research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 199-202
doi:10.1107/S205698901600058X

Crystal structures of (1E,4E)-1,5-bis­­(5-bromo­thio­phen-2-yl)-2,4-di­methyl­penta-1,4-dien-3-one and (E)-4-(5-bromo­thio­phen-2-yl)-1,3-di­phenyl­but-3-en-2-one

CROSSMARK_Color_square_no_text.svg
C. Nithya,a M. Sithambaresanb* and M. R. Prathapachandra Kurupa

aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and bDepartment of Chemistry, Faculty of Science, Eastern University, Chenkalady, Sri Lanka
*Correspondence e-mail: msithambaresan@gmail.com

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 18 December 2015; accepted 12 January 2016; online 20 January 2016)

The title compounds, C15H12Br2OS2, (I), and C20H15BrOS, (II), were synthesized by employing Claisen–Schmidt condensation of pentan-3-one and di­benzyl­acetone with 5-bromo­thio­phene-2-carbaldehyde in the presence of methano­lic KOH. Even though 1:2 products were expected in both of the reactions, 1:2 and 1:1 products were obtained as (I) and (II), respectively. In (I), the two methyl groups are trans to each other, 29.5 (7) and 28.7 (7)° away from the central carbonyl bond between them, whereas the two phenyl rings of di­benzyl­acetone subtend a dihedral angle of 53.09 (18)°. In the crystal of (I), C—H⋯O hydrogen bonds define mol­ecular chains along c. A second type of mol­ecular chain is formed along b by means of C—Br⋯π inter­actions. These two families of mol­ecular chains are stacked by π–π inter­actions, forming a three-dimensional supra­molecular architecture. In (II), similar C—H⋯O hydrogen bonds as in (I) define inversion dimers, whilst C—H⋯.π inter­actions build a staircase structure along the a axis.

CCDC references: 1446725; 1446724

1. Chemical context

Claisen–Schmidt reaction (Claisen & Claparede, 1881[Claisen, L. & Claparede, A. (1881). Berichte, 14, 2460-2468.]; Schmidt, 1881[Schmidt, J. G. (1881). Berachte, 14,1459-1463.]) is the condensation of aromatic aldehydes (or between ketones and aldehydes lacking α-hydrogen with aliphatic or mixed alkyl aryl ketones in the presence of a relatively strong base to form α,β-unsaturated ketones. This reaction is of tremendous value in synthetic organic chemistry (Wayne & Adkins 1940[Wayne, W. & Adkins, H. (1940). J. Am. Chem. Soc. 62, 3401-3404.]; Marvel & King, 1944[Marvel, C. C. & King, W. B. (1944). Org. Synth. 1, 252-255.]) and is frequently encountered as a key step in several elegant total synthesis protocols. Claisen–Schmidt condensation can also be catalysed by acid. The first step is a condensation of an aldol type; enols or enolates are involved as inter­mediates in this reaction. This reaction involves the nucleophilic addition of enol or an enolate ion derived from methyl ketone to the carbonyl carbon of the aromatic aldehyde. Dehydration of the hy­droxy­lketone to form the conjugated unsaturated carbonyl compound occurs spontaneously (see Scheme 1) (Stiles et al., 1959[Stiles, M., Wolf, D. & Hudson, G. V. (1959). J. Am. Chem. Soc. 81, 628-632.]). Cyclo­alkanones like cyclo­hexa­none, cyclo­hepta­none readily undergo Claisen–Schmidt condensation (Nithya et al., 2014[Nithya, C., Sithambaresan, M., Prathapan, S. & Kurup, M. R. P. (2014). Acta Cryst. E70, o722.]). In addition to cyclo­alkanones we attempted open-chain alkanones.

[Scheme 1]
[Scheme 2]

The title compounds (I)[link] and (II)[link] were synthesized by employing Claisen–Schmidt condensation of pentan-3-one and di­benzyl­acetone with 5-bromo­thio­phene-2-carbaldehyde in the presence of methano­lic KOH (Schemes 1[link] and 2[link]). Although we anti­cipated getting 1:2 products in both of the reactions, a 1:2 product was obtained for the former case, (I)[link], and a 1:1 product for the latter, (II)[link]. In compound (II)[link], the bulky phenyl ring hinders the possibility of a second bromo­thio­phene ring being attached and hence only a 1:1 product was formed in this case. We present herein the structures of (1E,4E)-1,5-bis­(5-bromo­thio­phen-2-yl)-2,4-di­methyl­penta-1,4-dien-3-one (I)[link] and (E)-4-(5-bromo­thio­phen-2-yl)-1,3-di­phenyl­but-3-en-2-one (II)[link].

2. Structural commentary

The mol­ecular structures of (I)[link] and (II)[link] are shown in Fig. 1[link]. The asymmetric unit of (I)[link] comprises one mol­ecule of bis(bromothiophenyl)dimethylpentanone and two of 5-bromothiophenyldiphenylbutanone. The two methyl groups (C14 and C15) of (I)[link] are twisted away from each other with C14—C6—C7—O1 and C15—C8—C7—O1 torsion angles of 29.5 (7) and 28.7 (7)°, respectively.

[Figure 1]
Figure 1
View of the title compounds (I)[link] and (II)[link] drawn with 50% probability displacement ellipsoids for the non-H atoms.

The asymmetric unit of (II)[link] comprises one mol­ecule of 5-bromo­thio­phene-2-carbaldehyde with one mol­ecule of di­benzyl­acetone. The two phenyl rings of the di­benzyl­acetone subtend a dihedral angle of 53.09 (18)°. One of the phenyl rings (C15–C20) of the di­benzyl­acetone and the thio­phene ring are normal to one another, forming a dihedral angle of 89.96 (16)°.

3. Supra­molecular features

In the crystal structure of (I)[link], a non-classical C—H⋯O hydrogen bond (Table 1[link]) links the mol­ecules into a chain along the c axis (Fig. 2[link]). Another mol­ecular chain is formed along the b axis through a C13—Br2⋯π(C1–C4/S1)ii inter­action [symmetry code: (ii) 1 − x, 1 + y, [1\over2] − z], Br⋯Cg = 3.556 (2) Å (Fig. 3[link]). The two mol­ecular chains are in turn stacked by π–π inter­actions between the two thio­phene rings, (C1–C4/S1) and (C10–C13/S2)iii [symmetry code: (iii) 1 − x, y, [{1\over 2}] − z], Cg⋯Cg = 3.718 (3) Å, forming a three-dimensional supra­molecular architecture (Fig. 4[link]).

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3⋯O1i 0.93 2.57 3.233 (7) 129
Symmetry code: (i) [x, -y+2, z-{\script{1\over 2}}].
[Figure 2]
Figure 2
C—H⋯O hydrogen-bonding inter­action in (I)[link], forming a mol­ecular chain along the c axis.
[Figure 3]
Figure 3
The mol­ecular chain in (I)[link], formed along the b axis through C—Br⋯π inter­actions.
[Figure 4]
Figure 4
The two mol­ecular chains in (I)[link], stacked by π–π inter­actions to form a three-dimensional supra­molecular architecture.

In structure (II)[link] a C—H⋯O hydrogen bond (Table 2[link]) links pairs of mol­ecules, forming inversion dimers (Fig. 5[link]). The dimers are linked together by means of C19–H19⋯π(C1–C4/S1) inter­action, building a staircase structure along the a axis (Fig. 6[link]).

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg is the centroid of the C1–C4/S1 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3⋯O1i 0.93 2.54 3.320 (4) 141
C19—H19⋯Cgii 0.93 2.90 3.768 (3) 156
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x-1, y, z.
[Figure 5]
Figure 5
C—H⋯O inter­actions in (II)[link], forming an inversion dimer.
[Figure 6]
Figure 6
Dimers in (II)[link] linked together by means of C—H⋯π inter­actions building a staircase structure along the a axis.

4. Synthesis and crystallization

The title compounds were prepared by adapting a reported procedure (Alkskas et al., 2013[Alkskas, A. I., Alhubge, A. M. & Azam, F. (2013). Chin. J. Polym. Sci. 31, 471-480.]). Title compound (I)[link] was prepared by adding a mixture of pentan-3-one (0.50 g, 1.2 mmol) and 5-bromothio­phene-2-carbaldehyde (2.2 g, 2.4 mmol) in methanol (25 mL) and potassium hydroxide pellets (0.2 g, 2.4 mmol) was also added. The reaction mixture was stirred at room temperature overnight whilst a pale-yellow product separated out. The crude product was washed several times with cold ethanol (1 mL). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 401–403 K. Yield: 85%. IR (KBr): 1680 (C=O), 3061(=C—H). 1H NMR: (CDCl3): δ2.20 (3H, s), δ6.97–6.96 (1H, d), δ7.08–7.07 (1H, d), δ7.18–7.17 (1H, s). MS: m/z 431 (M+); analysis calculated for C15H12Br2S2O: C: 41.69, H: 2.80, Br: 36.98, S: 14.84; found: C: 41.59, H: 2.78, Br: 36.90, S: 14.74.

Title compound (II)[link] was prepared by mixing di­benzyl­ketone (1 g, 4.7 mmol) and 5-bromothio­phene-2-carbaldehyde (1.8 g, 9.5 mmol) in methanol (25 mL) and potassium hydroxide pellets (0.6 g, 9.5 mmol) were also added. The reaction mixture was stirred at room temperature overnight whilst a yellow product separated out. The crude product was washed several times with cold ethanol (1 mL). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 383–385 K. Yield: 90%. IR (KBr): 1627 (C=O), 3080 (=C—H). 1H NMR (CDCl3): δ3.78 (2H, s), δ7.80 (1H, s), 7.51–7.48 (1H, m), 7.47 (1H, m), 7.23–7.20 (2H, m), 7.15–7.14 (2H, m), 7.13–7.12 (2H, m), 7.04–7.02 (2H, m), 6.97–6.96 (1H, d), 6.90–6.89 (1H, d). MS: m/z 383 (M+); analysis calculated for C20H15BrOS: C: 62.67, H: 3.94, Br: 20.85, S: 8.37; found: C: 62.57, H: 3.92, Br: 20.77, S: 8.27.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. In both compounds, all H atoms on C were placed in calculated positions, guided by difference Fourier maps, with C—H bond distances of 0.93–0.97 Å. H atoms were assigned as Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq (methyl C). Four reflections were omitted owing to bad agreement for compound (I)[link].

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C15H12Br2OS2 C20H15BrOS
Mr 432.19 383.29
Crystal system, space group Monoclinic, P2/c Triclinic, P[\overline{1}]
Temperature (K) 296 296
a, b, c (Å) 16.564 (2), 6.3581 (7), 15.962 (2) 7.5879 (4), 8.5361 (6), 14.0970 (8)
α, β, γ (°) 90, 105.239 (5), 90 99.510 (3), 97.673 (3), 101.956 (3)
V (Å3) 1622.0 (4) 867.58 (9)
Z 4 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 5.25 2.49
Crystal size (mm) 0.60 × 0.50 × 0.40 0.60 × 0.50 × 0.35
 
Data collection
Diffractometer Bruker Kappa APEXII CCD Bruker Kappa APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.049, 0.115 0.307, 0.456
No. of measured, independent and observed [I > 2σ(I)] reflections 13847, 4051, 2012 6863, 4363, 3040
Rint 0.059 0.025
(sin θ/λ)max (Å−1) 0.667 0.670
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.181, 0.98 0.043, 0.118, 1.05
No. of reflections 4042 4363
No. of parameters 183 208
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.88, −0.80 0.56, −0.86
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004[Bruker (2004). SADABS, APEX2, XPREP and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC references: 1446725; 1446724

Crystal structure: contains datablocks I, II. DOI: 10.1107/S205698901600058X/bg2578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901600058X/bg2578Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S205698901600058X/bg2578IIsup3.hkl

Supporting information file. DOI: 10.1107/S205698901600058X/bg2578Isup4.cml

Supporting information file. DOI: 10.1107/S205698901600058X/bg2578IIsup5.cml

checkCIF report


Chemical context top

\ Claisen–Schmidt reaction (Claisen & Claparede, 1881; Schmidt, 1881) is the condensation of aromatic aldehydes (or between ketones and aldehydes lacking a-hydrogen) with aliphatic or mixed alkyl aryl ketones in the presence of a relatively strong base to form α,β-unsaturated ketones. This reaction is of tremendous value in synthetic organic chemistry (Wayne & Adkins 1940; Marvel & King, 1944) and is frequently encountered as a key step in several elegant total synthesis protocols. Claisen–Schmidt condensation can also be catalysed by acid. The first step is a condensation of an aldol type; enols or enolates are involved as inter­mediates in this reaction. This reaction involves the nucleophilic addition of enol or an enolate ion derived from methyl ketone to the carbonyl carbon of the aromatic aldehyde. Dehydration of the hy­droxy­lketone to form the conjugated unsaturated carbonyl compound occurs spontaneously (see Scheme 1) (Stiles et al., 1959). Cyclo­alkanones like cyclo­hexanone, cyclo­heptanone readily undergo Claisen–Schmidt condensation (Nithya et al., 2014). In addition to cyclo­alkanones we attempted open-chain alkanones.

The title compounds (I) and (II) were synthesized by employing Claisen–Schmidt condensation of pentan-3-one and di­benzyl­acetone with 5-bromo­thio­phene-2-carbaldehyde in the presence of methano­lic KOH (Schemes 1 and 2). Although we anti­cipated getting 1:2 products in both of the reactions, a 1:2 product was obtained for the former case, (I), whereas a 1:1 product for the latter, (II). The SCXRD data obtained for compound (II) suggests that the bulky phenyl ring hinders the possibility of a second bromo­thio­phene ring being attached and hence only a 1:1 product was formed in this case. We present herein the structures of (1E,4E)-1,5-bis­(5-bromo­thio­phen-2-yl)-2,4-di­methyl­penta-1,4-\ dien-3-one (I) and (E)-4-(5-bromo­thio­phen-2-yl)-1,3-di­phenyl­but-3-en-2-one (II).

Structural commentary top

The molecular structures of (I) and (II) are shown in Fig. 1. The asymmetric unit of (I) comprises one molecule of pentan-3-one and two of 5-bromo­thio­phene-2-carbaldehyde. The two methyl groups (C14 and C15) of (I) are twisted away from each other with C14—C6—C7—O1 and C15—C8—C7—O1torsion angles of 29.5 (7) and 28.7 (7)°, respectively.

The asymmetric unit of (II) comprises one molecule of 5-bromo­thio­phene-2-carbaldehyde with one molecule of di­benzyl­acetone. The two phenyl rings of the di­benzyl­acetone subtend a dihedral angle of 53.09 (18)°. One of the phenyl rings (C15–C20) of the di­benzyl­acetone and the thio­phene ring are flanked almost perpendicularly, forming a dihedral angle of 89.96 (16)°.

Supra­molecular features top

In the crystal structure of (I), a non-classical C—H···O hydrogen bond (Table 1) links the molecules into a chain along the c axis (Fig 2). Another molecular chain is formed along the b axis through a C13—Br2···π(C1–C4/S1)ii inter­action [symmetry code: (ii) 1 − x, 1 + y, 1/2 − z], Br···Cg = 3.556 (2) Å (Fig 3). The two molecular chains are in turn stacked by π–π inter­actions between the two thio­phene rings, (C1–C4/S1) and (C10–C13/S2)iii [symmetry code: (iii):1 − x, y, 1/2 − z], Cg···Cg = 3.718 (3) Å, forming a three-dimensional supra­molecular architecture (Fig. 4).

In structure (II) a C—H···O hydrogen bond (Table 2) links pairs of molecules, forming centrosymmetric dimers (Fig. 5). Such dimers are linked together by means of C19–H19···π(C1–C4/S1) inter­action, building a staircase structure along the a axis (Fig. 6).

Synthesis and crystallization top

The title compounds were prepared by adapting a reported procedure (Alkskas et al., 2013). Title compound (I) was prepared by adding a mixture of pentan-3-one (0.50 g, 1.2 mmol) and 5-bromo-thio­phene-2-carbaldehyde (2.2 g, 2.4 mmol) in methanol (25 ml) and potassium hydroxide pellets (0.2 g, 2.4 mmol) was also added. The reaction mixture was stirred at room temperature overnight whilst a pale-yellow product separated out. The crude product was washed several times with cold ethanol (1 ml). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 401–403 K. Yield: 85%. IR (KBr): 1680 (C═O), 3061(═ C—H). 1H NMR: (CDCl3): δ2.20 (3H, s), δ6.97–6.96 (1H, d), δ7.08–7.07 (1H, d), δ7.18–7.17 (1H, s). MS: m/z 431 (M+); analysis calculated for C15H12Br2S2O: C: 41.69, H: 2.80, Br: 36.98, S: 14.84; found: C: 41.59, H: 2.78, Br: 36.90, S: 14.74.

Title compound (II) was prepared by mixing di­benzyl­ketone (1 g, 4.7 mmol) and 5-bromo-thio­phene-2-carbaldehyde (1.8 g, 9.5 mmol) in methanol (25 ml) and potassium hydroxide pellets (0.6 g, 9.5 mmol) were also added. The reaction mixture was stirred at room temperature overnight whilst a yellow product separated out. The crude product was washed several times with cold ethanol (1 ml). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 383–385 K. Yield: 90%. IR (KBr): 1627 (C═O), 3080 (═C—H). 1H NMR (CDCl3): δ3.78 (2H, s), δ7.80 (1H, s), 7.51–7.48 (1H, m), 7.47 (1H, m), 7.23–7.20 (2H, m), 7.15–7.14 (2H, m), 7.13–7.12 (2H, m), 7.04–7.02 (2H, m), 6.97–6.96 (1H, d), 6.90–6.89 (1H, d). MS: m/z 383 (M+); analysis calculated for C20H15BrOS: C: 62.67, H: 3.94, Br: 20.85, S: 8.37; found: C: 62.57, H: 3.92, Br: 20.77, S: 8.27.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. In both compounds, all H atoms on C were placed in calculated positions, guided by difference Fourier maps, with C—H bond distances of 0.93–0.97 Å. H atoms were assigned as Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq (methyl C). Four reflections were omitted owing to bad agreement (1 0 0) for compound (I).

Structure description top

\ Claisen–Schmidt reaction (Claisen & Claparede, 1881; Schmidt, 1881) is the condensation of aromatic aldehydes (or between ketones and aldehydes lacking a-hydrogen) with aliphatic or mixed alkyl aryl ketones in the presence of a relatively strong base to form α,β-unsaturated ketones. This reaction is of tremendous value in synthetic organic chemistry (Wayne & Adkins 1940; Marvel & King, 1944) and is frequently encountered as a key step in several elegant total synthesis protocols. Claisen–Schmidt condensation can also be catalysed by acid. The first step is a condensation of an aldol type; enols or enolates are involved as inter­mediates in this reaction. This reaction involves the nucleophilic addition of enol or an enolate ion derived from methyl ketone to the carbonyl carbon of the aromatic aldehyde. Dehydration of the hy­droxy­lketone to form the conjugated unsaturated carbonyl compound occurs spontaneously (see Scheme 1) (Stiles et al., 1959). Cyclo­alkanones like cyclo­hexanone, cyclo­heptanone readily undergo Claisen–Schmidt condensation (Nithya et al., 2014). In addition to cyclo­alkanones we attempted open-chain alkanones.

The title compounds (I) and (II) were synthesized by employing Claisen–Schmidt condensation of pentan-3-one and di­benzyl­acetone with 5-bromo­thio­phene-2-carbaldehyde in the presence of methano­lic KOH (Schemes 1 and 2). Although we anti­cipated getting 1:2 products in both of the reactions, a 1:2 product was obtained for the former case, (I), whereas a 1:1 product for the latter, (II). The SCXRD data obtained for compound (II) suggests that the bulky phenyl ring hinders the possibility of a second bromo­thio­phene ring being attached and hence only a 1:1 product was formed in this case. We present herein the structures of (1E,4E)-1,5-bis­(5-bromo­thio­phen-2-yl)-2,4-di­methyl­penta-1,4-\ dien-3-one (I) and (E)-4-(5-bromo­thio­phen-2-yl)-1,3-di­phenyl­but-3-en-2-one (II).

The molecular structures of (I) and (II) are shown in Fig. 1. The asymmetric unit of (I) comprises one molecule of pentan-3-one and two of 5-bromo­thio­phene-2-carbaldehyde. The two methyl groups (C14 and C15) of (I) are twisted away from each other with C14—C6—C7—O1 and C15—C8—C7—O1torsion angles of 29.5 (7) and 28.7 (7)°, respectively.

The asymmetric unit of (II) comprises one molecule of 5-bromo­thio­phene-2-carbaldehyde with one molecule of di­benzyl­acetone. The two phenyl rings of the di­benzyl­acetone subtend a dihedral angle of 53.09 (18)°. One of the phenyl rings (C15–C20) of the di­benzyl­acetone and the thio­phene ring are flanked almost perpendicularly, forming a dihedral angle of 89.96 (16)°.

In the crystal structure of (I), a non-classical C—H···O hydrogen bond (Table 1) links the molecules into a chain along the c axis (Fig 2). Another molecular chain is formed along the b axis through a C13—Br2···π(C1–C4/S1)ii inter­action [symmetry code: (ii) 1 − x, 1 + y, 1/2 − z], Br···Cg = 3.556 (2) Å (Fig 3). The two molecular chains are in turn stacked by π–π inter­actions between the two thio­phene rings, (C1–C4/S1) and (C10–C13/S2)iii [symmetry code: (iii):1 − x, y, 1/2 − z], Cg···Cg = 3.718 (3) Å, forming a three-dimensional supra­molecular architecture (Fig. 4).

In structure (II) a C—H···O hydrogen bond (Table 2) links pairs of molecules, forming centrosymmetric dimers (Fig. 5). Such dimers are linked together by means of C19–H19···π(C1–C4/S1) inter­action, building a staircase structure along the a axis (Fig. 6).

Synthesis and crystallization top

The title compounds were prepared by adapting a reported procedure (Alkskas et al., 2013). Title compound (I) was prepared by adding a mixture of pentan-3-one (0.50 g, 1.2 mmol) and 5-bromo-thio­phene-2-carbaldehyde (2.2 g, 2.4 mmol) in methanol (25 ml) and potassium hydroxide pellets (0.2 g, 2.4 mmol) was also added. The reaction mixture was stirred at room temperature overnight whilst a pale-yellow product separated out. The crude product was washed several times with cold ethanol (1 ml). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 401–403 K. Yield: 85%. IR (KBr): 1680 (C═O), 3061(═ C—H). 1H NMR: (CDCl3): δ2.20 (3H, s), δ6.97–6.96 (1H, d), δ7.08–7.07 (1H, d), δ7.18–7.17 (1H, s). MS: m/z 431 (M+); analysis calculated for C15H12Br2S2O: C: 41.69, H: 2.80, Br: 36.98, S: 14.84; found: C: 41.59, H: 2.78, Br: 36.90, S: 14.74.

Title compound (II) was prepared by mixing di­benzyl­ketone (1 g, 4.7 mmol) and 5-bromo-thio­phene-2-carbaldehyde (1.8 g, 9.5 mmol) in methanol (25 ml) and potassium hydroxide pellets (0.6 g, 9.5 mmol) were also added. The reaction mixture was stirred at room temperature overnight whilst a yellow product separated out. The crude product was washed several times with cold ethanol (1 ml). Good quality single crystals suitable for X-ray analysis were obtained by recrystallization from chloro­form, m.p. 383–385 K. Yield: 90%. IR (KBr): 1627 (C═O), 3080 (═C—H). 1H NMR (CDCl3): δ3.78 (2H, s), δ7.80 (1H, s), 7.51–7.48 (1H, m), 7.47 (1H, m), 7.23–7.20 (2H, m), 7.15–7.14 (2H, m), 7.13–7.12 (2H, m), 7.04–7.02 (2H, m), 6.97–6.96 (1H, d), 6.90–6.89 (1H, d). MS: m/z 383 (M+); analysis calculated for C20H15BrOS: C: 62.67, H: 3.94, Br: 20.85, S: 8.37; found: C: 62.57, H: 3.92, Br: 20.77, S: 8.27.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 3. In both compounds, all H atoms on C were placed in calculated positions, guided by difference Fourier maps, with C—H bond distances of 0.93–0.97 Å. H atoms were assigned as Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq (methyl C). Four reflections were omitted owing to bad agreement (1 0 0) for compound (I).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. View of the title compounds (I) and (II) drawn with 50% probability displacement ellipsoids for the non-H atoms.
[Figure 2] Fig. 2. C—H···O hydrogen-bonding interaction in (I), forming a molecular chain along the c axis.
[Figure 3] Fig. 3. The molecular chain in (I), formed along the b axis through C—Br···π interactions.
[Figure 4] Fig. 4. The two molecular chains in (I), stacked by π–π interactions to form a three-dimensional supramolecular architecture.
[Figure 5] Fig. 5. C—H···O interactions in (II), forming a centrosymmetric dimer.
[Figure 6] Fig. 6. Dimers in (II) linked together by means of C—H···π interactions building a staircase structure along a.
(I) (1E,4E)-1,5-Bis(5-bromothiophen-2-yl)-2,4-dimethylpenta-1,4-dien-3-one top
Crystal data top
C15H12Br2OS2F(000) = 848
Mr = 432.19Dx = 1.770 Mg m−3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
a = 16.564 (2) ÅCell parameters from 3021 reflections
b = 6.3581 (7) Åθ = 2.6–23.4°
c = 15.962 (2) ŵ = 5.25 mm−1
β = 105.239 (5)°T = 296 K
V = 1622.0 (4) Å3Block, yellow
Z = 40.60 × 0.50 × 0.40 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4051 independent reflections
Radiation source: fine-focus sealed tube2012 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
ω and φ scanθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −22→21
Tmin = 0.049, Tmax = 0.115k = −5→8
13847 measured reflectionsl = −21→21
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.181 w = 1/[σ2(Fo2) + (0.0913P)2 + 0.2774P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.001
4042 reflectionsΔρmax = 0.88 e Å−3
183 parametersΔρmin = −0.80 e Å−3
Crystal data top
C15H12Br2OS2V = 1622.0 (4) Å3
Mr = 432.19Z = 4
Monoclinic, P2/cMo Kα radiation
a = 16.564 (2) ŵ = 5.25 mm−1
b = 6.3581 (7) ÅT = 296 K
c = 15.962 (2) Å0.60 × 0.50 × 0.40 mm
β = 105.239 (5)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4051 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2012 reflections with I > 2σ(I)
Tmin = 0.049, Tmax = 0.115Rint = 0.059
13847 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.181H-atom parameters constrained
S = 0.98Δρmax = 0.88 e Å−3
4042 reflectionsΔρmin = −0.80 e Å−3
183 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0832 (3)0.4182 (8)0.1493 (4)0.0604 (15)
C20.1111 (4)0.5540 (9)0.0976 (4)0.0642 (15)
H20.10090.53920.03770.077*
C30.1566 (3)0.7172 (8)0.1450 (4)0.0578 (15)
H30.18090.82270.11950.069*
C40.1631 (3)0.7115 (7)0.2316 (3)0.0455 (12)
C50.2056 (3)0.8689 (7)0.2940 (3)0.0462 (12)
H50.23980.96040.27330.055*
C60.2036 (3)0.9036 (7)0.3762 (3)0.0453 (12)
C70.2488 (3)1.0879 (8)0.4230 (3)0.0505 (12)
C80.3296 (3)1.1597 (7)0.4070 (3)0.0466 (12)
C90.3833 (3)1.0165 (7)0.3931 (3)0.0456 (12)
H90.36430.87840.39040.055*
C100.4668 (3)1.0418 (7)0.3816 (3)0.0435 (11)
C110.5166 (3)0.8833 (8)0.3700 (4)0.0636 (16)
H110.50000.74330.36910.076*
C120.5950 (3)0.9419 (10)0.3595 (4)0.0687 (17)
H120.63580.84850.35220.082*
C130.6027 (3)1.1518 (9)0.3616 (4)0.0572 (14)
C140.1503 (4)0.7812 (9)0.4221 (4)0.0624 (15)
H14A0.14930.85190.47500.094*
H14B0.17310.64260.43530.094*
H14C0.09430.77090.38540.094*
C150.3465 (4)1.3911 (8)0.4187 (4)0.0690 (17)
H15A0.30191.45700.43710.104*
H15B0.35001.45140.36460.104*
H15C0.39841.41280.46190.104*
S10.11240 (8)0.4921 (2)0.25627 (10)0.0591 (4)
S20.51728 (9)1.2768 (2)0.37862 (11)0.0610 (4)
Br20.69420 (4)1.31159 (11)0.34996 (5)0.0869 (3)
Br10.01821 (5)0.17864 (10)0.11612 (6)0.0937 (3)
O10.2192 (3)1.1834 (6)0.4736 (3)0.0749 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.044 (3)0.057 (3)0.077 (4)0.004 (3)0.009 (3)−0.013 (3)
C20.065 (4)0.077 (4)0.050 (4)0.009 (3)0.014 (3)−0.016 (3)
C30.060 (3)0.063 (3)0.055 (4)0.004 (3)0.025 (3)0.002 (3)
C40.039 (3)0.054 (3)0.047 (3)0.001 (2)0.017 (2)−0.003 (2)
C50.045 (3)0.052 (3)0.046 (3)−0.002 (2)0.020 (2)0.005 (2)
C60.044 (3)0.047 (3)0.048 (3)0.000 (2)0.018 (2)0.004 (2)
C70.057 (3)0.057 (3)0.039 (3)0.007 (2)0.015 (3)−0.002 (3)
C80.049 (3)0.047 (3)0.042 (3)0.001 (2)0.012 (2)−0.004 (2)
C90.052 (3)0.039 (2)0.044 (3)−0.006 (2)0.009 (2)0.002 (2)
C100.048 (3)0.038 (2)0.045 (3)−0.004 (2)0.012 (2)−0.004 (2)
C110.058 (3)0.046 (3)0.088 (5)0.003 (2)0.023 (3)−0.003 (3)
C120.054 (3)0.067 (4)0.087 (5)0.009 (3)0.022 (3)−0.004 (3)
C130.050 (3)0.068 (4)0.053 (4)−0.009 (3)0.013 (3)−0.006 (3)
C140.064 (4)0.081 (4)0.050 (4)−0.005 (3)0.029 (3)0.005 (3)
C150.062 (4)0.050 (3)0.094 (5)0.000 (3)0.020 (3)−0.019 (3)
S10.0566 (8)0.0638 (8)0.0565 (10)−0.0148 (7)0.0141 (7)−0.0001 (7)
S20.0586 (8)0.0455 (7)0.0828 (12)−0.0091 (6)0.0255 (8)−0.0096 (7)
Br20.0666 (4)0.1003 (6)0.1022 (6)−0.0286 (4)0.0372 (4)−0.0157 (4)
Br10.0836 (5)0.0756 (5)0.1146 (7)−0.0153 (3)0.0128 (4)−0.0333 (4)
O10.077 (3)0.087 (3)0.069 (3)0.000 (2)0.036 (2)−0.028 (2)
Geometric parameters (Å, º) top
C1—C21.357 (8)C9—C101.450 (6)
C1—S11.714 (6)C9—H90.9300
C1—Br11.860 (5)C10—C111.346 (7)
C2—C31.385 (7)C10—S21.720 (4)
C2—H20.9300C11—C121.403 (8)
C3—C41.358 (7)C11—H110.9300
C3—H30.9300C12—C131.340 (8)
C4—C51.456 (7)C12—H120.9300
C4—S11.727 (5)C13—S21.705 (6)
C5—C61.340 (7)C13—Br21.874 (5)
C5—H50.9300C14—H14A0.9600
C6—C71.483 (7)C14—H14B0.9600
C6—C141.505 (7)C14—H14C0.9600
C7—O11.213 (6)C15—H15A0.9600
C7—C81.497 (7)C15—H15B0.9600
C8—C91.332 (6)C15—H15C0.9600
C8—C151.500 (7)
C2—C1—S1112.3 (4)C11—C10—C9125.0 (4)
C2—C1—Br1127.7 (5)C11—C10—S2109.1 (4)
S1—C1—Br1119.9 (4)C9—C10—S2125.9 (3)
C1—C2—C3111.6 (5)C10—C11—C12115.9 (5)
C1—C2—H2124.2C10—C11—H11122.0
C3—C2—H2124.2C12—C11—H11122.0
C4—C3—C2115.0 (5)C13—C12—C11110.3 (5)
C4—C3—H3122.5C13—C12—H12124.9
C2—C3—H3122.5C11—C12—H12124.9
C3—C4—C5124.9 (5)C12—C13—S2113.0 (4)
C3—C4—S1109.9 (4)C12—C13—Br2127.7 (4)
C5—C4—S1125.2 (4)S2—C13—Br2119.3 (3)
C6—C5—C4130.6 (4)C6—C14—H14A109.5
C6—C5—H5114.7C6—C14—H14B109.5
C4—C5—H5114.7H14A—C14—H14B109.5
C5—C6—C7119.0 (4)C6—C14—H14C109.5
C5—C6—C14124.1 (5)H14A—C14—H14C109.5
C7—C6—C14116.5 (4)H14B—C14—H14C109.5
O1—C7—C6119.5 (5)C8—C15—H15A109.5
O1—C7—C8119.8 (5)C8—C15—H15B109.5
C6—C7—C8120.7 (4)H15A—C15—H15B109.5
C9—C8—C7119.1 (4)C8—C15—H15C109.5
C9—C8—C15125.4 (5)H15A—C15—H15C109.5
C7—C8—C15115.0 (4)H15B—C15—H15C109.5
C8—C9—C10130.3 (4)C1—S1—C491.2 (3)
C8—C9—H9114.9C13—S2—C1091.7 (2)
C10—C9—H9114.9
S1—C1—C2—C30.4 (6)C7—C8—C9—C10−175.6 (5)
Br1—C1—C2—C3178.9 (4)C15—C8—C9—C10−3.3 (9)
C1—C2—C3—C4−1.0 (7)C8—C9—C10—C11178.2 (6)
C2—C3—C4—C5−178.1 (5)C8—C9—C10—S2−3.0 (8)
C2—C3—C4—S11.2 (6)C9—C10—C11—C12179.6 (5)
C3—C4—C5—C6166.0 (5)S2—C10—C11—C120.6 (7)
S1—C4—C5—C6−13.1 (8)C10—C11—C12—C13−1.3 (8)
C4—C5—C6—C7−175.4 (5)C11—C12—C13—S21.4 (7)
C4—C5—C6—C14−2.5 (8)C11—C12—C13—Br2−179.5 (4)
C5—C6—C7—O1143.9 (5)C2—C1—S1—C40.2 (4)
C14—C6—C7—O1−29.5 (7)Br1—C1—S1—C4−178.4 (3)
C5—C6—C7—C8−34.8 (7)C3—C4—S1—C1−0.8 (4)
C14—C6—C7—C8151.8 (5)C5—C4—S1—C1178.5 (4)
O1—C7—C8—C9144.4 (5)C12—C13—S2—C10−1.0 (5)
C6—C7—C8—C9−36.9 (7)Br2—C13—S2—C10179.9 (3)
O1—C7—C8—C15−28.7 (7)C11—C10—S2—C130.2 (5)
C6—C7—C8—C15150.0 (5)C9—C10—S2—C13−178.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.573.233 (7)129
Symmetry code: (i) x, −y+2, z−1/2.
(II) (E)-4-(5-Bromothiophen-2-yl)-1,3-diphenylbut-3-en-2-one top
Crystal data top
C20H15BrOSZ = 2
Mr = 383.29F(000) = 388
Triclinic, P1Dx = 1.467 Mg m−3
a = 7.5879 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.5361 (6) ÅCell parameters from 3038 reflections
c = 14.0970 (8) Åθ = 2.5–28.2°
α = 99.510 (3)°µ = 2.49 mm−1
β = 97.673 (3)°T = 296 K
γ = 101.956 (3)°Block, yellow
V = 867.58 (9) Å30.60 × 0.50 × 0.35 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4363 independent reflections
Radiation source: fine-focus sealed tube3040 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω and φ scanθmax = 28.4°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −10→8
Tmin = 0.307, Tmax = 0.456k = −7→11
6863 measured reflectionsl = −18→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0571P)2 + 0.3404P]
where P = (Fo2 + 2Fc2)/3
4363 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.86 e Å−3
Crystal data top
C20H15BrOSγ = 101.956 (3)°
Mr = 383.29V = 867.58 (9) Å3
Triclinic, P1Z = 2
a = 7.5879 (4) ÅMo Kα radiation
b = 8.5361 (6) ŵ = 2.49 mm−1
c = 14.0970 (8) ÅT = 296 K
α = 99.510 (3)°0.60 × 0.50 × 0.35 mm
β = 97.673 (3)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer		4363 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		3040 reflections with I > 2σ(I)
Tmin = 0.307, Tmax = 0.456Rint = 0.025
6863 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.05Δρmax = 0.56 e Å−3
4363 reflectionsΔρmin = −0.86 e Å−3
208 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2982 (4)0.1132 (4)0.6105 (2)0.0364 (6)
C20.4114 (4)0.0812 (4)0.6841 (2)0.0415 (7)
H20.4737−0.00190.67720.050*
C30.4219 (4)0.1897 (4)0.7720 (2)0.0382 (7)
H30.49430.18630.82990.046*
C40.3170 (4)0.3012 (3)0.76546 (19)0.0316 (6)
C50.3029 (4)0.4239 (4)0.84553 (19)0.0337 (6)
H50.37870.42880.90400.040*
C60.1973 (4)0.5323 (3)0.84900 (19)0.0333 (6)
C70.2176 (4)0.6463 (4)0.9441 (2)0.0438 (7)
C80.1294 (6)0.7885 (5)0.9442 (3)0.0665 (12)
H8A0.16600.84380.89270.080*
H8B−0.00220.74690.92870.080*
C90.1747 (4)0.9109 (4)1.0380 (2)0.0388 (7)
C100.0910 (5)0.8834 (4)1.1161 (3)0.0503 (8)
H100.00460.78611.11050.060*
C110.1308 (6)0.9941 (6)1.2013 (3)0.0640 (11)
H110.07040.97241.25260.077*
C120.2550 (6)1.1327 (6)1.2122 (3)0.0657 (11)
H120.28311.20621.27170.079*
C130.3413 (5)1.1690 (5)1.1382 (4)0.0695 (12)
H130.42601.26801.14610.083*
C140.3023 (5)1.0560 (5)1.0490 (3)0.0585 (10)
H140.36241.07920.99780.070*
C150.0666 (4)0.5442 (3)0.76278 (18)0.0319 (6)
C160.1236 (4)0.6394 (4)0.6970 (2)0.0449 (7)
H160.24330.70160.70840.054*
C170.0051 (5)0.6430 (5)0.6150 (2)0.0562 (9)
H170.04460.70850.57180.067*
C18−0.1706 (5)0.5505 (5)0.5968 (2)0.0541 (9)
H18−0.24930.55060.54020.065*
C19−0.2302 (4)0.4582 (4)0.6615 (2)0.0487 (8)
H19−0.35040.39710.64970.058*
C20−0.1119 (4)0.4551 (4)0.7449 (2)0.0392 (7)
H20−0.15350.39250.78910.047*
O10.3037 (4)0.6264 (4)1.01810 (17)0.0792 (10)
S10.20165 (10)0.27183 (10)0.64654 (5)0.03775 (18)
Br10.24497 (5)0.00369 (5)0.48059 (2)0.05710 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0317 (14)0.0387 (17)0.0340 (14)0.0078 (12)0.0032 (11)−0.0036 (12)
C20.0421 (17)0.0437 (18)0.0401 (15)0.0192 (14)0.0055 (13)0.0022 (13)
C30.0386 (15)0.0444 (18)0.0317 (13)0.0158 (13)−0.0006 (11)0.0060 (12)
C40.0297 (13)0.0339 (15)0.0284 (12)0.0067 (11)−0.0008 (10)0.0043 (11)
C50.0323 (14)0.0356 (16)0.0283 (12)0.0059 (12)−0.0033 (10)0.0020 (11)
C60.0334 (14)0.0305 (15)0.0306 (13)0.0051 (12)−0.0027 (11)0.0006 (11)
C70.0514 (18)0.0439 (18)0.0333 (14)0.0233 (15)−0.0089 (13)−0.0029 (13)
C80.090 (3)0.063 (2)0.0447 (18)0.050 (2)−0.0185 (18)−0.0109 (17)
C90.0452 (17)0.0361 (17)0.0362 (14)0.0227 (14)−0.0028 (12)0.0013 (12)
C100.053 (2)0.0428 (19)0.059 (2)0.0140 (16)0.0056 (16)0.0203 (16)
C110.085 (3)0.077 (3)0.0439 (19)0.045 (3)0.0142 (19)0.0162 (19)
C120.073 (3)0.065 (3)0.056 (2)0.038 (2)−0.007 (2)−0.0122 (19)
C130.0398 (19)0.039 (2)0.113 (4)0.0005 (16)−0.009 (2)−0.002 (2)
C140.046 (2)0.070 (3)0.071 (2)0.0238 (19)0.0259 (17)0.022 (2)
C150.0385 (15)0.0278 (14)0.0277 (12)0.0102 (12)−0.0012 (11)0.0034 (11)
C160.0454 (18)0.0441 (19)0.0448 (17)0.0057 (15)0.0059 (13)0.0154 (14)
C170.074 (3)0.061 (2)0.0400 (17)0.022 (2)0.0095 (16)0.0229 (16)
C180.068 (2)0.062 (2)0.0315 (15)0.0255 (19)−0.0081 (15)0.0069 (15)
C190.0401 (17)0.050 (2)0.0470 (18)0.0074 (15)−0.0093 (14)0.0025 (15)
C200.0413 (16)0.0378 (17)0.0378 (15)0.0082 (13)−0.0001 (12)0.0124 (13)
O10.116 (2)0.082 (2)0.0394 (13)0.0695 (18)−0.0269 (14)−0.0153 (12)
S10.0383 (4)0.0438 (4)0.0285 (3)0.0154 (3)−0.0040 (3)0.0001 (3)
Br10.0493 (2)0.0780 (3)0.03575 (18)0.01993 (18)0.00201 (13)−0.01404 (15)
Geometric parameters (Å, º) top
C1—C21.357 (4)C10—C111.355 (5)
C1—S11.706 (3)C10—H100.9300
C1—Br11.863 (3)C11—C121.323 (6)
C2—C31.401 (4)C11—H110.9300
C2—H20.9300C12—C131.347 (6)
C3—C41.368 (4)C12—H120.9300
C3—H30.9300C13—C141.408 (6)
C4—C51.439 (4)C13—H130.9300
C4—S11.737 (3)C14—H140.9300
C5—C61.343 (4)C15—C201.376 (4)
C5—H50.9300C15—C161.385 (4)
C6—C71.489 (4)C16—C171.376 (5)
C6—C151.494 (4)C16—H160.9300
C7—O11.211 (4)C17—C181.369 (5)
C7—C81.503 (4)C17—H170.9300
C8—C91.493 (4)C18—C191.363 (5)
C8—H8A0.9700C18—H180.9300
C8—H8B0.9700C19—C201.389 (4)
C9—C101.372 (5)C19—H190.9300
C9—C141.377 (5)C20—H200.9300
C2—C1—S1113.4 (2)C9—C10—H10119.1
C2—C1—Br1126.5 (2)C12—C11—C10120.6 (4)
S1—C1—Br1120.05 (16)C12—C11—H11119.7
C1—C2—C3111.1 (3)C10—C11—H11119.7
C1—C2—H2124.5C11—C12—C13120.9 (4)
C3—C2—H2124.5C11—C12—H12119.5
C4—C3—C2114.5 (2)C13—C12—H12119.5
C4—C3—H3122.8C12—C13—C14119.6 (4)
C2—C3—H3122.8C12—C13—H13120.2
C3—C4—C5125.0 (2)C14—C13—H13120.2
C3—C4—S1110.0 (2)C9—C14—C13119.5 (3)
C5—C4—S1124.9 (2)C9—C14—H14120.2
C6—C5—C4130.1 (2)C13—C14—H14120.2
C6—C5—H5114.9C20—C15—C16118.5 (3)
C4—C5—H5114.9C20—C15—C6120.5 (2)
C5—C6—C7116.9 (2)C16—C15—C6120.9 (3)
C5—C6—C15123.1 (2)C17—C16—C15120.7 (3)
C7—C6—C15120.0 (2)C17—C16—H16119.7
O1—C7—C6121.4 (3)C15—C16—H16119.7
O1—C7—C8121.3 (3)C18—C17—C16120.2 (3)
C6—C7—C8117.3 (2)C18—C17—H17119.9
C9—C8—C7115.1 (3)C16—C17—H17119.9
C9—C8—H8A108.5C19—C18—C17120.0 (3)
C7—C8—H8A108.5C19—C18—H18120.0
C9—C8—H8B108.5C17—C18—H18120.0
C7—C8—H8B108.5C18—C19—C20120.1 (3)
H8A—C8—H8B107.5C18—C19—H19119.9
C10—C9—C14117.5 (3)C20—C19—H19119.9
C10—C9—C8121.5 (3)C15—C20—C19120.4 (3)
C14—C9—C8121.0 (3)C15—C20—H20119.8
C11—C10—C9121.8 (4)C19—C20—H20119.8
C11—C10—H10119.1C1—S1—C490.98 (13)
S1—C1—C2—C3−0.8 (4)C11—C12—C13—C14−1.7 (6)
Br1—C1—C2—C3178.9 (2)C10—C9—C14—C13−0.2 (5)
C1—C2—C3—C40.7 (4)C8—C9—C14—C13179.7 (3)
C2—C3—C4—C5179.2 (3)C12—C13—C14—C90.9 (5)
C2—C3—C4—S1−0.3 (3)C5—C6—C15—C2090.7 (4)
C3—C4—C5—C6−175.7 (3)C7—C6—C15—C20−90.4 (4)
S1—C4—C5—C63.7 (5)C5—C6—C15—C16−86.7 (4)
C4—C5—C6—C7−179.0 (3)C7—C6—C15—C1692.2 (4)
C4—C5—C6—C15−0.1 (5)C20—C15—C16—C17−0.9 (5)
C5—C6—C7—O1−10.8 (5)C6—C15—C16—C17176.5 (3)
C15—C6—C7—O1170.2 (3)C15—C16—C17—C18−0.8 (5)
C5—C6—C7—C8168.2 (3)C16—C17—C18—C192.0 (6)
C15—C6—C7—C8−10.7 (5)C17—C18—C19—C20−1.3 (5)
O1—C7—C8—C96.9 (6)C16—C15—C20—C191.5 (5)
C6—C7—C8—C9−172.1 (3)C6—C15—C20—C19−175.9 (3)
C7—C8—C9—C10−78.8 (5)C18—C19—C20—C15−0.4 (5)
C7—C8—C9—C14101.3 (4)C2—C1—S1—C40.6 (3)
C14—C9—C10—C110.2 (5)Br1—C1—S1—C4−179.13 (18)
C8—C9—C10—C11−179.7 (3)C3—C4—S1—C1−0.2 (2)
C9—C10—C11—C12−0.9 (5)C5—C4—S1—C1−179.7 (3)
C10—C11—C12—C131.7 (6)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C4/S1 ring.
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.543.320 (4)141
C19—H19···Cgii0.932.903.768 (3)156
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.573.233 (7)128.6
Symmetry code: (i) x, −y+2, z−1/2.
Hydrogen-bond geometry (Å, º) for (II) top
Cg is the centroid of the C1–C4/S1 ring.
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.543.320 (4)141.2
C19—H19···Cgii0.932.903.768 (3)156
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC15H12Br2OS2C20H15BrOS
Mr432.19383.29
Crystal system, space groupMonoclinic, P2/cTriclinic, P1
Temperature (K)296296
a, b, c (Å)16.564 (2), 6.3581 (7), 15.962 (2)7.5879 (4), 8.5361 (6), 14.0970 (8)
α, β, γ (°)90, 105.239 (5), 9099.510 (3), 97.673 (3), 101.956 (3)
V (Å3)1622.0 (4)867.58 (9)
Z42
Radiation typeMo KαMo Kα
µ (mm−1)5.252.49
Crystal size (mm)0.60 × 0.50 × 0.400.60 × 0.50 × 0.35
Data collection
DiffractometerBruker Kappa APEXII CCDBruker Kappa APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)		Multi-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.049, 0.1150.307, 0.456
No. of measured, independent and
observed [I > 2σ(I)] reflections		13847, 4051, 2012 6863, 4363, 3040
Rint0.0590.025
(sin θ/λ)max (Å−1)0.6670.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.181, 0.98 0.043, 0.118, 1.05
No. of reflections40424363
No. of parameters183208
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.88, −0.800.56, −0.86

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

 

Acknowledgements

NC is obliged to Dr S. Prathapan for valuable suggestions and is also grateful to INSPIRE, DST, for financial assistance in the form of a Research Fellowship. The authors are thankful to SAIF (STIC) CUSAT, Kochi, India, for the spectroscopic analytical and single-crystal X-ray diffraction measurements.

References

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ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 199-202
doi:10.1107/S205698901600058X
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