Three anilides of 2,2′-thio­di­benzoic acid

The structures of N,N′-bis­(2-methyl­phenyl)-2,2′-thio­dibenz­amide, C₂₈H₂₄N₂O₂S, (Ia), N,N′-bis­(2-ethyl­phenyl)-2,2′-thio­dibenzamide, C₃₀H₂₈N₂O₂S, (Ib), and N,N′-bis­(2-bromo­phenyl)-2,2′-thio­dibenzamide, C₂₆H₁₈Br₂N₂O₂S, (Ic), are com­pared with each other. For the 19 atoms of the consistent thiodibenzamide core, the r.m.s. deviations of the mol­ecules in pairs are 0.29, 0.90 and 0.80 Å for (Ia)/(Ib), (Ia)/(Ic) and (Ib)/(Ic), respectively. The conformations of the central parts of mol­ecules (Ia) and (Ib) are similar due to an intra­molecular N—H...O hydrogen-bonding inter­action. The mol­ecules of (Ia) are further linked into infinite chains along the c axis by inter­molecular N—H...O inter­actions, whereas the mol­ecules of (Ib) are linked into chains along b by an inter­molecular N—H...π contact. The conformation of (Ic) is quite different from those of (Ia) and (Ib), since there is no intra­molecular N—H...O hydrogen bond, but instead there is a possible intra­molecular N—H...Br hydrogen bond. The mol­ecules are linked into chains along c by inter­molecular N—H...O hydrogen bonds.

S1. Comment

Diaryl sulfides have attracted much attention because of their synthesis (Eichman & Stambuli, 2011), reactivity (Kondo & Mitsudo, 2000) and biological importance (Jiang et al., 2003). They also constitute an important class of pharmaceutical agents (Goordazi et al., 2010; Fernando-Gomez et al., 1995; Girault et al., 2001; Stump et al., 2007). The three-dimensional structures of some diaryl sulfides have been determined by X-ray crystallography (Muhammad et al., 2008) and were found to adopt equatorial, planar or skew conformations (Kucsman et al., 1984). In the present study, three 2,2'-thiodibenzamides were synthesized by the reaction of 2,2'-thiodibenzoic acid chloride with three anilines, 2-methylbenzeneamine, 2-ethylbenzeneamine and 2-bromobenzeneamine, namely N,N'-bis(2-methylphenyl)-2,2'-thiodibenzamide, (Ia), N,N'-bis(2-ethylphenyl)-2,2'-thiodibenzamide, (Ib), and N,N'-bis(2-bromophenyl)-2,2'-thiodibenzamide, (Ic) (Fig. 1). A paper describing these amides and other related substances, and their biological properties, has been accepted for publication elsewhere (Moosun et al., 2013). X-ray diffraction analyses have now been carried out to ascertain the constitution of the molecules, as well as to determine the effect of different substituents on the conformation and configuration of the synthesized molecules.

Considering first the diaryl sulfide units in the three structures, the C9—S1—C14 angles vary little, being 104.92 (6), 103.04 (6) and 103.9 (1)° for (Ia), (Ib) and (Ic), respectively. The relative orientations of the two benzene rings around S are described by two dihedral angles, C10—C9—S1—C14 and C15—C14—S1—C9, where `C—C' are two C atoms of one ring with the second attached to S and `C' is the first C atom of the other ring, attached to S. Thus, for (Ia), the values are -48.9 (1) and 39.0 (1)°, for (Ib) -42.7 (1) and -57.5 (1)°, and for (Ic) -16.0 (3) and -86.8 (3)°. These dihedral angles measure the extent to which the benzene rings are not coplanar with the C—S—C plane.

Moving away from the S atom, the orientation of the amide carbonyl groups with respect to the their attached benzene rings is measured by the torsion angle O—C—C—C, where O—C is the carbonyl group and the last two C atoms are in the benzene ring. There are two such angles, O1—C7—C8—C13 and O2—C20—C15—C14, for each of the three amides: for (Ia) these are -45.4 (2) and -49.0 (2)°, for (Ib) -45.4 (2) and -51.3 (2)°, and for (Ic) -111.7 (5) and 45.3 (3)°. Thus, in each case, there is considerably reduced overlap between the carbonyl π-system and that of the attached benzene ring, i.e. little conjugation.

The sums of the angles at the N atoms are 360.0 and 359.1° for (Ia), 360.0 and 359.6° for (Ib), and 360.5 and 359.5° for (Ic). Clearly, the six amide N atoms are all essentially planar. This allows one to measure the extent of amide resonance by the torsion angles C—N—C—O, where the first C atom is the benzene ring C atom to which the N atom is attached. There are thus two torsion angles for each compound, viz. C1—N1—C7—O1 and C21—N2—C20—O2: -10.4 (2) and 2.6 (2)° for (Ia), -9.4 (2) and 3.4 (2)° for (Ib), and -0.8 (7) and 0.7 (5)° for (Ic), respectively. Each of the six amide units is very close to being planar, which is ideal for amide resonance.

At the extremities of the three structures, it is relevant to ask to what extent the nitrogen p-orbital interacts with the π system of the attached benzene ring, especially remembering that that ring has an ortho substituent. This can be measured from the C—N—C—C torsion angles (where the first C is the carbonyl C atom and the last two are the attached C atoms of the benzene ring), i.e. C7—N1—C1—C6 and C20—N2—C21—C22: -36.5 (2) and -62.5 (2)° for (Ia), -43.9 (2) and -92.0 (2)° for (Ib), and -0.6 (7) and 142.6 (3)° for (Ic), respectively. These torsion angles show that in only one amide out of six is there good overlap between the nitrogen lone pair and the attached benzene ring, namely, the amide containing atom N1 in (Ic).

We have also estimated the similarity between these three structures by overlaying them with one another (Fig. 2). Structures (Ia) and (Ib) are quite similar, with an r.m.s. difference of 0.29 Å when fitting the S, N, O and C7–C20 atoms (the terminal benzene rings were omitted; see figure in Supplementary Materials). This finding is in accord with the comparison of torsion angles starting at the central S1 atom and working out to the extremities of the molecules shown above, i.e. that the conformations of the central portions of molecules (Ia) and (Ib) are similar and that the molecules only deviate from one another by a large amount in the C20—N2—C21—C22 torsion angle. The bromine-containing diamide, (Ic), is much less similar with either (Ia) or (Ib), with r.m.s. differences for the same atoms of 0.90 and 0.80 Å, respectively (see figure in Supplementary Materials). This is consistent with the fact that all the torsion angles of (Ic) are quite different from those of (Ia) and (Ib)..

The differences in the conformations of the three molecules can be rationalized in terms of the similarities and differences in their hydrogen-bonding interactions. The central parts of molecules (Ia) and (Ib) are similar due to the intramolecular N1—H1···O2 hydrogen bond seen in both structures (Figs. 1a, 1b, 3a and 3b). In (Ic), this intramolecular interaction does not occur, but instead a possible intramolecular N1—H1···Br1 bond is observed (Figs. 1c and 3c). The geometry of this hydrogen bond, with an N1—H1···Br1 angle of 120 (4)°, indicates that its stabilization energy is low and therefore it may not be significant (Wood et al. 2009).

Due to the differing intramolecular hydrogen bonding observed for (Ic) compared with (Ia) and (Ib), the conformation of the central portion of the molecule of (Ic) is not similar to those of (Ia) and (Ib). The hydrogen-bonding patterns otherwise differ in all three molecules. In (Ia), an intermolecular N2—H2···O1 hydrogen bond [symmetry code (x, -y + 3/2, z - 1/2)] links the molecules into chains along c (Fig. 3a). In (Ib), the molecules are linked into chains along b by an intermolecular N—H···π contact, N2—H2N···Cg1 [Cg1 is the centroid of the C1–C6 benzene ring; symmetry code (-x + 3/2, y - 1/2, -z + 3/2)] (Fig. 3b). In (Ic), the molecules are linked into chains along c by an intermolecular hydrogen bond N2—H2N···O2(x, -y + 3/2, z - 1/2) (Fig. 3c).

Related literature

For related literature, see: Eichman & Stambuli (2011); Fernando-Gomez, Moutiez, Aumercier, Bthegnies, Luyckx, Ouaissi, Tartar & Sergheraert (1995); Girault et al. (2001); Goordazi et al. (2010); Jiang et al. (2003); Kondo & Mitsudo (2000); Kucsman et al. (1984); Moosun et al. (2013); Muhammad et al. (2008); Stump et al. (2007); Wood et al. (2009).

S2. Experimental

The general method used for the synthesis of the amides was as follows. Thionyl chloride (2 ml) was added to 2,2'-thiodibenzoic acid (0.49 g, 1.8 mM mmol?) dissolved in dichloromethane (20 ml) and the resulting solution was heated at reflux for 2 h. The excess thionyl chloride was removed by distillation and the resulting double acid chloride used without further purification. The aniline (2-methylbenzenamine, 2-ethylbenzenamine or 2-bromobenzenamine) (3.6 mM mmol?) was added to the freshly prepared 2,2'-thiodibenzoic acid chloride. The mixture was heated at reflux for 2 h and then stirred at room temperature for 24 h. The resulting precipitate was filtered off, washed with water and ethanol, dissolved in warm acetonitrile (15 ml), filtered, and the filtrate cooled and left in the dark. After two weeks, crystals of the anilides had deposited.

Analysis for N,N'-bis(2-methylphenyl)-2,2'-thiodibenzamide, (Ia): long brown needles; yield 55%; m.p. 437 K; IR (solid, ν, cm^-1): 3249, 1716, 1642, 740; ¹H NMR (250 MHz, DMSO-d₆, δ, p.p.m.): 2.22 (6H, s, 2CH₃), 7.25–7.09 (9H, m, ArH), 7.40–7.35 (6H, m, ArH), 7.65–7.62 (2H, t, J = 5 Hz, ArH), 9.89 (2H, s, NH); ¹³C NMR (62.5 MHz, DMSO-d₆, δ, p.p.m.): 18.5, 126.4, 127.7, 128.6, 130.9, 131.0, 134.1, 134.6, 136.6, 139.6, 167.0. Analysis calculated for C₂₈H₂₄N₂O₂S: C 74.3, H 5.35, N 6.19, S 7.09%; found: C 73.8, H 5.40, N 5.85, S 7.82%.

Analysis for N,N'-bis(2-ethylphenyl)-2,2'-thiodibenzamide, (Ib): colourless crystals; yield 70%; m.p. 436 K; IR (solid, ν, cm^-1): 3363, 1664, 1650, 1529, 1305, 1252, 734, 730; ¹H NMR (250 MHz, DMSO-d₆, δ, p.p.m.): 1.09–1.03 (6H, t, J = 8 Hz, 2CH₃), 2.64–2.55 (4H, q, J = 11 Hz, 2CH₂), 7.17–7.14 (4H, m, ArH), 7.24–7.20 (6H, m, ArH), 7.40–7.37 (4H, t, J = 4 Hz, ArH), 7.61–7.57 (2H, t, J = 5 Hz, ArH), 9.90 (2H, s, NH). ¹³C NMR (62.5 MHz, DMSO-d₆, δ, p.p.m.): 14.1, 23.8, 125.9, 126.4, 127.0, 127.2, 127.9, 128.7, 130.5, 132.6, 134.0, 135.2, 139.1, 139.3, 166.7. Analysis calculated for C₃₀H₃₄N₂O₂S: C 75.0, H 5.87, N 5.83, S 6.67%; found: C 75.0, H 5.87, N 6.26, S 6.67%.

Analysis for N,N'-bis(2-bromophenyl)-2,2'-thiodibenzamide, (Ic): shiny white needles; yield 30%; m.p. 421 K; IR (solid, ν, cm^-1): 3376, 1662, 1651, 1520, 1301, 1248, 734, 730; ¹H NMR (250 MHz, DMSO-d₆, δ, p.p.m.): 7.24–7.13 (4H, m, ArH), 7.45–7.31 (8H, m, ArH), 7.65–7.32 (4H, d, J = 5 Hz, ArH), 10.0 (2H, s, NH); ¹³C NMR (62.5 MHz, DMSO-d₆, δ, p.p.m.): 119.5, 127.3, 127.9, 128.0, 130.8, 132.6, 132.8, 134.4, 135.9, 137.8, 166.6. Analysis calculated for C₂₆H₁₈BrN₂O₂S: C 53.6, H 3.12, N 4.81, S 5.51%; found: C 53.6, H 3.12, N 4.18, S 5.51%.

S3. Refinement

H atoms bonded to C atoms were included in calculated positions using the riding model (C—H = 0.93–0.97 Å), with U_iso(H) = 1.2 or 1.5U_eq(C). H atoms bonded to N atoms were found by difference Fourier methods and refined isotropically [N—H = 0.79 (5)–0.86 (2) Å].

Computing details

For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) for (Ia), (Ic); SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009) for (Ib).

Figures

	Fig. 1. Plots of (a) (Ia), (b) (Ib) and (c) (Ic). Displacement ellipsoids are drawn at the 30% probability level and intramolecular hydrogen-bonding interactions are shown as double-dashed lines.
	Fig. 2. Overlay of the three molecules, with (Ia) shown with dashed bonds, (Ib) with solid bonds and (Ic) with double-dashed bonds (blue, green and red, respectively, in the electronic version of the paper). H atoms have been omitted for clarity.
	Fig. 3. Packing arrangements of the molecules. (a) (Ia), viewed down a [symmetry codes: (i) x, 3/2 - y, z - 1/2; (ii) x, 3/2 - y, z + 1/2]. (b) (Ib), viewed down a [symmetry codes: (i) 3/2 - x, -1/2 + y, -z + 3/2; (ii) 3/2 - x, 1/2 + y, -z + 3/2]. (c) (Ic), viewed approximately down a [symmetry codes: (i) x, 3/2 - y, z - 1/2; (ii) x, 3/2 - y, z + 1/2]. Only H atoms involved in hydrogen-bonding or N—H···π interactions are shown, and these interactions are shown as dashed lines.

(Ia) N,N'-bis(2-methylphenyl)-2,2'-thiodibenzamide

Crystal data

C28H24N2O2S	F(000) = 952
Mr = 452.55	Dx = 1.283 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P2ybc	Cell parameters from 7594 reflections
a = 14.9815 (1) Å	θ = 5.1–71.0°
b = 10.9355 (1) Å	µ = 1.44 mm^−1
c = 15.5490 (2) Å	T = 296 K
β = 113.107 (1)°	Rod, colourless
V = 2343.03 (4) Å^3	0.35 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	4396 independent reflections
Radiation source: fine-focus sealed tube	3811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 71.9°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −18→18
Tmin = 0.646, Tmax = 0.754	k = −13→13
15959 measured reflections	l = −15→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.448P] where P = (Fo^2 + 2Fc^2)/3
4396 reflections	(Δ/σ)max = 0.001
308 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.27 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
S1	0.85477 (3)	0.50561 (3)	0.54750 (2)	0.04865 (12)
O1	0.86223 (7)	0.58452 (9)	0.81303 (6)	0.0457 (2)
O2	0.70288 (7)	0.73150 (9)	0.50785 (7)	0.0455 (2)
N1	0.73949 (8)	0.57946 (11)	0.66898 (8)	0.0405 (3)
N2	0.75647 (9)	0.86725 (10)	0.42861 (8)	0.0423 (3)
C1	0.67265 (10)	0.50389 (12)	0.68909 (9)	0.0413 (3)
C2	0.57365 (10)	0.53057 (15)	0.64768 (10)	0.0502 (3)
C3	0.51029 (12)	0.45191 (19)	0.66640 (13)	0.0680 (5)
H3	0.4440	0.4678	0.6396	0.082*
C4	0.54286 (14)	0.35197 (19)	0.72316 (14)	0.0726 (5)
H4	0.4988	0.3011	0.7342	0.087*
C5	0.64001 (14)	0.32653 (16)	0.76369 (13)	0.0659 (5)
H5	0.6620	0.2589	0.8026	0.079*
C6	0.70530 (12)	0.40168 (14)	0.74657 (11)	0.0525 (4)
H6	0.7713	0.3840	0.7735	0.063*
C7	0.83001 (9)	0.60733 (12)	0.72885 (9)	0.0368 (3)
C8	0.89203 (9)	0.67572 (12)	0.68895 (9)	0.0378 (3)
C9	0.90482 (9)	0.64316 (12)	0.60761 (9)	0.0393 (3)
C10	0.96419 (10)	0.71513 (15)	0.57788 (11)	0.0514 (4)
H10	0.9740	0.6932	0.5245	0.062*
C11	1.00829 (11)	0.81805 (17)	0.62671 (12)	0.0620 (4)
H11	1.0462	0.8667	0.6052	0.074*
C12	0.99656 (12)	0.84954 (17)	0.70762 (12)	0.0632 (4)
H12	1.0266	0.9191	0.7408	0.076*
C13	0.94015 (10)	0.77758 (15)	0.73896 (10)	0.0507 (3)
H13	0.9342	0.7976	0.7946	0.061*
C14	0.80373 (10)	0.54675 (13)	0.42760 (9)	0.0427 (3)
C15	0.75404 (9)	0.65510 (12)	0.39024 (9)	0.0390 (3)
C16	0.71566 (11)	0.67116 (14)	0.29364 (10)	0.0488 (3)
H16	0.6835	0.7436	0.2684	0.059*
C17	0.72433 (14)	0.58191 (18)	0.23446 (11)	0.0649 (5)
H17	0.6977	0.5938	0.1701	0.078*
C18	0.77235 (15)	0.47602 (19)	0.27149 (13)	0.0730 (5)
H18	0.7781	0.4154	0.2320	0.088*
C19	0.81246 (13)	0.45825 (16)	0.36714 (12)	0.0618 (4)
H19	0.8457	0.3862	0.3914	0.074*
C20	0.73615 (9)	0.75368 (12)	0.44878 (9)	0.0376 (3)
C21	0.74673 (11)	0.97692 (12)	0.47378 (9)	0.0436 (3)
C22	0.65718 (12)	1.01548 (14)	0.47036 (11)	0.0532 (4)
C23	0.65551 (17)	1.12731 (17)	0.51404 (14)	0.0726 (5)
H23	0.5972	1.1543	0.5153	0.087*
C24	0.7364 (2)	1.19767 (17)	0.55472 (14)	0.0819 (6)
H24	0.7323	1.2718	0.5823	0.098*
C25	0.82331 (18)	1.15974 (17)	0.55508 (13)	0.0777 (6)
H25	0.8783	1.2082	0.5821	0.093*
C26	0.82896 (13)	1.04846 (15)	0.51494 (12)	0.0591 (4)
H26	0.8882	1.0217	0.5156	0.071*
C27	0.53535 (12)	0.63948 (19)	0.58554 (13)	0.0678 (5)
H27A	0.4676	0.6497	0.5726	0.102*
H27B	0.5437	0.6273	0.5280	0.102*
H27C	0.5702	0.7113	0.6163	0.102*
C28	0.56627 (13)	0.94523 (19)	0.41900 (15)	0.0734 (5)
H28A	0.5631	0.8763	0.4559	0.110*
H28B	0.5662	0.9171	0.3605	0.110*
H28C	0.5111	0.9971	0.4076	0.110*
H2N	0.7868 (11)	0.8730 (15)	0.3922 (11)	0.047 (4)*
H1N	0.7198 (11)	0.6080 (15)	0.6130 (11)	0.046 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0662 (2)	0.03604 (19)	0.0476 (2)	0.00710 (15)	0.02661 (18)	0.00063 (14)
O1	0.0455 (5)	0.0561 (6)	0.0383 (5)	0.0040 (4)	0.0194 (4)	0.0031 (4)
O2	0.0546 (6)	0.0437 (5)	0.0496 (5)	0.0082 (4)	0.0327 (5)	0.0111 (4)
N1	0.0388 (6)	0.0470 (7)	0.0375 (6)	−0.0035 (5)	0.0169 (5)	0.0034 (5)
N2	0.0545 (7)	0.0382 (6)	0.0453 (6)	0.0003 (5)	0.0314 (6)	0.0023 (5)
C1	0.0458 (7)	0.0435 (7)	0.0397 (7)	−0.0075 (6)	0.0223 (6)	−0.0065 (5)
C2	0.0440 (7)	0.0611 (9)	0.0465 (8)	−0.0084 (7)	0.0188 (6)	−0.0040 (7)
C3	0.0490 (9)	0.0850 (13)	0.0714 (11)	−0.0191 (9)	0.0252 (8)	−0.0025 (10)
C4	0.0733 (12)	0.0748 (12)	0.0801 (12)	−0.0285 (10)	0.0413 (10)	−0.0027 (10)
C5	0.0846 (12)	0.0496 (9)	0.0726 (11)	−0.0102 (9)	0.0406 (10)	0.0050 (8)
C6	0.0570 (9)	0.0469 (8)	0.0590 (9)	−0.0027 (7)	0.0285 (7)	0.0006 (7)
C7	0.0386 (6)	0.0362 (6)	0.0397 (7)	0.0043 (5)	0.0200 (5)	−0.0006 (5)
C8	0.0319 (6)	0.0414 (7)	0.0402 (7)	0.0015 (5)	0.0143 (5)	0.0020 (5)
C9	0.0346 (6)	0.0423 (7)	0.0418 (7)	0.0041 (5)	0.0157 (5)	0.0034 (5)
C10	0.0419 (7)	0.0691 (10)	0.0486 (8)	−0.0008 (7)	0.0235 (6)	0.0068 (7)
C11	0.0458 (8)	0.0766 (12)	0.0623 (10)	−0.0193 (8)	0.0198 (7)	0.0104 (9)
C12	0.0567 (9)	0.0639 (10)	0.0615 (10)	−0.0254 (8)	0.0152 (8)	−0.0056 (8)
C13	0.0472 (8)	0.0568 (9)	0.0458 (8)	−0.0092 (7)	0.0158 (6)	−0.0069 (7)
C14	0.0471 (7)	0.0408 (7)	0.0448 (7)	−0.0024 (6)	0.0231 (6)	−0.0067 (6)
C15	0.0408 (6)	0.0395 (7)	0.0414 (7)	−0.0069 (5)	0.0211 (6)	−0.0027 (5)
C16	0.0528 (8)	0.0518 (8)	0.0422 (7)	−0.0119 (6)	0.0189 (6)	−0.0022 (6)
C17	0.0794 (11)	0.0723 (12)	0.0425 (8)	−0.0181 (9)	0.0235 (8)	−0.0137 (8)
C18	0.0973 (14)	0.0674 (12)	0.0589 (10)	−0.0084 (10)	0.0356 (10)	−0.0290 (9)
C19	0.0778 (11)	0.0498 (9)	0.0615 (10)	0.0053 (8)	0.0314 (9)	−0.0139 (8)
C20	0.0387 (6)	0.0390 (7)	0.0380 (7)	0.0032 (5)	0.0180 (5)	0.0045 (5)
C21	0.0628 (9)	0.0347 (7)	0.0396 (7)	0.0043 (6)	0.0268 (6)	0.0065 (5)
C22	0.0707 (10)	0.0452 (8)	0.0548 (9)	0.0143 (7)	0.0365 (8)	0.0150 (7)
C23	0.1105 (15)	0.0501 (10)	0.0806 (12)	0.0278 (11)	0.0629 (12)	0.0177 (9)
C24	0.147 (2)	0.0432 (9)	0.0725 (12)	0.0037 (12)	0.0608 (14)	−0.0031 (9)
C25	0.1140 (17)	0.0480 (10)	0.0657 (11)	−0.0159 (10)	0.0295 (11)	−0.0054 (8)
C26	0.0717 (10)	0.0465 (8)	0.0592 (9)	−0.0045 (8)	0.0256 (8)	0.0023 (7)
C27	0.0448 (8)	0.0837 (13)	0.0678 (11)	0.0002 (8)	0.0143 (8)	0.0128 (9)
C28	0.0588 (10)	0.0724 (12)	0.0944 (14)	0.0171 (9)	0.0360 (10)	0.0187 (10)

Geometric parameters (Å, º)

S1—C14	1.7732 (14)	C12—H12	0.9300
S1—C9	1.7743 (14)	C13—H13	0.9300
O1—C7	1.2300 (15)	C14—C19	1.391 (2)
O2—C20	1.2289 (15)	C14—C15	1.399 (2)
N1—C7	1.3445 (17)	C15—C16	1.3928 (19)
N1—C1	1.4244 (16)	C15—C20	1.5014 (18)
N1—H1N	0.861 (16)	C16—C17	1.382 (2)
N2—C20	1.3448 (17)	C16—H16	0.9300
N2—C21	1.4259 (17)	C17—C18	1.366 (3)
N2—H2N	0.856 (16)	C17—H17	0.9300
C1—C6	1.394 (2)	C18—C19	1.382 (3)
C1—C2	1.396 (2)	C18—H18	0.9300
C2—C3	1.394 (2)	C19—H19	0.9300
C2—C27	1.499 (2)	C21—C26	1.386 (2)
C3—C4	1.369 (3)	C21—C22	1.387 (2)
C3—H3	0.9300	C22—C23	1.404 (2)
C4—C5	1.369 (3)	C22—C28	1.493 (3)
C4—H4	0.9300	C23—C24	1.363 (3)
C5—C6	1.381 (2)	C23—H23	0.9300
C5—H5	0.9300	C24—C25	1.365 (3)
C6—H6	0.9300	C24—H24	0.9300
C7—C8	1.5032 (17)	C25—C26	1.385 (3)
C8—C13	1.387 (2)	C25—H25	0.9300
C8—C9	1.3976 (18)	C26—H26	0.9300
C9—C10	1.3953 (19)	C27—H27A	0.9600
C10—C11	1.373 (2)	C27—H27B	0.9600
C10—H10	0.9300	C27—H27C	0.9600
C11—C12	1.380 (2)	C28—H28A	0.9600
C11—H11	0.9300	C28—H28B	0.9600
C12—C13	1.376 (2)	C28—H28C	0.9600
C14—S1—C9	104.92 (6)	C16—C15—C14	118.81 (12)
C7—N1—C1	125.77 (12)	C16—C15—C20	117.83 (12)
C7—N1—H1N	118.1 (10)	C14—C15—C20	123.31 (12)
C1—N1—H1N	116.2 (10)	C17—C16—C15	121.48 (15)
C20—N2—C21	125.84 (11)	C17—C16—H16	119.3
C20—N2—H2N	116.7 (11)	C15—C16—H16	119.3
C21—N2—H2N	116.6 (11)	C18—C17—C16	119.32 (15)
C6—C1—C2	120.33 (13)	C18—C17—H17	120.3
C6—C1—N1	120.38 (13)	C16—C17—H17	120.3
C2—C1—N1	119.24 (13)	C17—C18—C19	120.51 (16)
C3—C2—C1	117.51 (15)	C17—C18—H18	119.7
C3—C2—C27	120.35 (15)	C19—C18—H18	119.7
C1—C2—C27	122.14 (13)	C18—C19—C14	120.87 (17)
C4—C3—C2	121.86 (17)	C18—C19—H19	119.6
C4—C3—H3	119.1	C14—C19—H19	119.6
C2—C3—H3	119.1	O2—C20—N2	123.50 (12)
C5—C4—C3	120.32 (16)	O2—C20—C15	122.19 (12)
C5—C4—H4	119.8	N2—C20—C15	114.28 (11)
C3—C4—H4	119.8	C26—C21—C22	121.14 (14)
C4—C5—C6	119.74 (17)	C26—C21—N2	117.26 (13)
C4—C5—H5	120.1	C22—C21—N2	121.41 (14)
C6—C5—H5	120.1	C21—C22—C23	116.55 (17)
C5—C6—C1	120.24 (15)	C21—C22—C28	121.97 (15)
C5—C6—H6	119.9	C23—C22—C28	121.42 (16)
C1—C6—H6	119.9	C24—C23—C22	122.34 (19)
O1—C7—N1	123.97 (12)	C24—C23—H23	118.8
O1—C7—C8	119.48 (11)	C22—C23—H23	118.8
N1—C7—C8	116.48 (11)	C23—C24—C25	120.21 (18)
C13—C8—C9	119.08 (12)	C23—C24—H24	119.9
C13—C8—C7	115.95 (12)	C25—C24—H24	119.9
C9—C8—C7	124.97 (12)	C24—C25—C26	119.5 (2)
C10—C9—C8	119.20 (13)	C24—C25—H25	120.3
C10—C9—S1	119.75 (11)	C26—C25—H25	120.3
C8—C9—S1	120.86 (10)	C25—C26—C21	120.23 (18)
C11—C10—C9	120.66 (14)	C25—C26—H26	119.9
C11—C10—H10	119.7	C21—C26—H26	119.9
C9—C10—H10	119.7	C2—C27—H27A	109.5
C10—C11—C12	120.17 (14)	C2—C27—H27B	109.5
C10—C11—H11	119.9	H27A—C27—H27B	109.5
C12—C11—H11	119.9	C2—C27—H27C	109.5
C13—C12—C11	119.70 (15)	H27A—C27—H27C	109.5
C13—C12—H12	120.1	H27B—C27—H27C	109.5
C11—C12—H12	120.1	C22—C28—H28A	109.5
C12—C13—C8	121.12 (14)	C22—C28—H28B	109.5
C12—C13—H13	119.4	H28A—C28—H28B	109.5
C8—C13—H13	119.4	C22—C28—H28C	109.5
C19—C14—C15	119.00 (14)	H28A—C28—H28C	109.5
C19—C14—S1	114.71 (12)	H28B—C28—H28C	109.5
C15—C14—S1	126.24 (10)
C7—N1—C1—C6	−36.53 (19)	C9—S1—C14—C19	143.53 (12)
C7—N1—C1—C2	145.95 (14)	C9—S1—C14—C15	−39.00 (13)
C6—C1—C2—C3	0.2 (2)	C19—C14—C15—C16	−0.5 (2)
N1—C1—C2—C3	177.71 (14)	S1—C14—C15—C16	−177.92 (10)
C6—C1—C2—C27	179.92 (15)	C19—C14—C15—C20	176.85 (13)
N1—C1—C2—C27	−2.6 (2)	S1—C14—C15—C20	−0.52 (19)
C1—C2—C3—C4	0.0 (3)	C14—C15—C16—C17	1.1 (2)
C27—C2—C3—C4	−179.69 (18)	C20—C15—C16—C17	−176.48 (13)
C2—C3—C4—C5	0.1 (3)	C15—C16—C17—C18	−0.6 (2)
C3—C4—C5—C6	−0.5 (3)	C16—C17—C18—C19	−0.4 (3)
C4—C5—C6—C1	0.7 (3)	C17—C18—C19—C14	0.9 (3)
C2—C1—C6—C5	−0.6 (2)	C15—C14—C19—C18	−0.4 (2)
N1—C1—C6—C5	−178.07 (14)	S1—C14—C19—C18	177.26 (15)
C1—N1—C7—O1	−10.4 (2)	C21—N2—C20—O2	2.6 (2)
C1—N1—C7—C8	172.55 (12)	C21—N2—C20—C15	−179.54 (13)
O1—C7—C8—C13	−45.41 (17)	C16—C15—C20—O2	128.45 (14)
N1—C7—C8—C13	131.75 (13)	C14—C15—C20—O2	−48.97 (19)
O1—C7—C8—C9	133.77 (14)	C16—C15—C20—N2	−49.40 (16)
N1—C7—C8—C9	−49.07 (18)	C14—C15—C20—N2	133.17 (13)
C13—C8—C9—C10	−1.2 (2)	C20—N2—C21—C26	122.49 (15)
C7—C8—C9—C10	179.68 (12)	C20—N2—C21—C22	−62.50 (19)
C13—C8—C9—S1	173.71 (10)	C26—C21—C22—C23	−2.6 (2)
C7—C8—C9—S1	−5.44 (18)	N2—C21—C22—C23	−177.47 (13)
C14—S1—C9—C10	−48.92 (12)	C26—C21—C22—C28	174.44 (15)
C14—S1—C9—C8	136.24 (11)	N2—C21—C22—C28	−0.4 (2)
C8—C9—C10—C11	−1.2 (2)	C21—C22—C23—C24	2.5 (2)
S1—C9—C10—C11	−176.11 (12)	C28—C22—C23—C24	−174.56 (17)
C9—C10—C11—C12	1.9 (3)	C22—C23—C24—C25	−0.8 (3)
C10—C11—C12—C13	−0.3 (3)	C23—C24—C25—C26	−0.9 (3)
C11—C12—C13—C8	−2.1 (3)	C24—C25—C26—C21	0.8 (3)
C9—C8—C13—C12	2.8 (2)	C22—C21—C26—C25	1.1 (2)
C7—C8—C13—C12	−177.94 (14)	N2—C21—C26—C25	176.12 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.861 (16)	2.058 (17)	2.8747 (15)	158.1 (15)
N2—H2N···O1^i	0.856 (16)	2.024 (17)	2.8728 (14)	170.6 (15)

Symmetry code: (i) x, −y+3/2, z−1/2.

(Ib) N,N'-bis(2-ethylphenyl)-2,2'-thiodibenzamide

Crystal data

C30H28N2O2S	F(000) = 1016
Mr = 480.60	Dx = 1.278 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P2yn	Cell parameters from 9904 reflections
a = 7.8786 (1) Å	θ = 4.8–71.2°
b = 17.3269 (2) Å	µ = 1.38 mm^−1
c = 18.3960 (2) Å	T = 293 K
β = 95.787 (1)°	Rod, colourless
V = 2498.47 (5) Å^3	0.40 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	4817 independent reflections
Radiation source: fine-focus sealed tube	4541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 72.0°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −7→9
Tmin = 0.632, Tmax = 0.754	k = −21→20
23191 measured reflections	l = −22→22

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0432P)^2 + 0.5935P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4817 reflections	Δρmax = 0.18 e Å^−3
327 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (2)

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
S1	0.74753 (4)	0.153849 (18)	0.581843 (16)	0.04065 (11)
O1	0.56505 (13)	0.37544 (6)	0.61944 (6)	0.0588 (3)
O2	0.86606 (13)	0.16248 (5)	0.74962 (5)	0.0486 (2)
N1	0.77801 (14)	0.30569 (7)	0.67962 (7)	0.0444 (3)
H1N	0.7989 (19)	0.2638 (9)	0.7007 (8)	0.047 (4)*
N2	0.69702 (16)	0.07604 (7)	0.79770 (6)	0.0456 (3)
H2N	0.651 (2)	0.0344 (10)	0.7922 (10)	0.063 (5)*
C1	0.90841 (16)	0.36277 (7)	0.68273 (8)	0.0444 (3)
C2	1.00947 (17)	0.37522 (8)	0.74851 (9)	0.0496 (3)
C3	1.13859 (19)	0.43086 (9)	0.74777 (11)	0.0648 (5)
H3	1.2073	0.4410	0.7908	0.078*
C4	1.1671 (2)	0.47087 (10)	0.68575 (13)	0.0718 (5)
H4	1.2541	0.5073	0.6872	0.086*
C5	1.0671 (2)	0.45701 (10)	0.62178 (11)	0.0671 (5)
H5	1.0866	0.4837	0.5795	0.080*
C6	0.9372 (2)	0.40328 (8)	0.62022 (9)	0.0544 (4)
H6	0.8687	0.3942	0.5769	0.065*
C7	0.62031 (16)	0.31427 (7)	0.64470 (7)	0.0408 (3)
C8	0.50655 (15)	0.24423 (7)	0.64185 (6)	0.0378 (3)
C9	0.54993 (15)	0.17066 (7)	0.61843 (6)	0.0372 (3)
C10	0.43014 (17)	0.11136 (8)	0.61725 (9)	0.0517 (3)
H10	0.4579	0.0626	0.6009	0.062*
C11	0.27108 (18)	0.12406 (10)	0.63992 (10)	0.0599 (4)
H11	0.1938	0.0835	0.6404	0.072*
C12	0.22635 (17)	0.19648 (10)	0.66184 (9)	0.0567 (4)
H12	0.1183	0.2052	0.6764	0.068*
C13	0.34204 (17)	0.25611 (8)	0.66216 (8)	0.0473 (3)
H13	0.3103	0.3052	0.6761	0.057*
C14	0.80635 (15)	0.06033 (7)	0.61526 (7)	0.0384 (3)
C15	0.82712 (15)	0.04101 (7)	0.68965 (7)	0.0380 (3)
C16	0.88308 (17)	−0.03256 (8)	0.71047 (8)	0.0493 (3)
H16	0.8951	−0.0459	0.7597	0.059*
C17	0.9212 (2)	−0.08614 (9)	0.65869 (10)	0.0609 (4)
H17	0.9613	−0.1348	0.6732	0.073*
C18	0.8995 (2)	−0.06723 (9)	0.58577 (10)	0.0646 (4)
H18	0.9243	−0.1033	0.5510	0.078*
C19	0.84090 (19)	0.00521 (9)	0.56393 (8)	0.0526 (3)
H19	0.8245	0.0171	0.5144	0.063*
C20	0.79803 (15)	0.09890 (7)	0.74767 (6)	0.0369 (3)
C21	0.65255 (17)	0.12530 (7)	0.85554 (7)	0.0409 (3)
C22	0.75010 (18)	0.12515 (8)	0.92267 (7)	0.0475 (3)
C23	0.6978 (2)	0.17315 (9)	0.97682 (9)	0.0621 (4)
H23	0.7613	0.1743	1.0223	0.075*
C24	0.5567 (3)	0.21850 (10)	0.96531 (10)	0.0683 (5)
H24	0.5254	0.2502	1.0025	0.082*
C25	0.4603 (2)	0.21744 (10)	0.89884 (11)	0.0673 (5)
H25	0.3630	0.2480	0.8910	0.081*
C26	0.5088 (2)	0.17052 (9)	0.84339 (9)	0.0546 (4)
H26	0.4444	0.1696	0.7982	0.066*
C27	0.9826 (2)	0.32938 (9)	0.81598 (9)	0.0623 (4)
H27A	1.0401	0.2802	0.8130	0.075*
H27B	0.8616	0.3188	0.8155	0.075*
C28	1.0436 (3)	0.36621 (13)	0.88849 (11)	0.0861 (6)
H28A	1.1655	0.3713	0.8925	0.129*
H28B	1.0114	0.3344	0.9276	0.129*
H28C	0.9926	0.4163	0.8914	0.129*
C29	0.9075 (2)	0.07640 (10)	0.93881 (10)	0.0676 (4)
H29A	0.8983	0.0311	0.9076	0.081*
H29B	0.9140	0.0589	0.9891	0.081*
C30	1.0694 (2)	0.11914 (14)	0.92706 (12)	0.0853 (6)
H30A	1.0698	0.1313	0.8762	0.128*
H30B	1.1661	0.0874	0.9425	0.128*
H30C	1.0751	0.1660	0.9550	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.04085 (18)	0.04641 (19)	0.03570 (17)	0.00041 (12)	0.00877 (12)	0.00206 (12)
O1	0.0541 (6)	0.0446 (5)	0.0748 (7)	0.0039 (4)	−0.0077 (5)	0.0120 (5)
O2	0.0614 (6)	0.0438 (5)	0.0411 (5)	−0.0156 (4)	0.0070 (4)	0.0010 (4)
N1	0.0431 (6)	0.0354 (6)	0.0522 (6)	−0.0006 (4)	−0.0072 (5)	0.0013 (5)
N2	0.0549 (7)	0.0416 (6)	0.0420 (6)	−0.0126 (5)	0.0130 (5)	−0.0034 (5)
C1	0.0378 (6)	0.0353 (6)	0.0598 (8)	0.0040 (5)	0.0031 (6)	−0.0085 (6)
C2	0.0382 (7)	0.0402 (7)	0.0681 (9)	0.0068 (5)	−0.0050 (6)	−0.0117 (6)
C3	0.0421 (8)	0.0506 (8)	0.0984 (13)	0.0015 (6)	−0.0088 (8)	−0.0192 (9)
C4	0.0446 (8)	0.0515 (9)	0.1210 (16)	−0.0064 (7)	0.0159 (9)	−0.0094 (10)
C5	0.0604 (10)	0.0537 (9)	0.0915 (13)	−0.0017 (7)	0.0296 (9)	−0.0006 (8)
C6	0.0548 (8)	0.0484 (8)	0.0614 (9)	0.0003 (6)	0.0124 (7)	−0.0060 (7)
C7	0.0422 (7)	0.0409 (6)	0.0388 (6)	0.0027 (5)	0.0011 (5)	−0.0002 (5)
C8	0.0345 (6)	0.0437 (6)	0.0341 (6)	0.0029 (5)	−0.0018 (5)	0.0031 (5)
C9	0.0310 (6)	0.0440 (6)	0.0355 (6)	0.0002 (5)	−0.0012 (4)	0.0020 (5)
C10	0.0386 (7)	0.0459 (7)	0.0693 (9)	−0.0031 (6)	−0.0009 (6)	−0.0017 (6)
C11	0.0339 (7)	0.0607 (9)	0.0838 (11)	−0.0085 (6)	0.0003 (7)	0.0111 (8)
C12	0.0315 (6)	0.0712 (10)	0.0678 (9)	0.0066 (6)	0.0071 (6)	0.0130 (8)
C13	0.0385 (7)	0.0537 (8)	0.0494 (7)	0.0105 (6)	0.0032 (5)	0.0049 (6)
C14	0.0308 (6)	0.0436 (6)	0.0418 (6)	−0.0011 (5)	0.0088 (5)	−0.0035 (5)
C15	0.0301 (5)	0.0408 (6)	0.0436 (6)	−0.0022 (5)	0.0060 (5)	0.0006 (5)
C16	0.0441 (7)	0.0451 (7)	0.0590 (8)	0.0019 (6)	0.0069 (6)	0.0060 (6)
C17	0.0560 (9)	0.0440 (8)	0.0848 (12)	0.0108 (6)	0.0169 (8)	0.0007 (7)
C18	0.0665 (10)	0.0531 (9)	0.0782 (11)	0.0083 (7)	0.0263 (8)	−0.0174 (8)
C19	0.0525 (8)	0.0573 (8)	0.0503 (8)	0.0024 (7)	0.0173 (6)	−0.0097 (6)
C20	0.0360 (6)	0.0397 (6)	0.0341 (6)	−0.0021 (5)	−0.0004 (5)	0.0043 (5)
C21	0.0459 (7)	0.0388 (6)	0.0391 (6)	−0.0047 (5)	0.0101 (5)	0.0029 (5)
C22	0.0545 (8)	0.0432 (7)	0.0446 (7)	−0.0006 (6)	0.0032 (6)	0.0016 (5)
C23	0.0849 (12)	0.0586 (9)	0.0428 (8)	−0.0005 (8)	0.0065 (7)	−0.0057 (7)
C24	0.0874 (12)	0.0556 (9)	0.0672 (11)	0.0017 (9)	0.0332 (9)	−0.0084 (8)
C25	0.0571 (9)	0.0536 (9)	0.0947 (13)	0.0122 (7)	0.0257 (9)	0.0072 (9)
C26	0.0505 (8)	0.0563 (8)	0.0565 (8)	0.0015 (7)	0.0028 (6)	0.0103 (7)
C27	0.0659 (10)	0.0534 (8)	0.0624 (9)	0.0056 (7)	−0.0188 (8)	−0.0065 (7)
C28	0.0929 (14)	0.0887 (13)	0.0705 (12)	0.0031 (11)	−0.0226 (10)	−0.0186 (10)
C29	0.0728 (11)	0.0605 (9)	0.0655 (10)	0.0142 (8)	−0.0131 (8)	−0.0010 (8)
C30	0.0600 (11)	0.1153 (17)	0.0790 (13)	0.0179 (11)	−0.0009 (9)	0.0041 (12)

Geometric parameters (Å, º)

S1—C14	1.7779 (13)	C14—C15	1.4023 (17)
S1—C9	1.7813 (12)	C15—C16	1.3899 (18)
O1—C7	1.2198 (16)	C15—C20	1.4990 (17)
O2—C20	1.2241 (15)	C16—C17	1.384 (2)
N1—C7	1.3481 (17)	C16—H16	0.9300
N1—C1	1.4230 (17)	C17—C18	1.375 (3)
N1—H1N	0.831 (16)	C17—H17	0.9300
N2—C20	1.3361 (16)	C18—C19	1.383 (2)
N2—C21	1.4346 (17)	C18—H18	0.9300
N2—H2N	0.810 (18)	C19—H19	0.9300
C1—C6	1.386 (2)	C21—C26	1.377 (2)
C1—C2	1.397 (2)	C21—C22	1.3872 (19)
C2—C3	1.403 (2)	C22—C23	1.392 (2)
C2—C27	1.506 (2)	C22—C29	1.505 (2)
C3—C4	1.373 (3)	C23—C24	1.361 (3)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.370 (3)	C24—C25	1.373 (3)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.382 (2)	C25—C26	1.388 (2)
C5—H5	0.9300	C25—H25	0.9300
C6—H6	0.9300	C26—H26	0.9300
C7—C8	1.5064 (18)	C27—C28	1.513 (2)
C8—C9	1.3990 (17)	C27—H27A	0.9700
C8—C13	1.3998 (18)	C27—H27B	0.9700
C9—C10	1.3937 (18)	C28—H28A	0.9600
C10—C11	1.378 (2)	C28—H28B	0.9600
C10—H10	0.9300	C28—H28C	0.9600
C11—C12	1.375 (2)	C29—C30	1.509 (3)
C11—H11	0.9300	C29—H29A	0.9700
C12—C13	1.377 (2)	C29—H29B	0.9700
C12—H12	0.9300	C30—H30A	0.9600
C13—H13	0.9300	C30—H30B	0.9600
C14—C19	1.3890 (18)	C30—H30C	0.9600
C14—S1—C9	103.04 (6)	C18—C17—C16	119.82 (14)
C7—N1—C1	124.72 (11)	C18—C17—H17	120.1
C7—N1—H1N	116.6 (11)	C16—C17—H17	120.1
C1—N1—H1N	118.7 (11)	C17—C18—C19	120.32 (14)
C20—N2—C21	122.79 (11)	C17—C18—H18	119.8
C20—N2—H2N	118.0 (13)	C19—C18—H18	119.8
C21—N2—H2N	118.8 (13)	C18—C19—C14	120.60 (14)
C6—C1—C2	120.94 (13)	C18—C19—H19	119.7
C6—C1—N1	119.79 (13)	C14—C19—H19	119.7
C2—C1—N1	119.24 (13)	O2—C20—N2	122.41 (12)
C1—C2—C3	116.64 (15)	O2—C20—C15	121.69 (11)
C1—C2—C27	121.15 (13)	N2—C20—C15	115.89 (11)
C3—C2—C27	122.19 (14)	C26—C21—C22	121.23 (13)
C4—C3—C2	122.35 (17)	C26—C21—N2	118.46 (13)
C4—C3—H3	118.8	C22—C21—N2	120.29 (12)
C2—C3—H3	118.8	C21—C22—C23	117.30 (14)
C5—C4—C3	119.81 (15)	C21—C22—C29	123.24 (13)
C5—C4—H4	120.1	C23—C22—C29	119.46 (14)
C3—C4—H4	120.1	C24—C23—C22	122.02 (16)
C4—C5—C6	119.78 (17)	C24—C23—H23	119.0
C4—C5—H5	120.1	C22—C23—H23	119.0
C6—C5—H5	120.1	C23—C24—C25	120.05 (15)
C5—C6—C1	120.48 (16)	C23—C24—H24	120.0
C5—C6—H6	119.8	C25—C24—H24	120.0
C1—C6—H6	119.8	C24—C25—C26	119.59 (15)
O1—C7—N1	123.62 (12)	C24—C25—H25	120.2
O1—C7—C8	119.90 (11)	C26—C25—H25	120.2
N1—C7—C8	116.38 (11)	C21—C26—C25	119.81 (15)
C9—C8—C13	118.53 (12)	C21—C26—H26	120.1
C9—C8—C7	125.58 (11)	C25—C26—H26	120.1
C13—C8—C7	115.85 (12)	C2—C27—C28	116.46 (15)
C10—C9—C8	119.37 (12)	C2—C27—H27A	108.2
C10—C9—S1	119.33 (10)	C28—C27—H27A	108.2
C8—C9—S1	121.02 (9)	C2—C27—H27B	108.2
C11—C10—C9	120.85 (14)	C28—C27—H27B	108.2
C11—C10—H10	119.6	H27A—C27—H27B	107.3
C9—C10—H10	119.6	C27—C28—H28A	109.5
C12—C11—C10	120.16 (14)	C27—C28—H28B	109.5
C12—C11—H11	119.9	H28A—C28—H28B	109.5
C10—C11—H11	119.9	C27—C28—H28C	109.5
C11—C12—C13	119.79 (13)	H28A—C28—H28C	109.5
C11—C12—H12	120.1	H28B—C28—H28C	109.5
C13—C12—H12	120.1	C22—C29—C30	112.81 (15)
C12—C13—C8	121.25 (13)	C22—C29—H29A	109.0
C12—C13—H13	119.4	C30—C29—H29A	109.0
C8—C13—H13	119.4	C22—C29—H29B	109.0
C19—C14—C15	119.19 (12)	C30—C29—H29B	109.0
C19—C14—S1	116.98 (10)	H29A—C29—H29B	107.8
C15—C14—S1	123.76 (9)	C29—C30—H30A	109.5
C16—C15—C14	119.36 (12)	C29—C30—H30B	109.5
C16—C15—C20	118.99 (11)	H30A—C30—H30B	109.5
C14—C15—C20	121.59 (11)	C29—C30—H30C	109.5
C17—C16—C15	120.68 (14)	H30A—C30—H30C	109.5
C17—C16—H16	119.7	H30B—C30—H30C	109.5
C15—C16—H16	119.7
C7—N1—C1—C6	−43.91 (19)	C19—C14—C15—C16	0.52 (18)
C7—N1—C1—C2	138.25 (14)	S1—C14—C15—C16	−176.26 (10)
C6—C1—C2—C3	0.66 (19)	C19—C14—C15—C20	177.71 (12)
N1—C1—C2—C3	178.48 (12)	S1—C14—C15—C20	0.93 (16)
C6—C1—C2—C27	−177.86 (13)	C14—C15—C16—C17	1.2 (2)
N1—C1—C2—C27	−0.05 (19)	C20—C15—C16—C17	−176.11 (13)
C1—C2—C3—C4	−0.8 (2)	C15—C16—C17—C18	−1.6 (2)
C27—C2—C3—C4	177.75 (15)	C16—C17—C18—C19	0.4 (3)
C2—C3—C4—C5	0.2 (2)	C17—C18—C19—C14	1.3 (2)
C3—C4—C5—C6	0.5 (2)	C15—C14—C19—C18	−1.7 (2)
C4—C5—C6—C1	−0.6 (2)	S1—C14—C19—C18	175.27 (12)
C2—C1—C6—C5	0.0 (2)	C21—N2—C20—O2	3.4 (2)
N1—C1—C6—C5	−177.80 (13)	C21—N2—C20—C15	−178.15 (11)
C1—N1—C7—O1	−9.4 (2)	C16—C15—C20—O2	125.95 (13)
C1—N1—C7—C8	174.37 (12)	C14—C15—C20—O2	−51.25 (17)
O1—C7—C8—C9	132.17 (14)	C16—C15—C20—N2	−52.53 (16)
N1—C7—C8—C9	−51.44 (17)	C14—C15—C20—N2	130.27 (13)
O1—C7—C8—C13	−45.39 (17)	C20—N2—C21—C26	89.90 (17)
N1—C7—C8—C13	131.01 (13)	C20—N2—C21—C22	−92.03 (16)
C13—C8—C9—C10	−1.15 (18)	C26—C21—C22—C23	−0.7 (2)
C7—C8—C9—C10	−178.65 (12)	N2—C21—C22—C23	−178.72 (13)
C13—C8—C9—S1	172.69 (9)	C26—C21—C22—C29	179.59 (15)
C7—C8—C9—S1	−4.81 (17)	N2—C21—C22—C29	1.6 (2)
C14—S1—C9—C10	−42.67 (12)	C21—C22—C23—C24	0.3 (2)
C14—S1—C9—C8	143.48 (10)	C29—C22—C23—C24	179.97 (16)
C8—C9—C10—C11	−1.1 (2)	C22—C23—C24—C25	0.4 (3)
S1—C9—C10—C11	−175.00 (12)	C23—C24—C25—C26	−0.7 (3)
C9—C10—C11—C12	2.2 (2)	C22—C21—C26—C25	0.5 (2)
C10—C11—C12—C13	−1.0 (2)	N2—C21—C26—C25	178.52 (13)
C11—C12—C13—C8	−1.2 (2)	C24—C25—C26—C21	0.2 (2)
C9—C8—C13—C12	2.32 (19)	C1—C2—C27—C28	−156.28 (15)
C7—C8—C13—C12	−179.95 (13)	C3—C2—C27—C28	25.3 (2)
C9—S1—C14—C19	125.61 (10)	C21—C22—C29—C30	94.42 (19)
C9—S1—C14—C15	−57.54 (11)	C23—C22—C29—C30	−85.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.831 (16)	2.020 (17)	2.8490 (15)	176.0 (15)
N2—H2N···Cg1^i	0.810 (18)	2.587 (17)	3.3591 (14)	160.1 (16)

Symmetry code: (i) −x+3/2, y−1/2, −z+3/2.

(Ic) N,N'-bis(2-bromophenyl)-2,2'-thiodibenzamide

Crystal data

C26H18Br2N2O2S	F(000) = 1160
Mr = 582.30	Dx = 1.634 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P2ybc	Cell parameters from 3941 reflections
a = 20.6504 (3) Å	θ = 3.6–72.5°
b = 15.3378 (2) Å	µ = 5.39 mm^−1
c = 7.5101 (1) Å	T = 296 K
β = 95.520 (1)°	Plate, colourless
V = 2367.66 (6) Å^3	0.30 × 0.30 × 0.01 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	4681 independent reflections
Radiation source: fine-focus sealed tube	3752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 74.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −25→24
Tmin = 0.454, Tmax = 0.754	k = −18→14
17010 measured reflections	l = −9→9

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0644P)^2 + 1.9041P] where P = (Fo^2 + 2Fc^2)/3
4681 reflections	(Δ/σ)max = 0.001
306 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.66 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
Br1	0.59962 (3)	0.45743 (5)	0.74372 (9)	0.1004 (2)
Br2	0.74240 (2)	0.95912 (3)	0.61736 (7)	0.07080 (17)
S1	0.87768 (4)	0.52798 (5)	0.52702 (10)	0.04400 (19)
O1	0.81248 (15)	0.3434 (2)	0.4746 (5)	0.0814 (9)
O2	0.79907 (12)	0.64694 (15)	0.7654 (3)	0.0523 (6)
N1	0.72734 (16)	0.3972 (3)	0.6097 (5)	0.0626 (8)
H1N	0.719 (2)	0.424 (3)	0.695 (6)	0.061 (13)*
N2	0.77499 (13)	0.76491 (18)	0.5901 (4)	0.0454 (6)
H2N	0.7879 (19)	0.796 (3)	0.512 (5)	0.050 (10)*
C1	0.67429 (18)	0.3799 (2)	0.4819 (5)	0.0573 (9)
C2	0.6122 (2)	0.4043 (3)	0.5202 (6)	0.0690 (11)
C3	0.5583 (2)	0.3907 (4)	0.4028 (8)	0.0901 (15)
H3	0.5173	0.4072	0.4321	0.108*
C4	0.5659 (3)	0.3518 (4)	0.2388 (8)	0.0936 (17)
H4	0.5299	0.3433	0.1562	0.112*
C5	0.6264 (3)	0.3262 (3)	0.1991 (7)	0.0813 (14)
H5	0.6310	0.2987	0.0906	0.098*
C6	0.6808 (2)	0.3406 (3)	0.3185 (6)	0.0696 (11)
H6	0.7217	0.3238	0.2890	0.084*
C7	0.79066 (17)	0.3796 (2)	0.6005 (5)	0.0499 (8)
C8	0.83342 (15)	0.41127 (19)	0.7605 (5)	0.0438 (7)
C9	0.87627 (14)	0.48091 (17)	0.7433 (4)	0.0381 (6)
C10	0.91476 (15)	0.5100 (2)	0.8919 (4)	0.0433 (6)
H10	0.9431	0.5564	0.8816	0.052*
C11	0.91124 (17)	0.4705 (2)	1.0551 (5)	0.0510 (8)
H11	0.9372	0.4908	1.1545	0.061*
C12	0.86999 (19)	0.4014 (2)	1.0736 (5)	0.0568 (9)
H12	0.8681	0.3749	1.1845	0.068*
C13	0.83159 (18)	0.3719 (2)	0.9266 (5)	0.0551 (8)
H13	0.8039	0.3249	0.9383	0.066*
C14	0.91761 (15)	0.62996 (19)	0.5697 (4)	0.0397 (6)
C15	0.88383 (14)	0.70553 (19)	0.6110 (4)	0.0378 (6)
C16	0.91694 (16)	0.7839 (2)	0.6217 (4)	0.0453 (7)
H16	0.8950	0.8346	0.6473	0.054*
C17	0.98240 (17)	0.7883 (2)	0.5951 (5)	0.0510 (8)
H17	1.0040	0.8415	0.6042	0.061*
C18	1.01526 (16)	0.7141 (2)	0.5553 (5)	0.0527 (8)
H18	1.0592	0.7167	0.5374	0.063*
C19	0.98259 (16)	0.6355 (2)	0.5420 (5)	0.0477 (7)
H19	1.0048	0.5854	0.5139	0.057*
C20	0.81513 (15)	0.70130 (19)	0.6599 (4)	0.0401 (6)
C21	0.70995 (15)	0.7783 (2)	0.6296 (4)	0.0468 (7)
C22	0.68653 (17)	0.8626 (3)	0.6428 (5)	0.0537 (8)
C23	0.6230 (2)	0.8777 (3)	0.6746 (6)	0.0739 (12)
H23	0.6076	0.9345	0.6809	0.089*
C24	0.5824 (2)	0.8085 (4)	0.6968 (7)	0.0875 (16)
H24	0.5393	0.8184	0.7174	0.105*
C25	0.6051 (2)	0.7253 (4)	0.6887 (7)	0.0826 (14)
H25	0.5776	0.6788	0.7066	0.099*
C26	0.66868 (19)	0.7090 (3)	0.6542 (6)	0.0638 (10)
H26	0.6836	0.6519	0.6476	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0610 (3)	0.1508 (6)	0.0891 (4)	0.0117 (3)	0.0063 (3)	−0.0293 (4)
Br2	0.0735 (3)	0.0497 (2)	0.0894 (3)	0.00888 (17)	0.0093 (2)	−0.0086 (2)
S1	0.0565 (4)	0.0365 (4)	0.0390 (4)	−0.0021 (3)	0.0046 (3)	−0.0030 (3)
O1	0.0671 (18)	0.087 (2)	0.090 (2)	−0.0041 (15)	0.0079 (16)	−0.0401 (18)
O2	0.0592 (14)	0.0455 (12)	0.0553 (13)	0.0062 (10)	0.0215 (11)	0.0105 (11)
N1	0.0478 (17)	0.079 (2)	0.0602 (19)	−0.0008 (15)	0.0024 (14)	−0.0157 (18)
N2	0.0439 (14)	0.0446 (14)	0.0487 (14)	0.0044 (11)	0.0097 (12)	0.0088 (12)
C1	0.054 (2)	0.058 (2)	0.058 (2)	−0.0106 (15)	−0.0014 (16)	0.0008 (17)
C2	0.055 (2)	0.082 (3)	0.068 (2)	−0.0128 (19)	−0.0011 (18)	−0.001 (2)
C3	0.059 (3)	0.118 (4)	0.090 (4)	−0.012 (3)	−0.008 (2)	−0.003 (3)
C4	0.071 (3)	0.125 (5)	0.079 (3)	−0.030 (3)	−0.019 (2)	0.001 (3)
C5	0.092 (4)	0.082 (3)	0.068 (3)	−0.025 (3)	−0.004 (2)	−0.010 (2)
C6	0.071 (3)	0.075 (3)	0.062 (2)	−0.013 (2)	0.0009 (19)	−0.004 (2)
C7	0.0506 (18)	0.0343 (15)	0.065 (2)	−0.0050 (12)	0.0063 (15)	−0.0028 (14)
C8	0.0421 (16)	0.0345 (14)	0.0550 (18)	0.0033 (11)	0.0052 (13)	−0.0005 (13)
C9	0.0408 (14)	0.0288 (12)	0.0446 (15)	0.0053 (10)	0.0043 (12)	0.0015 (11)
C10	0.0432 (15)	0.0389 (15)	0.0473 (16)	0.0008 (12)	0.0018 (13)	0.0012 (13)
C11	0.0495 (18)	0.0566 (19)	0.0459 (17)	0.0094 (14)	−0.0012 (14)	0.0016 (15)
C12	0.060 (2)	0.058 (2)	0.0524 (19)	0.0124 (16)	0.0101 (16)	0.0183 (17)
C13	0.057 (2)	0.0404 (16)	0.068 (2)	−0.0022 (14)	0.0096 (17)	0.0105 (16)
C14	0.0453 (16)	0.0371 (14)	0.0368 (14)	0.0013 (11)	0.0049 (12)	0.0043 (12)
C15	0.0433 (15)	0.0368 (14)	0.0333 (13)	0.0025 (11)	0.0042 (11)	0.0043 (11)
C16	0.0533 (18)	0.0353 (14)	0.0468 (16)	0.0002 (12)	0.0034 (13)	0.0026 (13)
C17	0.0503 (18)	0.0444 (17)	0.057 (2)	−0.0105 (13)	−0.0009 (15)	0.0082 (15)
C18	0.0389 (16)	0.059 (2)	0.060 (2)	−0.0008 (14)	0.0049 (14)	0.0144 (16)
C19	0.0464 (17)	0.0451 (16)	0.0521 (17)	0.0080 (13)	0.0083 (13)	0.0087 (14)
C20	0.0477 (16)	0.0346 (14)	0.0384 (14)	0.0017 (11)	0.0072 (12)	−0.0024 (12)
C21	0.0387 (15)	0.0581 (19)	0.0436 (16)	0.0004 (13)	0.0043 (12)	0.0021 (14)
C22	0.0457 (17)	0.065 (2)	0.0500 (18)	0.0106 (15)	0.0034 (14)	−0.0019 (16)
C23	0.056 (2)	0.094 (3)	0.072 (3)	0.022 (2)	0.0087 (19)	−0.006 (2)
C24	0.042 (2)	0.132 (5)	0.089 (3)	0.010 (2)	0.012 (2)	0.008 (3)
C25	0.047 (2)	0.111 (4)	0.091 (3)	−0.016 (2)	0.010 (2)	0.008 (3)
C26	0.051 (2)	0.069 (2)	0.071 (2)	−0.0059 (17)	0.0055 (17)	0.006 (2)

Geometric parameters (Å, º)

Br1—C2	1.906 (5)	C10—H10	0.9300
Br2—C22	1.898 (4)	C11—C12	1.375 (5)
S1—C9	1.780 (3)	C11—H11	0.9300
S1—C14	1.783 (3)	C12—C13	1.373 (6)
O1—C7	1.219 (5)	C12—H12	0.9300
O2—C20	1.218 (4)	C13—H13	0.9300
N1—C7	1.344 (5)	C14—C19	1.380 (4)
N1—C1	1.410 (5)	C14—C15	1.403 (4)
N1—H1N	0.79 (5)	C15—C16	1.382 (4)
N2—C20	1.353 (4)	C15—C20	1.501 (4)
N2—C21	1.418 (4)	C16—C17	1.387 (5)
N2—H2N	0.82 (4)	C16—H16	0.9300
C1—C6	1.385 (6)	C17—C18	1.373 (5)
C1—C2	1.393 (6)	C17—H17	0.9300
C2—C3	1.368 (6)	C18—C19	1.380 (5)
C3—C4	1.391 (8)	C18—H18	0.9300
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.370 (8)	C21—C26	1.386 (5)
C4—H4	0.9300	C21—C22	1.388 (5)
C5—C6	1.387 (6)	C22—C23	1.376 (5)
C5—H5	0.9300	C23—C24	1.373 (8)
C6—H6	0.9300	C23—H23	0.9300
C7—C8	1.502 (5)	C24—C25	1.364 (8)
C8—C13	1.390 (5)	C24—H24	0.9300
C8—C9	1.401 (4)	C25—C26	1.385 (6)
C9—C10	1.381 (4)	C25—H25	0.9300
C10—C11	1.376 (5)	C26—H26	0.9300
C9—S1—C14	103.86 (14)	C12—C13—C8	121.0 (3)
C7—N1—C1	128.5 (4)	C12—C13—H13	119.5
C7—N1—H1N	115 (3)	C8—C13—H13	119.5
C1—N1—H1N	116 (3)	C19—C14—C15	119.6 (3)
C20—N2—C21	125.5 (3)	C19—C14—S1	117.8 (2)
C20—N2—H2N	118 (3)	C15—C14—S1	122.2 (2)
C21—N2—H2N	117 (3)	C16—C15—C14	118.6 (3)
C6—C1—C2	118.0 (4)	C16—C15—C20	119.8 (3)
C6—C1—N1	123.3 (4)	C14—C15—C20	121.3 (3)
C2—C1—N1	118.7 (4)	C15—C16—C17	121.2 (3)
C3—C2—C1	122.3 (5)	C15—C16—H16	119.4
C3—C2—Br1	117.5 (4)	C17—C16—H16	119.4
C1—C2—Br1	120.2 (3)	C18—C17—C16	120.0 (3)
C2—C3—C4	118.8 (5)	C18—C17—H17	120.0
C2—C3—H3	120.6	C16—C17—H17	120.0
C4—C3—H3	120.6	C17—C18—C19	119.4 (3)
C5—C4—C3	119.9 (4)	C17—C18—H18	120.3
C5—C4—H4	120.0	C19—C18—H18	120.3
C3—C4—H4	120.0	C18—C19—C14	121.3 (3)
C4—C5—C6	120.9 (5)	C18—C19—H19	119.4
C4—C5—H5	119.6	C14—C19—H19	119.4
C6—C5—H5	119.6	O2—C20—N2	123.4 (3)
C1—C6—C5	120.0 (5)	O2—C20—C15	120.8 (3)
C1—C6—H6	120.0	N2—C20—C15	115.6 (3)
C5—C6—H6	120.0	C26—C21—C22	118.8 (3)
O1—C7—N1	124.5 (4)	C26—C21—N2	121.6 (3)
O1—C7—C8	122.3 (3)	C22—C21—N2	119.6 (3)
N1—C7—C8	113.2 (3)	C23—C22—C21	120.9 (4)
C13—C8—C9	119.1 (3)	C23—C22—Br2	119.1 (3)
C13—C8—C7	120.8 (3)	C21—C22—Br2	120.0 (3)
C9—C8—C7	120.1 (3)	C24—C23—C22	119.7 (5)
C10—C9—C8	119.4 (3)	C24—C23—H23	120.2
C10—C9—S1	123.2 (2)	C22—C23—H23	120.2
C8—C9—S1	117.4 (2)	C25—C24—C23	120.1 (4)
C11—C10—C9	120.2 (3)	C25—C24—H24	120.0
C11—C10—H10	119.9	C23—C24—H24	120.0
C9—C10—H10	119.9	C24—C25—C26	121.0 (5)
C12—C11—C10	121.1 (3)	C24—C25—H25	119.5
C12—C11—H11	119.5	C26—C25—H25	119.5
C10—C11—H11	119.5	C25—C26—C21	119.5 (4)
C13—C12—C11	119.2 (3)	C25—C26—H26	120.3
C13—C12—H12	120.4	C21—C26—H26	120.3
C11—C12—H12	120.4
C7—N1—C1—C6	−0.6 (7)	C9—S1—C14—C19	100.2 (3)
C7—N1—C1—C2	−179.9 (4)	C9—S1—C14—C15	−86.8 (3)
C6—C1—C2—C3	0.0 (7)	C19—C14—C15—C16	0.3 (4)
N1—C1—C2—C3	179.3 (5)	S1—C14—C15—C16	−172.6 (2)
C6—C1—C2—Br1	179.2 (3)	C19—C14—C15—C20	−173.9 (3)
N1—C1—C2—Br1	−1.4 (6)	S1—C14—C15—C20	13.2 (4)
C1—C2—C3—C4	−0.5 (9)	C14—C15—C16—C17	−0.9 (5)
Br1—C2—C3—C4	−179.8 (4)	C20—C15—C16—C17	173.4 (3)
C2—C3—C4—C5	1.4 (9)	C15—C16—C17—C18	0.7 (5)
C3—C4—C5—C6	−1.8 (9)	C16—C17—C18—C19	0.0 (5)
C2—C1—C6—C5	−0.3 (7)	C17—C18—C19—C14	−0.6 (5)
N1—C1—C6—C5	−179.6 (4)	C15—C14—C19—C18	0.4 (5)
C4—C5—C6—C1	1.2 (8)	S1—C14—C19—C18	173.7 (3)
C1—N1—C7—O1	−0.8 (7)	C21—N2—C20—O2	0.7 (5)
C1—N1—C7—C8	177.5 (4)	C21—N2—C20—C15	−174.4 (3)
O1—C7—C8—C13	−111.7 (4)	C16—C15—C20—O2	−128.8 (3)
N1—C7—C8—C13	69.9 (4)	C14—C15—C20—O2	45.3 (4)
O1—C7—C8—C9	67.7 (5)	C16—C15—C20—N2	46.5 (4)
N1—C7—C8—C9	−110.6 (4)	C14—C15—C20—N2	−139.4 (3)
C13—C8—C9—C10	−1.2 (4)	C20—N2—C21—C26	−37.9 (5)
C7—C8—C9—C10	179.3 (3)	C20—N2—C21—C22	142.6 (3)
C13—C8—C9—S1	179.0 (2)	C26—C21—C22—C23	−1.9 (6)
C7—C8—C9—S1	−0.4 (4)	N2—C21—C22—C23	177.6 (4)
C14—S1—C9—C10	−16.0 (3)	C26—C21—C22—Br2	178.0 (3)
C14—S1—C9—C8	163.7 (2)	N2—C21—C22—Br2	−2.4 (5)
C8—C9—C10—C11	0.4 (5)	C21—C22—C23—C24	1.2 (7)
S1—C9—C10—C11	−179.9 (2)	Br2—C22—C23—C24	−178.7 (4)
C9—C10—C11—C12	0.4 (5)	C22—C23—C24—C25	0.5 (8)
C10—C11—C12—C13	−0.3 (5)	C23—C24—C25—C26	−1.4 (8)
C11—C12—C13—C8	−0.6 (6)	C24—C25—C26—C21	0.8 (8)
C9—C8—C13—C12	1.3 (5)	C22—C21—C26—C25	0.9 (6)
C7—C8—C13—C12	−179.2 (3)	N2—C21—C26—C25	−178.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2^i	0.82 (4)	2.08 (4)	2.873 (4)	162 (4)
N1—H1N···Br1	0.79 (5)	2.58 (5)	3.055 (4)	120 (4)

Symmetry code: (i) x, −y+3/2, z−1/2.