Vasant S Naik1, Hemmige S Yathirajan2, Jerry P Jasinski3, Victoria A Smolenski3, Christopher Glidewell4. 1. Department of Physics, Government First Grade College, Kumta 581 343, India, Research and Development Centre, Bharathiar University, Coimbatore 641 046, India. 2. Department of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India. 3. Department of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA. 4. School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland.
Abstract
The structures of six chalcones containing 5-halogeno-thio-phen-2-yl substituents are reported: (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13ClOS, (I), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13BrOS, (II), are isostructural in space group P-1, while (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one, C15H13ClO2S, (III), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one C15H13BrO2S, (IV), are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the mol-ecules are linked into C(7) chains by means of C-H⋯O hydrogen bonds. In the structure of (2E)-3-(4-bromo-phen-yl)-1-(5-chloro-thio-phen-2-yl)prop-2-en-1-one, C13H8BrClOS, (V), there are again no hydrogen bonds nor π-π stacking inter-actions but in that of (2E)-1-(5-bromo-thio-phen-2-yl)-3-(3-meth-oxy-phen-yl)prop-2-en-1-one, C14H11BrO2S, (VI), the mol-ecules are linked into C(5) chains by C-H⋯O hydrogen bonds. In each of compounds (I)-(VI), the mol-ecular skeletons are close to planarity, and there are short halogen⋯halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). Comparisons are made with the structures of some similar compounds.
The structures of six chalcones containing 5-halogeno-thio-phen-2-yl substituents are reported: (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13ClOS, (I), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13BrOS, (II), are isostructural in space group P-1, while (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one, C15H13ClO2S, (III), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one C15H13BrO2S, (IV), are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the mol-ecules are linked into C(7) chains by means of C-H⋯O hydrogen bonds. In the structure of (2E)-3-(4-bromo-phen-yl)-1-(5-chloro-thio-phen-2-yl)prop-2-en-1-one, C13H8BrClOS, (V), there are again no hydrogen bonds nor π-π stacking inter-actions but in that of (2E)-1-(5-bromo-thio-phen-2-yl)-3-(3-meth-oxy-phen-yl)prop-2-en-1-one, C14H11BrO2S, (VI), the mol-ecules are linked into C(5) chains by C-H⋯O hydrogen bonds. In each of compounds (I)-(VI), the mol-ecular skeletons are close to planarity, and there are short halogen⋯halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). Comparisons are made with the structures of some similar compounds.
Chalcones are important constituents of many natural products, and they are abundant in edible plants where they are considered to be precursors of flavonoids and isoflavonoids. They display a wide range of pharmacological properties including antibacterial (Tang et al., 2008 ▸; Kumar et al., 2013a
▸), anticancer (Shin et al., 2013 ▸), antifungal (Domínguez et al., 2001 ▸; Kumar et al., 2013a
▸,b
▸), antimalarial (Li et al., 1995 ▸) and antitubercular (Lin et al., 2002 ▸) activity. In addition, chalcone derivatives are also important materials in photonic applications because of their excellent blue-light transmittance and good crystallization ability (Goto et al., 1991 ▸; Uchida et al.,1998 ▸; Indira et al., 2002 ▸; Sarojini et al., 2006 ▸). In a continuation of our work on chalcones containing a thiophen moiety (Naik et al., 2015 ▸), six new chalcones of this type, compounds (I)–(VI) (Figs. 1 ▸–6 ▸
▸
▸
▸
▸) have now been synthesized and we report herein on their molecular structures and supramolecular assembly. Compounds (I)–(VI) were all prepared using condensation reactions, under basic conditions, between 2-acetyl-5-halogenothiophens and substituted benzaldehydes.
Figure 1
The molecular structure of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 2
The molecular structure of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 3
The molecular structure of compound (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 4
The molecular structure of compound (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 5
The molecular structure of compound (V), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 6
The molecular structure of compound (VI), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Structural commentary
Compounds (I) and (II) are isostructural in space group P
, while compounds (III) and (IV) are isostructural in space group P21/c. Although the unit-cell dimensions for compound (V) are similar to those for compounds (I) and (II), a detailed comparison of the atomic coordinates for compounds (I), (II) and (V) indicates that there is no simple relationship between those of (I) and (II) on the one hand and those of (V) on the other. Although compound (VI) crystallizes in the same space group as compounds (III) and (IV), the unit-cell dimensions for (VI) are very different from those for (III) and (IV).Although the molecules of compounds (I)–(VI) all lie in general positions, the non-H atoms of the molecular skeletons are quite close to being co-planar, apart from the terminal C atoms of the ethyl groups in compounds (I)–(IV), as shown by the dihedral angles in Table 1 ▸. The values of these angles demonstrate the very close conformational similarity between the molecules of the three compounds, (I), (II) and (V), which crystallize in space group P
, and between those of the three compounds, (III), (IV) and (VI), in P21/c. In the molecules of each of (I)–(V), the 5-halogenothienyl unit adopts the same orientation, with S11—C12—C1—C2 torsion angles close to 180° (Table 1 ▸). There is no evidence in any of the structures reported here for orientational disorder of the type commonly observed with otherwise unsubstituted thienyl units; this is presumably a direct consequence of the presence of the halogen substituent.
Table 1
Selected dihedral, bond and torsion angles (°) for compounds (I)–(VI)
Parameter
(I)
(II)
(III)
(IV)
(V)
(VI)
Dihedral 1
2.74 (9)
3.46 (18)
2.80 (14)
3.11 (18)
3.66 (16)
7.70 (13)
Dihedral 2
10.23 (11)
10.5 (2)
3.71 (12)
2.99915)
9.74 (19)
3.10 (11)
Dihedral 3
11.62 (9)
11.78 (16)
6.49 (7)
6.03 (9)
11.96 (14)
5.20 (13)
C32—C33—O33
124.89 (19)
C34—C33—O33
114.96 (17)
C33—O33—C37
117.69 (16)
C33—C34—O34
116.33 (13)
116.2 (2)
C35—C34—O34
123.98 (13)
124.2 (2)
C34—O34—C37
117.57 (12)
117.45 (18)
S11—C12—C1—C2
178.07 (10)
177.34 (18)
−178.36 (12)
−178.48 (16)
177.99 (19)
−172.61 (16)
C32—C33—O33—C37
7.9 (3)
C33—C34—C37—C38
−97.5 (2)
−92.6 (3)
C33—C34—O34—C37
−175.99 (15)
−176.45 (19)
C34—O34—C37—C38
169.60 (16)
171.3 (2)
‘Dihedral 1’ represents the dihedral angle between the spacer unit (C12,C1,C2,C3,C31) and the thienyl ring. ‘Dihedral 2’ represents the dihedral angle between the spacer unit (C12,C1,C2,C3,C31) and the aryl ring. ‘Dihedral 3’ represents the dihedral angle between the thienyl and aryl rings.
In each of compounds (III), (IV) and (VI), all of which carry an alkoxy substituent, the atom C37 (Figs. 3 ▸, 4 ▸ and 6 ▸) lies close to the plane of the adjacent aryl ring: the displacements of the atoms C37 from these planes are 0.117 (3), 0.097 (4) and 0.186 (4) Å, respectively. Consistent with these observations, the corresponding pairs of exocyclic C—C—O angles (Table 1 ▸) differ significantly, as typically found for alkoxybenzenes with near-planar molecular skeletons (Seip & Seip, 1973 ▸; Ferguson et al., 1996 ▸). Whereas the whole ethoxy group in each of compounds (III) and (IV) is nearly coplanar with the adjacent aryl ring, this is far from the case for compounds (I) and (II) (Table 1 ▸, Figs. 1 ▸–4 ▸
▸
▸).The bond distances in compounds (I)–(VI) all lie within the usual ranges (Allen et al., 1987 ▸).
Supramolecular interactions
There are no direction-specific intermolecular interactions in the structure of compound (I); hydrogen bonds of C—H⋯O and C—H⋯π types are absent, as are π–π stacking interactions. Hydrogen bonds and π–π stacking interactions are also absent from the structure of compound (II), but in this structure there is a short intermolecular Br⋯Br contact, with parameters Br15⋯Br15i = 3.4917 (5) Å and C15—Br15⋯Br15i = 151.37 (8)° [symmetry code: (i) −x + 1, −y + 1, −z + 2]. The Br ⋯Br distance is significantly shorter than the van der Waals contact distance of 3.70 Å (Bondi, 1964 ▸; Rowland & Taylor, 1996 ▸), while the observed C—Br⋯Br angle is consistent with the results of a database analysis of such contacts (Ramasubbu et al., 1986 ▸), which found that such angles were, in general, clustered around 165°.In each of compounds (III) and (IV), a single C—H⋯O hydrogen bond having the carbonyl O atom as the acceptor (Table 2 ▸) links molecules related by c-glide symmetry into zigzag C(7) (Bernstein et al., 1995 ▸) chains running parallel to the [001] direction (Fig. 7 ▸). Two chains of this type, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains: in particular there are no short intermolecular Br⋯Br contacts in the structure of compound (IV), thus differing in this respect from compound (II).
Table 2
Hydrogen bond parameters (Å, °) for compounds (III), (IV) and (VI)
Compound
D—H⋯A
D—H
H⋯A
D⋯A
D—H⋯A
(III)
C36—H36⋯O6i
0.95
2.52
3.4649 (18)
173
(IV)
C36—H36⋯O6i
0.95
2.52
3.464 (2)
172
(VI)
C13—H13⋯O1ii
0.95
2.54
3.446 (3)
159
Symmetry codes: (i) x, −y + , z + ; (ii) −x + 1, y − , −z + .
Figure 7
Part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded C(7) chain running parallel to the [001] direction. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, −y + , z + ) and (x, −y + , z + ), respectively.
There are neither hydrogen bonds nor π–π stacking interactions in the structure of compound (V). However, the structure contains a fairly short intermolecular Cl⋯Cl contact, although, rather surprisingly, there are no short contacts of either Br⋯Br or Br⋯Cl types. For the contact C15—Cl15⋯Cl15ii [symmetry code: (ii) −x + 1, −y, −z + 2], the geometrical parameters are Cl⋯Clii = 3.4825 (11) Å and C—Cl⋯Clii = 167.83 (10)°. The Cl⋯Cl distances is thus just at the van der Waals contact distance 3.48 Å (Rowland & Taylor, 1996 ▸) and so this contact cannot be regarded as structurally significant: however, it may be noted that the angle C—Cl⋯Clii is entirely consistent with the results of a database analysis (Ramasubbu et al., 1986 ▸).A single C—H⋯O hydrogen bond (Table 2 ▸) links the molecules of compound (VI) which are related by the 21 screw axis along (, y, ) into a C(5) chain running parallel to the [010] direction (Fig. 8 ▸). Two chains of this type, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains. Not only are C—H⋯π hydrogen bonds and π–π stacking interactions absent from the crystal structure of compound (VI), but neither are there any short Br⋯Br contacts of the type found in compound (II). There is however a short intermolecular Br⋯O contact with parameters Br15⋯O33iii = 2.9770 (16) Å and C15—Br15⋯O33iii = 167.21 (7)° [symmetry code: (iii) x − , y, z + 1].
Figure 8
Part of the crystal structure of compound (VI), showing the formation of a hydrogen-bonded C(5) chain running parallel to the [010] direction. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (−x + 1, y − , −z + ), (−x + 1, y + , −z + ) and (x, y − 1, z), respectively.
All of the compounds reported here crystallize either in space group P
or in P21/c, and there appear to be some interesting connections between the space groups and the nature of the direction-specific intermolecular interactions manifested in the various structures. Thus although all six of the compounds described here contain carbonyl groups, only in compounds (III), (IV) and (VI) do the O atoms of these units participate as acceptors in C—H⋯O hydrogen bonds: these happen to be the three examples which crystallize in space group P21/c. Of the three 5-bromothienyl derivatives reported here, a short Br⋯Br contact occurs only in compound (II), the only example of this group which crystallizes in space group P
.
Database survey
The structures of a number of (2E)-3-aryl-1-(5-chlorothiophen-2-yl)-prop-2-en-1-one derivatives closely related to compounds (I)–(VI) have been reported recently, usually in the form of brief reports on single structures in which no comparisons with related compounds were made, and sometimes with little or no mention of the supramolecular assembly. It is thus of interest briefly to compare the supramolecular assembly in these compounds with that in compounds (I)–(VI). Compound (VII) (see Scheme below) is isomeric with compound (V), and these two compounds differ only in the exchange of the halogen location. Despite this, they are not isomorphous as compound (VII) crystallizes in space group P21/c (Kavitha et al., 2013 ▸), as opposed to P
for compound (V). There are two C—H⋯π contacts in the structure of compound (VII), but both of these have long H⋯D distances and small D—H⋯A angles, and so are probably not structurally significant. There is, however, a short intermolecular Br⋯Cl contact for which the Br⋯Cl distance of 3.5746 (11) Å (not 3.698 (1) Å as stated in the original report), is larger than the sum, 3.55 Å (Rowland & Taylor (1996 ▸), of the van der Waals radii.For compound (VIII) (Vepuri et al., 2012 ▸), which provides a genuine example of Z′ = 2 in space group Cc (Baur & Kassner, 1992 ▸; Marsh, 1997 ▸, 2004 ▸), there are no significant direction interactions in the structure: in particular there are neither C—H⋯O hydrogen bonds nor short Br⋯Br contacts. Compounds (IX) (Prabhu et al., 2011b
▸) and (X) (Prabhu et al., 2014 ▸) are isostructural, and (X) was described as forming chains built from two independent C—H⋯O hydrogen bonds. However, one of these contacts involves a methyl C—H bond and the other has a C—H⋯O angle of only 130° (cf. Wood et al., 2009 ▸), so that neither can be regarded as structurally significant. On the other hand the structure of (IX) contains a significant aromatic π–π stacking interaction between the phenyl rings of inversion-related molecules, although this was apparently overlooked in the original report. The phenyl rings of the molecules at (x, y, z) and (−x + 2, −y + 2, −z + 2) are strictly parallel with an interplanar spacing of 3.5113 (8) Å: the ring centroid separation is 3.6535 (11) Å, corresponding to a ring-centroid offset of 1.009 (2) Å, so leading to the formation of a centrosymmetric π-stacked dimer (Fig. 9 ▸).
Figure 9
Part of the crystal structure of compound (IX), showing the formation of a centrosymmetric π-stacked dimer. For the sake of clarity, the H atoms and the unit-cell outline have been omitted. The original atomic coordinates (Prabhu et al., 2011b
▸) have been used and the S atom marked with an asterisk (*) is at the symmetry position (−x + 2, −y + 2, −z + 2).
The original report on compound (XI) (Sunitha et al., 2012 ▸) provides no analysis or description of the supramolecular assembly. Examination of the original atomic coordinates shows firstly that molecules related by a c-glide plane are linked by a nearly linear C—H⋯O hydrogen bond, forming a C(6) chain running parallel to the [001] direction, and secondly that inversion-related pairs of molecules are linked by a π–π stacking interaction involving the phenyl rings of the molecules at (x, y, z) and (−x + 1, −y + 1, −z), with interplanar spacing 3.4465 (10) Å, ring-centroid separation 3.749 (3) Å and ring-centroid offset 1.475 (3) Å. The combined effect of these two types of interaction is the formation of a sheet lying parallel to (100); see Fig. 10 ▸.
Figure 10
A stereoview of part of the crystal structure of compound (XI), showing the formation of sheets parallel to (100) built from π-stacked hydrogen-bonded C(6) chains. The original atomic coordinates (Sunitha et al., 2012 ▸) have been used and, for the sake of clarity, the H atoms not involved in the motif shown have been omitted.
There are two intermolecular C—H⋯O contacts in the structure of compound (XII) which were described (Prabhu et al., 2011a
▸) as joining the molecules into chains: however, for these two contacts the H⋯O distances, 2.68 and 2.71 Å, both exceed the sum of the van der Waals radii, 2.65 Å (Rowland & Taylor, 1996 ▸), so that these contacts certainly cannot be regarded as hydrogen bonds. Simple C(11) chains are formed in the structure of compound (XIII) built from C—H⋯O hydrogen bonds (Vepuri et al., 2011 ▸), but there are no short Br⋯Br contacts in either of (XI) and (XIII).
Synthesis and crystallization
For the synthesis of each compound, an equimolar mixture (0.01 mol of each component) of the appropriate 2-acetyl-5-halogenothiophen and the appropriately-substituted benzaldehyde was dissolved in a mixture of methanol (20 ml) and aqueous sodium hydroxide solution (5 ml of 30% w/v solution). The mixtures were all stirred at ambient temperature for 4 h, and then poured into ice-cold water (250 ml): the resulting solid products were collected by filtration and dried in air at 323 K. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in acetone: melting points: (I) 384 K, (II) 423 K, (III) 415 K. (IV) 403 K, (V) 423 K and (VI) 390 K.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were located in difference Fourier maps and subsequently treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (alkenyl, aromatic and heteroaromatic), 0.98 Å (CH3) or 0.99 Å (CH2), and with U
iso(H) = kU
eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for other H atoms. The low-angle reflections (,2,1) for compound (III) and (2,1,2) for compound (VI), which had been attenuated by the beam stop, were omitted from the final refinements for these structures.Crystal structure: contains datablock(s) global, I, II, III, IV, V, VI. DOI: 10.1107/S2056989015015534/su5193sup1.cifStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015534/su5193Isup2.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015015534/su5193IIsup3.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989015015534/su5193IIIsup4.hklStructure factors: contains datablock(s) IV. DOI: 10.1107/S2056989015015534/su5193IVsup5.hklStructure factors: contains datablock(s) V. DOI: 10.1107/S2056989015015534/su5193Vsup6.hklStructure factors: contains datablock(s) VI. DOI: 10.1107/S2056989015015534/su5193VIsup7.hklClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193Isup8.cmlClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193IIsup9.cmlClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193IIIsup10.cmlClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193IVsup11.cmlClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193Vsup12.cmlClick here for additional data file.Supporting information file. DOI: 10.1107/S2056989015015534/su5193VIsup13.cmlCCDC references: 1419530, 1419529, 1419528, 1419527, 1419526, 1419525Additional supporting information: crystallographic information; 3D view; checkCIF report
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.
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.
Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041
H-atom parameters constrained
wR(F2) = 0.111
w = 1/[σ2(Fo2) + (0.0511P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06
(Δ/σ)max < 0.001
3933 reflections
Δρmax = 0.28 e Å−3
173 parameters
Δρmin = −0.39 e Å−3
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.
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.
Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042
H-atom parameters constrained
wR(F2) = 0.100
w = 1/[σ2(Fo2) + (0.0428P)2 + 0.3839P] where P = (Fo2 + 2Fc2)/3
S = 1.03
(Δ/σ)max < 0.001
3599 reflections
Δρmax = 1.43 e Å−3
154 parameters
Δρmin = −0.53 e Å−3
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.
Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034
H-atom parameters constrained
wR(F2) = 0.075
w = 1/[σ2(Fo2) + (0.0293P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02
(Δ/σ)max = 0.003
3722 reflections
Δρmax = 0.49 e Å−3
164 parameters
Δρmin = −0.46 e Å−3
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.
x
y
z
Uiso*/Ueq
C1
0.4180 (2)
0.29186 (18)
0.72203 (17)
0.0205 (4)
O1
0.41175 (17)
0.39954 (13)
0.71617 (13)
0.0310 (4)
C2
0.5005 (2)
0.22053 (19)
0.64696 (17)
0.0217 (4)
H2
0.5078
0.1382
0.6584
0.026*
C3
0.5653 (2)
0.26916 (19)
0.56325 (15)
0.0204 (4)
H3
0.5545
0.3516
0.5549
0.024*
S11
0.22557 (6)
0.31118 (4)
0.88317 (4)
0.02124 (12)
C12
0.3390 (2)
0.23001 (18)
0.80567 (16)
0.0180 (4)
C13
0.3392 (2)
0.11390 (18)
0.83642 (17)
0.0232 (4)
H13
0.3952
0.0553
0.8031
0.028*
C14
0.2474 (2)
0.09085 (19)
0.92288 (17)
0.0245 (5)
H14
0.2342
0.0155
0.9542
0.029*
C15
0.1805 (2)
0.18936 (17)
0.95556 (16)
0.0192 (4)
Br15
0.05413 (2)
0.20408 (2)
1.06918 (2)
0.02654 (8)
C31
0.6513 (2)
0.20960 (18)
0.48261 (16)
0.0178 (4)
C32
0.7142 (2)
0.27779 (18)
0.40207 (16)
0.0185 (4)
H32
0.6980
0.3601
0.3996
0.022*
C33
0.7994 (2)
0.22577 (18)
0.32643 (16)
0.0192 (4)
C34
0.8214 (2)
0.10536 (18)
0.32844 (17)
0.0242 (5)
H34
0.8796
0.0695
0.2761
0.029*
C35
0.7583 (2)
0.0380 (2)
0.40685 (17)
0.0279 (5)
H35
0.7730
−0.0445
0.4078
0.034*
C36
0.6737 (2)
0.08920 (18)
0.48427 (17)
0.0237 (5)
H36
0.6314
0.0420
0.5382
0.028*
O33
0.86717 (16)
0.28429 (13)
0.24569 (13)
0.0256 (3)
C37
0.8641 (3)
0.40869 (19)
0.24766 (19)
0.0309 (5)
H37A
0.9166
0.4394
0.1861
0.046*
H37B
0.9099
0.4368
0.3174
0.046*
H37C
0.7637
0.4358
0.2408
0.046*
U11
U22
U33
U12
U13
U23
C1
0.0191 (10)
0.0234 (11)
0.0194 (10)
0.0018 (8)
0.0043 (8)
−0.0007 (9)
O1
0.0368 (9)
0.0211 (8)
0.0371 (9)
0.0005 (7)
0.0201 (7)
0.0008 (7)
C2
0.0216 (10)
0.0232 (10)
0.0208 (10)
0.0029 (9)
0.0072 (8)
−0.0020 (9)
C3
0.0200 (10)
0.0211 (10)
0.0204 (10)
0.0034 (8)
0.0038 (8)
−0.0012 (9)
S11
0.0244 (3)
0.0195 (2)
0.0210 (3)
0.0029 (2)
0.0104 (2)
−0.0005 (2)
C12
0.0177 (10)
0.0208 (10)
0.0161 (9)
0.0013 (8)
0.0051 (7)
−0.0045 (8)
C13
0.0277 (11)
0.0197 (10)
0.0229 (11)
0.0033 (9)
0.0071 (8)
−0.0024 (9)
C14
0.0305 (12)
0.0203 (10)
0.0237 (11)
0.0000 (9)
0.0099 (9)
0.0023 (9)
C15
0.0179 (10)
0.0249 (11)
0.0152 (9)
−0.0025 (8)
0.0042 (7)
0.0017 (8)
Br15
0.02519 (12)
0.03558 (14)
0.01992 (12)
0.00135 (9)
0.01063 (8)
0.00304 (9)
C31
0.0153 (9)
0.0249 (10)
0.0133 (9)
−0.0004 (8)
0.0020 (7)
−0.0016 (8)
C32
0.0194 (10)
0.0184 (9)
0.0179 (9)
0.0011 (8)
0.0026 (7)
−0.0005 (8)
C33
0.0175 (10)
0.0233 (10)
0.0169 (9)
0.0017 (8)
0.0029 (7)
0.0029 (9)
C34
0.0296 (11)
0.0234 (10)
0.0206 (10)
0.0044 (9)
0.0100 (8)
−0.0038 (9)
C35
0.0384 (13)
0.0199 (10)
0.0265 (11)
0.0052 (9)
0.0103 (9)
0.0017 (9)
C36
0.0306 (11)
0.0214 (11)
0.0197 (10)
−0.0008 (9)
0.0079 (8)
0.0025 (9)
O33
0.0301 (8)
0.0232 (8)
0.0252 (8)
0.0013 (6)
0.0166 (6)
0.0030 (7)
C37
0.0375 (13)
0.0220 (11)
0.0346 (13)
−0.0010 (10)
0.0147 (10)
0.0066 (10)
C1—O1
1.230 (2)
C31—C36
1.388 (3)
C1—C12
1.467 (3)
C31—C32
1.402 (3)
C1—C2
1.469 (3)
C32—C33
1.380 (3)
C2—C3
1.331 (3)
C32—H32
0.9500
C2—H2
0.9500
C33—O33
1.368 (2)
C3—C31
1.465 (3)
C33—C34
1.387 (3)
C3—H3
0.9500
C34—C35
1.379 (3)
S11—C15
1.708 (2)
C34—H34
0.9500
S11—C12
1.7206 (19)
C35—C36
1.387 (3)
C12—C13
1.375 (3)
C35—H35
0.9500
C13—C14
1.414 (3)
C36—H36
0.9500
C13—H13
0.9500
O33—C37
1.418 (2)
C14—C15
1.353 (3)
C37—H37A
0.9800
C14—H14
0.9500
C37—H37B
0.9800
C15—Br15
1.8681 (18)
C37—H37C
0.9800
O1—C1—C12
119.71 (18)
C32—C31—C3
118.29 (19)
O1—C1—C2
122.72 (19)
C33—C32—C31
120.24 (19)
C12—C1—C2
117.57 (19)
C33—C32—H32
119.9
C3—C2—C1
121.2 (2)
C31—C32—H32
119.9
C3—C2—H2
119.4
O33—C33—C32
124.89 (19)
C1—C2—H2
119.4
O33—C33—C34
114.96 (17)
C2—C3—C31
127.2 (2)
C32—C33—C34
120.15 (18)
C2—C3—H3
116.4
C35—C34—C33
119.68 (18)
C31—C3—H3
116.4
C35—C34—H34
120.2
C15—S11—C12
91.15 (10)
C33—C34—H34
120.2
C13—C12—C1
131.11 (18)
C34—C35—C36
120.8 (2)
C13—C12—S11
111.13 (14)
C34—C35—H35
119.6
C1—C12—S11
117.76 (15)
C36—C35—H35
119.6
C12—C13—C14
112.87 (18)
C35—C36—C31
119.76 (19)
C12—C13—H13
123.6
C35—C36—H36
120.1
C14—C13—H13
123.6
C31—C36—H36
120.1
C15—C14—C13
111.69 (18)
C33—O33—C37
117.69 (16)
C15—C14—H14
124.2
O33—C37—H37A
109.5
C13—C14—H14
124.2
O33—C37—H37B
109.5
C14—C15—S11
113.17 (15)
H37A—C37—H37B
109.5
C14—C15—Br15
127.49 (15)
O33—C37—H37C
109.5
S11—C15—Br15
119.32 (11)
H37A—C37—H37C
109.5
C36—C31—C32
119.33 (18)
H37B—C37—H37C
109.5
C36—C31—C3
122.38 (18)
O1—C1—C2—C3
−4.7 (4)
C12—S11—C15—Br15
178.16 (13)
C12—C1—C2—C3
174.42 (19)
C2—C3—C31—C36
1.0 (3)
C1—C2—C3—C31
179.66 (19)
C2—C3—C31—C32
−178.2 (2)
O1—C1—C12—C13
−172.7 (2)
C36—C31—C32—C33
−1.0 (3)
C2—C1—C12—C13
8.2 (4)
C3—C31—C32—C33
178.14 (18)
O1—C1—C12—S11
6.5 (3)
C31—C32—C33—O33
−179.10 (19)
C2—C1—C12—S11
−172.61 (16)
C31—C32—C33—C34
1.1 (3)
C15—S11—C12—C13
0.11 (17)
O33—C33—C34—C35
179.8 (2)
C15—S11—C12—C1
−179.23 (17)
C32—C33—C34—C35
−0.4 (3)
C1—C12—C13—C14
179.2 (2)
C33—C34—C35—C36
−0.4 (4)
S11—C12—C13—C14
0.0 (2)
C34—C35—C36—C31
0.5 (4)
C12—C13—C14—C15
−0.2 (3)
C32—C31—C36—C35
0.2 (3)
C13—C14—C15—S11
0.3 (3)
C3—C31—C36—C35
−178.9 (2)
C13—C14—C15—Br15
−177.96 (15)
C32—C33—O33—C37
7.9 (3)
C12—S11—C15—C14
−0.22 (18)
C34—C33—O33—C37
−172.3 (2)
D—H···A
D—H
H···A
D···A
D—H···A
C13—H13···O1i
0.95
2.54
3.446 (3)
159
(I)
(II)
(III)
Crystal data
Chemical formula
C15H13ClOS
C15H13BrOS
C15H13ClO2S
Mr
276.76
321.21
292.76
Crystal system, space group
Triclinic, P
Triclinic, P
Monoclinic, P21/c
Temperature (K)
173
173
173
a, b, c (Å)
6.0154 (5), 8.6358 (5), 14.0548 (9)
5.9745 (6), 8.6636 (7), 14.3039 (12)
16.3577 (6), 7.4518 (4), 11.0892 (4)
α, β, γ (°)
74.428 (5), 88.225 (6), 70.417 (6)
74.731 (7), 88.146 (7), 70.334 (8)
90, 92.260 (3), 90
V (Å3)
661.23 (8)
671.29 (11)
1350.66 (10)
Z
2
2
4
Radiation type
Mo Kα
Mo Kα
Mo Kα
μ (mm−1)
0.43
3.20
0.43
Crystal size (mm)
0.58 × 0.32 × 0.29
0.45 × 0.22 × 0.16
0.50 × 0.28 × 0.17
Data collection
Diffractometer
Agilent Eos Gemini
Agilent Eos Gemini
Agilent Eos Gemini
Absorption correction
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Tmin, Tmax
0.750, 0.883
0.326, 0.599
0.789, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections
6596, 3861, 3262
6997, 3915, 3089
7925, 3933, 3102
Rint
0.028
0.042
0.038
(sin θ/λ)max (Å−1)
0.703
0.703
0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S
0.042, 0.119, 1.06
0.041, 0.090, 1.04
0.041, 0.111, 1.06
No. of reflections
3861
3915
3933
No. of parameters
165
165
173
H-atom treatment
H-atom parameters constrained
H-atom parameters constrained
H-atom parameters constrained
Δρmax, Δρmin (e Å−3)
0.57, −0.34
0.59, −0.63
0.28, −0.39
(IV)
(V)
(VI)
Crystal data
Chemical formula
C15H13BrO2S
C13H8BrClOS
C14H11BrO2S
Mr
337.21
327.60
323.19
Crystal system, space group
Monoclinic, P21/c
Triclinic, P
Monoclinic, P21/c
Temperature (K)
173
173
173
a, b, c (Å)
16.5498 (7), 7.5069 (4), 11.1574 (5)
6.0152 (8), 8.5691 (12), 13.1824 (9)
9.2726 (6), 11.3948 (8), 12.1472 (7)
α, β, γ (°)
90, 92.618 (4), 90
75.25 (1), 81.446 (8), 70.281 (12)
90, 93.273 (6), 90
V (Å3)
1384.72 (11)
617.09 (14)
1281.37 (14)
Z
4
2
4
Radiation type
Mo Kα
Mo Kα
Mo Kα
μ (mm−1)
3.11
3.69
3.36
Crystal size (mm)
0.58 × 0.32 × 0.29
0.41 × 0.20 × 0.18
0.54 × 0.42 × 0.31
Data collection
Diffractometer
Agilent Eos Gemini
Agilent Eos Gemini
Agilent Eos Gemini
Absorption correction
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Multi-scan (CrysAlis RED; Agilent, 2012 ▸)
Tmin, Tmax
0.261, 0.405
0.298, 0.514
0.216, 0.353
No. of measured, independent and observed [I > 2σ(I)] reflections
8866, 4040, 3189
6674, 3599, 2817
8260, 3722, 2914
Rint
0.037
0.026
0.035
(sin θ/λ)max (Å−1)
0.703
0.703
0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S
0.038, 0.078, 1.03
0.042, 0.100, 1.03
0.034, 0.075, 1.02
No. of reflections
4040
3599
3722
No. of parameters
174
154
164
H-atom treatment
H-atom parameters constrained
H-atom parameters constrained
H-atom parameters constrained
Δρmax, Δρmin (e Å−3)
0.54, −0.43
1.43, −0.53
0.49, −0.46
Computer programs: CrysAlis PRO and CrysAlis RED (Agilent, 2012 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and PLATON (Spek, 2008 ▸).
Authors: H D Kavitha; K R Roopashree; Suresh B Vepuri; H C Devarajegowda; Venkatesh B Devaru Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2013-05-11
Authors: K Sunitha; H C Devarajegowda; Waleed Fadl Ali Al-Eryani; Y Rajendra Prasad; A Uma Mahesh Kumar Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2011-12-10
Authors: Suresh B Vepuri; H C Devarajegowda; S Jeyaseelan; S Anbazhagan; Y Rajendra Prasad Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2012-11-28
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10