Three anilides of 2,2′-thiodibenzoic acid

organic compounds

Acta Crystallographica Section C

Crystal Structure

Communications

(Ic), respectively (Fig. 1). A paper describing these amides and

other related substances, and their biological properties, has

been published elsewhere (Moosun et al., 2012). X-ray

diffraction analyses have now been carried out to ascertain the

three-dimensional constitution of the molecules, as well as to

determine the effect of different substituents on the confor-

mation and conﬁguration of the synthesized molecules.

ISSN 0108-2701

Three anilides of 2,2⁰-thiodibenzoic

acid

Madeleine Helliwell,^aSalma Moosun,^bMinu G. Bhowon,^b

Sabina Jhaumeer-Laulloo^b* and John A. Joule^a

^aSchool of Chemistry, University of Manchester, Manchester M13 9PL, England, and

^bChemistry Department, University of Mauritius, Reduit, Mauritius

Correspondence e-mail: sabina@uom.ac.mu

Received 27 June 2012

Accepted 15 August 2012

Online 7 September 2012

The structures of N,N⁰-bis(2-methylphenyl)-2,2⁰-thiodibenz-

amide, C₂₈H₂₄N₂O₂S, (Ia), N,N⁰-bis(2-ethylphenyl)-2,2⁰-thio-

dibenzamide, C₃₀H₂₈N₂O₂S, (Ib), and N,N⁰-bis(2-bromo-

phenyl)-2,2⁰-thiodibenzamide, C₂₆H₁₈Br₂N₂O₂S, (Ic), are com-

pared 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 A 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—Hꢀ ꢀ ꢀO hydrogen-bonding interaction. The molecules of

(Ia) are further linked into inﬁnite chains along the c axis by

intermolecular N—Hꢀ ꢀ ꢀO interactions, whereas the molecules

of (Ib) are linked into chains along b by an intermolecular N—

Hꢀ ꢀ ꢀꢀ contact. The conformation of (Ic) is quite different

from those of (Ia) and (Ib), since there is no intramolecular

N—Hꢀ ꢀ ꢀO hydrogen bond, but instead there is a possible

intramolecular N—Hꢀ ꢀ ꢀBr hydrogen bond. The molecules are

linked into chains along c by intermolecular N—Hꢀ ꢀ ꢀO

hydrogen bonds.

Considering ﬁrst the diaryl sulﬁde units in the three struc-

tures, 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 the

S atom are described by two torsion 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 ꢂ48.9 (1) and 39.0 (1)^ꢁ, for (Ib) ꢂ42.7 (1) and ꢂ57.5 (1)^ꢁ,

and for (Ic) ꢂ16.0 (3) and ꢂ86.8 (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 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, viz. O1—C7—C8—

C13 and O2—C20—C15—C14, for each of the three amides,

with values of ꢂ45.4 (2) and ꢂ49.0 (2)^ꢁ, respectively, for (Ia),

ꢂ45.4 (2) and ꢂ51.3 (2)^ꢁfor (Ib), and ꢂ111.7 (5) and 45.3 (3)^ꢁ

for (Ic). Thus, in each case, there is considerably reduced

overlap between the carbonyl ꢀ-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—

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, the reaction of

2,2⁰-thiodibenzoic acid chloride with the anilines 2-methyl-

aniline, 2-ethylaniline and 2-bromoaniline produced three

2,2⁰-thiodibenzamides, namely N,N⁰-bis(2-methylphenyl)-2,2⁰-

thiodibenzamide, (Ia), N,N⁰-bis(2-ethylphenyl)-2,2⁰-thiodibenz-

amide, (Ib), and N,N⁰-bis(2-bromophenyl)-2,2⁰-thiodibenzamide,

Acta Cryst. (2012). C68, o387–o391

doi:10.1107/S0108270112035962

# 2012 International Union of Crystallography o387

organic compounds

At the extremities of the three structures, it is relevant to

ask to what extent the nitrogen p-orbital interacts with the ꢀ

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), viz. C7—N1—C1—C6 and C20—N2—

C21—C22, with values of ꢂ36.5 (2) and ꢂ62.5 (2)^ꢁ, respec-

tively, for (Ia), ꢂ43.9 (2) and ꢂ92.0 (2)^ꢁfor (Ib), and ꢂ0.6 (7)

and 142.6 (3)^ꢁfor (Ic). 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, i.e. in 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 A when ﬁtting the S, N and O atoms and

atoms C7–C20 (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 to either (Ia) or

(Ib), with r.m.s. differences for the same atoms of 0.90 and

˚

0.80 A, 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—H1ꢀ ꢀ ꢀO2 hydrogen bond seen in both structures (Figs. 1a,

1b, 3a and 3b). In (Ic), this intramolecular interaction does not

Figure 1

Plots of (a) (Ia), (b) (Ib) and (c) (Ic). In each case, displacement ellipsoids

are drawn at the 30% probability level and intramolecular hydrogen-

bonding interactions are shown as double-dashed lines.

C7—O1 and C21—N2—C20—O2, with values of ꢂ10.4 (2)

and 2.6 (2)^ꢁ, respectively, for (Ia), ꢂ9.4 (2) and 3.4 (2)^ꢁfor

(Ib), and ꢂ0.8 (7) and 0.7 (5)^ꢁfor (Ic). Each of the six amide

units is very close to being planar, which is ideal for amide

resonance.

Figure 2

An 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.

ꢃ

o388 Helliwell et al.

C₂₈H₂₄N₂O₂S, C₃₀H₂₈N₂O₂S and C₂₆H₁₈Br₂N₂O₂S

Acta Cryst. (2012). C68, o387–o391

organic compounds

occur, but instead a possible intramolecular N1—H1ꢀ ꢀ ꢀBr1

bond is observed (Figs. 1c and 3c). The geometry of this

hydrogen bond, with an N1—H1ꢀ ꢀ ꢀ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 confor-

mation 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—H2ꢀ ꢀ ꢀO1ⁱhydrogen bond [symmetry

1

code: (i) x, ꢂy + ³₂, z ꢂ ] links the molecules into chains along c

2

(Fig. 3a). In (Ib), the molecules are linked into chains along b

by an intermolecular N—Hꢀ ꢀ ꢀꢀ contact, viz. N2—

H2Nꢀ ꢀ ꢀCg1ⁱⁱ[Cg1 is the centroid of the C1–C6 benzene ring;

1

symmetry code: (ii) ꢂx + ₂³, y ꢂ , ꢂz + ³₂] (Fig. 3b). In (Ic), the

2

molecules are linked into chains along c by an intermolecular

N2—H2Nꢀ ꢀ ꢀO2ⁱhydrogen bond (Fig. 3c).

Experimental

The general method used for the synthesis of the title amides was as

follows. Thionyl chloride (2 ml) was added to 2,2⁰-thiodibenzoic acid

(0.49 g, 1.8 mmol) dissolved in dichloromethane (20 ml) and the

resulting solution was maintained under reﬂux for 2 h. The excess

thionyl chloride was removed by distillation and the resulting double

acid chloride used without further puriﬁcation. The appropriate

aniline (2-methylaniline, 2-ethylaniline or 2-bromoaniline) (3.6 mmol)

was added to the freshly prepared 2,2⁰-thiodibenzoic acid chloride.

The mixture was maintained under 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 allowed to cool and left in the dark.

After two weeks, crystals of the anilides had deposited.

Analysis for N,N⁰-bis(2-methylphenyl)-2,2⁰-thiodibenzamide, (Ia):

colourless rods; yield 55% (m.p. 437 K); IR (solid, ꢁ, cm^ꢂ1): 3249,

1716, 1642, 740; ¹H NMR (250 MHz, DMSO-d₆): ꢂ 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): ꢂ

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,N⁰-bis(2-ethylphenyl)-2,2⁰-thiodibenzamide, (Ib):

colourless rods; yield 70% (m.p. 436 K); IR (solid, ꢁ, cm^ꢂ1): 3363,

1

1664, 1650, 1529, 1305, 1252, 734, 730; H NMR (250 MHz, DMSO-

d₆): ꢂ 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): ꢂ 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,N⁰-bis(2-bromophenyl)-2,2⁰-thiodibenzamide, (Ic):

colourless plates; yield 30% (m.p. 421 K); IR (solid, ꢁ, cm^ꢂ1): 3376,

1

1662, 1651, 1520, 1301, 1248, 734, 730; H NMR (250 MHz, DMSO-

Figure 3

Packing arrangements of the molecules: (a) (Ia), viewed down a

d₆): ꢂ 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):

ꢂ 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%.

3

1

3

1

[symmetry codes: (i) x, ꢂy + , z ꢂ ; (iv) x, ꢂy + , z + ], (b) (Ib),

2

1

2

viewed down a [symmetry codes: (ii) ꢂx + ³₂, y ꢂ , ꢂz + ₂³; (v) ꢂx + ³₂, y + ₂¹,

ꢂz + ³₂], and (c) (Ic), viewed approximately down a. Only H atoms

involved in hydrogen-bonding or N—Hꢀ ꢀ ꢀꢀ interactions are shown, and

these interactions are indicated by dashed lines.

ꢃ

Acta Cryst. (2012). C68, o387–o391

Helliwell et al.

C₂₈H₂₄N₂O₂S, C₃₀H₂₈N₂O₂S and C₂₆H₁₈Br₂N₂O₂S o389

organic compounds

Data collection

Anilide (Ia)

Bruker APEXII CCD area-detector

diffractometer

Absorption correction: multi-scan

(SADABS; Bruker, 2003)

T_min= 0.632, T_max= 0.754

23191 measured reﬂections

4817 independent reﬂections

4541 reﬂections with I > 2ꢆ(I)

R_int= 0.031

Crystal data

3

˚

V = 2343.03 (4) A

Z = 4

Cu Kꢄ radiation

ꢅ = 1.44 mm^ꢂ1

T = 296 K

C₂₈H₂₄N₂O₂S

M_r= 452.55

Monoclinic, P2₁=c

˚

a = 14.9815 (1) A

b = 10.9355 (1) A

Reﬁnement

˚

c = 15.5490 (2) A

0.35 ꢄ 0.10 ꢄ 0.08 mm

ꢃ = 113.107 (1)^ꢁ

R[F²> 2ꢆ(F²)] = 0.035

wR(F²) = 0.092

S = 1.06

4817 reﬂections

327 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

Data collection

ꢂ3

˚

Áꢇ_max= 0.18 e A

Bruker APEXII CCD area-detector

diffractometer

Absorption correction: multi-scan

(SADABS; Bruker, 2003)

T_min= 0.646, T_max= 0.754

15959 measured reﬂections

4396 independent reﬂections

3811 reﬂections with I > 2ꢆ(I)

R_int= 0.028

ꢂ3

˚

Áꢇ_min= ꢂ0.19 e A

Anilide (Ic)

Reﬁnement

Crystal data

R[F²> 2ꢆ(F²)] = 0.035

wR(F²) = 0.095

S = 1.04

4396 reﬂections

308 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

3

˚

V = 2367.66 (6) A

Z = 4

C₂₆H₁₈Br₂N₂O₂S

M_r= 582.30

Monoclinic, P2₁=c

Cu Kꢄ radiation

ꢅ = 5.39 mm^ꢂ1

T = 296 K

0.30 ꢄ 0.30 ꢄ 0.01 mm

ꢂ3

˚

Áꢇ_max= 0.19 e A

˚

a = 20.6504 (3) A

ꢂ3

˚

Áꢇ_min= ꢂ0.27 e A

˚

b = 15.3378 (2) A

˚

c = 7.5101 (1) A

ꢃ = 95.520 (1)^ꢁ

Anilide (Ib)

Data collection

Crystal data

Bruker APEXII CCD area-detector

diffractometer

Absorption correction: multi-scan

(SADABS; Bruker, 2003)

T_min= 0.454, T_max= 0.754

17010 measured reﬂections

4681 independent reﬂections

3752 reﬂections with I > 2ꢆ(I)

R_int= 0.049

3

˚

V = 2498.47 (5) A

Z = 4

Cu Kꢄ radiation

ꢅ = 1.38 mm^ꢂ1

T = 293 K

C₃₀H₂₈N₂O₂S

M_r= 480.60

Monoclinic, P2₁=n

˚

a = 7.8786 (1) A

˚

b = 17.3269 (2) A

˚

c = 18.3960 (2) A

0.40 ꢄ 0.25 ꢄ 0.20 mm

ꢃ = 95.787 (1)^ꢁ

Reﬁnement

R[F²> 2ꢆ(F²)] = 0.048

wR(F²) = 0.140

S = 1.04

4681 reﬂections

306 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

ꢂ3

Table 1

Hydrogen-bond geometry (A, ) for (Ia).

˚

Áꢇ_max= 0.83 e A

ꢁ

˚

ꢂ3

˚

Áꢇ_min= ꢂ0.66 e A

D—Hꢀ ꢀ ꢀA

D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

N1—H1Nꢀ ꢀ ꢀO2

0.861 (16)

0.856 (16)

2.058 (17)

2.024 (17)

2.8747 (15)

2.8728 (14)

158.1 (15)

170.6 (15)

For all compounds, H atoms bonded to C atoms were included in

˚

calculated positions using a riding model (C—H = 0.93–0.97 A), with

N2—H2Nꢀ ꢀ ꢀO1ⁱ

3

1

Symmetry code: (i) x; ꢂy þ ; z ꢂ .

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 =

2

˚

0.79 (5)–0.86 (2) A].

For all compounds, data collection: APEX2 (Bruker, 2004); cell

reﬁnement: SAINT (Bruker, 2003); data reduction: SAINT;

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 publi-

cation: SHELXTL and PLATON (Spek, 2009).

Table 2

Hydrogen-bond geometry (A, ) for (Ib).

ꢁ

˚

Cg1 is the centroid of the C1–C6 benzene ring.

D—Hꢀ ꢀ ꢀA

D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

N1—H1Nꢀ ꢀ ꢀO2

0.831 (16)

0.810 (18)

2.020 (17)

2.587 (17)

2.8490 (15)

3.3591 (14)

176.0 (15)

160.1 (16)

N2—H2Nꢀ ꢀ ꢀCg1ⁱⁱ

3

1

3

2

Symmetry code: (ii) ꢂx þ ; y ꢂ ; ꢂz þ .

2

Supplementary data for this paper are available from the IUCr electronic

archives (Reference: FG3262). Services for accessing these data are

described at the back of the journal.

Table 3

Hydrogen-bond geometry (A, ) for (Ic).

ꢁ

˚

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D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

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ꢃ

o390 Helliwell et al.

C₂₈H₂₄N₂O₂S, C₃₀H₂₈N₂O₂S and C₂₆H₁₈Br₂N₂O₂S

Acta Cryst. (2012). C68, o387–o391

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Acta Cryst. (2012). C68, o387–o391

Helliwell et al.

C₂₈H₂₄N₂O₂S, C₃₀H₂₈N₂O₂S and C₂₆H₁₈Br₂N₂O₂S o391

supplementary materials

Acta Cryst. (2012). C68, o387–o391 [doi:10.1107/S0108270112035962]

Three anilides of 2,2′-thiodibenzoic acid

Madeleine Helliwell, Salma Moosun, Minu G. Bhowon, Sabina Jhaumeer-Laulloo and John A.

Joule

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

Crystal data

C₂₈H₂₄N₂O₂S

M_r= 452.55

F(000) = 952

D_x= 1.283 Mg m⁻³

Cu Kα radiation, λ = 1.54178 Å

Cell parameters from 7594 reflections

θ = 5.1–71.0°

Monoclinic, P2₁/c

Hall symbol: -P2ybc

a = 14.9815 (1) Å

b = 10.9355 (1) Å

c = 15.5490 (2) Å

β = 113.107 (1)°

V = 2343.03 (4) Å³

Z = 4

µ = 1.44 mm⁻¹

T = 296 K

Rod, colourless

0.35 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector

diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

φ and ω scans

15959 measured reflections

4396 independent reflections

3811 reflections with I > 2σ(I)

R_int= 0.028

θ

_max= 71.9°, θ_min= 3.2°

Absorption correction: multi-scan

(SADABS; Bruker, 2003)

h = −18→18

k = −13→13

l = −15→18

T

_min= 0.646, T_max= 0.754

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.035

wR(F²) = 0.095

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.04

4396 reflections

308 parameters

0 restraints

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0494P)²+ 0.448P]

where P = (F_o²+ 2F_c²)/3

Primary atom site location: structure-invariant

direct methods

(Δ/σ)_max= 0.001

Δρ_max= 0.19 e Å⁻³

Δρ_min= −0.27 e Å⁻³

Acta Cryst. (2012). C68, o387–o391

sup-1

supplementary materials

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 F²against 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 (Å²)

x

y

z

U_iso*/U_eq

S1

0.85477 (3)

0.86223 (7)

0.70288 (7)

0.73949 (8)

0.75647 (9)

0.67265 (10)

0.57365 (10)

0.51029 (12)

0.4440

0.50561 (3)

0.58452 (9)

0.73150 (9)

0.57946 (11)

0.86725 (10)

0.50389 (12)

0.53057 (15)

0.45191 (19)

0.4678

0.54750 (2)

0.81303 (6)

0.50785 (7)

0.66898 (8)

0.42861 (8)

0.68909 (9)

0.64768 (10)

0.66640 (13)

0.6396

0.04865 (12)

0.0457 (2)

0.0455 (2)

0.0405 (3)

0.0423 (3)

0.0413 (3)

0.0502 (3)

0.0680 (5)

0.082*

O1

O2

N1

N2

C1

C2

C3

H3

C4

0.54286 (14)

0.4988

0.35197 (19)

0.3011

0.72316 (14)

0.7342

0.0726 (5)

0.087*

H4

C5

0.64001 (14)

0.6620

0.32653 (16)

0.2589

0.76369 (13)

0.8026

0.0659 (5)

0.079*

H5

C6

0.70530 (12)

0.7713

0.40168 (14)

0.3840

0.74657 (11)

0.7735

0.0525 (4)

0.063*

H6

C7

0.83001 (9)

0.89203 (9)

0.90482 (9)

0.96419 (10)

0.9740

0.60733 (12)

0.67572 (12)

0.64316 (12)

0.71513 (15)

0.6932

0.72885 (9)

0.68895 (9)

0.60761 (9)

0.57788 (11)

0.5245

0.0368 (3)

0.0378 (3)

0.0393 (3)

0.0514 (4)

0.062*

C8

C9

C10

H10

C11

H11

C12

H12

C13

H13

C14

C15

C16

H16

C17

H17

C18

H18

C19

H19

C20

1.00829 (11)

1.0462

0.81805 (17)

0.8667

0.62671 (12)

0.6052

0.0620 (4)

0.074*

0.99656 (12)

1.0266

0.84954 (17)

0.9191

0.70762 (12)

0.7408

0.0632 (4)

0.076*

0.94015 (10)

0.9342

0.77758 (15)

0.7976

0.73896 (10)

0.7946

0.0507 (3)

0.061*

0.80373 (10)

0.75404 (9)

0.71566 (11)

0.6835

0.54675 (13)

0.65510 (12)

0.67116 (14)

0.7436

0.42760 (9)

0.39024 (9)

0.29364 (10)

0.2684

0.0427 (3)

0.0390 (3)

0.0488 (3)

0.059*

0.72433 (14)

0.6977

0.58191 (18)

0.5938

0.23446 (11)

0.1701

0.0649 (5)

0.078*

0.77235 (15)

0.7781

0.47602 (19)

0.4154

0.27149 (13)

0.2320

0.0730 (5)

0.088*

0.81246 (13)

0.8457

0.45825 (16)

0.3862

0.36714 (12)

0.3914

0.0618 (4)

0.074*

0.73615 (9)

0.75368 (12)

0.44878 (9)

0.0376 (3)

Acta Cryst. (2012). C68, o387–o391

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supplementary materials

C21

0.74673 (11)

0.65718 (12)

0.65551 (17)

0.5972

0.97692 (12)

1.01548 (14)

1.12731 (17)

1.1543

0.47378 (9)

0.47036 (11)

0.51404 (14)

0.5153

0.0436 (3)

0.0532 (4)

0.0726 (5)

0.087*

C22

C23

H23

C24

0.7364 (2)

0.7323

1.19767 (17)

1.2718

0.55472 (14)

0.5823

0.0819 (6)

0.098*

H24

C25

0.82331 (18)

0.8783

1.15974 (17)

1.2082

0.55508 (13)

0.5821

0.0777 (6)

0.093*

H25

C26

0.82896 (13)

0.8882

1.04846 (15)

1.0217

0.51494 (12)

0.5156

0.0591 (4)

0.071*

H26

C27

0.53535 (12)

0.4676

0.63948 (19)

0.6497

0.58554 (13)

0.5726

0.0678 (5)

0.102*

H27A

H27B

H27C

C28

0.5437

0.6273

0.5280

0.102*

0.5702

0.7113

0.6163

0.102*

0.56627 (13)

0.5631

0.94523 (19)

0.8763

0.41900 (15)

0.4559

0.0734 (5)

0.110*

H28A

H28B

H28C

H2N

H1N

0.5662

0.9171

0.3605

0.110*

0.5111

0.9971

0.4076

0.110*

0.7868 (11)

0.7198 (11)

0.8730 (15)

0.6080 (15)

0.3922 (11)

0.6130 (11)

0.047 (4)*

0.046 (4)*

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

S1

0.0662 (2)

0.0455 (5)

0.0546 (6)

0.0388 (6)

0.0545 (7)

0.0458 (7)

0.0440 (7)

0.0490 (9)

0.0733 (12)

0.0846 (12)

0.0570 (9)

0.0386 (6)

0.0319 (6)

0.0346 (6)

0.0419 (7)

0.0458 (8)

0.0567 (9)

0.0472 (8)

0.0471 (7)

0.0408 (6)

0.0528 (8)

0.0794 (11)

0.0973 (14)

0.0778 (11)

0.0387 (6)

0.0628 (9)

0.03604 (19)

0.0561 (6)

0.0437 (5)

0.0470 (7)

0.0382 (6)

0.0435 (7)

0.0611 (9)

0.0850 (13)

0.0748 (12)

0.0496 (9)

0.0469 (8)

0.0362 (6)

0.0414 (7)

0.0423 (7)

0.0691 (10)

0.0766 (12)

0.0639 (10)

0.0568 (9)

0.0408 (7)

0.0395 (7)

0.0518 (8)

0.0723 (12)

0.0674 (12)

0.0498 (9)

0.0390 (7)

0.0347 (7)

0.0476 (2)

0.00710 (15)

0.0040 (4)

0.02661 (18)

0.0194 (4)

0.0327 (5)

0.0169 (5)

0.0314 (6)

0.0223 (6)

0.0188 (6)

0.0252 (8)

0.0413 (10)

0.0406 (10)

0.0285 (7)

0.0200 (5)

0.0143 (5)

0.0157 (5)

0.0235 (6)

0.0198 (7)

0.0152 (8)

0.0158 (6)

0.0231 (6)

0.0211 (6)

0.0189 (6)

0.0235 (8)

0.0356 (10)

0.0314 (9)

0.0180 (5)

0.0268 (6)

0.00063 (14)

0.0031 (4)

0.0111 (4)

O1

0.0383 (5)

0.0496 (5)

0.0375 (6)

0.0453 (6)

0.0397 (7)

0.0465 (8)

0.0714 (11)

0.0801 (12)

0.0726 (11)

0.0590 (9)

0.0397 (7)

0.0402 (7)

0.0418 (7)

0.0486 (8)

0.0623 (10)

0.0615 (10)

0.0458 (8)

0.0448 (7)

0.0414 (7)

0.0422 (7)

0.0425 (8)

0.0589 (10)

0.0615 (10)

0.0380 (7)

0.0396 (7)

O2

0.0082 (4)

−0.0035 (5)

0.0003 (5)

−0.0075 (6)

−0.0084 (7)

−0.0191 (9)

−0.0285 (10)

−0.0102 (9)

−0.0027 (7)

0.0043 (5)

N1

0.0034 (5)

0.0023 (5)

−0.0065 (5)

−0.0040 (7)

−0.0025 (10)

−0.0027 (10)

0.0050 (8)

0.0006 (7)

−0.0006 (5)

0.0020 (5)

0.0034 (5)

0.0068 (7)

0.0104 (9)

−0.0056 (8)

−0.0069 (7)

−0.0067 (6)

−0.0027 (5)

−0.0022 (6)

−0.0137 (8)

−0.0290 (9)

−0.0139 (8)

0.0045 (5)

0.0065 (5)

N2

C1

C2

C3

C4

C5

C6

C7

C8

0.0015 (5)

C9

0.0041 (5)

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

−0.0008 (7)

−0.0193 (8)

−0.0254 (8)

−0.0092 (7)

−0.0024 (6)

−0.0069 (5)

−0.0119 (6)

−0.0181 (9)

−0.0084 (10)

0.0053 (8)

0.0032 (5)

0.0043 (6)

Acta Cryst. (2012). C68, o387–o391

sup-3

supplementary materials

C22

C23

C24

C25

C26

C27

C28

0.0707 (10)

0.1105 (15)

0.147 (2)

0.0452 (8)

0.0501 (10)

0.0432 (9)

0.0480 (10)

0.0465 (8)

0.0837 (13)

0.0724 (12)

0.0548 (9)

0.0806 (12)

0.0725 (12)

0.0657 (11)

0.0592 (9)

0.0678 (11)

0.0944 (14)

0.0143 (7)

0.0278 (11)

0.0037 (12)

−0.0159 (10)

−0.0045 (8)

0.0002 (8)

0.0171 (9)

0.0365 (8)

0.0629 (12)

0.0608 (14)

0.0295 (11)

0.0256 (8)

0.0143 (8)

0.0360 (10)

0.0150 (7)

0.0177 (9)

−0.0031 (9)

−0.0054 (8)

0.0023 (7)

0.0128 (9)

0.0187 (10)

0.1140 (17)

0.0717 (10)

0.0448 (8)

0.0588 (10)

Geometric parameters (Å, º)

S1—C14

S1—C9

1.7732 (14)

C12—H12

0.9300

1.7743 (14)

1.2300 (15)

1.2289 (15)

1.3445 (17)

1.4244 (16)

0.861 (16)

1.3448 (17)

1.4259 (17)

0.856 (16)

1.394 (2)

1.396 (2)

1.394 (2)

1.499 (2)

1.369 (3)

0.9300

C13—H13

C14—C19

C14—C15

C15—C16

C15—C20

C16—C17

C16—H16

C17—C18

C17—H17

C18—C19

C18—H18

C19—H19

C21—C26

C21—C22

C22—C23

C22—C28

C23—C24

C23—H23

C24—C25

C24—H24

C25—C26

C25—H25

C26—H26

C27—H27A

C27—H27B

C27—H27C

C28—H28A

C28—H28B

C28—H28C

0.9300

O1—C7

O2—C20

N1—C7

N1—C1

N1—H1N

N2—C20

N2—C21

N2—H2N

C1—C6

1.391 (2)

1.399 (2)

1.3928 (19)

1.5014 (18)

1.382 (2)

0.9300

1.366 (3)

0.9300

1.382 (3)

0.9300

C1—C2

C2—C3

0.9300

C2—C27

C3—C4

1.386 (2)

1.387 (2)

1.404 (2)

1.493 (3)

1.363 (3)

0.9300

C3—H3

C4—C5

1.369 (3)

0.9300

C4—H4

C5—C6

1.381 (2)

0.9300

C5—H5

C6—H6

C7—C8

1.365 (3)

0.9300

1.5032 (17)

1.387 (2)

1.3976 (18)

1.3953 (19)

1.373 (2)

0.9300

1.385 (3)

0.9300

C8—C13

C8—C9

0.9300

C9—C10

C10—C11

C10—H10

C11—C12

C11—H11

C12—C13

0.9600

1.380 (2)

0.9300

0.9600

1.376 (2)

0.9600

C14—S1—C9

C7—N1—C1

104.92 (6)

125.77 (12)

118.1 (10)

116.2 (10)

125.84 (11)

116.7 (11)

116.6 (11)

120.33 (13)

120.38 (13)

C16—C15—C14

C16—C15—C20

C14—C15—C20

C17—C16—C15

C17—C16—H16

C15—C16—H16

C18—C17—C16

C18—C17—H17

C16—C17—H17

118.81 (12)

117.83 (12)

123.31 (12)

121.48 (15)

119.3

C7—N1—H1N

C1—N1—H1N

C20—N2—C21

C20—N2—H2N

C21—N2—H2N

C6—C1—C2

119.3

119.32 (15)

120.3

C6—C1—N1

120.3

Acta Cryst. (2012). C68, o387–o391

sup-4

supplementary materials

C2—C1—N1

C3—C2—C1

119.24 (13)

117.51 (15)

120.35 (15)

122.14 (13)

121.86 (17)

119.1

C17—C18—C19

C17—C18—H18

C19—C18—H18

C18—C19—C14

C18—C19—H19

C14—C19—H19

O2—C20—N2

120.51 (16)

119.7

C3—C2—C27

C1—C2—C27

C4—C3—C2

119.7

120.87 (17)

119.6

C4—C3—H3

C2—C3—H3

C5—C4—C3

119.6

119.1

123.50 (12)

122.19 (12)

114.28 (11)

121.14 (14)

117.26 (13)

121.41 (14)

116.55 (17)

121.97 (15)

121.42 (16)

122.34 (19)

118.8

120.32 (16)

119.8

O2—C20—C15

N2—C20—C15

C26—C21—C22

C26—C21—N2

C22—C21—N2

C21—C22—C23

C21—C22—C28

C23—C22—C28

C24—C23—C22

C24—C23—H23

C22—C23—H23

C23—C24—C25

C23—C24—H24

C25—C24—H24

C24—C25—C26

C24—C25—H25

C26—C25—H25

C25—C26—C21

C25—C26—H26

C21—C26—H26

C2—C27—H27A

C2—C27—H27B

C5—C4—H4

C3—C4—H4

C4—C5—C6

119.8

119.74 (17)

120.1

C4—C5—H5

C6—C5—H5

C5—C6—C1

120.1

120.24 (15)

119.9

C5—C6—H6

C1—C6—H6

O1—C7—N1

O1—C7—C8

N1—C7—C8

C13—C8—C9

C13—C8—C7

C9—C8—C7

119.9

123.97 (12)

119.48 (11)

116.48 (11)

119.08 (12)

115.95 (12)

124.97 (12)

119.20 (13)

119.75 (11)

120.86 (10)

120.66 (14)

119.7

118.8

120.21 (18)

119.9

119.5 (2)

120.3

C10—C9—C8

C10—C9—S1

C8—C9—S1

120.3

120.23 (18)

119.9

C11—C10—C9

C11—C10—H10

C9—C10—H10

C10—C11—C12

C10—C11—H11

C12—C11—H11

C13—C12—C11

C13—C12—H12

C11—C12—H12

C12—C13—C8

C12—C13—H13

C8—C13—H13

C19—C14—C15

C19—C14—S1

C15—C14—S1

119.9

119.7

109.5

120.17 (14)

119.9

109.5

H27A—C27—H27B

C2—C27—H27C

109.5

119.9

119.70 (15)

120.1

H27A—C27—H27C

H27B—C27—H27C

C22—C28—H28A

C22—C28—H28B

H28A—C28—H28B

C22—C28—H28C

H28A—C28—H28C

H28B—C28—H28C

120.1

121.12 (14)

119.4

119.00 (14)

114.71 (12)

126.24 (10)

C7—N1—C1—C6

C7—N1—C1—C2

C6—C1—C2—C3

N1—C1—C2—C3

C6—C1—C2—C27

N1—C1—C2—C27

C1—C2—C3—C4

C27—C2—C3—C4

−36.53 (19)

145.95 (14)

0.2 (2)

C9—S1—C14—C19

C9—S1—C14—C15

C19—C14—C15—C16

S1—C14—C15—C16

C19—C14—C15—C20

S1—C14—C15—C20

C14—C15—C16—C17

C20—C15—C16—C17

143.53 (12)

−39.00 (13)

−0.5 (2)

177.71 (14)

179.92 (15)

−2.6 (2)

−177.92 (10)

176.85 (13)

−0.52 (19)

1.1 (2)

0.0 (3)

−179.69 (18)

−176.48 (13)

Acta Cryst. (2012). C68, o387–o391

sup-5

supplementary materials

C2—C3—C4—C5

C3—C4—C5—C6

C4—C5—C6—C1

C2—C1—C6—C5

N1—C1—C6—C5

C1—N1—C7—O1

C1—N1—C7—C8

O1—C7—C8—C13

N1—C7—C8—C13

O1—C7—C8—C9

N1—C7—C8—C9

C13—C8—C9—C10

C7—C8—C9—C10

C13—C8—C9—S1

C7—C8—C9—S1

C14—S1—C9—C10

C14—S1—C9—C8

C8—C9—C10—C11

S1—C9—C10—C11

C9—C10—C11—C12

C10—C11—C12—C13

C11—C12—C13—C8

C9—C8—C13—C12

C7—C8—C13—C12

0.1 (3)

C15—C16—C17—C18

−0.6 (2)

−0.5 (3)

C16—C17—C18—C19

C17—C18—C19—C14

C15—C14—C19—C18

S1—C14—C19—C18

C21—N2—C20—O2

C21—N2—C20—C15

C16—C15—C20—O2

C14—C15—C20—O2

C16—C15—C20—N2

C14—C15—C20—N2

C20—N2—C21—C26

C20—N2—C21—C22

C26—C21—C22—C23

N2—C21—C22—C23

C26—C21—C22—C28

N2—C21—C22—C28

C21—C22—C23—C24

C28—C22—C23—C24

C22—C23—C24—C25

C23—C24—C25—C26

C24—C25—C26—C21

C22—C21—C26—C25

N2—C21—C26—C25

−0.4 (3)

0.7 (3)

0.9 (3)

−0.6 (2)

−0.4 (2)

−178.07 (14)

−10.4 (2)

172.55 (12)

−45.41 (17)

131.75 (13)

133.77 (14)

−49.07 (18)

−1.2 (2)

177.26 (15)

2.6 (2)

−179.54 (13)

128.45 (14)

−48.97 (19)

−49.40 (16)

133.17 (13)

122.49 (15)

−62.50 (19)

−2.6 (2)

179.68 (12)

173.71 (10)

−5.44 (18)

−48.92 (12)

136.24 (11)

−1.2 (2)

−177.47 (13)

174.44 (15)

−0.4 (2)

2.5 (2)

−176.11 (12)

1.9 (3)

−174.56 (17)

−0.8 (3)

−0.3 (3)

−0.9 (3)

−2.1 (3)

0.8 (3)

2.8 (2)

1.1 (2)

−177.94 (14)

176.12 (14)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

N1—H1N···O2

N2—H2N···O1ⁱ

0.861 (16)

0.856 (16)

2.058 (17)

2.024 (17)

2.8747 (15)

2.8728 (14)

158.1 (15)

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

M_r= 480.60

F(000) = 1016

D_x= 1.278 Mg m⁻³

Monoclinic, P2₁/n

Hall symbol: -P2yn

a = 7.8786 (1) Å

b = 17.3269 (2) Å

c = 18.3960 (2) Å

β = 95.787 (1)°

V = 2498.47 (5) Å³

Z = 4

Cu Kα radiation, λ = 1.54178 Å

Cell parameters from 9904 reflections

θ = 4.8–71.2°

µ = 1.38 mm⁻¹

T = 293 K

Rod, colourless

0.40 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector

diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

φ and ω scans

Absorption correction: multi-scan

(SADABS; Bruker, 2003)

T

_min= 0.632, T_max= 0.754

Acta Cryst. (2012). C68, o387–o391

sup-6

supplementary materials

23191 measured reflections

4817 independent reflections

4541 reflections with I > 2σ(I)

R_int= 0.031

θ_max= 72.0°, θ_min= 3.5°

h = −7→9

k = −21→20

l = −22→22

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.035

wR(F²) = 0.092

S = 1.06

4817 reflections

Hydrogen site location: inferred from

neighbouring sites

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0432P)²+ 0.5935P]

where P = (F_o²+ 2F_c²)/3

327 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier

map

(Δ/σ)_max= 0.001

Δρ_max= 0.18 e Å⁻³

Δρ_min= −0.19 e Å⁻³

Extinction correction: SHELXL97 (Sheldrick,

2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4

Extinction coefficient: 0.0039 (2)