organic compounds
N-(1,3-thiazol-2-yl)benzamide
of 2-fluoro-aDepartamento de Química – Facultad de Ciencias Naturales y Exactas, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, bDepartamento de Química, Universidad de los Andes, Carrera 1 No 18A12, Bogotá, Colombia, cFacultad de Química Ambiental, Universidad Santo Tomás, Campus Universitario Floridablanca, Santander, Colombia, and dEscuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, Apartado 678, Bucaramanga, Colombia
*Correspondence e-mail: rodimo26@yahoo.es
In the title compound, C10H7FN2OS, the mean plane of the central amide fragment (r.m.s. deviation = 0.048 Å) makes dihedral angles of 35.28 (8) and 10.14 (12)° with those of the fluorobenzene and thiazole rings, respectively. The thiazole S and amide O atoms lie to the same side of the molecule. In the crystal, pairs of N—H⋯N hydrogen bonds connect the molecules into inversion dimers with R22(8) motifs, and weak C—H⋯O interactions connect the molecules into C(6) [001] chains. Together, the N—H⋯N and C—H⋯O hydrogen bonds generate (100) sheets.
Keywords: crystal structure; thiazole derivatives; cancer cell-growth inhibitors; carboxamides; 1,3-thiazole; benzamide; hydrogen bonding.
CCDC reference: 1430605
1. Related literature
For thiazole derivatives as inhibitors for cancer cell growth, see: Schade et al. (2008). For with synthetic and biological interest, see: Moreno-Fuquen et al. (2014a,b). For related structures, see: Zonouzi et al. (2009); Saeed et al. (2010).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 1430605
https://doi.org/10.1107/S2056989015019192/hb7520sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019192/hb7520Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015019192/hb7520Isup3.cml
2-Fluorobenzoyl chloride (143 µl, 1.2 mmol) was added dropwise to a solution of 2-aminothiazole (100 mg, 1.0 mmol) and triethylamine (278 µl, 2.0 mmol) in dichloromethane (3.0 mL). The mixture was stirred at room temperature for 4 h until the starting amine was not longer detected by
After solvent was removed under reduced pressure, the resulting solid was dissolved in H2O (3.0 ml) and extracted with EtOAc (2 × 3.0 ml). The combined organic layers were dried with MgSO4 anhydrous and the solvent was removed under reduced pressure to afford the pure amide product. Colourless plates of (I) were grown by slow evaporation, at room temperature and in air, from a solution in methanol [61% yield, m.p. 443 (1) K].All H-atoms were located in difference Fourier maps and were positioned geometrically [C—H = 0.93 Å for aromatic and N—H= 0.86 Å] and were refined using a riding-model approximation with Uiso(H) constrained to 1.2 times Ueq of the respective parent atom.
Continuing with our current studies on the synthesis of new N-heterocyclic carboxamide derivatives of synthetic and biological interest (Moreno-Fuquen et al., 2014a, Moreno-Fuquen et al., 2014b), the title compound 2-fluoro-N-(thiazol-2-yl)benzamide (I) was obtained by direct reaction of 2-fluorobenzoyl chloride and 2-aminothiazole in the presence of triethylamine as base under mild conditions. Structures of similar molecules were compared with (I), i.e. N-(1,3-thiazol-2-yl)benzamide (Zonouzi et al., 2009) and 2,4-dichloro-N-(1,3-thiazol-2-yl)benzamide (Saeed et al., 2010). The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8-N1-C7(-O1)-C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.048 Å) and it forms dihedral angles of 35.28 (8)° with the C1-C6 ring and 10.14 (12)° with the thiazole ring. The C=O bond is anti to the o-F1 substituent in the aromatic ring. The N-H and C=O bonds in the central amide group are also anti to each other. Comparing (I) with the two aforementioned similar structures, reveals that significant differences in bond lengths and bond angles are not observed. In the
dimer formation is observed. Molecules of (I) are linked by hydrogen bonding of moderate strength. The N-H group of the central amide moiety, in the molecule at (x,y,z) acts as hydrogen bond donor to N2 atom of the thiazole molecule at (-x,-y+1,-z+2), (see Table 1). In turn these dimers are connected by weak hydrogen bonds: The C-H group in the molecule at (x,y,z) acts as hydrogen bond donor to carbonyl O1 atom in the molecule at (x,-y+3/2,z+1/2), forming chains C(6) of molecules along [001], see Fig. 2.For thiazole derivatives as inhibitors for cancer cell growth, see: Schade et al. (2008). For
with synthetic and biological interest, see: Moreno-Fuquen et al. (2014a,b). For related structures, see: Zonouzi et al. (2009); Saeed et al. (2010).Data collection: CrystalClear (Rigaku, 2008); cell
CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).C10H7FN2OS | Dx = 1.534 Mg m−3 |
Mr = 222.24 | Melting point: 443(1) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2171 (8) Å | Cell parameters from 8732 reflections |
b = 5.0741 (3) Å | θ = 3.3–27.5° |
c = 15.7078 (10) Å | µ = 0.32 mm−1 |
β = 98.820 (6)° | T = 295 K |
V = 962.22 (11) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.17 × 0.08 mm |
F(000) = 456 |
Rigaku Pilatus 200K diffractometer | 2169 independent reflections |
Radiation source: Sealed tube_Mo | 1556 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.060 |
profile data from ω–scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan CrystalClear; Rigaku, 2008 | h = −15→15 |
Tmin = 0.701, Tmax = 1.000 | k = −6→6 |
8722 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0481P)2] where P = (Fo2 + 2Fc2)/3 |
2169 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C10H7FN2OS | V = 962.22 (11) Å3 |
Mr = 222.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.2171 (8) Å | µ = 0.32 mm−1 |
b = 5.0741 (3) Å | T = 295 K |
c = 15.7078 (10) Å | 0.40 × 0.17 × 0.08 mm |
β = 98.820 (6)° |
Rigaku Pilatus 200K diffractometer | 2169 independent reflections |
Absorption correction: multi-scan CrystalClear; Rigaku, 2008 | 1556 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 1.000 | Rint = 0.060 |
8722 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.22 e Å−3 |
2169 reflections | Δρmin = −0.30 e Å−3 |
136 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.18106 (4) | 0.17354 (10) | 0.85154 (3) | 0.04570 (16) | |
F1 | 0.21170 (8) | 0.5331 (2) | 1.16166 (6) | 0.0518 (3) | |
C1 | 0.30360 (13) | 0.7730 (4) | 1.06395 (10) | 0.0358 (4) | |
O1 | 0.31999 (9) | 0.5432 (3) | 0.93486 (8) | 0.0496 (3) | |
C8 | 0.11054 (13) | 0.3206 (3) | 0.92625 (10) | 0.0343 (4) | |
N1 | 0.15631 (11) | 0.5105 (3) | 0.98371 (9) | 0.0383 (3) | |
H1 | 0.1156 | 0.5758 | 1.0185 | 0.046* | |
C3 | 0.32638 (15) | 0.8821 (4) | 1.21586 (12) | 0.0479 (5) | |
H3 | 0.3093 | 0.8492 | 1.2706 | 0.057* | |
N2 | 0.01031 (11) | 0.2339 (3) | 0.92704 (9) | 0.0398 (3) | |
C2 | 0.28064 (13) | 0.7317 (4) | 1.14663 (11) | 0.0380 (4) | |
C5 | 0.42365 (16) | 1.1283 (4) | 1.12149 (14) | 0.0533 (5) | |
H5 | 0.4722 | 1.2635 | 1.1129 | 0.064* | |
C9 | −0.01271 (15) | 0.0323 (4) | 0.86792 (11) | 0.0432 (4) | |
H9 | −0.0799 | −0.0572 | 0.8604 | 0.052* | |
C7 | 0.26161 (13) | 0.6006 (4) | 0.98871 (10) | 0.0362 (4) | |
C10 | 0.06810 (15) | −0.0259 (4) | 0.82218 (11) | 0.0466 (5) | |
H10 | 0.0636 | −0.1565 | 0.7802 | 0.056* | |
C6 | 0.37735 (14) | 0.9737 (4) | 1.05305 (12) | 0.0442 (4) | |
H6 | 0.3959 | 1.0045 | 0.9987 | 0.053* | |
C4 | 0.39778 (16) | 1.0819 (4) | 1.20273 (14) | 0.0549 (5) | |
H4 | 0.4289 | 1.1864 | 1.2488 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0485 (3) | 0.0515 (3) | 0.0392 (3) | 0.0029 (2) | 0.01349 (19) | −0.0103 (2) |
F1 | 0.0561 (6) | 0.0604 (8) | 0.0405 (6) | −0.0113 (6) | 0.0126 (5) | 0.0059 (5) |
C1 | 0.0343 (8) | 0.0378 (9) | 0.0358 (9) | 0.0023 (8) | 0.0067 (6) | −0.0007 (7) |
O1 | 0.0485 (7) | 0.0616 (9) | 0.0425 (7) | −0.0039 (7) | 0.0198 (6) | −0.0084 (6) |
C8 | 0.0403 (9) | 0.0355 (9) | 0.0279 (8) | 0.0032 (7) | 0.0077 (6) | 0.0002 (7) |
N1 | 0.0380 (7) | 0.0433 (9) | 0.0351 (7) | −0.0017 (7) | 0.0109 (6) | −0.0090 (6) |
C3 | 0.0443 (9) | 0.0626 (13) | 0.0361 (9) | 0.0066 (9) | 0.0042 (7) | −0.0049 (9) |
N2 | 0.0415 (8) | 0.0404 (8) | 0.0385 (8) | −0.0017 (7) | 0.0097 (6) | −0.0049 (7) |
C2 | 0.0345 (8) | 0.0425 (10) | 0.0375 (9) | 0.0023 (8) | 0.0065 (6) | 0.0019 (8) |
C5 | 0.0442 (10) | 0.0454 (12) | 0.0687 (14) | −0.0062 (9) | 0.0037 (9) | −0.0016 (10) |
C9 | 0.0482 (10) | 0.0382 (10) | 0.0421 (10) | −0.0024 (9) | 0.0037 (8) | −0.0026 (8) |
C7 | 0.0392 (8) | 0.0370 (10) | 0.0335 (9) | 0.0012 (8) | 0.0088 (7) | 0.0014 (7) |
C10 | 0.0588 (11) | 0.0410 (11) | 0.0392 (10) | 0.0036 (9) | 0.0047 (8) | −0.0094 (8) |
C6 | 0.0401 (9) | 0.0467 (11) | 0.0470 (10) | −0.0022 (8) | 0.0105 (8) | 0.0036 (9) |
C4 | 0.0489 (10) | 0.0569 (13) | 0.0551 (12) | 0.0012 (10) | −0.0045 (9) | −0.0170 (11) |
S1—C10 | 1.716 (2) | C3—C2 | 1.375 (2) |
S1—C8 | 1.7280 (16) | C3—H3 | 0.9300 |
F1—C2 | 1.357 (2) | N2—C9 | 1.381 (2) |
C1—C2 | 1.386 (2) | C5—C6 | 1.380 (3) |
C1—C6 | 1.388 (2) | C5—C4 | 1.381 (3) |
C1—C7 | 1.496 (2) | C5—H5 | 0.9300 |
O1—C7 | 1.2223 (18) | C9—C10 | 1.340 (2) |
C8—N2 | 1.303 (2) | C9—H9 | 0.9300 |
C8—N1 | 1.379 (2) | C10—H10 | 0.9300 |
N1—C7 | 1.356 (2) | C6—H6 | 0.9300 |
N1—H1 | 0.8600 | C4—H4 | 0.9300 |
C3—C4 | 1.373 (3) | ||
C10—S1—C8 | 88.45 (8) | C6—C5—H5 | 120.1 |
C2—C1—C6 | 117.07 (16) | C4—C5—H5 | 120.1 |
C2—C1—C7 | 123.89 (16) | C10—C9—N2 | 115.65 (16) |
C6—C1—C7 | 118.82 (15) | C10—C9—H9 | 122.2 |
N2—C8—N1 | 121.13 (14) | N2—C9—H9 | 122.2 |
N2—C8—S1 | 115.33 (13) | O1—C7—N1 | 121.90 (16) |
N1—C8—S1 | 123.50 (12) | O1—C7—C1 | 121.34 (15) |
C7—N1—C8 | 124.02 (14) | N1—C7—C1 | 116.75 (14) |
C7—N1—H1 | 118.0 | C9—C10—S1 | 110.75 (14) |
C8—N1—H1 | 118.0 | C9—C10—H10 | 124.6 |
C4—C3—C2 | 118.77 (18) | S1—C10—H10 | 124.6 |
C4—C3—H3 | 120.6 | C5—C6—C1 | 121.16 (18) |
C2—C3—H3 | 120.6 | C5—C6—H6 | 119.4 |
C8—N2—C9 | 109.78 (14) | C1—C6—H6 | 119.4 |
F1—C2—C3 | 117.53 (15) | C3—C4—C5 | 120.35 (18) |
F1—C2—C1 | 119.71 (15) | C3—C4—H4 | 119.8 |
C3—C2—C1 | 122.75 (17) | C5—C4—H4 | 119.8 |
C6—C5—C4 | 119.88 (19) | ||
C10—S1—C8—N2 | −1.98 (14) | C8—N1—C7—O1 | 9.4 (3) |
C10—S1—C8—N1 | 175.93 (15) | C8—N1—C7—C1 | −170.15 (15) |
N2—C8—N1—C7 | 177.02 (16) | C2—C1—C7—O1 | −140.34 (18) |
S1—C8—N1—C7 | −0.8 (2) | C6—C1—C7—O1 | 34.1 (3) |
N1—C8—N2—C9 | −175.59 (15) | C2—C1—C7—N1 | 39.2 (2) |
S1—C8—N2—C9 | 2.38 (19) | C6—C1—C7—N1 | −146.37 (16) |
C4—C3—C2—F1 | 179.02 (16) | N2—C9—C10—S1 | 0.2 (2) |
C4—C3—C2—C1 | 0.0 (3) | C8—S1—C10—C9 | 0.94 (14) |
C6—C1—C2—F1 | −178.05 (14) | C4—C5—C6—C1 | 0.8 (3) |
C7—C1—C2—F1 | −3.6 (3) | C2—C1—C6—C5 | −1.3 (3) |
C6—C1—C2—C3 | 0.9 (3) | C7—C1—C6—C5 | −176.13 (16) |
C7—C1—C2—C3 | 175.41 (16) | C2—C3—C4—C5 | −0.6 (3) |
C8—N2—C9—C10 | −1.6 (2) | C6—C5—C4—C3 | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.86 | 2.11 | 2.944 (2) | 165 |
C3—H3···O1ii | 0.93 | 2.62 | 3.474 (2) | 153 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2i | 0.86 | 2.11 | 2.944 (2) | 165 |
C3—H3···O1ii | 0.93 | 2.62 | 3.474 (2) | 153 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+3/2, z+1/2. |
Acknowledgements
RMF is grateful to the Universidad del Valle, Colombia, for partial financial support. JAH also wants to thank Universidad Industrial de Santander (UIS) and Laboratorio de Rayos X, Guatiguara, for partial financial support.
References
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Continuing with our current studies on the synthesis of new N-heterocyclic carboxamide derivatives of synthetic and biological interest (Moreno-Fuquen et al., 2014a, Moreno-Fuquen et al., 2014b), the title compound 2-fluoro-N-(thiazol-2-yl)benzamide (I) was obtained by direct reaction of 2-fluorobenzoyl chloride and 2-aminothiazole in the presence of triethylamine as base under mild conditions. Structures of similar molecules were compared with (I), i.e. N-(1,3-thiazol-2-yl)benzamide (Zonouzi et al., 2009) and 2,4-dichloro-N-(1,3-thiazol-2-yl)benzamide (Saeed et al., 2010). The molecular structure of (I) is shown in Fig. 1. The central amide moiety, C8-N1-C7(-O1)-C1, is essentially planar (r.m.s. deviation for all non-H atoms = 0.048 Å) and it forms dihedral angles of 35.28 (8)° with the C1-C6 ring and 10.14 (12)° with the thiazole ring. The C=O bond is anti to the o-F1 substituent in the aromatic ring. The N-H and C=O bonds in the central amide group are also anti to each other. Comparing (I) with the two aforementioned similar structures, reveals that significant differences in bond lengths and bond angles are not observed. In the crystal structure, dimer formation is observed. Molecules of (I) are linked by hydrogen bonding of moderate strength. The N-H group of the central amide moiety, in the molecule at (x,y,z) acts as hydrogen bond donor to N2 atom of the thiazole molecule at (-x,-y+1,-z+2), (see Table 1). In turn these dimers are connected by weak hydrogen bonds: The C-H group in the molecule at (x,y,z) acts as hydrogen bond donor to carbonyl O1 atom in the molecule at (x,-y+3/2,z+1/2), forming chains C(6) of molecules along [001], see Fig. 2.