Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030278/ac6203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030278/ac6203Isup2.hkl |
CCDC reference: 287434
A solution of o-fluoroaniline (1.11 g, 0.01 mol) in acetone (50 ml) was added dropwise to an acetone solution (50 ml) containing an equimolar amount of 3-chloroacetylacetone and ammonium thiocyanate in a two-necked round-bottomed flask. The solution was refluxed for about 2 h. The light-yellow solution was filtered off and colourless crystals of (I) were obtained after evaporation for 5 d (yield 85%; m.p. 447.8–449.3 K).
All H atoms were located in a difference map. The H atom on N1 was refined isotropically. All other H atoms were fixed geometrically in ideal positions and allowed to ride on their parent C atoms, with C—H distances in the range 0.93–0.96 Å and with Uiso(H) = 1.5Ueq(methyl C), or 1.2Ueq(C) for CH groups.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker or Sheldrick version?); software used to prepare material for publication: SHELXTL (Bruker or Sheldrick version?), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C12H11FN2OS | F(000) = 520 |
Mr = 250.29 | Dx = 1.450 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2840 reflections |
a = 5.0205 (11) Å | θ = 1.9–26.5° |
b = 13.081 (3) Å | µ = 0.28 mm−1 |
c = 17.598 (4) Å | T = 273 K |
β = 97.085 (4)° | Block, colourless |
V = 1146.9 (4) Å3 | 0.43 × 0.28 × 0.17 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2115 independent reflections |
Radiation source: fine-focus sealed tube | 1931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 83.66 pixels mm-1 | θmax = 25.5°, θmin = 1.9° |
ω scans | h = −6→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −15→13 |
Tmin = 0.889, Tmax = 0.954 | l = −13→21 |
6015 measured reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.5434P] where P = (Fo2 + 2Fc2)/3 |
2115 reflections | (Δ/σ)max < 0.001 |
160 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C12H11FN2OS | V = 1146.9 (4) Å3 |
Mr = 250.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.0205 (11) Å | µ = 0.28 mm−1 |
b = 13.081 (3) Å | T = 273 K |
c = 17.598 (4) Å | 0.43 × 0.28 × 0.17 mm |
β = 97.085 (4)° |
Bruker SMART APEX CCD area-detector diffractometer | 2115 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1931 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.954 | Rint = 0.018 |
6015 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | Δρmax = 0.23 e Å−3 |
2115 reflections | Δρmin = −0.19 e Å−3 |
160 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.12589 (13) | 0.32229 (5) | 0.26414 (4) | 0.0482 (2) | |
F1 | 0.7508 (4) | 0.08384 (12) | 0.41401 (12) | 0.0833 (7) | |
O1 | −0.1910 (4) | 0.58918 (14) | 0.20516 (12) | 0.0619 (6) | |
N1 | 0.5354 (4) | 0.26099 (17) | 0.36559 (13) | 0.0484 (6) | |
N2 | 0.4506 (4) | 0.43875 (16) | 0.34993 (13) | 0.0482 (5) | |
C1 | 0.8706 (5) | 0.16954 (19) | 0.44555 (16) | 0.0514 (7) | |
C2 | 1.0930 (6) | 0.1598 (2) | 0.49819 (18) | 0.0609 (8) | |
H2 | 1.1612 | 0.0955 | 0.5122 | 0.073* | |
C3 | 1.2139 (6) | 0.2462 (2) | 0.52995 (17) | 0.0617 (8) | |
H3 | 1.3641 | 0.2413 | 0.5664 | 0.074* | |
C4 | 1.1114 (7) | 0.3399 (2) | 0.50755 (19) | 0.0659 (9) | |
H4 | 1.1938 | 0.3986 | 0.5290 | 0.079* | |
C5 | 0.8872 (6) | 0.3490 (2) | 0.45356 (17) | 0.0592 (8) | |
H5 | 0.8214 | 0.4134 | 0.4390 | 0.071* | |
C6 | 0.7606 (5) | 0.26238 (19) | 0.42121 (14) | 0.0438 (6) | |
C7 | 0.3968 (5) | 0.34279 (18) | 0.33349 (15) | 0.0432 (6) | |
C8 | 0.2696 (5) | 0.50203 (18) | 0.30804 (15) | 0.0457 (6) | |
C9 | 0.0779 (5) | 0.45396 (18) | 0.25846 (15) | 0.0450 (6) | |
C10 | 0.3032 (6) | 0.6140 (2) | 0.32002 (19) | 0.0655 (8) | |
H10A | 0.2222 | 0.6341 | 0.3643 | 0.098* | |
H10B | 0.2182 | 0.6497 | 0.2759 | 0.098* | |
H10C | 0.4909 | 0.6305 | 0.3276 | 0.098* | |
C11 | −0.1413 (5) | 0.4983 (2) | 0.20652 (15) | 0.0463 (6) | |
C12 | −0.3048 (6) | 0.4262 (2) | 0.15331 (17) | 0.0595 (8) | |
H12A | −0.4243 | 0.3882 | 0.1813 | 0.089* | |
H12B | −0.1873 | 0.3797 | 0.1314 | 0.089* | |
H12C | −0.4072 | 0.4643 | 0.1132 | 0.089* | |
H1 | 0.469 (6) | 0.201 (2) | 0.3525 (15) | 0.051 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0497 (4) | 0.0313 (4) | 0.0586 (4) | −0.0017 (2) | −0.0131 (3) | 0.0014 (3) |
F1 | 0.0770 (12) | 0.0352 (9) | 0.1239 (16) | −0.0048 (8) | −0.0427 (11) | 0.0047 (9) |
O1 | 0.0627 (12) | 0.0372 (11) | 0.0792 (14) | 0.0083 (9) | −0.0179 (10) | 0.0002 (9) |
N1 | 0.0513 (13) | 0.0307 (11) | 0.0578 (13) | −0.0010 (9) | −0.0142 (10) | 0.0026 (9) |
N2 | 0.0505 (12) | 0.0342 (11) | 0.0558 (13) | −0.0006 (9) | −0.0101 (10) | 0.0007 (9) |
C1 | 0.0504 (15) | 0.0355 (13) | 0.0642 (17) | −0.0039 (11) | −0.0087 (13) | 0.0027 (11) |
C2 | 0.0588 (17) | 0.0445 (16) | 0.0728 (19) | 0.0029 (12) | −0.0184 (14) | 0.0097 (13) |
C3 | 0.0600 (17) | 0.0560 (17) | 0.0623 (18) | 0.0022 (13) | −0.0191 (14) | 0.0013 (14) |
C4 | 0.0686 (19) | 0.0481 (17) | 0.0726 (19) | −0.0023 (14) | −0.0255 (15) | −0.0089 (14) |
C5 | 0.0678 (18) | 0.0369 (14) | 0.0657 (18) | 0.0032 (12) | −0.0204 (14) | −0.0010 (12) |
C6 | 0.0453 (14) | 0.0383 (13) | 0.0458 (14) | −0.0003 (10) | −0.0023 (11) | 0.0028 (10) |
C7 | 0.0451 (13) | 0.0344 (12) | 0.0477 (14) | −0.0011 (10) | −0.0040 (11) | 0.0029 (10) |
C8 | 0.0474 (14) | 0.0333 (13) | 0.0538 (15) | 0.0006 (10) | −0.0049 (11) | −0.0002 (10) |
C9 | 0.0448 (13) | 0.0337 (13) | 0.0541 (15) | 0.0007 (10) | −0.0036 (11) | 0.0014 (10) |
C10 | 0.0717 (19) | 0.0354 (14) | 0.081 (2) | 0.0028 (13) | −0.0234 (16) | −0.0052 (13) |
C11 | 0.0439 (14) | 0.0392 (14) | 0.0538 (15) | 0.0021 (10) | −0.0027 (11) | 0.0024 (11) |
C12 | 0.0564 (16) | 0.0480 (15) | 0.0678 (18) | 0.0040 (13) | −0.0169 (14) | −0.0043 (13) |
S1—C7 | 1.733 (3) | C4—C5 | 1.385 (4) |
S1—C9 | 1.740 (2) | C4—H4 | 0.9300 |
F1—C1 | 1.358 (3) | C5—C6 | 1.386 (4) |
O1—C11 | 1.214 (3) | C5—H5 | 0.9300 |
N1—C7 | 1.360 (3) | C8—C9 | 1.370 (4) |
N1—C6 | 1.401 (3) | C8—C10 | 1.486 (4) |
N1—H1 | 0.87 (3) | C9—C11 | 1.461 (3) |
N2—C7 | 1.309 (3) | C10—H10A | 0.9600 |
N2—C8 | 1.375 (3) | C10—H10B | 0.9600 |
C1—C2 | 1.366 (4) | C10—H10C | 0.9600 |
C1—C6 | 1.380 (3) | C11—C12 | 1.501 (4) |
C2—C3 | 1.369 (4) | C12—H12A | 0.9600 |
C2—H2 | 0.9300 | C12—H12B | 0.9600 |
C3—C4 | 1.368 (4) | C12—H12C | 0.9600 |
C3—H3 | 0.9300 | ||
C7—S1—C9 | 88.76 (11) | N2—C7—S1 | 115.27 (18) |
C7—N1—C6 | 127.4 (2) | N1—C7—S1 | 119.17 (18) |
C7—N1—H1 | 116.2 (18) | C9—C8—N2 | 115.6 (2) |
C6—N1—H1 | 116.3 (18) | C9—C8—C10 | 127.0 (2) |
C7—N2—C8 | 110.8 (2) | N2—C8—C10 | 117.5 (2) |
F1—C1—C2 | 119.0 (2) | C8—C9—C11 | 129.2 (2) |
F1—C1—C6 | 117.3 (2) | C8—C9—S1 | 109.66 (18) |
C2—C1—C6 | 123.7 (2) | C11—C9—S1 | 121.15 (19) |
C1—C2—C3 | 118.9 (3) | C8—C10—H10A | 109.5 |
C1—C2—H2 | 120.5 | C8—C10—H10B | 109.5 |
C3—C2—H2 | 120.5 | H10A—C10—H10B | 109.5 |
C4—C3—C2 | 119.3 (3) | C8—C10—H10C | 109.5 |
C4—C3—H3 | 120.3 | H10A—C10—H10C | 109.5 |
C2—C3—H3 | 120.3 | H10B—C10—H10C | 109.5 |
C3—C4—C5 | 121.3 (3) | O1—C11—C9 | 122.6 (2) |
C3—C4—H4 | 119.4 | O1—C11—C12 | 120.6 (2) |
C5—C4—H4 | 119.4 | C9—C11—C12 | 116.9 (2) |
C4—C5—C6 | 120.3 (3) | C11—C12—H12A | 109.5 |
C4—C5—H5 | 119.9 | C11—C12—H12B | 109.5 |
C6—C5—H5 | 119.9 | H12A—C12—H12B | 109.5 |
C1—C6—C5 | 116.5 (2) | C11—C12—H12C | 109.5 |
C1—C6—N1 | 117.6 (2) | H12A—C12—H12C | 109.5 |
C5—C6—N1 | 126.0 (2) | H12B—C12—H12C | 109.5 |
N2—C7—N1 | 125.6 (2) | ||
F1—C1—C2—C3 | 180.0 (3) | C6—N1—C7—S1 | 179.0 (2) |
C6—C1—C2—C3 | 0.9 (5) | C9—S1—C7—N2 | −1.2 (2) |
C1—C2—C3—C4 | −0.8 (5) | C9—S1—C7—N1 | 179.2 (2) |
C2—C3—C4—C5 | 0.2 (5) | C7—N2—C8—C9 | −0.8 (3) |
C3—C4—C5—C6 | 0.3 (5) | C7—N2—C8—C10 | −179.9 (3) |
F1—C1—C6—C5 | −179.4 (3) | N2—C8—C9—C11 | 179.8 (3) |
C2—C1—C6—C5 | −0.4 (5) | C10—C8—C9—C11 | −1.1 (5) |
F1—C1—C6—N1 | −0.4 (4) | N2—C8—C9—S1 | −0.1 (3) |
C2—C1—C6—N1 | 178.6 (3) | C10—C8—C9—S1 | 178.9 (3) |
C4—C5—C6—C1 | −0.2 (5) | C7—S1—C9—C8 | 0.7 (2) |
C4—C5—C6—N1 | −179.2 (3) | C7—S1—C9—C11 | −179.2 (2) |
C7—N1—C6—C1 | −179.7 (3) | C8—C9—C11—O1 | −5.2 (5) |
C7—N1—C6—C5 | −0.8 (5) | S1—C9—C11—O1 | 174.8 (2) |
C8—N2—C7—N1 | −179.1 (3) | C8—C9—C11—C12 | 174.3 (3) |
C8—N2—C7—S1 | 1.4 (3) | S1—C9—C11—C12 | −5.8 (3) |
C6—N1—C7—N2 | −0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1 | 0.87 (3) | 2.27 (3) | 2.653 (3) | 107 (2) |
C5—H5···N2 | 0.93 | 2.30 | 2.919 (4) | 123 |
C10—H10B···O1 | 0.96 | 2.40 | 3.018 (4) | 122 |
N1—H1···O1i | 0.87 (3) | 2.18 (3) | 3.010 (3) | 158 (3) |
C12—H12C···F1ii | 0.96 | 2.33 | 3.165 (3) | 144 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H11FN2OS |
Mr | 250.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 5.0205 (11), 13.081 (3), 17.598 (4) |
β (°) | 97.085 (4) |
V (Å3) | 1146.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.43 × 0.28 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.889, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6015, 2115, 1931 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.133, 1.19 |
No. of reflections | 2115 |
No. of parameters | 160 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.19 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL (Sheldrick, 1997), SHELXTL (Bruker or Sheldrick version?), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
S1—C7 | 1.733 (3) | N1—C6 | 1.401 (3) |
S1—C9 | 1.740 (2) | N2—C7 | 1.309 (3) |
F1—C1 | 1.358 (3) | N2—C8 | 1.375 (3) |
O1—C11 | 1.214 (3) | C8—C9 | 1.370 (4) |
N1—C7 | 1.360 (3) | ||
C7—S1—C9 | 88.76 (11) | C7—N2—C8 | 110.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F1 | 0.87 (3) | 2.27 (3) | 2.653 (3) | 107 (2) |
C5—H5···N2 | 0.93 | 2.30 | 2.919 (4) | 123 |
C10—H10B···O1 | 0.96 | 2.40 | 3.018 (4) | 122 |
N1—H1···O1i | 0.87 (3) | 2.18 (3) | 3.010 (3) | 158 (3) |
C12—H12C···F1ii | 0.96 | 2.33 | 3.165 (3) | 144 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
The title compound, (I), is isostructural with 5-acetyl-4-methyl-2-(o-toluidinyl)-1,3-thiazole (Yamin et al., 2005), except that the F atom is bonded at the ortho position of the phenylamino fragment. The whole molecule is essentially planar, with a maximum deviation for atom C12 of 0.127 (3) Å from the least-squares plane; in the molecule of 5-acetyl-4-methyl-2-(o-toluidinyl)-1,3-thiazole, the benzene group is inclined to the thiazole ring by 73.44 (10)°. All bond lengths and angles are in normal ranges (Allen et al., 1987) and are comparable with those in the analogue.
There are weak intramolecular N1—H1···F1, C10—H10B···O1 and C5—H5···N2 hydrogen bonds (Table 2) in the molecule. In the crystal structure, the molecules are linked by intermolecular N1—H1···O1i and C12–H12C···F1ii hydrogen bonds (symmetry codes as in Table 2) to form one-dimensional zigzag polymeric chains parallel to the b axis (Fig. 2).