From small structural modifications to adjustment of structurally dependent properties: 1-methyl-3,5-bis­[(E)-2-thienyl­idene]-4-piperidone and 3,5-bis­[(E)-5-bromo-2-thienyl­idene]-1-methyl-4-piperidone

The mol­ecules of the title compounds, C₁₆H₁₅NOS₂, (I), and C₁₆H₁₃Br₂NOS₂, (II), are E,E-isomers and consist of an extensive conjugated system, which determines their mol­ecular geometries. Compound (I) crystallizes in the monoclinic space group P2₁/c. It has one thio­phene ring disordered over two positions, with a minor component contribution of 0.100 (3). Compound (II) crystallizes in the noncentrosymmetric ortho­rhom­bic space group Pca2₁ with two independent mol­ecules in the unit cell. These mol­ecules are related by a noncrystallographic pseudo-inversion center and possess very similar geometries. The crystal packings of (I) and (II) have a topologically common structural motif, viz. stacks along the b axis, in which the mol­ecules are bound by weak C—H...O hydrogen bonds. The noncentrosymmetric packing of (II) is governed by attractive inter­molecular Br...Br and Br...N inter­actions, which are also responsible for the very high density of (II) (1.861 Mg m⁻³).

S1. Comment

Cross-conjugated dienones of the bis-arylidenecycloalkanone series and related piperidones have recently attracted considerable attention. These compounds are used in the construction of different polymers (Yakimansky et al., 2002; Aly et al., 2003), and in the design of crystals with nonlinear optical (Kishore & Kishore, 1993; Kawamata et al., 1995, 1996; Sarkisov et al., 2005) and fluorescent (Nesterov et al., 2003, 2008) properties. Furthermore, it is well known that they possess a variety of biological activities, such as antiviral (El-Subbagh et al., 2000), antibacterial (Lyrand et al., 1999; Amal Raj et al., 2003) and antiphlogistic (Rovnyak et al., 1982).

Recently, instead of aryl substituents, the use of heterocyclic ligands was suggested, as these are able to bind important metal cations to form diverse coordination associates (Vatsadze et al., 2006). However, to our knowledge, there are a very few structurally characterized compounds of this type in the literature (Vatsadze et al., 2006). In this paper, we describe two new cross-conjugated piperidones with thienylidene substituents in the side chains, 1-methyl-3,5-bis[(E)-2-thienylidene]-4-piperidone, (I), and 3,5-bis[(E)-5-bromo-2-thienylidene]-1-methyl-4-piperidone, (II), which represent modified analogs of the very recently reported compounds 2,6-bis[(2-thienyl)methylidene]cyclohexanone, (III) (Vatsadze et al., 2006), and 2,6-bis[(5-methylthiophene-2-yl)methylene]cyclohexanone, (IV) (Liang et al., 2007) (see first scheme). One purpose of our investigation was to analyze the influence of small structural modifications of the molecules on their structurally dependent properties. It should be noted that these compounds are potential antitumor (anticancer) agents (Dimmock et al., 1992, 1994, 2001), and even small differences in the structures may cause significant changes in their biological activity.

Compound (I) crystallizes in the monoclinic space group P2₁/c. One thiophene ring is disordered over two positions related by a 180° rotation about the C6—C7 bond. The minor component contribution refined to 0.100 (3) (Fig. 1).

In general, the extended planar structure of conjugated bonds is the more favorable, and deviations from this rule are usually caused by specific reasons such as steric factors, hydrogen bonds and different attractive interactions. Quantum-chemical calculations using the density functional theory method of the GAUSSIAN03 program, B3LYP functional, 6-31G* basis set (Frisch et al., 2003), also show that the minimum of the potential energy surface corresponds to the major conformer (conformer A) found experimentally in the crystal structure of (I) (see second scheme; 1 kcal mol^-1 = 4.184 kJ mol^-1). Although the energy differences between the three conformers, A, B and C, are not large, there is a clear trend for compounds with larger disruptions of the conjugated system to be less stable. In the crystal structure of (I), the presence of the minor conformer B may be explained by the weak intermolecular C6—H6A···S1'(1-x, -y, -z) hydrogen bond [C6···S1' = 3.487 (2), H6A···S1' = 2.78 Å and C6—H6A···S1' = 132°].

Compound (II) crystallizes in the noncentrosymmetric orthorhombic space group Pca2₁, with two independent molecules, A and B, in the unit cell (Fig. 2). However, in the crystal structure, molecules A and B are related by a noncrystallographic pseudo-inversion center with coordinates [0.3045 (2), 0.7536 (6), 0.5553 (2)]. Consequently, molecules A and B possess very similar geometries (Fig. 3), and only the average values of the geometric parameters of (II) are discussed below.

In the molecules of both compounds, the central piperidone ring adopts a flattened boat conformation; atoms N1 and C1 lie 0.702 (1) and 0.242 (1) Å in (I), and 0.699 (3) and 0.158 (3) Å in (II), respectively, out of the C2/C3/C4/C5 plane. Atom N1 of the heterocycle has a pyramidal coordination, as revealed by the sums of the bond angles about this atom of 332.6 (2)° in (I) and 330.2 (3)° in (II). The methyl group occupies the more sterically favored equatorial position.

Both (I) and (II) contain three planar fragments. The first of these includes the plane of the piperidone cycle ([Please list atoms] P_A), while the planar fragments P_B [Please list atoms] and P_C [Please list atoms] include a thiophene ring and adjacent atoms. The dihedral angles P_A/P_B, P_A/P_C and P_B/P_C between these fragments are 13.2 (1), 17.0 (1) and 27.4 (1)°, respectively, in (I), and 10.9 (3), 13.9 (3) and 23.4 (3)°, respectively, in (II).

The molecules of (I) and (II) can exist as E,E-, Z,E- and Z,Z-isomers (see third scheme). Evidently, the E,E-isomers observed for (I) and (II), both in the solid state and in solution (see ¹H NMR data in Experimental), are preferred due to steric reasons. Nevertheless, they may undergo isomerization into the Z,E- and Z,Z-isomers in solution upon irradiation with visible light (Vatsadze et al., 2006).

Interestingly, the introduction of the Br atoms in the thiophene rings of (II) does not give rise to significant changes to its molecular geometry compared with that of (I). Moreover, their structural features are similar to those of compounds (III) and (IV). It is surprising that, despite the presence of a bulkier N—CH₃ fragment on the central piperidone ring compared with a CH₂ fragment, compounds (I) and (III) are isostructural. These findings allow us to propose that the molecular structures of compounds (I)–(IV), as well as the crystal structures of compounds (I) and (III), are defined by similar effects.

The molecular geometries of compounds (I)–(IV) are determined by an extensive conjugated system that is quite stable to the influence of substituents of different types. For this reason, neither the introduction of simple substituents (Me, Hal) to peripheral parts, nor the replacement of one fragment on the saturated part of the central piperidone cycle by another of comparable dimensions, can alter its structure substantially. Thus, any small modifications of compounds containing analogous systems will mainly affect their molecular arrangement (or their crystal packing in the case of the solid state), and, consequently, their chemical properties as a whole.

In the case of dibenzylidenecycloalkanones, it has previously been established that intermolecular C—H···O hydrogen bonds between the carbonyl O atom and an H atom of the methylene groups of the central ring are an important factor in the design of crystals with nonlinear optical properties (Kawamata et al., 1998). Hydrogen bonds of this type binding the molecules within stacks along the b axis are also revealed in the crystal structures of (I)–(IV) (Table 1). Apparently, these hydrogen bonds alone are responsible for the isostructurality of (I) and (III). The topologically common structural motif (stacks along the b axis, in which the molecules are bound by C—H···O hydrogen bonds) is also maintained in the crystal structures of (II) and (IV). However, in the crystal structure of (IV), the stacks are shifted relative to each other compared with the crystal structures of (I) and (III), due to the presence of additional peripheral methyl groups, resulting in the space group P2₁/n.

It is very important to note that the crystal packing of the molecules of (I), (III) and (IV) is centrosymmetric. However, in order for any compound to display nonlinear optical properties, its crystal packing should be noncentrosymmetric. To this end, we decided to use the well known attractive intermolecular interactions of halogen–halogen (Desiraju & Parthasarathy, 1989; Price et al., 1994; Saha et al., 2006) and halogen–nitrogen (Desiraju & Harlow, 1989; Lucassen et al., 2007) types. It was suggested that, owing to these interactions, the introduction of Br atoms at the peripheral positions of the thiophene rings of (III) does not destroy its common structural motif, but results in a shift of the stacks in such a manner that the crystal packing of the compound loses the crystallographic inversion center. Indeed, compound (II) has a noncentrosymmetric crystal structure (see above), while the common structural motif is preserved.

The Br···Br [Br1A···Br2B(1/2 - x, 1 + y, 1/2 + z) = 3.591 (2) Å] and Br···N [Br1A···N1B(1 - x, 2 - y, 1/2 + z) = 3.168 (4) Å] intermolecular interactions result in a very high density for (II) (1.861 Mg m^-3), even among bromine-containing compounds. The average crystal density of bromine-containing organic compounds with short Br···Br contacts is 1.75 (2) Mg m^-3, but without such contacts the density is lower, at 1.619 (6) Mg m^-3 [Cambridge Structural Database (Allen, 2002), 2009 release, [How many hits in each case?]). The crystal packing of (II), which resembles that of dendro-epithelium [Reference?], is presented in Fig. 4.

Comparison of the structures of (I) and (II) with analogous compounds has shown that their molecules are similar to piperidones used as anticancer agents (Das et al., 2007). Their combination of remarkable features suggests potential application of these compounds as agents for cancer treatment.

S2. Experimental

For the preparation of (I), a mixture of 1-methyl-4-piperidone (1.13 g, 0.01 mol) and 2-thiophene carboxaldehyde (2.24 g, 0.02 mol) was treated with alcoholic NaOH (50 ml, 10%) and stirred at room temperature for 30 min. The crude product was filtered and recrystallized from ethanol to give yellow plate-like crystals of (I) (yield 2.41 g, 80%; m.p. 385–387 K). Analysis: ¹H NMR (CDCl₃, 300 MHz, δ, p.p.m.): 7.89 [s, 2H, CH (vinyl)], 7.11–7.52 [m, 6H, CH (thiophene)], 3.76 (s, 4H, CH₂), 2.55 (s, 3H, CH₃).

For the preparation of (II), a mixture of 1-methyl-4-piperidone (1.13 g, 0.01 mol) and 5-bromo-2-thiophene carboxaldehyde (3.82 g, 0.02 mol) was treated with alcoholic NaOH (50 ml, 10%) and stirred at room temperature for 30 min. The crude product was filtered and recrystallized from methanol to give pink needle-like crystals of (II) (yield 4.32 g, 94%; m.p. 422–423 K). Analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.74 [s, 2H, CH (vinyl)], 7.04–7.09 [m, 4H, CH (thiophene)], 3.67 (s, 4H, CH₂), 2.56 (s, 3H, CH₃).

S3. Refinement

H atoms were placed in calculated positions and refined in the riding model, with C—H = 0.95–0.99 Å [Please check added text] and with U_iso(H) = 1.5U_eq(C) for CH₃ groups or 1.2U_eq(C) for other groups.

Twenty distance restraints were used to fit the ideal conformations for both orientations of the disordered thiophene ring in compound (I). The S—C distances were fixed at 1.740 (2) (S1—C7 and S1'—C7) and 1.710 (2) Å (S1—C10 and S1'—C10') (four restraints). Single-bond C—C distances were fixed at 1.420 (2) Å (two restraints), and double-bond C═C distances were fixed at 1.400 (2) (C7═C8 and C7═C8') and 1.360 (2) Å (C9═C10 and C9'═C10') (four restraints). 1–3 [Meaning?] S···C distances were fixed at 2.570 (2) (S1···C9 and S1'···C9') and 2.550 (2) Å (S1···C8 and S1'···C8') (four restraints). 1–3 [Meaning?] C···C distances were fixed at 2.490 (2) (C7···C10 and C7···C10'), 2.340 (2) (C7···C9 and C7···C9') and 2.320 (2) Å (C8···C10 and C8···C10') (six restraints). Moreover, it was taken into account that the thiophene ring is flat (two restraints), and the anisotropic displacement parameters for both the S atoms and the corresponding C atoms of the thiophene ring are equal (three restraints). Twenty on [twenty one?] reflections, with experimentally observed F² deviating significantly from the theoretically calculated F², were omitted from the refinement.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Both positions of the disordered thiophene ring are drawn by open lines [This is not shown - please revise]. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. The two independent molecules, A and B, related by a noncrystallographic pseudo-inversion center, are depicted. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 3. A comparison of the conformations of molecules A (solid lines) and B (dashed lines) in (II). [Dashed lines indicate what?] Fig. 4. A packing diagram of (II), along the b axis. Dashed lines indicate intermolecular non-valent Br···Br and Br···N interactions. H atoms have been omitted for clarity.

(I) 1-methyl-3,5-bis[(E)-2-thienylidene]-4-piperidone

Crystal data

C16H15NOS2	F(000) = 632
Mr = 301.41	Dx = 1.400 Mg m^−3
Monoclinic, P21/c	Melting point = 385–387 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.108 (5) Å	Cell parameters from 4122 reflections
b = 12.609 (4) Å	θ = 2.7–29.9°
c = 7.523 (2) Å	µ = 0.37 mm^−1
β = 93.962 (4)°	T = 100 K
V = 1429.8 (8) Å^3	Plate, yellow
Z = 4	0.55 × 0.24 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	3779 independent reflections
Radiation source: fine-focus sealed tube	2841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ and ω scans	θmax = 29.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −20→20
Tmin = 0.824, Tmax = 0.957	k = −17→17
14615 measured reflections	l = −10→10

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) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 0.8P] where P = (Fo^2 + 2Fc^2)/3
3779 reflections	(Δ/σ)max = 0.001
188 parameters	Δρmax = 0.51 e Å^−3
24 restraints	Δρmin = −0.49 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	Occ. (<1)
S1	0.46374 (4)	0.30311 (5)	0.14860 (9)	0.02256 (15)	0.90
S1'	0.4277 (3)	0.0812 (4)	0.1280 (10)	0.02256 (15)	0.10
O1	0.76774 (10)	0.07327 (11)	0.05425 (19)	0.0222 (3)
N1	0.74434 (11)	0.37859 (13)	−0.0014 (2)	0.0176 (3)
C1	0.75997 (13)	0.16789 (17)	0.0867 (3)	0.0182 (4)
S2	1.01848 (4)	0.37264 (4)	0.28291 (7)	0.02318 (15)
C2	0.67093 (13)	0.21910 (16)	0.0923 (2)	0.0179 (4)
C3	0.66677 (13)	0.33782 (16)	0.0822 (3)	0.0191 (4)
H3A	0.6120	0.3598	0.0118	0.023*
H3B	0.6650	0.3677	0.2035	0.023*
C4	0.82526 (13)	0.35558 (16)	0.1100 (3)	0.0189 (4)
H4A	0.8213	0.3881	0.2289	0.023*
H4B	0.8770	0.3869	0.0551	0.023*
C5	0.83809 (13)	0.23790 (16)	0.1298 (2)	0.0171 (4)
C6	0.60143 (13)	0.15425 (17)	0.1119 (3)	0.0184 (4)
H6A	0.6154	0.0808	0.1128	0.022*
C7	0.50961 (8)	0.17788 (11)	0.1317 (2)	0.0184 (4)
C8	0.44331 (11)	0.10069 (11)	0.1357 (3)	0.0182 (5)	0.90
H8A	0.4541	0.0267	0.1283	0.022*	0.90
C9	0.35798 (10)	0.14540 (13)	0.1522 (3)	0.0245 (4)	0.90
H9A	0.3055	0.1042	0.1568	0.029*	0.90
C10	0.35904 (9)	0.25310 (13)	0.1607 (3)	0.0245 (4)	0.90
H10A	0.3078	0.2955	0.1719	0.029*	0.90
C8'	0.4723 (4)	0.2775 (3)	0.1595 (17)	0.0182 (5)	0.10
H8B	0.5055	0.3416	0.1661	0.022*	0.10
C9'	0.3795 (5)	0.2722 (7)	0.177 (3)	0.0245 (4)	0.10
H9B	0.3439	0.3327	0.1960	0.029*	0.10
C10'	0.3466 (2)	0.1720 (8)	0.163 (2)	0.0245 (4)	0.10
H10B	0.2859	0.1545	0.1709	0.029*	0.10
C12	0.99763 (13)	0.23799 (16)	0.2543 (3)	0.0187 (4)
C11	0.91457 (13)	0.19097 (17)	0.1888 (3)	0.0195 (4)
H11A	0.9138	0.1156	0.1871	0.023*
C13	1.07333 (13)	0.17977 (18)	0.3098 (3)	0.0222 (4)
H13A	1.0764	0.1046	0.3063	0.027*
C14	1.14501 (14)	0.24562 (18)	0.3721 (3)	0.0231 (5)
H14A	1.2014	0.2190	0.4144	0.028*
C15	1.12484 (14)	0.35068 (18)	0.3650 (3)	0.0244 (5)
H15A	1.1653	0.4054	0.4016	0.029*
C16	0.73609 (14)	0.49166 (17)	−0.0372 (3)	0.0229 (4)
H16A	0.7888	0.5166	−0.0937	0.034*
H16B	0.7307	0.5299	0.0750	0.034*
H16C	0.6832	0.5047	−0.1171	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0163 (3)	0.0271 (3)	0.0243 (3)	0.0008 (2)	0.0017 (2)	0.0002 (2)
S1'	0.0163 (3)	0.0271 (3)	0.0243 (3)	0.0008 (2)	0.0017 (2)	0.0002 (2)
O1	0.0197 (8)	0.0244 (7)	0.0226 (7)	−0.0002 (6)	0.0013 (6)	−0.0031 (6)
N1	0.0157 (8)	0.0232 (8)	0.0141 (8)	−0.0016 (7)	0.0017 (6)	0.0014 (6)
C1	0.0164 (10)	0.0266 (10)	0.0114 (9)	−0.0012 (8)	0.0007 (7)	0.0003 (7)
S2	0.0194 (3)	0.0266 (3)	0.0233 (3)	−0.0034 (2)	−0.0004 (2)	0.0016 (2)
C2	0.0164 (10)	0.0244 (10)	0.0127 (9)	−0.0006 (8)	−0.0012 (7)	0.0001 (7)
C3	0.0157 (10)	0.0245 (10)	0.0174 (9)	0.0004 (8)	0.0020 (8)	0.0003 (8)
C4	0.0163 (10)	0.0234 (10)	0.0169 (9)	−0.0020 (8)	−0.0001 (8)	−0.0002 (7)
C5	0.0162 (10)	0.0238 (10)	0.0116 (9)	−0.0016 (8)	0.0029 (7)	−0.0007 (7)
C6	0.0163 (10)	0.0246 (10)	0.0142 (9)	−0.0002 (8)	−0.0006 (7)	−0.0002 (7)
C7	0.0163 (10)	0.0247 (10)	0.0138 (9)	−0.0005 (8)	−0.0013 (7)	0.0004 (7)
C8	0.0125 (12)	0.0251 (13)	0.0173 (11)	−0.0044 (9)	0.0023 (9)	0.0013 (10)
C9	0.0142 (7)	0.0373 (10)	0.0219 (8)	−0.0033 (7)	0.0015 (6)	0.0077 (8)
C10	0.0142 (7)	0.0373 (10)	0.0219 (8)	−0.0033 (7)	0.0015 (6)	0.0077 (8)
C8'	0.0125 (12)	0.0251 (13)	0.0173 (11)	−0.0044 (9)	0.0023 (9)	0.0013 (10)
C9'	0.0142 (7)	0.0373 (10)	0.0219 (8)	−0.0033 (7)	0.0015 (6)	0.0077 (8)
C10'	0.0142 (7)	0.0373 (10)	0.0219 (8)	−0.0033 (7)	0.0015 (6)	0.0077 (8)
C12	0.0169 (10)	0.0226 (9)	0.0165 (9)	−0.0021 (8)	0.0012 (7)	0.0008 (7)
C11	0.0168 (10)	0.0264 (10)	0.0157 (9)	−0.0016 (8)	0.0033 (8)	−0.0001 (8)
C13	0.0155 (10)	0.0321 (12)	0.0190 (10)	−0.0029 (8)	0.0014 (8)	0.0011 (8)
C14	0.0147 (10)	0.0323 (12)	0.0220 (10)	−0.0009 (9)	−0.0010 (8)	0.0026 (8)
C15	0.0180 (10)	0.0347 (12)	0.0206 (10)	−0.0073 (9)	0.0012 (8)	0.0007 (9)
C16	0.0217 (11)	0.0256 (10)	0.0213 (10)	−0.0017 (9)	0.0011 (8)	0.0012 (8)

Geometric parameters (Å, º)

S1—C10	1.7112 (15)	C7—C8	1.399 (3)
S1—C7	1.7326 (14)	C8—C9	1.420 (3)
S1'—C10'	1.7097 (18)	C8—H8A	0.9500
S1'—C7	1.7353 (18)	C9—C10	1.360 (4)
O1—C1	1.225 (2)	C9—H9A	0.9500
N1—C16	1.455 (3)	C10—H10A	0.9500
N1—C3	1.461 (3)	C8'—C9'	1.419 (4)
N1—C4	1.463 (3)	C8'—H8B	0.9500
C1—C5	1.492 (3)	C9'—C10'	1.359 (4)
C1—C2	1.495 (3)	C9'—H9B	0.9500
S2—C15	1.704 (2)	C10'—H10B	0.9500
S2—C12	1.737 (2)	C12—C13	1.398 (3)
C2—C6	1.347 (3)	C12—C11	1.443 (3)
C2—C3	1.500 (3)	C11—H11A	0.9500
C3—H3A	0.9900	C13—C14	1.418 (3)
C3—H3B	0.9900	C13—H13A	0.9500
C4—C5	1.503 (3)	C14—C15	1.360 (3)
C4—H4A	0.9900	C14—H14A	0.9500
C4—H4B	0.9900	C15—H15A	0.9500
C5—C11	1.346 (3)	C16—H16A	0.9800
C6—C7	1.437 (2)	C16—H16B	0.9800
C6—H6A	0.9500	C16—H16C	0.9800
C7—C8'	1.398 (4)
C10—S1—C7	92.52 (7)	C9—C8—H8A	123.8
C10'—S1'—C7	92.59 (9)	C10—C9—C8	113.13 (11)
C16—N1—C3	111.32 (16)	C10—C9—H9A	123.4
C16—N1—C4	110.98 (16)	C8—C9—H9A	123.4
C3—N1—C4	110.34 (16)	C9—C10—S1	111.94 (9)
O1—C1—C5	122.30 (19)	C9—C10—H10A	124.0
O1—C1—C2	121.68 (18)	S1—C10—H10A	124.0
C5—C1—C2	115.98 (18)	C7—C8'—C9'	112.48 (12)
C15—S2—C12	92.56 (11)	C7—C8'—H8B	123.8
C6—C2—C1	116.78 (19)	C9'—C8'—H8B	123.8
C6—C2—C3	125.53 (19)	C10'—C9'—C8'	113.27 (12)
C1—C2—C3	117.66 (17)	C10'—C9'—H9B	123.4
N1—C3—C2	109.93 (16)	C8'—C9'—H9B	123.4
N1—C3—H3A	109.7	C9'—C10'—S1'	111.83 (11)
C2—C3—H3A	109.7	C9'—C10'—H10B	124.1
N1—C3—H3B	109.7	S1'—C10'—H10B	124.1
C2—C3—H3B	109.7	C13—C12—C11	124.1 (2)
H3A—C3—H3B	108.2	C13—C12—S2	109.78 (16)
N1—C4—C5	110.46 (16)	C11—C12—S2	126.13 (16)
N1—C4—H4A	109.6	C5—C11—C12	129.7 (2)
C5—C4—H4A	109.6	C5—C11—H11A	115.2
N1—C4—H4B	109.6	C12—C11—H11A	115.2
C5—C4—H4B	109.6	C12—C13—C14	112.4 (2)
H4A—C4—H4B	108.1	C12—C13—H13A	123.8
C11—C5—C1	117.38 (19)	C14—C13—H13A	123.8
C11—C5—C4	124.67 (19)	C15—C14—C13	113.2 (2)
C1—C5—C4	117.92 (17)	C15—C14—H14A	123.4
C2—C6—C7	130.62 (19)	C13—C14—H14A	123.4
C2—C6—H6A	114.7	C14—C15—S2	112.06 (17)
C7—C6—H6A	114.7	C14—C15—H15A	124.0
C8'—C7—C6	127.1 (3)	S2—C15—H15A	124.0
C8—C7—C6	123.78 (14)	N1—C16—H16A	109.5
C6—C7—S1	126.20 (12)	N1—C16—H16B	109.5
C6—C7—S1'	123.0 (3)	H16A—C16—H16B	109.5
C8'—C7—S1'	109.83 (11)	N1—C16—H16C	109.5
C8—C7—S1	110.00 (10)	H16A—C16—H16C	109.5
C7—C8—C9	112.42 (11)	H16B—C16—H16C	109.5
C7—C8—H8A	123.8
O1—C1—C2—C6	18.7 (3)	C2—C6—C7—C8	174.33 (17)
C5—C1—C2—C6	−159.01 (17)	C2—C6—C7—S1	−4.0 (3)
O1—C1—C2—C3	−163.39 (18)	C2—C6—C7—S1'	171.8 (3)
C5—C1—C2—C3	18.9 (2)	C10—S1—C7—C6	178.56 (18)
C16—N1—C3—C2	171.57 (16)	C10'—S1'—C7—C6	178.9 (6)
C4—N1—C3—C2	−64.8 (2)	C6—C7—C8—C9	−178.57 (17)
C6—C2—C3—N1	−159.61 (18)	C6—C7—C8'—C9'	−178.9 (6)
C1—C2—C3—N1	22.7 (2)	C15—S2—C12—C13	0.31 (16)
C16—N1—C4—C5	−173.94 (16)	C15—S2—C12—C11	178.43 (18)
C3—N1—C4—C5	62.2 (2)	C1—C5—C11—C12	−174.16 (19)
O1—C1—C5—C11	−21.1 (3)	C4—C5—C11—C12	3.8 (3)
C2—C1—C5—C11	156.57 (17)	C13—C12—C11—C5	−179.0 (2)
O1—C1—C5—C4	160.81 (18)	S2—C12—C11—C5	3.1 (3)
C2—C1—C5—C4	−21.5 (2)	C11—C12—C13—C14	−178.51 (18)
N1—C4—C5—C11	164.33 (18)	S2—C12—C13—C14	−0.3 (2)
N1—C4—C5—C1	−17.7 (2)	C12—C13—C14—C15	0.2 (3)
C1—C2—C6—C7	176.19 (18)	C13—C14—C15—S2	0.0 (2)
C3—C2—C6—C7	−1.6 (3)	C12—S2—C15—C14	−0.20 (17)
C2—C6—C7—C8'	−9.4 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1^i	0.99	2.67	3.624 (3)	161
C15—H15A···O1^ii	0.95	2.36	3.278 (3)	163

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

(II) 3,5-bis[(E)-5-bromo-2-thienylidene]-1-methyl-4-piperidone

Crystal data

C16H13Br2NOS2	Dx = 1.861 Mg m^−3
Mr = 459.21	Melting point = 422–423 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 6205 reflections
a = 23.222 (3) Å	θ = 2.4–26.8°
b = 5.8840 (7) Å	µ = 5.20 mm^−1
c = 23.994 (3) Å	T = 100 K
V = 3278.6 (7) Å^3	Needle, pink
Z = 8	0.50 × 0.30 × 0.20 mm
F(000) = 1808

Data collection

Bruker APEXII CCD diffractometer	10192 independent reflections
Radiation source: fine-focus sealed tube	7285 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.099
ϕ and ω scans	θmax = 30.8°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −33→33
Tmin = 0.111, Tmax = 0.353	k = −8→8
49136 measured reflections	l = −34→34

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.060P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
10192 reflections	Δρmax = 1.48 e Å^−3
400 parameters	Δρmin = −1.20 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.347 (7)

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
Br1A	0.689885 (18)	1.05022 (7)	0.783258 (18)	0.02059 (10)
Br2A	0.102389 (19)	1.04778 (8)	0.576412 (19)	0.02223 (10)
S1A	0.56950 (5)	0.89985 (18)	0.73920 (5)	0.0178 (2)
S2A	0.22088 (5)	0.89080 (19)	0.62297 (5)	0.0182 (2)
O1A	0.40998 (13)	0.3274 (5)	0.64442 (13)	0.0207 (7)
N1A	0.37507 (16)	0.8598 (6)	0.74114 (15)	0.0163 (8)
C1A	0.4018 (2)	0.5155 (7)	0.66477 (17)	0.0167 (10)
C2A	0.4502 (2)	0.6433 (7)	0.69223 (18)	0.0165 (10)
C3A	0.43719 (18)	0.8576 (7)	0.72381 (19)	0.0175 (10)
H3A	0.4621	0.8669	0.7572	0.021*
H3B	0.4453	0.9912	0.7000	0.021*
C4A	0.3376 (2)	0.8555 (7)	0.69200 (19)	0.0200 (10)
H4A	0.3464	0.9875	0.6679	0.024*
H4B	0.2969	0.8678	0.7039	0.024*
C5A	0.34581 (18)	0.6401 (7)	0.65961 (17)	0.0155 (10)
C6A	0.5044 (2)	0.5607 (8)	0.68478 (18)	0.0189 (10)
H6A	0.5063	0.4228	0.6643	0.023*
C7A	0.55891 (18)	0.6464 (8)	0.70261 (18)	0.0159 (10)
C8A	0.61105 (18)	0.5449 (8)	0.69159 (18)	0.0173 (10)
H8A	0.6146	0.4094	0.6703	0.021*
C9A	0.6589 (2)	0.6595 (7)	0.71462 (18)	0.0187 (10)
H9A	0.6975	0.6072	0.7119	0.022*
C10A	0.64290 (19)	0.8546 (8)	0.7413 (2)	0.0204 (11)
C11A	0.30750 (19)	0.5517 (7)	0.62361 (18)	0.0175 (10)
H11A	0.3190	0.4109	0.6077	0.021*
C12A	0.2523 (2)	0.6317 (7)	0.60489 (17)	0.0179 (10)
C13A	0.21806 (19)	0.5186 (7)	0.5673 (2)	0.0193 (10)
H13A	0.2280	0.3744	0.5523	0.023*
C14A	0.16653 (19)	0.6346 (7)	0.55278 (19)	0.0178 (10)
H14A	0.1383	0.5785	0.5276	0.021*
C15A	0.16322 (18)	0.8376 (7)	0.58004 (18)	0.0158 (9)
C16A	0.3627 (2)	1.0627 (8)	0.77440 (18)	0.0238 (11)
H16A	0.3258	1.0434	0.7936	0.036*
H16B	0.3607	1.1957	0.7499	0.036*
H16C	0.3934	1.0848	0.8019	0.036*
Br1B	0.505326 (19)	0.46082 (8)	0.533274 (19)	0.02180 (10)
Br2B	−0.077918 (19)	0.40833 (7)	0.337559 (19)	0.02079 (9)
S1B	0.38547 (5)	0.61760 (19)	0.48936 (5)	0.0178 (2)
S2B	0.04182 (5)	0.59775 (19)	0.37172 (5)	0.0193 (3)
O1B	0.19818 (13)	1.1861 (5)	0.46577 (13)	0.0194 (7)
N1B	0.23494 (16)	0.6637 (6)	0.36820 (15)	0.0189 (9)
C1B	0.20602 (18)	0.9974 (7)	0.44500 (18)	0.0160 (10)
C2B	0.26185 (19)	0.8781 (7)	0.45146 (18)	0.0174 (10)
C3B	0.27099 (19)	0.6598 (7)	0.41848 (18)	0.0175 (10)
H3C	0.3120	0.6459	0.4078	0.021*
H3D	0.2607	0.5271	0.4418	0.021*
C4B	0.17432 (18)	0.6648 (7)	0.38282 (19)	0.0173 (10)
H4C	0.1652	0.5277	0.4051	0.021*
H4D	0.1508	0.6604	0.3484	0.021*
C5B	0.15931 (18)	0.8750 (8)	0.41601 (18)	0.0166 (10)
C6B	0.29946 (18)	0.9646 (7)	0.48745 (19)	0.0163 (9)
H6B	0.2882	1.1059	0.5032	0.020*
C7B	0.3552 (2)	0.8799 (7)	0.50704 (18)	0.0184 (10)
C8B	0.3908 (2)	0.9926 (8)	0.54402 (18)	0.0199 (11)
H8B	0.3817	1.1368	0.5595	0.024*
C9B	0.4416 (2)	0.8737 (8)	0.55655 (18)	0.0184 (10)
H9B	0.4709	0.9303	0.5805	0.022*
C10B	0.44414 (19)	0.6701 (8)	0.53083 (19)	0.0190 (10)
C11B	0.10501 (19)	0.9514 (7)	0.42421 (18)	0.0169 (10)
H11B	0.1020	1.0886	0.4449	0.020*
C12B	0.05092 (19)	0.8550 (8)	0.40612 (19)	0.0181 (10)
C13B	−0.0025 (2)	0.9548 (8)	0.41573 (19)	0.0199 (10)
H13B	−0.0068	1.0980	0.4335	0.024*
C14B	−0.05021 (19)	0.8231 (8)	0.39649 (18)	0.0192 (11)
H14B	−0.0895	0.8654	0.4007	0.023*
C15B	−0.0319 (2)	0.6305 (8)	0.37156 (19)	0.0205 (11)
C16B	0.2466 (2)	0.4643 (7)	0.33360 (19)	0.0217 (10)
H16D	0.2288	0.4847	0.2969	0.032*
H16E	0.2306	0.3287	0.3515	0.032*
H16F	0.2883	0.4460	0.3292	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.01337 (19)	0.0189 (2)	0.0295 (2)	−0.00084 (16)	−0.00078 (18)	−0.0020 (2)
Br2A	0.01479 (19)	0.0238 (2)	0.0281 (2)	0.00409 (18)	−0.00157 (18)	−0.0022 (2)
S1A	0.0125 (5)	0.0164 (5)	0.0244 (5)	0.0002 (4)	−0.0001 (4)	−0.0024 (4)
S2A	0.0136 (5)	0.0167 (5)	0.0243 (5)	0.0014 (4)	−0.0024 (4)	−0.0038 (5)
O1A	0.0171 (16)	0.0175 (15)	0.0274 (16)	−0.0013 (13)	−0.0005 (13)	−0.0063 (13)
N1A	0.0151 (17)	0.0182 (18)	0.0155 (17)	0.0041 (15)	−0.0002 (14)	−0.0033 (15)
C1A	0.026 (2)	0.0097 (18)	0.015 (2)	−0.0042 (17)	−0.0005 (18)	0.0040 (15)
C2A	0.023 (2)	0.0106 (19)	0.016 (2)	0.0004 (17)	−0.0006 (18)	−0.0004 (16)
C3A	0.0113 (19)	0.020 (2)	0.022 (2)	0.0029 (16)	−0.0025 (17)	0.0011 (18)
C4A	0.019 (2)	0.016 (2)	0.025 (2)	−0.0026 (18)	0.0045 (19)	−0.0007 (18)
C5A	0.014 (2)	0.018 (2)	0.015 (2)	0.0016 (17)	0.0007 (16)	0.0038 (17)
C6A	0.018 (2)	0.023 (2)	0.0148 (19)	0.0042 (18)	−0.0015 (17)	−0.0022 (18)
C7A	0.0105 (19)	0.020 (2)	0.017 (2)	−0.0025 (16)	0.0019 (16)	−0.0007 (17)
C8A	0.0121 (19)	0.019 (2)	0.020 (2)	0.0039 (17)	0.0011 (17)	−0.0031 (18)
C9A	0.017 (2)	0.018 (2)	0.021 (2)	0.0017 (17)	−0.0013 (18)	−0.0010 (17)
C10A	0.013 (2)	0.017 (2)	0.031 (2)	−0.0012 (17)	0.0091 (19)	−0.0004 (19)
C11A	0.019 (2)	0.0119 (18)	0.021 (2)	0.0012 (17)	−0.0027 (17)	−0.0049 (17)
C12A	0.022 (2)	0.018 (2)	0.0131 (19)	−0.0004 (18)	0.0019 (17)	0.0010 (16)
C13A	0.015 (2)	0.0139 (19)	0.029 (2)	−0.0012 (17)	0.0008 (18)	−0.0050 (18)
C14A	0.0103 (19)	0.018 (2)	0.025 (2)	−0.0006 (17)	−0.0011 (17)	−0.0049 (18)
C15A	0.0130 (19)	0.0171 (19)	0.017 (2)	−0.0019 (16)	−0.0030 (17)	0.0000 (17)
C16A	0.025 (2)	0.029 (3)	0.017 (2)	0.003 (2)	−0.0045 (18)	−0.008 (2)
Br1B	0.0140 (2)	0.0232 (2)	0.0282 (2)	0.00452 (18)	−0.00166 (18)	−0.0019 (2)
Br2B	0.01694 (19)	0.02161 (19)	0.0238 (2)	−0.00367 (17)	−0.00273 (18)	0.00052 (18)
S1B	0.0141 (5)	0.0175 (5)	0.0217 (5)	−0.0001 (4)	−0.0029 (4)	−0.0023 (4)
S2B	0.0132 (5)	0.0188 (5)	0.0258 (6)	−0.0006 (4)	−0.0008 (4)	−0.0032 (5)
O1B	0.0109 (14)	0.0128 (14)	0.0343 (17)	0.0006 (12)	−0.0031 (13)	−0.0018 (13)
N1B	0.0145 (18)	0.0189 (18)	0.0234 (19)	−0.0011 (15)	−0.0021 (15)	−0.0030 (15)
C1B	0.0068 (18)	0.021 (2)	0.021 (2)	0.0036 (16)	−0.0008 (16)	−0.0050 (18)
C2B	0.013 (2)	0.017 (2)	0.022 (2)	−0.0018 (18)	−0.0033 (17)	0.0002 (18)
C3B	0.015 (2)	0.018 (2)	0.020 (2)	0.0011 (17)	−0.0056 (17)	−0.0047 (18)
C4B	0.0109 (19)	0.015 (2)	0.026 (2)	−0.0028 (16)	0.0000 (17)	−0.0018 (17)
C5B	0.0085 (18)	0.020 (2)	0.021 (2)	0.0005 (17)	−0.0009 (16)	−0.0017 (18)
C6B	0.015 (2)	0.0098 (17)	0.025 (2)	0.0032 (16)	0.0008 (17)	0.0035 (17)
C7B	0.019 (2)	0.0129 (19)	0.023 (2)	−0.0020 (17)	−0.0065 (18)	−0.0021 (18)
C8B	0.017 (2)	0.022 (2)	0.021 (2)	0.0014 (18)	−0.0006 (17)	0.0000 (18)
C9B	0.016 (2)	0.021 (2)	0.018 (2)	0.0023 (18)	−0.0008 (17)	0.0018 (18)
C10B	0.016 (2)	0.022 (2)	0.019 (2)	−0.0004 (17)	0.0009 (18)	−0.0018 (19)
C11B	0.018 (2)	0.0138 (19)	0.019 (2)	0.0000 (17)	−0.0024 (17)	0.0036 (17)
C12B	0.0102 (19)	0.020 (2)	0.024 (2)	0.0023 (17)	0.0044 (17)	−0.0018 (18)
C13B	0.014 (2)	0.022 (2)	0.024 (2)	−0.0014 (19)	−0.0026 (18)	−0.0017 (19)
C14B	0.010 (2)	0.023 (2)	0.025 (2)	−0.0034 (17)	−0.0004 (18)	0.0002 (19)
C15B	0.014 (2)	0.028 (2)	0.019 (2)	−0.0069 (19)	−0.0025 (18)	0.0025 (19)
C16B	0.017 (2)	0.023 (2)	0.025 (2)	−0.0099 (18)	0.0049 (19)	−0.006 (2)

Geometric parameters (Å, º)

Br1A—C10A	1.879 (5)	Br1B—C10B	1.881 (5)
Br2A—C15A	1.880 (4)	Br2B—C15B	1.875 (5)
S1A—C10A	1.726 (5)	S1B—C10B	1.715 (5)
S1A—C7A	1.748 (5)	S1B—C7B	1.748 (4)
S2A—C15A	1.718 (4)	S2B—C15B	1.724 (5)
S2A—C12A	1.745 (4)	S2B—C12B	1.737 (5)
O1A—C1A	1.225 (5)	O1B—C1B	1.231 (5)
N1A—C16A	1.464 (6)	N1B—C4B	1.451 (6)
N1A—C4A	1.466 (6)	N1B—C16B	1.462 (6)
N1A—C3A	1.502 (6)	N1B—C3B	1.469 (6)
C1A—C5A	1.497 (6)	C1B—C5B	1.476 (6)
C1A—C2A	1.506 (6)	C1B—C2B	1.482 (6)
C2A—C6A	1.359 (6)	C2B—C6B	1.330 (6)
C2A—C3A	1.502 (6)	C2B—C3B	1.523 (6)
C3A—H3A	0.9900	C3B—H3C	0.9900
C3A—H3B	0.9900	C3B—H3D	0.9900
C4A—C5A	1.499 (6)	C4B—C5B	1.512 (6)
C4A—H4A	0.9900	C4B—H4C	0.9900
C4A—H4B	0.9900	C4B—H4D	0.9900
C5A—C11A	1.345 (6)	C5B—C11B	1.353 (6)
C6A—C7A	1.429 (6)	C6B—C7B	1.465 (6)
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.376 (6)	C7B—C8B	1.381 (6)
C8A—C9A	1.412 (6)	C8B—C9B	1.404 (6)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.366 (6)	C9B—C10B	1.349 (6)
C9A—H9A	0.9500	C9B—H9B	0.9500
C11A—C12A	1.437 (6)	C11B—C12B	1.445 (6)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—C13A	1.375 (6)	C12B—C13B	1.391 (6)
C13A—C14A	1.421 (6)	C13B—C14B	1.429 (6)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.364 (6)	C14B—C15B	1.350 (7)
C14A—H14A	0.9500	C14B—H14B	0.9500
C16A—H16A	0.9800	C16B—H16D	0.9800
C16A—H16B	0.9800	C16B—H16E	0.9800
C16A—H16C	0.9800	C16B—H16F	0.9800
C10A—S1A—C7A	91.2 (2)	C10B—S1B—C7B	91.1 (2)
C15A—S2A—C12A	91.0 (2)	C15B—S2B—C12B	91.4 (2)
C16A—N1A—C4A	109.6 (3)	C4B—N1B—C16B	108.7 (3)
C16A—N1A—C3A	110.2 (3)	C4B—N1B—C3B	110.8 (3)
C4A—N1A—C3A	110.4 (3)	C16B—N1B—C3B	110.4 (3)
O1A—C1A—C5A	123.0 (4)	O1B—C1B—C5B	121.5 (4)
O1A—C1A—C2A	120.6 (4)	O1B—C1B—C2B	120.9 (4)
C5A—C1A—C2A	116.2 (4)	C5B—C1B—C2B	117.4 (4)
C6A—C2A—C3A	123.6 (4)	C6B—C2B—C1B	117.5 (4)
C6A—C2A—C1A	117.1 (4)	C6B—C2B—C3B	124.7 (4)
C3A—C2A—C1A	119.3 (4)	C1B—C2B—C3B	117.8 (4)
N1A—C3A—C2A	109.9 (4)	N1B—C3B—C2B	109.5 (3)
N1A—C3A—H3A	109.7	N1B—C3B—H3C	109.8
C2A—C3A—H3A	109.7	C2B—C3B—H3C	109.8
N1A—C3A—H3B	109.7	N1B—C3B—H3D	109.8
C2A—C3A—H3B	109.7	C2B—C3B—H3D	109.8
H3A—C3A—H3B	108.2	H3C—C3B—H3D	108.2
N1A—C4A—C5A	110.8 (4)	N1B—C4B—C5B	110.8 (3)
N1A—C4A—H4A	109.5	N1B—C4B—H4C	109.5
C5A—C4A—H4A	109.5	C5B—C4B—H4C	109.5
N1A—C4A—H4B	109.5	N1B—C4B—H4D	109.5
C5A—C4A—H4B	109.5	C5B—C4B—H4D	109.5
H4A—C4A—H4B	108.1	H4C—C4B—H4D	108.1
C11A—C5A—C1A	116.0 (4)	C11B—C5B—C1B	117.0 (4)
C11A—C5A—C4A	125.2 (4)	C11B—C5B—C4B	124.3 (4)
C1A—C5A—C4A	118.8 (4)	C1B—C5B—C4B	118.6 (4)
C2A—C6A—C7A	130.9 (4)	C2B—C6B—C7B	131.2 (4)
C2A—C6A—H6A	114.6	C2B—C6B—H6B	114.4
C7A—C6A—H6A	114.6	C7B—C6B—H6B	114.4
C8A—C7A—C6A	124.7 (4)	C8B—C7B—C6B	124.8 (4)
C8A—C7A—S1A	110.1 (3)	C8B—C7B—S1B	109.9 (3)
C6A—C7A—S1A	125.2 (3)	C6B—C7B—S1B	125.3 (3)
C7A—C8A—C9A	114.2 (4)	C7B—C8B—C9B	113.6 (4)
C7A—C8A—H8A	122.9	C7B—C8B—H8B	123.2
C9A—C8A—H8A	122.9	C9B—C8B—H8B	123.2
C10A—C9A—C8A	111.8 (4)	C10B—C9B—C8B	112.4 (4)
C10A—C9A—H9A	124.1	C10B—C9B—H9B	123.8
C8A—C9A—H9A	124.1	C8B—C9B—H9B	123.8
C9A—C10A—S1A	112.6 (3)	C9B—C10B—S1B	113.0 (3)
C9A—C10A—Br1A	127.5 (3)	C9B—C10B—Br1B	126.9 (4)
S1A—C10A—Br1A	119.6 (2)	S1B—C10B—Br1B	120.0 (3)
C5A—C11A—C12A	131.6 (4)	C5B—C11B—C12B	129.5 (4)
C5A—C11A—H11A	114.2	C5B—C11B—H11B	115.3
C12A—C11A—H11A	114.2	C12B—C11B—H11B	115.3
C13A—C12A—C11A	124.2 (4)	C13B—C12B—C11B	124.0 (4)
C13A—C12A—S2A	110.1 (3)	C13B—C12B—S2B	109.8 (3)
C11A—C12A—S2A	125.6 (3)	C11B—C12B—S2B	126.2 (3)
C12A—C13A—C14A	114.6 (4)	C12B—C13B—C14B	114.2 (4)
C12A—C13A—H13A	122.7	C12B—C13B—H13B	122.9
C14A—C13A—H13A	122.7	C14B—C13B—H13B	122.9
C15A—C14A—C13A	110.5 (4)	C15B—C14B—C13B	110.8 (4)
C15A—C14A—H14A	124.7	C15B—C14B—H14B	124.6
C13A—C14A—H14A	124.7	C13B—C14B—H14B	124.6
C14A—C15A—S2A	113.8 (3)	C14B—C15B—S2B	113.9 (3)
C14A—C15A—Br2A	126.6 (3)	C14B—C15B—Br2B	126.8 (4)
S2A—C15A—Br2A	119.6 (2)	S2B—C15B—Br2B	119.3 (3)
N1A—C16A—H16A	109.5	N1B—C16B—H16D	109.5
N1A—C16A—H16B	109.5	N1B—C16B—H16E	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16E	109.5
N1A—C16A—H16C	109.5	N1B—C16B—H16F	109.5
H16A—C16A—H16C	109.5	H16D—C16B—H16F	109.5
H16B—C16A—H16C	109.5	H16E—C16B—H16F	109.5
O1A—C1A—C2A—C6A	11.3 (6)	O1B—C1B—C2B—C6B	10.4 (7)
C5A—C1A—C2A—C6A	−163.4 (4)	C5B—C1B—C2B—C6B	−165.7 (4)
O1A—C1A—C2A—C3A	−171.4 (4)	O1B—C1B—C2B—C3B	−172.3 (4)
C5A—C1A—C2A—C3A	13.9 (6)	C5B—C1B—C2B—C3B	11.6 (6)
C16A—N1A—C3A—C2A	177.1 (4)	C4B—N1B—C3B—C2B	−64.2 (4)
C4A—N1A—C3A—C2A	−61.6 (4)	C16B—N1B—C3B—C2B	175.3 (4)
C6A—C2A—C3A—N1A	−160.7 (4)	C6B—C2B—C3B—N1B	−156.7 (4)
C1A—C2A—C3A—N1A	22.1 (5)	C1B—C2B—C3B—N1B	26.2 (5)
C16A—N1A—C4A—C5A	−175.4 (4)	C16B—N1B—C4B—C5B	−176.9 (4)
C3A—N1A—C4A—C5A	63.1 (4)	C3B—N1B—C4B—C5B	61.7 (5)
O1A—C1A—C5A—C11A	−10.5 (6)	O1B—C1B—C5B—C11B	−15.0 (6)
C2A—C1A—C5A—C11A	164.1 (4)	C2B—C1B—C5B—C11B	161.0 (4)
O1A—C1A—C5A—C4A	172.3 (4)	O1B—C1B—C5B—C4B	169.3 (4)
C2A—C1A—C5A—C4A	−13.1 (6)	C2B—C1B—C5B—C4B	−14.6 (6)
N1A—C4A—C5A—C11A	158.6 (4)	N1B—C4B—C5B—C11B	163.6 (4)
N1A—C4A—C5A—C1A	−24.5 (5)	N1B—C4B—C5B—C1B	−21.1 (6)
C3A—C2A—C6A—C7A	−0.6 (8)	C1B—C2B—C6B—C7B	174.0 (4)
C1A—C2A—C6A—C7A	176.6 (4)	C3B—C2B—C6B—C7B	−3.1 (8)
C2A—C6A—C7A—C8A	−179.4 (5)	C2B—C6B—C7B—C8B	178.2 (5)
C2A—C6A—C7A—S1A	−1.9 (7)	C2B—C6B—C7B—S1B	−4.3 (7)
C10A—S1A—C7A—C8A	−2.6 (4)	C10B—S1B—C7B—C8B	−0.8 (4)
C10A—S1A—C7A—C6A	179.6 (4)	C10B—S1B—C7B—C6B	−178.5 (4)
C6A—C7A—C8A—C9A	−178.8 (4)	C6B—C7B—C8B—C9B	179.3 (4)
S1A—C7A—C8A—C9A	3.4 (5)	S1B—C7B—C8B—C9B	1.6 (5)
C7A—C8A—C9A—C10A	−2.6 (6)	C7B—C8B—C9B—C10B	−1.8 (6)
C8A—C9A—C10A—S1A	0.5 (5)	C8B—C9B—C10B—S1B	1.1 (5)
C8A—C9A—C10A—Br1A	174.4 (3)	C8B—C9B—C10B—Br1B	177.2 (3)
C7A—S1A—C10A—C9A	1.2 (4)	C7B—S1B—C10B—C9B	−0.2 (4)
C7A—S1A—C10A—Br1A	−173.2 (3)	C7B—S1B—C10B—Br1B	−176.6 (3)
C1A—C5A—C11A—C12A	−174.7 (4)	C1B—C5B—C11B—C12B	−173.4 (4)
C4A—C5A—C11A—C12A	2.3 (8)	C4B—C5B—C11B—C12B	2.0 (8)
C5A—C11A—C12A—C13A	−179.9 (5)	C5B—C11B—C12B—C13B	−177.8 (5)
C5A—C11A—C12A—S2A	3.9 (7)	C5B—C11B—C12B—S2B	4.5 (7)
C15A—S2A—C12A—C13A	0.2 (4)	C15B—S2B—C12B—C13B	−0.3 (4)
C15A—S2A—C12A—C11A	176.9 (4)	C15B—S2B—C12B—C11B	177.8 (4)
C11A—C12A—C13A—C14A	−177.1 (4)	C11B—C12B—C13B—C14B	−177.0 (4)
S2A—C12A—C13A—C14A	−0.4 (5)	S2B—C12B—C13B—C14B	1.1 (5)
C12A—C13A—C14A—C15A	0.4 (6)	C12B—C13B—C14B—C15B	−1.6 (6)
C13A—C14A—C15A—S2A	−0.2 (5)	C13B—C14B—C15B—S2B	1.4 (5)
C13A—C14A—C15A—Br2A	−177.9 (3)	C13B—C14B—C15B—Br2B	−177.8 (3)
C12A—S2A—C15A—C14A	0.0 (4)	C12B—S2B—C15B—C14B	−0.7 (4)
C12A—S2A—C15A—Br2A	177.9 (3)	C12B—S2B—C15B—Br2B	178.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4A—H4A···O1A^i	0.99	2.55	3.441 (6)	150
C4B—H4C···O1B^ii	0.99	2.60	3.493 (6)	150
C13A—H13A···O1B^ii	0.95	2.45	3.159 (6)	131
C8B—H8B···O1A^i	0.95	2.42	3.144 (6)	133

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