Hydrogen-bonding patterns in enamino­nes: (2Z)-1-(4-bromo­phen­yl)-2-(pyrrolidin-2-yl­idene)ethanone and its piperidin-2-yl­idene and azepan-2-yl­idene analogues

The title compounds, namely (2Z)-1-(4-bromo­phenyl)-2-(pyrrolidin-2-yl­idene)ethanone, C₁₂H₁₂BrNO, (I), (2Z)-1-(4-bromo­phenyl)-2-(piperidin-2-yl­idene)ethanone, C₁₃H₁₄BrNO, (II), and (2Z)-2-(azepan-2-yl­idene)-1-(4-bromo­phenyl)­ethan­one, C₁₄H₁₆BrNO, (III), are characterized by bifurcated intra- and inter­molecular hydrogen bonding between the secondary amine and carbonyl groups. The former establishes a six-membered hydrogen-bonded ring, while the latter leads to the formation of centrosymmetric dimers. Weak C—H...Br inter­actions link the individual mol­ecules into chains that run along the [011], [101] and [101] directions in (I)–(III), respectively. Additional weak Br...O, C—H...π and C—H...O inter­actions further stabilize the crystal structures.

S1. Comment

Enaminones (β-acylated enamines) are valuable intermediates for the synthesis of alkaloids and other nitrogen-containing heterocycles (Stanovnik & Svete, 2004; Cheng et al., 2004; Negri et al., 2004; Elliott et al., 2006). These versatile systems play a pivotal role in our own research programme (Michael et al., 1999). We have recently observed discrepancies in the reactivity of N-heterocyclic enaminones of different ring sizes (Michael et al., 2001, 2002). The present investigation was undertaken in order to ascertain whether there might be underlying structural differences in the conjugated enaminone system as the size of the ring containing the N atom is varied. The three title compounds, (I)–(III), were selected as models to probe possible structural differences, in view of their ready preparation by the Eschenmoser sulfide contraction method (Roth et al., 1971).

In the event, the bond lengths and angles for the conjugated and essentially planar enaminone core (N—C═C—C═O) of the three compounds (Figs. 1–3) proved to be effectively the same, and within the expected ranges (Allen et al., 1987). More interesting, however, are their packing arrangements. Compounds (I)–(III) are characterized by bifurcated hydrogen bonds (one intramolecular and one intermolecular) between the secondary amine and carbonyl groups. The intramolecular N—H···O hydrogen bond between the donor atom N1 and the acceptor atom O1 can be described by the graph-set motif S(6) (Etter et al., 1990; Bernstein et al., 1995). In compound (I), atom N1 also acts as an intermolecular hydrogen-bond donor via atom H1 to atom O1 at (2 - x, 1 - y, -z). For compounds (II) and (III), the comparable intermolecular hydrogen bond is from atom N1 to atom O1 at (2 - x, -y, 1 - z) and (1 - x, 1 - y, 1 - z), respectively. This intermolecular hydrogen bonding leads to the formation of dimers described by the R²₂(12) graph-set motif.

In the crystal structures of each compound there is also a weak C—H···Br interaction (Figs. 4–6) that links the molecules together into chains along the [011], [101] and [101] directions in compounds (I), (II) and (III), respectively. The C—H···Br hydrogen-bond geometries (Tables 1–3) are comparable with values reported in the literature (Ponnuswamy & Sony, 2006).

In addition to C—H···Br interactions in compound (I), the chains of molecules extending along the [011] direction are further stabilized by Br···O interactions [Br1···O1ⁱ = 3.161 (2) Å, C10—Br1···O1ⁱ = 165.39 (7)° and C1ⁱ—O1ⁱ···Br1 = 98.2 (1)°; symmetry code: (i) -1/2 + x, 1/2 - y, 1/2 + z] (Fig. 4). These values compare favourably with those obtained from a study of short O···halogen interactions in biological molecules (Auffinger et al., 2004). The crystal structure of (I) also contains a weak C—H···Cg intermolecular interaction that extends along the [001] direction, where Cg is the centroid of the C7–C12 phenyl ring. The pyrrolidine ring has an envelope conformation with atom C5 at the flap. The Cremer & Pople puckering parameters (Cremer & Pople, 1975) for this molecule are q₂ = 0.264 (2) Å and ϕ₂ = 113.8 (4)°.

The hydrogen-bonded dimers in compound (II) are further reinforced by a weak C—H···O interaction between atom H7A and atom O1 at (2 - x, -y, 1 - z), producing a motif described by the graph set R²₂(12). A second set of C—H···O interactions, occurring between atom H5 and atom O1 at (2 - x, 1 - y, 1 - z), gives rise to another set of intermolecular bonded dimers described by the R²₂(14) graph set (Fig. 5). In this structure, the piperidine ring adopts a half-chair conformation [puckering amplitude Q_T = 0.483 (3) Å, θ = 136.7 (4)° and ϕ = 26.9 (5)°].

In addition to the N—H···O and C—H···Br interactions discussed earlier, the structure of (III) also contains C—H···Oⁱ and C—H···Cgⁱ interactions [symmetry code: (i) 1 - x, -1/2 + y, 3/2 - z] that link molecules together into chains along the [011] direction (Fig. 6). In this structure, the seven-membered ring has a total puckering amplitude Q of 0.7524 (17) Å.

Related literature

For related literature, see: Allen et al. (1987); Auffinger et al. (2004); Bernstein et al. (1995); Cheng et al. (2004); Cremer & Pople (1975); Curphey (2002); Elliott et al. (2006); Etter et al. (1990); Michael et al. (1999, 2001, 2002); Negri et al. (2004); Ponnuswamy & Sony (2006); Roth et al. (1971); Stanovnik & Svete (2004).

S2. Experimental

The synthesis of compounds (I)–(III) was adapted from the procedure described by Roth et al. (1971) for the preparation of (I). 4-Bromophenacyl bromide (1.05 equivalents) was added to a solution of the appropriate thiolactam [pyrrolidine-2-thione, piperidine-2-thione or azepane-2-thione; 1.0 equivalent; cf. Curphey (2002)] in CHCl₃ (5 ml per mmol). After 30 min at room temperature, the solvent was removed on a rotary evaporator. The resulting mixture was kept at room temperature for 48 h to ensure that the reaction went to completion. The resulting solid was partitioned between CH₂Cl₂ and aqueous saturated K₂CO₃ solution. The organic phase was separated off and the aqueous phase was extracted with a further portion of CH₂Cl₂. The combined organic extracts were dried (MgSO₄) and evaporated to yield the crude S-alkylated intermediate. This was dissolved in dry CHCl₃ (10 ml per mmol) to which triphenylphosphine (2 equivalents) was added. The solution was heated at reflux for 24 h, after which the solvent was evaporated. The crude enaminone product was purified by chromatography on silica gel with dichloromethane as eluant, followed by ethyl acetate–hexane (2:3), to afford the desired products, (I)–(III); characterization as described below.

For compound (I), yield 66%; m.p. 443–446 K [literature value 446–447 K (Roth et al., 1971)]. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 2.00–2.10 (2H, m, 5-H), 2.74 (2H, m, 4-H), 3.66 (2H, m, 6-H), 5.75 (1H, s, 2-H), 7.52 and 7.74 (4H, 2 × m, 8-H, 9-H, 11-H, 12-H), 10.28 (1H, s, NH); ¹³C NMR (75 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 186.4 (C═O), 170.0 (C3), 138.9 (C7), 131.3 and 128.7 (C8, C9, C11, C12), 125.1 (C10), 85.9 (C2), 47.9 (C6), 33.0 (C4), 21.3 (C5).

For compound (II), yield 55%; m.p. 388–390 K. Spectroscopic analysis: IR [Any data to be included here?]; ¹H NMR (300 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 1.76–1.88 (4H, m, 5-H and 6-H), 2.50 (2H, t, 4-H), 3.40 (2H, t, 7-H), 5.51 (1H, s, 2-H), 7.50 and 7.71 (4H, 2 × d, J = 8.2 Hz, 9-H, 10-H, 12-H, 13-H), 11.70 (1H, s, NH); ¹³C NMR (75 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 185.9 (C═ O), 166.6 (C3), 139.9 (C8), 131.6 and 128.8 (C9, C10, C12, C13), 125.0 (C11), 90.5 (C2), 41.6 (C7), 29.3 (C4), 22.5 and 19.6 (C5, C6). HRMS (EI), found: 281.0216; C₁₃H₁₄⁸¹BrNO requires: 281.0238.

For compound (III), yield 76%; m.p. 418–421 K. Spectroscopic analysis: IR [Any data to be included here?]; ¹H NMR (300 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 1.68–1.77 (6H, m, 5-H, 6-H, and 7-H), 2.44 (2H, m, 4-H), 3.43 (2H, d, 8-H), 5.61 (1H, s, 2-H), 7.51 and 7.73 (4H, 2 × m, 10-H, 11-H, 13-H, and 14-H), 11.54 (1H, s, NH); ¹³C NMR (75 MHz, CDCl₃, Me₄Si, δ, p.p.m.): 186.6 (C═O), 171.8 (C3), 139.4 (C9), 128.5 and 131.3 (C10, C11, C13, C14), 124.9 (C12), 90.8 (C2), 44.5 (C8), 35.4, 30.6, 29.2 and 25.7 (C4, C5, C6, C7). HRMS (EI), found: 295.0402; C₁₄H₁₆⁸¹BrNO requires: 295.0395.

S3. Refinement

For all three compounds, with the exception of atoms H1, all H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H bond lengths of 0.95 (aromatic CH), 0.99 (CH₂) or 0.98 Å (CH₃). Isotropic displacement parameters for these atoms were set equal to 1.2 (CH and CH₂) or 1.5 (CH₃) times U_eq of the parent atom. Atoms H1 were found in difference Fourier maps and refined freely.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The intramolecular hydrogen bond between atoms O1 and H1 is shown as a dashed bond.
	Fig. 2. The molecular structure of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The intramolecular hydrogen bond between atoms O1 and H1 is shown as a dashed bond.
	Fig. 3. The molecular structure of (III), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The intramolecular hydrogen bond between atoms O1 and H1 is shown as a dashed bond.
	Fig. 4. (a) Bifurcated N—H···O hydrogen bonding and weak C—H···Br and Br···O interactions in the structure of (I). (b) An alternative view of (I), showing the weak C—H···π and C—H···O hydrogen bonds. In both views, molecules A, B, C, D, E and F are at the symmetry positions (x, y, z), (3/2 - x, 1/2 + y, 1/2 - z), (2 - x, 1 - y, -z), (-1/2 + x, 1/2 - y, 1/2 + z), (1 + x, y, z) and (2 - x, 1 - y, 1 - z), respectively.
	Fig. 5. (a) Part of the crystal structure of (II), showing the formation of hydrogen-bonded dimers by intermolecular N—H···O and C—H···O interactions. The molecules are linked together into chains along [001] by weak C—H···Br interactions. (b) An alternative view of (II), showing the formation of intramolecular S(6), intermolecular R^22(12) and intermolecular R^22(14) rings built from N—H···O and C—H···O hydrogen bonds. In both views, molecules A, B, C, D, E and F are at the symmetry positions (x, y, z), (-1 + x, y, 1 + z), (2 - x, -y, 1 - z), (1 + x, y, -1 + z), (-1 + x, y, z) and (2 - x, 1 - y, 1 - z), respectively.
	Fig. 6. Part of the crystal structure of (III), showing the intra- and intermolecular N—H···O hydrogen-bonding pattern. Chains of molecules are linked together along the [101] direction by weak C—H···Br interactions, and along the [011] direction by weak C—H···π and C—H···O hydrogen bonds. Molecules A, B, C, D, E and F are at symmetry positions (x, y, z), (1 + x, 1/2 - y, -1/2 + z), (1 - x, 1 - y, 1 - z), (x, 3/2 - y, -1/2 + z), (-1 + x, 1/2 - y, 1/2 + z) and (1 - x, -1/2 + y, 3/2 - z), respectively.

(I) (2Z)-1-(4-Bromophenyl)-2-(pyrrolidin-2-ylidene)ethanone

Crystal data

C12H12BrNO	F(000) = 536
Mr = 266.14	Dx = 1.645 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4950 reflections
a = 5.6636 (3) Å	θ = 2.3–28.3°
b = 18.9255 (9) Å	µ = 3.80 mm^−1
c = 10.0500 (5) Å	T = 173 K
β = 94.136 (1)°	Irregular, colourless
V = 1074.42 (9) Å^3	0.37 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2595 independent reflections
Radiation source: fine-focus sealed tube	2307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2005) Ratio of minimum to maximum apparent transmission: 0.688943. In the Tmin line above, Tmin=Tmax*min_to_max_ratio	h = −7→7
Tmin = 0.334, Tmax = 0.517	k = −25→25
9815 measured reflections	l = −12→13

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 0.4602P] where P = (Fo^2 + 2Fc^2)/3
2595 reflections	(Δ/σ)max = 0.001
140 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.60 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
C1	0.9730 (3)	0.44906 (9)	0.25700 (16)	0.0210 (3)
C2	1.1484 (3)	0.49029 (9)	0.32778 (16)	0.0226 (3)
H2	1.1654	0.4864	0.4222	0.027*
C3	1.2965 (3)	0.53606 (9)	0.26607 (16)	0.0207 (3)
C4	1.5059 (3)	0.57216 (9)	0.33749 (17)	0.0244 (3)
H4A	1.6340	0.5379	0.3618	0.029*
H4B	1.4601	0.5961	0.4193	0.029*
C5	1.5838 (4)	0.62588 (11)	0.2353 (2)	0.0344 (4)
H5A	1.5132	0.6729	0.2499	0.041*
H5B	1.7583	0.6305	0.2404	0.041*
C6	1.4912 (3)	0.59493 (10)	0.10163 (18)	0.0259 (4)
H6A	1.4393	0.6326	0.0377	0.031*
H6B	1.6128	0.5655	0.0623	0.031*
C7	0.8607 (3)	0.39012 (9)	0.33071 (16)	0.0206 (3)
C8	0.9786 (3)	0.35747 (10)	0.44009 (17)	0.0243 (3)
H8	1.1283	0.3751	0.4737	0.029*
C9	0.8816 (3)	0.29946 (9)	0.50130 (19)	0.0267 (4)
H9	0.9644	0.2771	0.5754	0.032*
C10	0.6626 (3)	0.27499 (9)	0.45221 (18)	0.0239 (3)
C11	0.5389 (3)	0.30677 (9)	0.34419 (18)	0.0250 (4)
H11	0.3880	0.2895	0.3120	0.030*
C12	0.6394 (3)	0.36434 (9)	0.28375 (17)	0.0236 (3)
H12	0.5564	0.3864	0.2095	0.028*
N1	1.2910 (3)	0.55212 (8)	0.13813 (15)	0.0233 (3)
O1	0.9111 (2)	0.45751 (7)	0.13607 (12)	0.0269 (3)
Br1	0.53114 (3)	0.195674 (10)	0.535138 (19)	0.03230 (8)
H1	1.196 (4)	0.5339 (12)	0.088 (2)	0.029 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0214 (8)	0.0221 (8)	0.0194 (7)	0.0025 (6)	0.0011 (6)	−0.0006 (6)
C2	0.0256 (8)	0.0246 (8)	0.0172 (7)	−0.0012 (6)	−0.0013 (6)	−0.0010 (6)
C3	0.0221 (8)	0.0193 (7)	0.0202 (7)	0.0024 (6)	−0.0015 (6)	−0.0022 (6)
C4	0.0243 (8)	0.0280 (8)	0.0200 (8)	−0.0030 (6)	−0.0028 (6)	−0.0026 (7)
C5	0.0393 (11)	0.0355 (10)	0.0278 (9)	−0.0141 (8)	−0.0015 (8)	0.0000 (8)
C6	0.0253 (8)	0.0288 (9)	0.0237 (8)	−0.0030 (7)	0.0016 (7)	0.0031 (7)
C7	0.0218 (8)	0.0219 (7)	0.0183 (7)	0.0009 (6)	0.0030 (6)	−0.0035 (6)
C8	0.0211 (8)	0.0274 (8)	0.0240 (8)	−0.0023 (6)	−0.0015 (6)	0.0012 (7)
C9	0.0259 (9)	0.0277 (9)	0.0260 (9)	0.0004 (7)	−0.0013 (7)	0.0035 (7)
C10	0.0252 (8)	0.0222 (8)	0.0250 (8)	−0.0023 (6)	0.0060 (7)	−0.0019 (7)
C11	0.0219 (8)	0.0288 (9)	0.0241 (8)	−0.0033 (6)	0.0012 (7)	−0.0055 (7)
C12	0.0225 (8)	0.0282 (8)	0.0198 (8)	0.0010 (6)	−0.0009 (6)	−0.0025 (7)
N1	0.0243 (7)	0.0260 (7)	0.0189 (7)	−0.0038 (6)	−0.0029 (6)	−0.0003 (6)
O1	0.0299 (7)	0.0317 (7)	0.0182 (6)	−0.0038 (5)	−0.0040 (5)	0.0016 (5)
Br1	0.03206 (12)	0.02948 (12)	0.03574 (13)	−0.00845 (7)	0.00510 (8)	0.00426 (7)

Geometric parameters (Å, º)

C1—O1	1.251 (2)	C6—H6A	0.9900
C1—C2	1.414 (2)	C6—H6B	0.9900
C1—C7	1.505 (2)	C7—C8	1.389 (2)
C2—C3	1.383 (2)	C7—C12	1.395 (2)
C2—H2	0.9500	C8—C9	1.391 (2)
C3—N1	1.319 (2)	C8—H8	0.9500
C3—C4	1.506 (2)	C9—C10	1.382 (3)
C4—C5	1.532 (3)	C9—H9	0.9500
C4—H4A	0.9900	C10—C11	1.386 (3)
C4—H4B	0.9900	C10—Br1	1.8952 (17)
C5—C6	1.524 (3)	C11—C12	1.389 (2)
C5—H5A	0.9900	C11—H11	0.9500
C5—H5B	0.9900	C12—H12	0.9500
C6—N1	1.462 (2)	N1—H1	0.79 (2)
O1—C1—C2	123.77 (16)	N1—C6—H6B	111.3
O1—C1—C7	118.30 (15)	C5—C6—H6B	111.3
C2—C1—C7	117.89 (14)	H6A—C6—H6B	109.2
C3—C2—C1	123.14 (15)	C8—C7—C12	118.74 (16)
C3—C2—H2	118.4	C8—C7—C1	121.53 (15)
C1—C2—H2	118.4	C12—C7—C1	119.60 (15)
N1—C3—C2	127.51 (15)	C7—C8—C9	121.23 (16)
N1—C3—C4	108.80 (15)	C7—C8—H8	119.4
C2—C3—C4	123.56 (15)	C9—C8—H8	119.4
C3—C4—C5	103.69 (14)	C10—C9—C8	118.67 (17)
C3—C4—H4A	111.0	C10—C9—H9	120.7
C5—C4—H4A	111.0	C8—C9—H9	120.7
C3—C4—H4B	111.0	C9—C10—C11	121.62 (16)
C5—C4—H4B	111.0	C9—C10—Br1	118.66 (13)
H4A—C4—H4B	109.0	C11—C10—Br1	119.73 (13)
C6—C5—C4	103.80 (14)	C10—C11—C12	118.88 (16)
C6—C5—H5A	111.0	C10—C11—H11	120.6
C4—C5—H5A	111.0	C12—C11—H11	120.6
C6—C5—H5B	111.0	C11—C12—C7	120.85 (16)
C4—C5—H5B	111.0	C11—C12—H12	119.6
H5A—C5—H5B	109.0	C7—C12—H12	119.6
N1—C6—C5	102.45 (14)	C3—N1—C6	114.09 (15)
N1—C6—H6A	111.3	C3—N1—H1	119.2 (17)
C5—C6—H6A	111.3	C6—N1—H1	126.0 (17)
O1—C1—C2—C3	−11.1 (3)	C1—C7—C8—C9	−174.91 (16)
C7—C1—C2—C3	166.75 (15)	C7—C8—C9—C10	−0.8 (3)
C1—C2—C3—N1	4.6 (3)	C8—C9—C10—C11	0.0 (3)
C1—C2—C3—C4	−170.83 (16)	C8—C9—C10—Br1	179.71 (13)
N1—C3—C4—C5	13.44 (19)	C9—C10—C11—C12	0.4 (3)
C2—C3—C4—C5	−170.38 (17)	Br1—C10—C11—C12	−179.25 (13)
C3—C4—C5—C6	−24.22 (19)	C10—C11—C12—C7	−0.2 (3)
C4—C5—C6—N1	25.86 (19)	C8—C7—C12—C11	−0.5 (2)
O1—C1—C7—C8	152.04 (16)	C1—C7—C12—C11	175.47 (15)
C2—C1—C7—C8	−26.0 (2)	C2—C3—N1—C6	−172.20 (17)
O1—C1—C7—C12	−23.8 (2)	C4—C3—N1—C6	3.8 (2)
C2—C1—C7—C12	158.19 (16)	C5—C6—N1—C3	−19.3 (2)
C12—C7—C8—C9	1.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.79 (2)	2.25 (2)	2.798 (2)	128 (2)
N1—H1···O1^i	0.79 (2)	2.30 (2)	2.9124 (19)	136 (2)
C6—H6B···O1^ii	0.99	2.72	3.524 (3)	139
C4—H4B···Cg^iii	0.99	2.71	3.679 (2)	166
C6—H6A···Br1^iv	0.99	2.97	3.701 (2)	132

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y+1/2, −z+1/2.

(II) (2Z)-1-(4-Bromophenyl)-2-(piperidin-2-ylidene)ethanone

Crystal data

C13H14BrNO	Z = 2
Mr = 280.16	F(000) = 284
Triclinic, P1	Dx = 1.544 Mg m^−3
Hall symbol: -P 1	Melting point = 388–390 K
a = 6.9303 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6280 (2) Å	Cell parameters from 3654 reflections
c = 12.1060 (3) Å	θ = 2.8–28.2°
α = 99.844 (2)°	µ = 3.39 mm^−1
β = 99.545 (1)°	T = 173 K
γ = 102.189 (2)°	Block, colourless
V = 602.64 (3) Å^3	0.49 × 0.19 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2903 independent reflections
Radiation source: fine-focus sealed tube	2387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.0°, θmin = 1.8°
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)]	h = −9→8
Tmin = 0.380, Tmax = 0.593	k = −10→10
7739 measured reflections	l = −14→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0621P)^2] where P = (Fo^2 + 2Fc^2)/3
2903 reflections	(Δ/σ)max < 0.001
149 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.36 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
C1	0.7406 (3)	0.1877 (3)	0.5893 (2)	0.0228 (5)
C2	0.6673 (4)	0.2560 (3)	0.49363 (19)	0.0256 (5)
H2	0.5432	0.2910	0.4903	0.031*
C3	0.7663 (4)	0.2746 (3)	0.4045 (2)	0.0244 (5)
C4	0.6748 (4)	0.3425 (4)	0.3038 (2)	0.0316 (6)
H4A	0.6088	0.4397	0.3315	0.038*
H4B	0.5690	0.2401	0.2518	0.038*
C5	0.8283 (4)	0.4190 (4)	0.2362 (2)	0.0348 (6)
H5A	0.7570	0.4402	0.1636	0.042*
H5B	0.9163	0.5379	0.2814	0.042*
C6	0.9547 (5)	0.2851 (4)	0.2105 (2)	0.0364 (6)
H6A	1.0517	0.3329	0.1648	0.044*
H6B	0.8667	0.1663	0.1650	0.044*
C7	1.0681 (4)	0.2569 (4)	0.3216 (2)	0.0333 (6)
H7A	1.1257	0.1495	0.3049	0.040*
H7B	1.1815	0.3660	0.3560	0.040*
C8	0.6293 (3)	0.1936 (3)	0.6869 (2)	0.0216 (5)
C9	0.4242 (4)	0.1782 (3)	0.6708 (2)	0.0228 (5)
H9	0.3478	0.1635	0.5955	0.027*
C10	0.3268 (4)	0.1840 (3)	0.7629 (2)	0.0261 (5)
H10	0.1850	0.1710	0.7509	0.031*
C11	0.4411 (4)	0.2090 (3)	0.8718 (2)	0.0272 (5)
C12	0.6478 (4)	0.2225 (4)	0.8905 (2)	0.0316 (6)
H12	0.7245	0.2378	0.9658	0.038*
C13	0.7387 (4)	0.2131 (4)	0.7975 (2)	0.0288 (5)
H13	0.8793	0.2201	0.8090	0.035*
Br1	0.31212 (4)	0.22456 (4)	0.99788 (2)	0.04251 (14)
N1	0.9397 (3)	0.2276 (3)	0.40349 (18)	0.0275 (4)
H1	0.998 (5)	0.171 (5)	0.444 (3)	0.048 (10)*
O1	0.8965 (3)	0.1304 (3)	0.60014 (15)	0.0302 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0205 (11)	0.0259 (11)	0.0203 (11)	0.0061 (9)	0.0026 (9)	0.0022 (9)
C2	0.0257 (12)	0.0288 (12)	0.0219 (12)	0.0076 (10)	0.0021 (10)	0.0060 (10)
C3	0.0248 (12)	0.0233 (11)	0.0229 (11)	0.0049 (9)	0.0029 (9)	0.0026 (9)
C4	0.0331 (14)	0.0394 (14)	0.0277 (13)	0.0137 (11)	0.0086 (11)	0.0136 (11)
C5	0.0471 (16)	0.0316 (13)	0.0279 (13)	0.0082 (12)	0.0110 (12)	0.0114 (11)
C6	0.0493 (17)	0.0371 (14)	0.0292 (14)	0.0126 (13)	0.0199 (12)	0.0100 (11)
C7	0.0319 (14)	0.0370 (14)	0.0358 (14)	0.0109 (11)	0.0168 (12)	0.0081 (11)
C8	0.0221 (11)	0.0235 (11)	0.0208 (11)	0.0092 (9)	0.0052 (9)	0.0043 (9)
C9	0.0231 (11)	0.0251 (11)	0.0204 (11)	0.0079 (9)	0.0023 (9)	0.0050 (9)
C10	0.0233 (12)	0.0276 (12)	0.0280 (12)	0.0081 (10)	0.0052 (10)	0.0056 (10)
C11	0.0328 (13)	0.0296 (12)	0.0200 (11)	0.0072 (10)	0.0086 (10)	0.0052 (9)
C12	0.0297 (13)	0.0448 (15)	0.0193 (11)	0.0104 (11)	0.0008 (10)	0.0068 (10)
C13	0.0217 (12)	0.0419 (14)	0.0230 (12)	0.0104 (10)	0.0024 (9)	0.0067 (10)
Br1	0.0422 (2)	0.0624 (2)	0.02652 (17)	0.01429 (14)	0.01652 (12)	0.00835 (13)
N1	0.0272 (11)	0.0336 (11)	0.0237 (10)	0.0081 (9)	0.0068 (8)	0.0090 (9)
O1	0.0251 (9)	0.0455 (11)	0.0248 (9)	0.0166 (8)	0.0055 (7)	0.0104 (8)

Geometric parameters (Å, º)

C1—O1	1.244 (3)	C7—N1	1.452 (3)
C1—C2	1.412 (3)	C7—H7A	0.9900
C1—C8	1.513 (3)	C7—H7B	0.9900
C2—C3	1.382 (3)	C8—C9	1.379 (3)
C2—H2	0.9500	C8—C13	1.392 (3)
C3—N1	1.326 (3)	C9—C10	1.395 (3)
C3—C4	1.502 (3)	C9—H9	0.9500
C4—C5	1.527 (4)	C10—C11	1.381 (3)
C4—H4A	0.9900	C10—H10	0.9500
C4—H4B	0.9900	C11—C12	1.391 (4)
C5—C6	1.506 (4)	C11—Br1	1.892 (2)
C5—H5A	0.9900	C12—C13	1.378 (3)
C5—H5B	0.9900	C12—H12	0.9500
C6—C7	1.514 (4)	C13—H13	0.9500
C6—H6A	0.9900	N1—H1	0.82 (4)
C6—H6B	0.9900
O1—C1—C2	123.6 (2)	N1—C7—C6	112.3 (2)
O1—C1—C8	118.1 (2)	N1—C7—H7A	109.1
C2—C1—C8	118.2 (2)	C6—C7—H7A	109.1
C3—C2—C1	123.6 (2)	N1—C7—H7B	109.1
C3—C2—H2	118.2	C6—C7—H7B	109.1
C1—C2—H2	118.2	H7A—C7—H7B	107.9
N1—C3—C2	121.3 (2)	C9—C8—C13	118.7 (2)
N1—C3—C4	118.3 (2)	C9—C8—C1	122.9 (2)
C2—C3—C4	120.3 (2)	C13—C8—C1	118.4 (2)
C3—C4—C5	113.4 (2)	C8—C9—C10	121.3 (2)
C3—C4—H4A	108.9	C8—C9—H9	119.4
C5—C4—H4A	108.9	C10—C9—H9	119.4
C3—C4—H4B	108.9	C11—C10—C9	118.5 (2)
C5—C4—H4B	108.9	C11—C10—H10	120.8
H4A—C4—H4B	107.7	C9—C10—H10	120.8
C6—C5—C4	109.7 (2)	C10—C11—C12	121.6 (2)
C6—C5—H5A	109.7	C10—C11—Br1	118.87 (19)
C4—C5—H5A	109.7	C12—C11—Br1	119.58 (18)
C6—C5—H5B	109.7	C13—C12—C11	118.5 (2)
C4—C5—H5B	109.7	C13—C12—H12	120.8
H5A—C5—H5B	108.2	C11—C12—H12	120.8
C5—C6—C7	109.7 (2)	C12—C13—C8	121.5 (2)
C5—C6—H6A	109.7	C12—C13—H13	119.2
C7—C6—H6A	109.7	C8—C13—H13	119.2
C5—C6—H6B	109.7	C3—N1—C7	126.7 (2)
C7—C6—H6B	109.7	C3—N1—H1	131 (3)
H6A—C6—H6B	108.2	C7—N1—H1	102 (3)
O1—C1—C2—C3	−3.3 (4)	C13—C8—C9—C10	0.7 (4)
C8—C1—C2—C3	173.5 (2)	C1—C8—C9—C10	179.9 (2)
C1—C2—C3—N1	0.3 (4)	C8—C9—C10—C11	1.2 (4)
C1—C2—C3—C4	178.0 (2)	C9—C10—C11—C12	−2.1 (4)
N1—C3—C4—C5	−22.7 (3)	C9—C10—C11—Br1	178.10 (18)
C2—C3—C4—C5	159.5 (2)	C10—C11—C12—C13	1.0 (4)
C3—C4—C5—C6	49.1 (3)	Br1—C11—C12—C13	−179.2 (2)
C4—C5—C6—C7	−61.0 (3)	C11—C12—C13—C8	1.0 (4)
C5—C6—C7—N1	46.2 (3)	C9—C8—C13—C12	−1.8 (4)
O1—C1—C8—C9	−152.0 (2)	C1—C8—C13—C12	178.9 (2)
C2—C1—C8—C9	31.1 (3)	C2—C3—N1—C7	−173.5 (2)
O1—C1—C8—C13	27.2 (3)	C4—C3—N1—C7	8.8 (4)
C2—C1—C8—C13	−149.7 (2)	C6—C7—N1—C3	−20.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.82 (4)	2.17 (4)	2.656 (3)	118 (3)
N1—H1···O1^i	0.82 (4)	2.55 (4)	3.168 (3)	133 (3)
C5—H5B···O1^ii	0.99	2.63	3.609 (3)	172
C7—H7A···O1^i	0.99	2.58	3.297 (4)	129
C10—H10···O1^iii	0.95	2.40	3.194 (3)	141
C6—H6A···Br1^iv	0.99	3.05	3.894 (3)	144

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

(III) (2Z)-2-(Azepan-2-ylidene)-1-(4-bromophenyl)ethanone

Crystal data

C14H16BrNO	F(000) = 600
Mr = 294.19	Dx = 1.518 Mg m^−3
Monoclinic, P21/c	Melting point = 418–421 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.2867 (3) Å	Cell parameters from 4189 reflections
b = 8.2416 (2) Å	θ = 3.0–28.3°
c = 12.9404 (4) Å	µ = 3.18 mm^−1
β = 100.702 (2)°	T = 173 K
V = 1287.58 (6) Å^3	Plate, colourless
Z = 4	0.49 × 0.44 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3103 independent reflections
Radiation source: fine-focus sealed tube	2401 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ϕ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)]	h = −15→16
Tmin = 0.305, Tmax = 0.647	k = −10→10
9654 measured reflections	l = −14→17

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0326P)^2] where P = (Fo^2 + 2Fc^2)/3
3103 reflections	(Δ/σ)max = 0.001
158 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.41 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
C1	0.44846 (13)	0.25827 (19)	0.62676 (11)	0.0219 (3)
C2	0.53634 (14)	0.14673 (17)	0.63321 (12)	0.0232 (3)
H2	0.5436	0.0654	0.6861	0.028*
C3	0.61272 (13)	0.14880 (18)	0.56695 (12)	0.0220 (3)
C4	0.69894 (13)	0.01775 (19)	0.57524 (13)	0.0282 (4)
H4A	0.6855	−0.0463	0.5094	0.034*
H4B	0.6899	−0.0561	0.6334	0.034*
C5	0.81847 (15)	0.0794 (2)	0.59455 (14)	0.0334 (4)
H5A	0.8248	0.1725	0.6437	0.040*
H5B	0.8677	−0.0076	0.6291	0.040*
C6	0.85902 (15)	0.1325 (2)	0.49493 (15)	0.0348 (4)
H6A	0.9390	0.1578	0.5133	0.042*
H6B	0.8499	0.0409	0.4445	0.042*
C7	0.79852 (14)	0.2789 (2)	0.44183 (13)	0.0321 (4)
H7A	0.8297	0.3053	0.3786	0.039*
H7B	0.8130	0.3725	0.4904	0.039*
C8	0.67445 (14)	0.2583 (2)	0.40920 (12)	0.0296 (4)
H8A	0.6460	0.3450	0.3584	0.035*
H8B	0.6597	0.1531	0.3723	0.035*
C9	0.35676 (13)	0.22392 (17)	0.68635 (11)	0.0216 (3)
C10	0.37037 (14)	0.12603 (18)	0.77591 (12)	0.0243 (3)
H10	0.4409	0.0804	0.8029	0.029*
C11	0.28215 (14)	0.09483 (19)	0.82573 (13)	0.0274 (4)
H11	0.2920	0.0295	0.8873	0.033*
C12	0.17962 (14)	0.15991 (19)	0.78479 (13)	0.0258 (4)
C13	0.16334 (14)	0.25755 (19)	0.69635 (12)	0.0284 (4)
H13	0.0924	0.3017	0.6691	0.034*
C14	0.25294 (14)	0.28938 (19)	0.64840 (12)	0.0266 (4)
H14	0.2431	0.3575	0.5882	0.032*
Br1	0.058155 (15)	0.11948 (2)	0.852615 (15)	0.04177 (8)
N1	0.61284 (12)	0.26316 (17)	0.49508 (10)	0.0246 (3)
H1	0.5659 (16)	0.333 (2)	0.4903 (14)	0.033 (5)*
O1	0.43884 (10)	0.38178 (13)	0.56911 (9)	0.0282 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0238 (8)	0.0200 (8)	0.0212 (8)	−0.0019 (6)	0.0021 (6)	−0.0015 (6)
C2	0.0261 (8)	0.0206 (8)	0.0225 (8)	0.0014 (6)	0.0035 (6)	0.0025 (6)
C3	0.0212 (8)	0.0202 (8)	0.0231 (8)	0.0003 (6)	0.0003 (6)	−0.0017 (6)
C4	0.0285 (9)	0.0220 (8)	0.0353 (9)	0.0051 (7)	0.0086 (7)	0.0048 (7)
C5	0.0257 (9)	0.0335 (9)	0.0399 (10)	0.0079 (7)	0.0035 (8)	0.0073 (8)
C6	0.0249 (9)	0.0337 (9)	0.0477 (11)	0.0037 (8)	0.0119 (8)	0.0044 (8)
C7	0.0295 (9)	0.0334 (9)	0.0364 (10)	0.0023 (8)	0.0139 (8)	0.0049 (8)
C8	0.0308 (9)	0.0345 (9)	0.0249 (8)	0.0043 (8)	0.0092 (7)	0.0035 (7)
C9	0.0241 (8)	0.0184 (7)	0.0224 (8)	0.0007 (6)	0.0045 (6)	−0.0037 (6)
C10	0.0215 (8)	0.0251 (8)	0.0262 (8)	0.0019 (7)	0.0039 (6)	0.0008 (7)
C11	0.0291 (9)	0.0275 (9)	0.0263 (8)	−0.0009 (7)	0.0068 (7)	0.0032 (7)
C12	0.0229 (8)	0.0246 (8)	0.0315 (9)	−0.0047 (6)	0.0093 (7)	−0.0046 (7)
C13	0.0220 (8)	0.0289 (8)	0.0338 (9)	0.0047 (7)	0.0037 (7)	−0.0034 (7)
C14	0.0304 (9)	0.0222 (8)	0.0266 (8)	0.0043 (7)	0.0036 (7)	0.0021 (6)
Br1	0.02703 (11)	0.05149 (14)	0.05033 (14)	−0.00378 (9)	0.01638 (8)	0.00420 (9)
N1	0.0243 (7)	0.0243 (7)	0.0264 (7)	0.0074 (6)	0.0073 (6)	0.0027 (6)
O1	0.0308 (6)	0.0232 (6)	0.0325 (6)	0.0044 (5)	0.0106 (5)	0.0067 (5)

Geometric parameters (Å, º)

C1—O1	1.2546 (18)	C7—H7A	0.9900
C1—C2	1.409 (2)	C7—H7B	0.9900
C1—C9	1.506 (2)	C8—N1	1.4568 (19)
C2—C3	1.384 (2)	C8—H8A	0.9900
C2—H2	0.9500	C8—H8B	0.9900
C3—N1	1.324 (2)	C9—C14	1.388 (2)
C3—C4	1.503 (2)	C9—C10	1.396 (2)
C4—C5	1.530 (2)	C10—C11	1.384 (2)
C4—H4A	0.9900	C10—H10	0.9500
C4—H4B	0.9900	C11—C12	1.381 (2)
C5—C6	1.530 (2)	C11—H11	0.9500
C5—H5A	0.9900	C12—C13	1.383 (2)
C5—H5B	0.9900	C12—Br1	1.8961 (16)
C6—C7	1.514 (2)	C13—C14	1.385 (2)
C6—H6A	0.9900	C13—H13	0.9500
C6—H6B	0.9900	C14—H14	0.9500
C7—C8	1.514 (2)	N1—H1	0.811 (19)
O1—C1—C2	123.45 (14)	C6—C7—H7B	108.5
O1—C1—C9	117.41 (14)	C8—C7—H7B	108.5
C2—C1—C9	119.03 (13)	H7A—C7—H7B	107.5
C3—C2—C1	123.77 (14)	N1—C8—C7	115.03 (13)
C3—C2—H2	118.1	N1—C8—H8A	108.5
C1—C2—H2	118.1	C7—C8—H8A	108.5
N1—C3—C2	122.22 (14)	N1—C8—H8B	108.5
N1—C3—C4	117.97 (14)	C7—C8—H8B	108.5
C2—C3—C4	119.81 (14)	H8A—C8—H8B	107.5
C3—C4—C5	114.55 (14)	C14—C9—C10	118.60 (14)
C3—C4—H4A	108.6	C14—C9—C1	118.14 (14)
C5—C4—H4A	108.6	C10—C9—C1	123.24 (14)
C3—C4—H4B	108.6	C11—C10—C9	120.69 (15)
C5—C4—H4B	108.6	C11—C10—H10	119.7
H4A—C4—H4B	107.6	C9—C10—H10	119.7
C6—C5—C4	114.22 (15)	C12—C11—C10	119.12 (15)
C6—C5—H5A	108.7	C12—C11—H11	120.4
C4—C5—H5A	108.7	C10—C11—H11	120.4
C6—C5—H5B	108.7	C11—C12—C13	121.66 (15)
C4—C5—H5B	108.7	C11—C12—Br1	119.64 (12)
H5A—C5—H5B	107.6	C13—C12—Br1	118.69 (12)
C7—C6—C5	113.65 (14)	C12—C13—C14	118.43 (15)
C7—C6—H6A	108.8	C12—C13—H13	120.8
C5—C6—H6A	108.8	C14—C13—H13	120.8
C7—C6—H6B	108.8	C13—C14—C9	121.49 (15)
C5—C6—H6B	108.8	C13—C14—H14	119.3
H6A—C6—H6B	107.7	C9—C14—H14	119.3
C6—C7—C8	114.91 (15)	C3—N1—C8	125.78 (14)
C6—C7—H7A	108.5	C3—N1—H1	117.9 (13)
C8—C7—H7A	108.5	C8—N1—H1	115.1 (13)
O1—C1—C2—C3	−9.1 (2)	C14—C9—C10—C11	0.1 (2)
C9—C1—C2—C3	166.93 (14)	C1—C9—C10—C11	−178.08 (14)
C1—C2—C3—N1	4.0 (2)	C9—C10—C11—C12	1.0 (2)
C1—C2—C3—C4	−175.82 (15)	C10—C11—C12—C13	−1.1 (2)
N1—C3—C4—C5	56.6 (2)	C10—C11—C12—Br1	−179.59 (12)
C2—C3—C4—C5	−123.64 (16)	C11—C12—C13—C14	0.2 (2)
C3—C4—C5—C6	−83.04 (18)	Br1—C12—C13—C14	178.69 (12)
C4—C5—C6—C7	65.3 (2)	C12—C13—C14—C9	0.9 (2)
C5—C6—C7—C8	−58.5 (2)	C10—C9—C14—C13	−1.0 (2)
C6—C7—C8—N1	74.4 (2)	C1—C9—C14—C13	177.23 (14)
O1—C1—C9—C14	22.8 (2)	C2—C3—N1—C8	−167.04 (15)
C2—C1—C9—C14	−153.44 (14)	C4—C3—N1—C8	12.8 (2)
O1—C1—C9—C10	−159.06 (14)	C7—C8—N1—C3	−71.7 (2)
C2—C1—C9—C10	24.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.811 (19)	2.057 (19)	2.6841 (18)	134.0 (17)
N1—H1···O1^i	0.811 (19)	2.467 (19)	3.0757 (17)	132.7 (17)
C10—H10···O1^ii	0.95	2.59	3.439 (2)	149
C4—H4B···Cg^ii	0.99	2.67	3.5996 (17)	157
C7—H7A···Br1^iii	0.99	2.95	3.6838 (18)	131

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1, −y+1/2, z−1/2.