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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 176-179
doi:10.1107/S2056989015000195

Crystal structure of 3-benzoyl-2-[(5-bromo-2-hy­droxy-3-meth­­oxy­benzyl­­idene)amino]-4,5,6,7-tetra­hydro­benzo[b]thio­phene

Manpreet Kaur,a Jerry P. Jasinski,b* H. S. Yathirajan,a Christopher Glidewellc and K. Byrappad

aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, cSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland, and dMaterials Science Center, University of Mysore, Vijyana Bhavan Building, Manasagangotri, Mysore 570 006, India
*Correspondence e-mail: jjasinski@keene.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 31 December 2014; accepted 6 January 2015; online 17 January 2015)

In the cyclo­hexene ring of the title compound, C23H20BrNO3S, the –(CH2)4– atoms are positionally disordered [occupancy ratio = 0.753 (6):0.247 (6)]. The ring has a half-chair conformation for both the major and minor components. The dihedral angles between the mean plane of the thio­phene ring and those of the benzene and phenyl rings are 35.2 (4) and 57.7 (3)°, respectively. The planes of the two aryl rings are twisted with respect to each other by 86.4 (6)°. In the mol­ecule, there is an O—H⋯N hydrogen bond forming an S(6) ring motif. In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, forming chains parallel to [100].

CCDC reference: 1042320

1. Chemical context

2-Amino­thio­phene derivatives have been used in a number of applications in pesticides, dyes and pharmaceuticals. Reviews on the synthesis and properties of these compounds have been reported (Sabnis et al. 1999[Sabnis, R. W., Rangnekar, D. W. & Sonawane, N. D. (1999). J. Heterocycl. Chem. 36, 333-345.]; Puterová et al. 2010[Puterová, Z., Krutošiková, A. & Végh, D. (2010). Arkivoc, (i), 209-246.]). Schiff base compounds are an important class of compounds both synthetically and biologically. These compounds show bio­log­ical activities including anti­bacterial, anti­fungal, anti­cancer and herbicidal activities (Desai et al., 2001[Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Heterocycl. Commun. 7, 83-90.]; Karia & Parsania, 1999[Karia, F. D. & Parsania, P. H. (1999). Asian J. Chem. 11, 991-995.]; Samadhiya & Halve, 2001[Samadhiya, S. & Halve, A. (2001). Orient. J. Chem. 17 119-122.]; Singh & Dash, 1988[Singh, W. M. & Dash, B. C. (1988). Pesticides, 22, 33-37.]). Furthermore, Schiff bases are utilized as starting materials in the synthesis of compounds of industrial (Aydogan et al., 2001[Aydogan, F., Ocal, N., Turgut, Z. & Yolacan, C. (2001). Bull. Korean Chem. Soc. 22, 476-480.]) and biological inter­est, such as β-lactams (Taggi et al., 2002[Taggi, A. E., Hafez, A. M., Wack, H., Young, B., Ferraris, D. & Lectka, T. (2002). J. Am. Chem. Soc. 124, 6626-6635.]). The crystal and mol­ecular structures of two 2-amino­thio­phenes have been reported by our group (Kubicki et al., 2012[Kubicki, M., Dutkiewicz, G., Yathirajan, H. S., Dawar, P., Ramesha, A. R. & Dayananda, A. S. (2012). Crystals, 2, 1058-1066.]). In a continuation of our work on Schiff base derivatives of 2-amino­thio­phenes, we report herein on the synthesis and crystal structure of the title Schiff base compound.

[Scheme 1]

2. Structural commentary

In the title compound, Fig. 1[link], the cyclo­hexene ring is disordered with atoms C4/C44, C5/C45, C6/C46 and C7/C47 disordered about two positions with a refined occupancy ratio of 0.753 (6):0.247 (6). Both rings (C3A/C4–C7/C7A) and (C3A/C44–C47/C7A) adopt a half-chair conformation. The mean plane of the major component (C3A/C4–C7/C7A) is slightly twisted from the mean plane of the thio­phene ring (S1/C2/C3/C3A/C7A) by 5.18 (14)°. The dihedral angles between the mean plane of the thio­phene ring and the benzene (C21–C26) and phenyl (C31–C36) rings are 35.2 (4) and 57.7 (3)°, respectively. The two aryl rings are normal to each other, making a dihedral angle of 86.4 (6)°. In the mol­ecule there is an O—H⋯N hydrogen bond forming an S(6) ring motif (Table 1[link] and Fig. 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O22—H22⋯N2 0.84 2.00 2.731 (3) 145
C35—H35⋯O22i 0.95 2.54 3.212 (3) 128
Symmetry code: (i) x+1, y, z.
[Figure 1]
Figure 1
A view of the mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intra­molecular hydrogen bond is shown as a dashed line (see Table 1[link] for details).

3. Supra­molecular features

In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, observed between the benzene and phenyl rings of adjacent mol­ecules, forming chains parallel to the [100] direction (Fig. 2[link] and Table 1[link]).

[Figure 2]
Figure 2
A view along the b axis of the crystal packing of the title compound. Dashed lines indicate weak C—H⋯O hydrogen bonds (see Table 1[link] for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for the substructure 4,5,6,7-tetra­hydro­benzo[b]thio­phene gave over 110 hits. Limiting the search to phen­yl(4,5,6,7-tetra­hydro­benzo[b]thio­phen-3-yl)methanone derivatives gave eight hits, which include five structures closely related to the title compound. These include [2-[(2-hy­droxy­benzyl­idene)amino][4,5,6,7-tetra­hydro-1-benzothio­phene-3-yl](phen­yl)methanone (I)[link] [QOCGAS; Kaur et al., 2014a[Kaur, M., Jasinski, J. P., Kavitha, C. N., Yathirajan, H. S. & Byrappa, K. (2014a). Acta Cryst. E70, o476-o477.]], [2-[(4-nitro­benzyl­idene)amino]-4,5,6,7-tetra­hydro-1-benzo­thio­phene-3-yl](phen­yl)methanone (II) [SODGUP; Kaur et al., 2014b[Kaur, M., Jasinski, J. P., Kavitha, C. N., Yathirajan, H. S. & Byrappa, K. (2014b). Acta Cryst. E70, o738-o739.]], [2-(benzyl­idene­amino)-4,5,6,7-tetrahy­dro­benzo[b]thio­phen-3­yl](phen­yl)methanone (III) [YIYDAN; Kaur et al., 2014c[Kaur, M., Jasinski, J. P., Kavitha, C. N., Yathirajan, H. S. & Byrappa, K. (2014c). Acta Cryst. E70, o507-o508.]], [2-[(1H-indol-3-yl­methylidene)amino]-4,5,6,7-tetra­hydro­benzo[b]thio­phen-3-yl](phen­­yl)methanone (IV) [YIWJUL; Kaur et al., 2014d[Kaur, M., Jasinski, J. P., Yamuna, T. S., Yathirajan, H. S. & Byrappa, K. (2014d). Acta Cryst. E70, o501-o502.]] and [2-[2-bromo-5-meth­oxy­benzyl­idene)amino]-4,5,6,7-tetrahydro­benzo[b]thio­phene-3-yl](phen­yl)methanone (V) [CIZYIV; Kaur et al., 2014e[Kaur, M., Jasinski, J. P., Yamuna, T. S., Yathirajan, H. S. & Byrappa, K. (2014e). Acta Cryst. E70, o581-o582.]]. Two of the compounds, (II) and (IV), crystallize in the monoclinic space group P21, while the others, including the title compound, crystallize in centrosymmetric monoclinic space groups.

A comparison of the structural properties of the title compound to these five closely related mol­ecules reveals the following:

(a) The cyclo­hexene ring is disordered in compounds (II), (III), and (V), and has a slightly distorted half-chair conformation in (I)[link], (III), (IV), and (V), and a distorted chair conformation in (II);

(b) The dihedral angle between the mean planes of the thio­phene and phenyl rings is 70.4 (5)° in (I)[link], ca. 63.6° in (II), 65.7 (3)° in (III), 63.0 (4) and 58.8 (9)° for the two independent mol­ecules in (IV) and 66.1 (2)° in (V). The same dihedral angle in the title compound is 57.7 (3)°;

(c) The dihedral angle between the mean planes of the thio­phene and benzene rings is 12.1 (9)° in (I)[link], 30.9 (8)° in (II), 8.3 (4)° in (III), 8.3 (5) and 6.7 (5)° for the two independent mol­ecules in (IV) and 9.2 (2)° in (V). In the title compound this dihedral angle is 35.2 (4)°, similar to the situation in compound (III);

(d) In (I)[link], (II), (III) and (V) the benzil­idene and phenyl rings are inclined to one another by 81.0 (6), ca. 84.6, 73.8 (4) and 74.8 (8)°, respectively, compared to 86.4 (6)° in the title compound;

(e) There is an O—H⋯N intra­molecular hydrogen bond in (I)[link], as in the title compound;

(f) In the crystals of (I)[link] and (III), C—H⋯O hydrogen bonds link mol­ecules into chains along [100], as in the crystal of the title compound. In the crystal of (II), an array of C—H⋯O hydrogen bonds along [001] and [101] forms sheets parallel to (011). In the crystal of (IV), N—H⋯O hydrogen bonds link the mol­ecules, forming chains along [101]. There are also π–π stacking inter­actions present, involving the thio­phene and pyrrole rings of the two independent mol­ecules, with an inter-centroid distance of 3.468 (2) Å. In the crystal of (V), mol­ecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers.

5. Synthesis and crystallization

To a solution of (2-amino-4,5,6,7-tetra­hydro-benzo[b]thiophen-3-yl)-phenyl­methanone (200 mg, 0.79 mmol) in 10 ml of methanol an equimolar amount of 5-bromo-2-hy­droxy-3-meth­oxy­benzaldehyde (183 mg, 0.79 mmol) was added with constant stirring. The mixture was refluxed for 6 h. A yellowish brown precipitate was obtained. Completion of the reaction was confirmed by thin layer chromatography. The precipitate obtained was filtered and dried at room temperature overnight. The solid was then recrystallized using a 1:1 solution of aceto­nitrile and di­chloro­methane, giving colourless block-like crystals.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. It was apparent from an early stage in the refinement that the saturated portion of the tetra­hydro­benzo­thio­phene unit exhibited conformational disorder over two sets of atomic sites having unequal occupancies. For the minor conformer, involving atoms C44–C47 (cf. Fig. 1[link]), the bonded distances and the one-angle non-bonded distances were restrained to be the same as the corresponding distances in the major conformer, involving atoms C4–C7, subject to uncertainties of 0.005 and 0.01 Å, respectively. The atomic coordinates of atoms C4 and C44 were constrained to be identical, as were those of atoms C7 and C47. In addition, the anisotropic displacement parameters for pairs of partial-occupancy atoms occupying essentially the same physical space were constrained to be identical. The ratio of the occupancies of the disordered components refined to 0.753 (6):0.247 (6).

Table 2
Experimental details

Crystal data
Chemical formula C23H20BrNO3S
Mr 470.36
Crystal system, space group Monoclinic, P21/c
Temperature (K) 173
a, b, c (Å) 4.81267 (18), 22.1919 (8), 18.7012 (7)
β (°) 97.392 (3)
V (Å3) 1980.73 (13)
Z 4
Radiation type Cu Kα
μ (mm−1) 4.03
Crystal size (mm) 0.32 × 0.22 × 0.16
 
Data collection
Diffractometer Agilent Eos Gemini
Absorption correction Multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])
Tmin, Tmax 0.281, 0.525
No. of measured, independent and observed [I > 2σ(I)] reflections 7659, 3787, 3569
Rint 0.024
(sin θ/λ)max (Å−1) 0.614
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.108, 1.10
No. of reflections 3787
No. of parameters 271
No. of restraints 5
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.97, −0.47
Computer programs: CrysAlis PRO and CrysAlis RED (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

The H atoms in the disordered portion of the mol­ecule were included in the refinement in calculated positions, but all of the H atoms in the ordered portion of the mol­ecule were located in difference maps. All the H atoms were then treated as riding atoms in geometrically idealized positions: O—H = 0.84 Å, C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(O,C) for the hydroxyl and methyl H atoms, and = 1.2Ueq(C) for other H atoms. A single weak outlier reflection ([\overline{4}],13,14) was omitted from the refinement.

Supporting information

CCDC reference: 1042320

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015000195/su5055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015000195/su5055Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015000195/su5055Isup3.cml

checkCIF report


Chemical context top

2-Amino­thio­phene derivatives have been used in a number of applications in pesticides, dyes and pharmaceuticals. Reviews on the synthesis and properties of these compounds have been reported (Sabnis et al. 1999; Puterová et al. 2010). Schiff base compounds are an important class of compounds both synthetically and biologically. These compounds show biological activities including anti­bacterial, anti­fungal, anti­cancer and herbicidal activities (Desai et al., 2001; Karia & Parsania, 1999; Samadhiya & Halve, 2001; Singh & Dash, 1988). Furthermore, Schiff bases are utilized as starting materials in the synthesis of compounds of industrial (Aydogan et al., 2001) and biological inter­est, such as β-la­ctams (Taggi et al., 2002). The crystal and molecular structures of two 2-amino­thio­phenes have been reported by our group (Kubicki et al., 2012). In a continuation of our work on Schiff base derivatives of 2-amino­thio­phenes, we report herein on the synthesis and crystal structure of the title Schiff base compound.

Structural commentary top

In the title compound, Fig. 1, the cyclo­hexene ring is disordered with atoms C4/C44, C5/C45, C6/C46 and C7/C47 disordered about two positions with a refined occupancy ratio of 0.753 (6):0.247 (6). Both rings (C3A/C4–C7/C7A) and (C3A/C44–C47/C7A) adopt a half-chair conformation. The mean plane of the major component (C3A/C4–C7/C7A) is slightly twisted from the mean plane of the thio­phene ring (S1/C2/C3/C3A/C7A) by 5.18 (14)°. The dihedral angles between the mean plane of the thio­phene ring and the benzene (C21–C26) and phenyl (C31–C36) rings are 35.2 (4) and 57.7 (3)°, respectively. The two aryl rings are normal to each other, making a dihedral angle of 86.4 (6)°. In the molecule there is an O—H···N hydrogen bond forming an S(6) ring motif (Table 1 and Fig. 1).

Supra­molecular features top

In the crystal, molecules are linked via C—H···O hydrogen bonds, observed between the benzene and phenyl rings of adjacent molecules, forming chains parallel to the [100] direction (Fig. 2 and Table 1).

Database survey top

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014) for the substructure 4,5,6,7-tetra­hydro­benzo[b]thio­phene gave over 110 hits. Limiting the search to phenyl­(4,5,6,7-tetra­hydro­benzo[b]thio­phen-3-yl)methanone derivatives gave eight hits, which include five structures closely related to the title compound. These include [2-[(2-hy­droxy­benzyl­idene)amino][4,5,6,7-tetra­hydro-1-benzo­thio­phene-3-yl](phenyl)­methanone (I) [QOCGAS; Kaur et al., 2014a], [2-[(4-nitro­benzyl­idene)amino]-4,5,6,7-tetra­hydro-1-benzo­thio­phene-3-yl](phenyl)­methanone (II) [SODGUP; Kaur et al., 2014b], [2-(benzyl­idene­amino)-4,5,6,7-tetra­hydro­benzo[b]thio­phen-3yl](phenyl)­methanone (III) [YIYDAN; Kaur et al., 2014c], [2-[(1H-indol-3-yl­methyl­idene)amino]-4,5,6,7-tetra­hydro­benzo[b]thio­phen-3-yl](phenyl)­methanone (IV) [YIWJUL; Kaur et al., 2014d] and [2-[2-bromo-5-meth­oxy­benzyl­idene)amino]-4,5,6,7-tetra­hydro­benzo[b]thio­phene-3-yl](phenyl)­methanone (V) [CIZYIV; Kaur et al., 2014e]. Two of the compounds, (II) and (IV), crystallize in the monoclinic space group P21, while the others, including the title compound, crystallize in centrosymmetric monoclinic space groups.

A comparison of the structural properties of the title compound to these five closely related molecules reveals the following:

(a) The cyclo­hexene ring is disordered in compounds (II), (III), and (V), and has a slightly distorted half-chair conformation in (I), (III), (IV), and (V), and a distorted chair conformation in (II);

(b) The dihedral angle between the mean planes of the thio­phene and phenyl rings is 70.4 (5)° in (I), ca. 63.6° in (II), 65.7 (3)° in (III), 63.0 (4) and 58.8 (9)° for the two independent molecules in (IV) and 66.1 (2)° in (V). The same dihedral angle in the title compound is 57.7 (3)°;

(c) The dihedral angle between the mean planes of the thio­phene and benzene rings is 12.1 (9)° in (I), 30.9 (8)° in (II), 8.3 (4)° in (III), 8.3 (5) and 6.7 (5)° for the two independent molecules in (IV) and 9.2 (2)° in (V). In the title compound this dihedral angle is 35.2 (4)°, similar to the situation in compound (III);

(d) In (I), (II), (III) and (V) the benzil­idene and phenyl rings are inclined to one another by 81.0 (6), ca. 84.6, 73.8 (4) and 74.8 (8)°, respectively, compared to 86.4 (6)° in the title compound;

(e) There is an O—H···N intra­molecular hydrogen bond in (I), as in the title compound;

(f) In the crystals of (I) and (III), C—H···O hydrogen bonds link molecules into chains along [100], as in the crystal of the title compound. In the crystal of (II), an array of C—H···O hydrogen bonds along [001] and [101] forms sheets parallel to (011). In the crystal of (IV), N—H···O hydrogen bonds link the molecules, forming chains along [101]. There are also π–π stacking inter­actions present, involving the thio­phene and pyrrole rings of the two independent molecules, with an inter-centroid distance of 3.468 (2) Å. In the crystal of (V), molecules are linked by pairs of C—H···O hydrogen bonds, forming inversion dimers.

Synthesis and crystallization top

To a solution of (2-amino-4,5,6,7-tetra­hydro-benzo[b]thio­phen-3-yl)-phenyl­methanone (200 mg, 0.79 mmol) in 10 ml of methanol an equimolar amount of 5-bromo-2-hy­droxy-3-meth­oxy­benzaldehyde (183 mg, 0.79 mmol) was added with constant stirring. The mixture was refluxed for 6 h. A yellowish brown precipitate was obtained. Completion of the reaction was confirmed by thin layer chromatography. The precipitate obtained was filtered and dried at room temperature overnight. The solid was then recrystallized using a 1:1 solution of aceto­nitrile and di­chloro­methane, giving colourless block-like crystals.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. It was apparent from an early stage in the refinement that the saturated portion of the tetra­hydro­benzo­thio­phene unit exhibited conformational disorder over two sets of atomic sites having unequal occupancies. For the minor conformer, involving atoms C44–C47 (cf. Fig. 1), the bonded distances and the one-angle non-bonded distances were restrained to be the same as the corresponding distances in the major conformer, involving atoms C4–C7, subject to uncertainties of 0.005 and 0.01 Å, respectively. The atomic coordinates of atoms C4 and C44 were constrained to be identical, as were those of atoms C7 and C47. In addition, the anisotropic displacement parameters for pairs of partial-occupancy atoms occupying essentially the same physical space were constrained to be identical. The ratio of the occupancies of the disordered components refined to 0.753 (6):0.247 (6).

The H atoms in the disordered portion of the molecule were included in the refinement in calculated positions, but all of the H atoms in the ordered portion of the molecule were located in difference maps. All the H atoms were then treated as riding atoms in geometrically idealized positions: O—H = 0.84 Å, C—H = 0.95–0.99 Å with Uiso(H) = 1.5Ueq(O,C) for the hydroxyl and methyl H atoms, and = 1.2Ueq(C) for other H atoms. A single weak outlier reflection (4,13,14) was omitted from the refinement.

Related literature top

For related literature, see: Aydogan et al. (2001); Desai et al. (2001); Groom & Allen (2014); Karia & Parsania (1999); Kaur et al. (2014a, 2014b, 2014c, 2014d, 2014e); Kubicki et al. (2012); Puterová et al. (2010); Sabnis et al. (1999); Samadhiya & Halve (2001); Singh & Dash (1988); Taggi et al. (2002).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009) and SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular hydrogen bond is shown as a dashed line (see Table 1 for details).
[Figure 2] Fig. 2. A view along the b axis of the crystal packing of the title compound. Dashed lines indicate weak C—H···O hydrogen bonds (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
3-Benzoyl-2-[(5-bromo-2-hydroxy-3-methoxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophene top
Crystal data top
C23H20BrNO3SF(000) = 960
Mr = 470.36Dx = 1.577 Mg m−3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
a = 4.81267 (18) ÅCell parameters from 3787 reflections
b = 22.1919 (8) Åθ = 4.0–71.1°
c = 18.7012 (7) ŵ = 4.03 mm−1
β = 97.392 (3)°T = 173 K
V = 1980.73 (13) Å3Block, colourless
Z = 40.32 × 0.22 × 0.16 mm
Data collection top
Agilent Eos Gemini
diffractometer		3787 independent reflections
Radiation source: Enhance (Cu) X-ray Source3569 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1Rint = 0.024
ω scansθmax = 71.1°, θmin = 4.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		h = −5→4
Tmin = 0.281, Tmax = 0.525k = −23→27
7659 measured reflectionsl = −19→22
Refinement top
Refinement on F25 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.108 w = 1/[σ2(Fo2) + (0.0688P)2 + 1.0707P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
3787 reflectionsΔρmax = 0.97 e Å−3
271 parametersΔρmin = −0.47 e Å−3
Crystal data top
C23H20BrNO3SV = 1980.73 (13) Å3
Mr = 470.36Z = 4
Monoclinic, P21/cCu Kα radiation
a = 4.81267 (18) ŵ = 4.03 mm−1
b = 22.1919 (8) ÅT = 173 K
c = 18.7012 (7) Å0.32 × 0.22 × 0.16 mm
β = 97.392 (3)°
Data collection top
Agilent Eos Gemini
diffractometer		3787 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		3569 reflections with I > 2σ(I)
Tmin = 0.281, Tmax = 0.525Rint = 0.024
7659 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0405 restraints
wR(F2) = 0.108H-atom parameters constrained
S = 1.10Δρmax = 0.97 e Å−3
3787 reflectionsΔρmin = −0.47 e Å−3
271 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*/UeqOcc. (<1)
S10.69785 (12)0.48921 (2)0.30795 (3)0.02408 (15)
C20.5317 (5)0.42375 (10)0.27216 (12)0.0209 (5)
C30.5569 (5)0.41833 (10)0.19965 (12)0.0217 (5)
C3A0.7019 (5)0.46860 (11)0.17283 (12)0.0230 (5)
C40.7525 (5)0.47825 (12)0.09563 (13)0.0292 (5)0.753 (6)
H4A0.57120.48600.06560.035*0.753 (6)
H4B0.83350.44110.07750.035*0.753 (6)
C50.9516 (10)0.53138 (18)0.0881 (2)0.0417 (11)0.753 (6)
H5A1.14740.51710.09870.050*0.753 (6)
H5B0.92360.54570.03750.050*0.753 (6)
C60.9090 (10)0.58370 (16)0.1374 (2)0.0405 (10)0.753 (6)
H6A0.71440.59880.12670.049*0.753 (6)
H6B1.03760.61690.12870.049*0.753 (6)
C70.9640 (6)0.56445 (12)0.21574 (15)0.0316 (5)0.753 (6)
H7A1.16600.55600.22920.038*0.753 (6)
H7B0.90930.59710.24720.038*0.753 (6)
C440.7525 (5)0.47825 (12)0.09563 (13)0.0292 (5)0.247 (6)
H44A0.58080.46810.06280.035*0.247 (6)
H44B0.90510.45140.08420.035*0.247 (6)
C450.833 (3)0.5441 (3)0.0844 (4)0.0417 (11)0.247 (6)
H45A0.89620.54850.03640.050*0.247 (6)
H45B0.66570.57000.08560.050*0.247 (6)
C461.063 (2)0.5648 (5)0.1419 (3)0.0405 (10)0.247 (6)
H46A1.12220.60600.13050.049*0.247 (6)
H46B1.22680.53780.14230.049*0.247 (6)
C470.9640 (6)0.56445 (12)0.21574 (15)0.0316 (5)0.247 (6)
H47A1.12810.56590.25350.038*0.247 (6)
H47B0.84800.60060.22110.038*0.247 (6)
C7A0.7954 (5)0.50878 (11)0.22528 (13)0.0248 (5)
N20.3809 (4)0.38630 (9)0.31246 (10)0.0214 (4)
C270.2835 (5)0.40820 (11)0.36777 (12)0.0228 (5)
H270.32260.44920.37980.027*
C210.1168 (5)0.37392 (10)0.41313 (12)0.0213 (4)
C220.0790 (4)0.31190 (10)0.40655 (11)0.0199 (4)
C23−0.0965 (5)0.28198 (10)0.45045 (12)0.0214 (4)
C24−0.2273 (5)0.31462 (10)0.49988 (12)0.0216 (4)
H24−0.34710.29500.52910.026*
C25−0.1808 (5)0.37664 (10)0.50617 (12)0.0221 (4)
Br25−0.34996 (6)0.42100 (2)0.57603 (2)0.03072 (12)
C26−0.0130 (5)0.40670 (11)0.46400 (12)0.0242 (5)
H260.01500.44890.46910.029*
O220.2048 (4)0.27806 (7)0.35966 (9)0.0251 (3)
H220.29570.30060.33500.038*
O23−0.1211 (4)0.22165 (8)0.44037 (10)0.0286 (4)
C28−0.3190 (5)0.19060 (11)0.47808 (14)0.0298 (5)
H28A−0.50670.20720.46380.045*
H28B−0.26740.19580.53010.045*
H28C−0.31830.14760.46610.045*
C370.4280 (5)0.36935 (11)0.15198 (12)0.0241 (5)
O370.3043 (4)0.38180 (9)0.09281 (10)0.0383 (5)
C310.4593 (5)0.30534 (11)0.17603 (12)0.0225 (4)
C320.2770 (5)0.26251 (12)0.14146 (14)0.0314 (5)
H320.13650.27460.10380.038*
C330.2995 (6)0.20244 (13)0.16173 (17)0.0377 (6)
H330.17370.17350.13840.045*
C340.5061 (6)0.18479 (12)0.21618 (16)0.0344 (6)
H340.52050.14370.23020.041*
C350.6910 (5)0.22637 (12)0.25018 (14)0.0305 (5)
H350.83320.21380.28720.037*
C360.6684 (5)0.28688 (11)0.23010 (13)0.0255 (5)
H360.79600.31560.25330.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0302 (3)0.0230 (3)0.0203 (3)−0.0042 (2)0.0079 (2)−0.0015 (2)
C20.0232 (11)0.0205 (10)0.0191 (11)0.0011 (8)0.0037 (8)−0.0007 (8)
C30.0228 (11)0.0244 (11)0.0183 (11)0.0047 (8)0.0042 (8)0.0013 (8)
C3A0.0218 (11)0.0254 (11)0.0232 (11)0.0045 (9)0.0084 (8)0.0049 (9)
C40.0350 (13)0.0341 (13)0.0204 (11)0.0045 (10)0.0108 (9)0.0041 (10)
C50.055 (3)0.041 (2)0.0355 (17)−0.005 (2)0.030 (2)0.0059 (15)
C60.056 (3)0.0313 (19)0.0381 (19)−0.0044 (16)0.0191 (19)0.0105 (15)
C70.0347 (13)0.0265 (12)0.0356 (14)−0.0045 (10)0.0120 (11)0.0022 (11)
C440.0350 (13)0.0341 (13)0.0204 (11)0.0045 (10)0.0108 (9)0.0041 (10)
C450.055 (3)0.041 (2)0.0355 (17)−0.005 (2)0.030 (2)0.0059 (15)
C460.056 (3)0.0313 (19)0.0381 (19)−0.0044 (16)0.0191 (19)0.0105 (15)
C470.0347 (13)0.0265 (12)0.0356 (14)−0.0045 (10)0.0120 (11)0.0022 (11)
C7A0.0264 (11)0.0251 (11)0.0239 (11)0.0025 (9)0.0077 (9)0.0034 (9)
N20.0231 (9)0.0230 (9)0.0185 (8)−0.0013 (7)0.0039 (7)0.0005 (7)
C270.0257 (11)0.0213 (10)0.0222 (11)−0.0024 (9)0.0055 (9)−0.0023 (9)
C210.0220 (10)0.0249 (11)0.0170 (10)−0.0009 (9)0.0024 (8)0.0002 (8)
C220.0194 (10)0.0249 (11)0.0149 (9)0.0013 (8)0.0002 (7)−0.0013 (8)
C230.0239 (11)0.0201 (10)0.0195 (10)−0.0016 (8)0.0006 (8)0.0005 (8)
C240.0221 (10)0.0249 (11)0.0180 (10)−0.0033 (8)0.0036 (8)0.0015 (8)
C250.0250 (11)0.0253 (11)0.0168 (10)0.0004 (9)0.0052 (8)−0.0035 (8)
Br250.04036 (19)0.02851 (18)0.02633 (17)−0.00364 (10)0.01589 (12)−0.00703 (9)
C260.0286 (12)0.0232 (10)0.0212 (10)−0.0024 (9)0.0044 (9)−0.0023 (9)
O220.0293 (9)0.0237 (8)0.0240 (8)−0.0016 (6)0.0099 (6)−0.0028 (6)
O230.0361 (9)0.0206 (8)0.0314 (8)−0.0038 (7)0.0141 (7)−0.0009 (7)
C280.0344 (13)0.0248 (11)0.0315 (12)−0.0091 (10)0.0094 (10)0.0014 (10)
C370.0241 (11)0.0288 (12)0.0198 (10)0.0029 (9)0.0037 (8)−0.0023 (9)
O370.0496 (11)0.0379 (10)0.0241 (9)0.0043 (9)−0.0088 (8)0.0008 (8)
C310.0215 (10)0.0279 (12)0.0185 (10)0.0025 (9)0.0043 (8)−0.0048 (9)
C320.0270 (12)0.0334 (13)0.0316 (12)0.0023 (10)−0.0044 (10)−0.0071 (11)
C330.0310 (13)0.0318 (13)0.0484 (16)−0.0062 (11)−0.0025 (11)−0.0100 (12)
C340.0349 (13)0.0248 (12)0.0441 (15)0.0034 (10)0.0076 (11)−0.0022 (11)
C350.0314 (12)0.0302 (13)0.0289 (12)0.0060 (10)0.0003 (10)−0.0012 (10)
C360.0247 (11)0.0257 (11)0.0256 (11)0.0004 (9)0.0009 (9)−0.0043 (9)
Geometric parameters (Å, º) top
S1—C7A1.728 (2)C21—C261.406 (3)
S1—C21.749 (2)C22—O221.355 (3)
C2—C31.382 (3)C22—C231.417 (3)
C2—N21.388 (3)C23—O231.355 (3)
C3—C3A1.440 (3)C23—C241.387 (3)
C3—C371.490 (3)C24—C251.397 (3)
C3A—C7A1.359 (3)C24—H240.9500
C3A—C41.510 (3)C25—C261.372 (3)
C4—C51.537 (4)C25—Br251.901 (2)
C4—H4A0.9900C26—H260.9500
C4—H4B0.9900O22—H220.8400
C5—C61.514 (5)O23—C281.433 (3)
C5—H5A0.9900C28—H28A0.9800
C5—H5B0.9900C28—H28B0.9800
C6—C71.516 (4)C28—H28C0.9800
C6—H6A0.9900C37—O371.219 (3)
C6—H6B0.9900C37—C311.492 (3)
C7—C7A1.501 (3)C31—C361.394 (3)
C7—H7A0.9900C31—C321.395 (3)
C7—H7B0.9900C32—C331.386 (4)
C45—C461.512 (7)C32—H320.9500
C45—H45A0.9900C33—C341.385 (4)
C45—H45B0.9900C33—H330.9500
C46—H46A0.9900C34—C351.379 (4)
C46—H46B0.9900C34—H340.9500
N2—C271.285 (3)C35—C361.395 (4)
C27—C211.455 (3)C35—H350.9500
C27—H270.9500C36—H360.9500
C21—C221.392 (3)
C7A—S1—C291.71 (12)C22—C21—C26120.5 (2)
C3—C2—N2126.8 (2)C22—C21—C27122.8 (2)
C3—C2—S1110.73 (17)C26—C21—C27116.7 (2)
N2—C2—S1122.33 (17)O22—C22—C21122.8 (2)
C2—C3—C3A112.5 (2)O22—C22—C23117.7 (2)
C2—C3—C37124.6 (2)C21—C22—C23119.5 (2)
C3A—C3—C37122.7 (2)O23—C23—C24124.7 (2)
C7A—C3A—C3112.8 (2)O23—C23—C22115.5 (2)
C7A—C3A—C4121.2 (2)C24—C23—C22119.8 (2)
C3—C3A—C4126.0 (2)C23—C24—C25119.3 (2)
C3A—C4—C5112.1 (2)C23—C24—H24120.4
C3A—C4—H4A109.2C25—C24—H24120.4
C5—C4—H4A109.2C26—C25—C24122.0 (2)
C3A—C4—H4B109.2C26—C25—Br25118.62 (18)
C5—C4—H4B109.2C24—C25—Br25119.34 (17)
H4A—C4—H4B107.9C25—C26—C21118.9 (2)
C6—C5—C4113.4 (3)C25—C26—H26120.6
C6—C5—H5A108.9C21—C26—H26120.6
C4—C5—H5A108.9C22—O22—H22109.5
C6—C5—H5B108.9C23—O23—C28117.29 (19)
C4—C5—H5B108.9O23—C28—H28A109.5
H5A—C5—H5B107.7O23—C28—H28B109.5
C5—C6—C7110.6 (3)H28A—C28—H28B109.5
C5—C6—H6A109.5O23—C28—H28C109.5
C7—C6—H6A109.5H28A—C28—H28C109.5
C5—C6—H6B109.5H28B—C28—H28C109.5
C7—C6—H6B109.5O37—C37—C3119.7 (2)
H6A—C6—H6B108.1O37—C37—C31120.5 (2)
C7A—C7—C6108.5 (2)C3—C37—C31119.8 (2)
C7A—C7—H7A110.0C36—C31—C32119.2 (2)
C6—C7—H7A110.0C36—C31—C37122.3 (2)
C7A—C7—H7B110.0C32—C31—C37118.4 (2)
C6—C7—H7B110.0C33—C32—C31120.4 (2)
H7A—C7—H7B108.4C33—C32—H32119.8
C46—C45—H45A109.3C31—C32—H32119.8
C46—C45—H45B109.3C34—C33—C32119.8 (2)
H45A—C45—H45B108.0C34—C33—H33120.1
C45—C46—H46A109.4C32—C33—H33120.1
C45—C46—H46B109.4C35—C34—C33120.6 (3)
H46A—C46—H46B108.0C35—C34—H34119.7
C3A—C7A—C7126.0 (2)C33—C34—H34119.7
C3A—C7A—S1112.21 (18)C34—C35—C36119.8 (2)
C7—C7A—S1121.76 (19)C34—C35—H35120.1
C27—N2—C2118.8 (2)C36—C35—H35120.1
N2—C27—C21123.9 (2)C31—C36—C35120.2 (2)
N2—C27—H27118.1C31—C36—H36119.9
C21—C27—H27118.1C35—C36—H36119.9
C7A—S1—C2—C30.59 (18)C27—C21—C22—C23−177.2 (2)
C7A—S1—C2—N2−175.17 (19)O22—C22—C23—O23−0.3 (3)
N2—C2—C3—C3A173.3 (2)C21—C22—C23—O23180.0 (2)
S1—C2—C3—C3A−2.2 (2)O22—C22—C23—C24179.26 (19)
N2—C2—C3—C37−1.4 (4)C21—C22—C23—C24−0.5 (3)
S1—C2—C3—C37−176.97 (18)O23—C23—C24—C25178.7 (2)
C2—C3—C3A—C7A3.3 (3)C22—C23—C24—C25−0.8 (3)
C37—C3—C3A—C7A178.1 (2)C23—C24—C25—C261.2 (3)
C2—C3—C3A—C4−176.9 (2)C23—C24—C25—Br25−177.96 (16)
C37—C3—C3A—C4−2.0 (4)C24—C25—C26—C21−0.3 (3)
C7A—C3A—C4—C58.5 (4)Br25—C25—C26—C21178.87 (17)
C3—C3A—C4—C5−171.4 (3)C22—C21—C26—C25−1.0 (3)
C3A—C4—C5—C6−37.5 (4)C27—C21—C26—C25177.6 (2)
C4—C5—C6—C761.4 (5)C24—C23—O23—C286.8 (3)
C5—C6—C7—C7A−51.5 (4)C22—C23—O23—C28−173.6 (2)
C3—C3A—C7A—C7177.3 (2)C2—C3—C37—O37133.9 (3)
C4—C3A—C7A—C7−2.6 (4)C3A—C3—C37—O37−40.3 (3)
C3—C3A—C7A—S1−2.8 (3)C2—C3—C37—C31−48.1 (3)
C4—C3A—C7A—S1177.36 (18)C3A—C3—C37—C31137.7 (2)
C6—C7—C7A—C3A24.3 (4)O37—C37—C31—C36158.4 (2)
C6—C7—C7A—S1−155.6 (2)C3—C37—C31—C36−19.6 (3)
C2—S1—C7A—C3A1.30 (19)O37—C37—C31—C32−19.7 (4)
C2—S1—C7A—C7−178.8 (2)C3—C37—C31—C32162.3 (2)
C3—C2—N2—C27−152.3 (2)C36—C31—C32—C331.4 (4)
S1—C2—N2—C2722.7 (3)C37—C31—C32—C33179.6 (2)
C2—N2—C27—C21178.5 (2)C31—C32—C33—C34−0.6 (4)
N2—C27—C21—C229.0 (4)C32—C33—C34—C35−0.4 (5)
N2—C27—C21—C26−169.6 (2)C33—C34—C35—C360.6 (4)
C26—C21—C22—O22−178.3 (2)C32—C31—C36—C35−1.2 (4)
C27—C21—C22—O223.1 (3)C37—C31—C36—C35−179.3 (2)
C26—C21—C22—C231.4 (3)C34—C35—C36—C310.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O22—H22···N20.842.002.731 (3)145
C35—H35···O22i0.952.543.212 (3)128
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O22—H22···N20.842.002.731 (3)145
C35—H35···O22i0.952.543.212 (3)128
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC23H20BrNO3S
Mr470.36
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)4.81267 (18), 22.1919 (8), 18.7012 (7)
β (°) 97.392 (3)
V (Å3)1980.73 (13)
Z4
Radiation typeCu Kα
µ (mm−1)4.03
Crystal size (mm)0.32 × 0.22 × 0.16
Data collection
DiffractometerAgilent Eos Gemini
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.281, 0.525
No. of measured, independent and
observed [I > 2σ(I)] reflections		7659, 3787, 3569
Rint0.024
(sin θ/λ)max (Å−1)0.614
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.108, 1.10
No. of reflections3787
No. of parameters271
No. of restraints5
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.97, −0.47

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and SHELXL2014 (Sheldrick, 2015).

 

Acknowledgements

MK is grateful to CPEPA–UGC for the award of a Junior Research Fellowship and thanks the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 176-179
doi:10.1107/S2056989015000195
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