—H320.9900
N1—C9A1.425 (3)C5—C5A1.509 (3)
N1—C21.494 (3)C5—C41.527 (3)
N1—H10.9466C5—H510.9900
C9A—C91.393 (3)C5—H520.9900
C9A—C5A1.406 (3)C4—H41.0000
C6—C71.378 (3)C9—H90.9500
C6—C5A1.396 (3)C21—C221.319 (4)
C6—H60.9500C21—C21.501 (3)
C7—C81.385 (4)C21—H220.9500
C8—C91.393 (3)C22—H2210.9500
C8—H80.9500C22—H2220.9500
C3—C21.523 (3)C2—H21.0000
C4—O41—H41103.4C4—C5—H52107.8
C9A—N1—C2115.71 (19)H51—C5—H52107.2
C9A—N1—H1106.8O41—C4—C3109.18 (19)
C2—N1—H1111.4O41—C4—C5108.54 (19)
C9—C9A—C5A120.0 (2)C3—C4—C5114.7 (2)
C9—C9A—N1120.1 (2)O41—C4—H4108.1
C5A—C9A—N1119.9 (2)C3—C4—H4108.1
C7—C6—C5A120.7 (2)C5—C4—H4108.1
C7—C6—H6119.6C8—C9—C9A121.2 (2)
C5A—C6—H6119.6C8—C9—H9119.4
C6—C7—C8121.6 (2)C9A—C9—H9119.4
C6—C7—Cl7119.1 (2)C22—C21—C2124.8 (2)
C8—C7—Cl7119.24 (19)C22—C21—H22117.6
C7—C8—C9118.1 (2)C2—C21—H22117.6
C7—C8—H8120.9C21—C22—H221120.0
C9—C8—H8120.9C21—C22—H222120.0
C2—C3—C4115.1 (2)H221—C22—H222120.0
C2—C3—H31108.5N1—C2—C21108.9 (2)
C4—C3—H31108.5N1—C2—C3111.41 (19)
C2—C3—H32108.5C21—C2—C3109.9 (2)
C4—C3—H32108.5N1—C2—H2108.9
H31—C3—H32107.5C21—C2—H2108.9
C5A—C5—C4117.9 (2)C3—C2—H2108.9
C5A—C5—H51107.8C6—C5A—C9A118.3 (2)
C4—C5—H51107.8C6—C5A—C5119.2 (2)
C5A—C5—H52107.8C9A—C5A—C5122.2 (2)
C2—N1—C9A—C9119.9 (2)C9A—N1—C2—C388.2 (2)
C2—N1—C9A—C5A61.7 (3)C22—C21—C2—N1132.4 (3)
C5A—C6—C7—C80.4 (4)C22—C21—C2—C3105.4 (3)
C5A—C6—C7—Cl7179.44 (18)C4—C3—C2—N168.8 (3)
C6—C7—C8—C91.2 (4)C4—C3—C2—C21170.5 (2)
Cl7—C7—C8—C9178.57 (18)C7—C6—C5A—C9A1.1 (3)
C2—C3—C4—O41179.11 (19)C7—C6—C5A—C5172.6 (2)
C2—C3—C4—C558.8 (3)C9—C9A—C5A—C61.8 (3)
C5A—C5—C4—O41168.40 (19)N1—C9A—C5A—C6179.9 (2)
C5A—C5—C4—C369.2 (3)C9—C9A—C5A—C5171.8 (2)
C7—C8—C9—C9A0.6 (4)N1—C9A—C5A—C56.6 (3)
C5A—C9A—C9—C80.9 (4)C4—C5—C5A—C6123.7 (2)
N1—C9A—C9—C8179.3 (2)C4—C5—C5A—C9A62.8 (3)
C9A—N1—C2—C21150.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O41i0.952.213.113 (3)159
O41—H41···N1ii1.002.003.002 (3)176
C5—H51···O41iii0.992.593.459 (3)147
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC12H15NOC12H14FNOC12H14ClNO
Mr189.25207.24223.69
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)120120120
a, b, c (Å)10.3466 (13), 7.488 (3), 13.227 (9)10.5258 (13), 7.4501 (13), 13.251 (2)11.0850 (7), 7.4214 (10), 13.4588 (11)
β (°) 92.94 (2) 93.441 (2) 94.721 (8)
V3)1023.4 (8)1037.2 (3)1103.45 (19)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.080.100.32
Crystal size (mm)0.39 × 0.36 × 0.080.10 × 0.07 × 0.020.56 × 0.41 × 0.05
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Bruker-Nonius APEX II CCD camera onκ goniostat
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Version 2.10; Sheldrick, 2003)
Multi-scan
(SADABS; Version 2007.2; Sheldrick, 2007)
Multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
Tmin, Tmax0.978, 0.9940.981, 0.9980.841, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
23550, 2360, 1626 11679, 2365, 1850 25737, 2535, 1691
Rint0.0660.0460.064
(sin θ/λ)max1)0.6500.6510.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.112, 1.11 0.056, 0.113, 1.10 0.051, 0.141, 1.12
No. of reflections236023652535
No. of parameters127136136
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.250.25, 0.240.40, 0.35

Computer programs: , DIRAX/LSQ (Duisenberg et al., 2000), DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1999), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Ring-puckering parameters (Å, °) and selected torsion angles (°) for compounds (I)–(III) top
Parameter(I)(II)(III)
ϕ2169.8 (3)169.7 (3)173.9 (4)
ϕ3231.2 (2)230.9 (2)231.1 (2)
Q0.744 (2)0.748 (2)0.734 (2)
N1—C2—C21—C22138.18 (19)135.5 (2)132.4 (3)
Ring-puckering parameters are defined for the atom sequence N1—C2—C3—C4—C5—C5A—C9A.
Hydrogen bonds and short intermolecular contacts (Å, °) for compounds (I)–(III) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)N1—H1···O41i0.952.263.154 (3)156
O41—H41···N1ii0.902.092.987 (3)173
C5—H51···O41iii0.992.653.523 (3)147
C4—H4···Cgiv1.002.793.749 (3)161
(II)N1—H1···O41i0.882.283.123 (2)159
O41—H41···N1ii0.862.142.995 (2)173
C5—H51···O41iii0.992.623.503 (2)149
C4—H4···Cgiv1.002.843.805 (2)163
(III)N1—H1···O41i0.952.213.113 (3)159
O41—H41···N1ii1.002.003.002 (2)176
C5—H51···O41iii0.992.593.805 (2)163
C4—H4···Cgiv1.003.054.045 (3)176
Note: Cg represents the centroid of the C5A/C6–C9/C9A ring. Symmetry codes: (i) x, y+1, z; (ii) -x+1/2, y-1/2, -z+1/2; (iii) -x+1/2, y+1/2, -z+1/2; (iv) -x+1, -y+1, -z.
 

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