Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001815/bm1400sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001815/bm1400IVsup2.hkl |
CCDC reference: 145547
A mixture of 2-amino-4-(3,4-dimethylphenyl)thiazole (1.0 g, 0.005 mol) and n-(2-hydroxybenzylidene)anthranilic acid (1.2 g, 0.005 mol) in freshly distilled phosphorus oxychloride (40 ml) was refluxed for 8 hrs. The progress of the reaction was monitored by thin-layer chromatography. After completion of the reaction, the contents were cooled and poured into ice-water. The solid that separated was filtered, washed with water, dried and crystallized from a mixture of DMF-C2H5OH as pale yellow needles (1.7 g, 81% yield, m.p. 502 K). IR(KBr)νmax: 3320, 3030, 2960, 1735, 1698, 1615, 1576, 1419, 1402, 1382, 1297, 1263, 1142, 1089, 1060, 990, 890, 820, 760 cm-1. 1H NMR (250 MHz, DMSO-d6): δ 2.22 and 2.51 (2 s, 3H each, 2 x CH3), 6.59 (m, 1H, H-3''), 6.73–6.82 (m, 2H, H-8 and H-4''), 6.85–6.91 (m, 2H, H-5'' and H-2'''), 7.02–7.15 (m, 2H, H-6 and H-5'''), 7.32 (m, 1H, H-7), 7.54–7.69 (m, 4H, H-2, H-5', H-6'' and H-6'''), 7.86 (dd, 1H, J = 7.9 and 1.5 Hz, H-5), 10.2 (s, 1H, NH). 13C NMR (62.9 MHz, DMSO-d6): δ 19.0, 19.4, 65.0, 108.8, 112.7, 115.3, 115.5, 117.7, 118.4, 123.0, 125.1, 125.9, 126.7, 127.8, 129.2, 129.6, 131.6, 134.8, 135.8, 136.2, 146.4, 148.3, 154.6, 156.4, 161.4. EIMS m/z (% int): 427(M+, 38), 333 (16), 308 (12), 275 (13), 243 (18), 239 (85), 238 (38), 224 (30), 204 (26), 199 (20), 180 (18), 158 (100), 105 (14), 91 (30), 86 (34) and 69 (19).
H atoms bonded to N, O and methyl C atoms were located from ΔF syntheses, while others bound to C atoms were placed geometrically. For refinement those bonded to N and O atoms were refined freely, those in CH3 groups were treated as part of rigid rotating groups with Uiso(H) = 1.5Ueq(C) and other H atoms bound to C were constrained to ride on these carrier atoms with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Siemens, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
Fig. 1. View of the molecule showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. Hydrogen atoms are shown as spheres of arbitrary radii. |
C25H21N3O2S | Z = 2 |
Mr = 427.51 | F(000) = 448 |
Triclinic, P1 | Dx = 1.384 Mg m−3 |
a = 8.9439 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.5231 (12) Å | Cell parameters from 3730 reflections |
c = 12.0135 (12) Å | θ = 2.0–28.6° |
α = 63.663 (3)° | µ = 0.19 mm−1 |
β = 68.248 (3)° | T = 180 K |
γ = 75.966 (3)° | Block, yellow |
V = 1026.06 (18) Å3 | 0.42 × 0.32 × 0.10 mm |
Siemens SMART CCD area detector diffractometer with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986) | 4545 independent reflections |
Radiation source: normal-focus sealed tube | 3162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 8.192 pixels mm-1 | θmax = 28.6°, θmin = 2.0° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→9 |
Tmin = 0.926, Tmax = 0.982 | l = −15→14 |
6303 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0603P)2] where P = (Fo2 + 2Fc2)/3 |
4545 reflections | (Δ/σ)max < 0.001 |
294 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C25H21N3O2S | γ = 75.966 (3)° |
Mr = 427.51 | V = 1026.06 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9439 (9) Å | Mo Kα radiation |
b = 11.5231 (12) Å | µ = 0.19 mm−1 |
c = 12.0135 (12) Å | T = 180 K |
α = 63.663 (3)° | 0.42 × 0.32 × 0.10 mm |
β = 68.248 (3)° |
Siemens SMART CCD area detector diffractometer with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986) | 4545 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3162 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.982 | Rint = 0.020 |
6303 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.31 e Å−3 |
4545 reflections | Δρmin = −0.32 e Å−3 |
294 parameters |
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. |
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. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). Data were collected over a hemisphere of reciprocal space, by a combination of three sets of exposures. Each set had a different ϕ angle for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal to detector distance was 5.01 cm. Crystal decay was monitored by repeating the initial frames at the end of the data collection and analyzing the duplicate reflections. |
x | y | z | Uiso*/Ueq | ||
S1' | 0.90489 (5) | 0.27276 (5) | 0.36923 (5) | 0.03164 (15) | |
O1 | 0.80359 (14) | 0.12134 (13) | 0.61581 (13) | 0.0340 (3) | |
O2 | 1.51436 (16) | 0.08272 (14) | 0.60838 (15) | 0.0385 (4) | |
H2"B | 1.599 (3) | 0.091 (3) | 0.617 (3) | 0.083 (9)* | |
N1 | 1.23189 (19) | −0.04198 (16) | 0.67536 (15) | 0.0289 (4) | |
H1A | 1.318 (2) | −0.070 (2) | 0.6880 (19) | 0.037 (6)* | |
N3 | 1.07767 (16) | 0.10911 (14) | 0.53902 (13) | 0.0233 (3) | |
N3' | 1.21346 (17) | 0.21290 (14) | 0.31535 (14) | 0.0252 (3) | |
C2 | 1.23302 (19) | 0.08345 (17) | 0.56794 (17) | 0.0230 (4) | |
H2A | 1.3231 | 0.0781 | 0.4899 | 0.028* | |
C4 | 0.9345 (2) | 0.08049 (18) | 0.63918 (17) | 0.0261 (4) | |
C5 | 0.8102 (2) | −0.0259 (2) | 0.87810 (19) | 0.0377 (5) | |
H5A | 0.7080 | 0.0157 | 0.8672 | 0.045* | |
C6 | 0.8202 (3) | −0.1089 (2) | 0.9997 (2) | 0.0509 (6) | |
H6A | 0.7260 | −0.1239 | 1.0731 | 0.061* | |
C7 | 0.9694 (3) | −0.1708 (2) | 1.0144 (2) | 0.0531 (6) | |
H7A | 0.9763 | −0.2292 | 1.0986 | 0.064* | |
C8 | 1.1082 (3) | −0.1495 (2) | 0.90920 (19) | 0.0421 (5) | |
H8A | 1.2092 | −0.1932 | 0.9212 | 0.051* | |
C9 | 1.0994 (2) | −0.06334 (18) | 0.78526 (17) | 0.0290 (4) | |
C10 | 0.9486 (2) | −0.00147 (18) | 0.76949 (17) | 0.0279 (4) | |
C2' | 1.0785 (2) | 0.19046 (17) | 0.41052 (17) | 0.0239 (4) | |
C4' | 1.1834 (2) | 0.30132 (18) | 0.19996 (17) | 0.0269 (4) | |
C5' | 1.0252 (2) | 0.3441 (2) | 0.21214 (19) | 0.0323 (5) | |
H5'A | 0.978 (2) | 0.4014 (19) | 0.1419 (19) | 0.038 (6)* | |
C1" | 1.2582 (2) | 0.19321 (17) | 0.59576 (16) | 0.0225 (4) | |
C2" | 1.4054 (2) | 0.18783 (18) | 0.61535 (17) | 0.0269 (4) | |
C3" | 1.4348 (2) | 0.2834 (2) | 0.64244 (19) | 0.0343 (5) | |
H3"A | 1.5348 | 0.2787 | 0.6557 | 0.041* | |
C4" | 1.3191 (2) | 0.3854 (2) | 0.65021 (19) | 0.0377 (5) | |
H4"A | 1.3395 | 0.4508 | 0.6691 | 0.045* | |
C5" | 1.1733 (2) | 0.39299 (19) | 0.63066 (19) | 0.0340 (5) | |
H5"B | 1.0934 | 0.4632 | 0.6364 | 0.041* | |
C6" | 1.1452 (2) | 0.29743 (18) | 0.60272 (17) | 0.0279 (4) | |
H6"B | 1.0457 | 0.3036 | 0.5880 | 0.034* | |
C1"' | 1.3194 (2) | 0.33737 (18) | 0.07721 (17) | 0.0281 (4) | |
C2"' | 1.3156 (2) | 0.46021 (19) | −0.02275 (18) | 0.0302 (4) | |
H2"A | 1.2259 | 0.5220 | −0.0102 | 0.036* | |
C3"' | 1.4398 (2) | 0.49490 (19) | −0.14068 (18) | 0.0302 (4) | |
C4"' | 1.5709 (2) | 0.4037 (2) | −0.15924 (18) | 0.0344 (5) | |
C5"' | 1.5742 (2) | 0.2811 (2) | −0.0599 (2) | 0.0373 (5) | |
H5"A | 1.6627 | 0.2185 | −0.0729 | 0.045* | |
C6"' | 1.4513 (2) | 0.2479 (2) | 0.05782 (19) | 0.0328 (4) | |
H6"A | 1.4574 | 0.1640 | 0.1250 | 0.039* | |
C7"' | 1.4332 (2) | 0.6297 (2) | −0.24574 (19) | 0.0391 (5) | |
H7"A | 1.4453 | 0.6232 | −0.3273 | 0.059* | |
H7"B | 1.5209 | 0.6757 | −0.2586 | 0.059* | |
H7"C | 1.3290 | 0.6776 | −0.2195 | 0.059* | |
C8"' | 1.7103 (3) | 0.4374 (3) | −0.2845 (2) | 0.0517 (6) | |
H8"A | 1.7885 | 0.3608 | −0.2813 | 0.078* | |
H8"B | 1.7631 | 0.5082 | −0.2948 | 0.078* | |
H8"C | 1.6693 | 0.4648 | −0.3585 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1' | 0.0226 (2) | 0.0352 (3) | 0.0351 (3) | −0.00144 (19) | −0.0138 (2) | −0.0086 (2) |
O1 | 0.0179 (6) | 0.0403 (8) | 0.0414 (8) | −0.0060 (6) | −0.0096 (6) | −0.0117 (7) |
O2 | 0.0196 (7) | 0.0435 (9) | 0.0628 (10) | 0.0015 (6) | −0.0179 (7) | −0.0276 (8) |
N1 | 0.0240 (8) | 0.0266 (9) | 0.0330 (9) | −0.0030 (7) | −0.0136 (7) | −0.0048 (7) |
N3 | 0.0184 (7) | 0.0261 (8) | 0.0260 (8) | −0.0044 (6) | −0.0092 (6) | −0.0075 (7) |
N3' | 0.0237 (8) | 0.0263 (9) | 0.0269 (8) | −0.0032 (6) | −0.0098 (6) | −0.0093 (7) |
C2 | 0.0155 (8) | 0.0281 (10) | 0.0239 (9) | −0.0028 (7) | −0.0070 (7) | −0.0079 (8) |
C4 | 0.0218 (9) | 0.0265 (10) | 0.0327 (10) | −0.0071 (7) | −0.0078 (8) | −0.0119 (8) |
C5 | 0.0313 (11) | 0.0460 (13) | 0.0359 (11) | −0.0136 (9) | −0.0014 (9) | −0.0181 (10) |
C6 | 0.0516 (15) | 0.0622 (17) | 0.0307 (11) | −0.0241 (12) | 0.0012 (10) | −0.0127 (11) |
C7 | 0.0679 (16) | 0.0592 (16) | 0.0279 (11) | −0.0244 (13) | −0.0143 (11) | −0.0041 (11) |
C8 | 0.0478 (13) | 0.0443 (13) | 0.0353 (11) | −0.0119 (10) | −0.0196 (10) | −0.0070 (10) |
C9 | 0.0333 (10) | 0.0265 (10) | 0.0290 (10) | −0.0107 (8) | −0.0104 (8) | −0.0076 (8) |
C10 | 0.0277 (10) | 0.0283 (10) | 0.0275 (9) | −0.0111 (8) | −0.0057 (8) | −0.0087 (8) |
C2' | 0.0240 (9) | 0.0213 (9) | 0.0300 (9) | −0.0036 (7) | −0.0126 (8) | −0.0089 (8) |
C4' | 0.0301 (10) | 0.0254 (10) | 0.0283 (9) | −0.0045 (8) | −0.0132 (8) | −0.0086 (8) |
C5' | 0.0315 (10) | 0.0315 (11) | 0.0315 (10) | −0.0041 (8) | −0.0170 (9) | −0.0036 (9) |
C1" | 0.0197 (8) | 0.0242 (10) | 0.0215 (8) | −0.0072 (7) | −0.0049 (7) | −0.0054 (7) |
C2" | 0.0193 (9) | 0.0311 (11) | 0.0291 (10) | −0.0036 (7) | −0.0069 (7) | −0.0105 (8) |
C3" | 0.0263 (10) | 0.0424 (13) | 0.0400 (11) | −0.0104 (9) | −0.0118 (9) | −0.0162 (10) |
C4" | 0.0395 (12) | 0.0395 (13) | 0.0428 (12) | −0.0124 (9) | −0.0109 (10) | −0.0204 (10) |
C5" | 0.0321 (10) | 0.0299 (11) | 0.0402 (11) | −0.0031 (8) | −0.0085 (9) | −0.0160 (9) |
C6" | 0.0203 (9) | 0.0316 (11) | 0.0300 (10) | −0.0050 (8) | −0.0070 (8) | −0.0096 (9) |
C1"' | 0.0289 (10) | 0.0322 (11) | 0.0260 (9) | −0.0074 (8) | −0.0115 (8) | −0.0091 (8) |
C2"' | 0.0298 (10) | 0.0310 (11) | 0.0321 (10) | −0.0032 (8) | −0.0144 (8) | −0.0102 (9) |
C3"' | 0.0315 (10) | 0.0361 (11) | 0.0288 (10) | −0.0108 (8) | −0.0147 (8) | −0.0094 (9) |
C4"' | 0.0291 (10) | 0.0482 (13) | 0.0302 (10) | −0.0107 (9) | −0.0092 (8) | −0.0153 (10) |
C5"' | 0.0289 (10) | 0.0457 (13) | 0.0405 (11) | 0.0006 (9) | −0.0123 (9) | −0.0202 (10) |
C6"' | 0.0341 (11) | 0.0322 (11) | 0.0331 (10) | −0.0030 (8) | −0.0145 (9) | −0.0100 (9) |
C7"' | 0.0414 (12) | 0.0401 (13) | 0.0326 (11) | −0.0155 (10) | −0.0133 (9) | −0.0040 (10) |
C8"' | 0.0391 (13) | 0.0687 (17) | 0.0426 (13) | −0.0117 (11) | −0.0017 (10) | −0.0230 (13) |
S1'—C5' | 1.716 (2) | C9—C10 | 1.403 (2) |
S1'—C2' | 1.7308 (17) | C4'—C5' | 1.355 (2) |
O1—C4 | 1.237 (2) | C4'—C1"' | 1.483 (2) |
O2—C2" | 1.371 (2) | C1"—C6" | 1.382 (2) |
N1—C9 | 1.379 (2) | C1"—C2" | 1.404 (2) |
N1—C2 | 1.448 (2) | C2"—C3" | 1.382 (3) |
N3—C4 | 1.381 (2) | C3"—C4" | 1.377 (3) |
N3—C2' | 1.405 (2) | C4"—C5" | 1.384 (3) |
N3—C2 | 1.485 (2) | C5"—C6" | 1.383 (3) |
N3'—C2' | 1.303 (2) | C1"'—C6"' | 1.389 (3) |
N3'—C4' | 1.387 (2) | C1"'—C2"' | 1.395 (2) |
C2—C1" | 1.527 (2) | C2"'—C3"' | 1.396 (3) |
C4—C10 | 1.461 (3) | C3"'—C4"' | 1.395 (3) |
C5—C6 | 1.368 (3) | C3"'—C7"' | 1.510 (3) |
C5—C10 | 1.400 (2) | C4"'—C5"' | 1.390 (3) |
C6—C7 | 1.386 (3) | C4"'—C8"' | 1.515 (3) |
C7—C8 | 1.381 (3) | C5"'—C6"' | 1.388 (3) |
C8—C9 | 1.395 (3) | ||
C5'—S1'—C2' | 87.98 (9) | C5'—C4'—C1"' | 126.13 (16) |
C9—N1—C2 | 117.71 (15) | N3'—C4'—C1"' | 119.55 (15) |
C4—N3—C2' | 121.23 (14) | C4'—C5'—S1' | 111.67 (14) |
C4—N3—C2 | 120.36 (14) | C6"—C1"—C2" | 118.03 (17) |
C2'—N3—C2 | 116.62 (13) | C6"—C1"—C2 | 124.06 (15) |
C2'—N3'—C4' | 110.18 (15) | C2"—C1"—C2 | 117.91 (15) |
N1—C2—N3 | 107.49 (13) | O2—C2"—C3" | 122.88 (16) |
N1—C2—C1" | 113.02 (14) | O2—C2"—C1" | 116.43 (17) |
N3—C2—C1" | 111.13 (14) | C3"—C2"—C1" | 120.68 (17) |
O1—C4—N3 | 120.11 (16) | C4"—C3"—C2" | 120.00 (17) |
O1—C4—C10 | 123.45 (16) | C3"—C4"—C5" | 120.33 (19) |
N3—C4—C10 | 116.41 (15) | C6"—C5"—C4" | 119.37 (18) |
C6—C5—C10 | 120.9 (2) | C1"—C6"—C5" | 121.58 (17) |
C5—C6—C7 | 119.2 (2) | C6"'—C1"'—C2"' | 118.53 (17) |
C8—C7—C6 | 121.4 (2) | C6"'—C1"'—C4' | 120.55 (16) |
C7—C8—C9 | 119.7 (2) | C2"'—C1"'—C4' | 120.89 (17) |
N1—C9—C8 | 122.68 (18) | C1"'—C2"'—C3"' | 121.90 (18) |
N1—C9—C10 | 118.06 (16) | C4"'—C3"'—C2"' | 118.97 (17) |
C8—C9—C10 | 119.14 (18) | C4"'—C3"'—C7"' | 120.61 (17) |
C5—C10—C9 | 119.62 (17) | C2"'—C3"'—C7"' | 120.42 (18) |
C5—C10—C4 | 120.20 (17) | C5"'—C4"'—C3"' | 119.12 (17) |
C9—C10—C4 | 120.03 (16) | C5"'—C4"'—C8"' | 119.86 (19) |
N3'—C2'—N3 | 121.08 (15) | C3"'—C4"'—C8"' | 121.01 (19) |
N3'—C2'—S1' | 115.87 (13) | C6"'—C5"'—C4"' | 121.61 (19) |
N3—C2'—S1' | 122.98 (13) | C5"'—C6"'—C1"' | 119.87 (18) |
C5'—C4'—N3' | 114.29 (16) | ||
C9—N1—C2—N3 | −51.2 (2) | C2'—N3'—C4'—C1"' | −177.56 (16) |
C9—N1—C2—C1" | 71.8 (2) | N3'—C4'—C5'—S1' | −1.2 (2) |
C4—N3—C2—N1 | 42.2 (2) | C1"'—C4'—C5'—S1' | 176.78 (15) |
C2'—N3—C2—N1 | −152.78 (15) | C2'—S1'—C5'—C4' | 1.12 (16) |
C4—N3—C2—C1" | −81.93 (19) | N1—C2—C1"—C6" | −116.39 (18) |
C2'—N3—C2—C1" | 83.06 (18) | N3—C2—C1"—C6" | 4.6 (2) |
C2'—N3—C4—O1 | 3.6 (3) | N1—C2—C1"—C2" | 63.7 (2) |
C2—N3—C4—O1 | 167.90 (16) | N3—C2—C1"—C2" | −175.37 (14) |
C2'—N3—C4—C10 | −177.93 (16) | C6"—C1"—C2"—O2 | 179.69 (16) |
C2—N3—C4—C10 | −13.6 (2) | C2—C1"—C2"—O2 | −0.4 (2) |
C10—C5—C6—C7 | −1.0 (4) | C6"—C1"—C2"—C3" | 0.8 (3) |
C5—C6—C7—C8 | 0.7 (4) | C2—C1"—C2"—C3" | −179.23 (16) |
C6—C7—C8—C9 | 0.4 (4) | O2—C2"—C3"—C4" | −178.91 (17) |
C2—N1—C9—C8 | −152.23 (18) | C1"—C2"—C3"—C4" | −0.1 (3) |
C2—N1—C9—C10 | 31.8 (2) | C2"—C3"—C4"—C5" | −0.2 (3) |
C7—C8—C9—N1 | −177.0 (2) | C3"—C4"—C5"—C6" | −0.3 (3) |
C7—C8—C9—C10 | −1.1 (3) | C2"—C1"—C6"—C5" | −1.3 (3) |
C6—C5—C10—C9 | 0.3 (3) | C2—C1"—C6"—C5" | 178.78 (17) |
C6—C5—C10—C4 | 175.9 (2) | C4"—C5"—C6"—C1" | 1.0 (3) |
N1—C9—C10—C5 | 176.88 (18) | C5'—C4'—C1"'—C6"' | −145.9 (2) |
C8—C9—C10—C5 | 0.7 (3) | N3'—C4'—C1"'—C6"' | 32.0 (3) |
N1—C9—C10—C4 | 1.3 (3) | C5'—C4'—C1"'—C2"' | 32.2 (3) |
C8—C9—C10—C4 | −174.83 (18) | N3'—C4'—C1"'—C2"' | −149.92 (17) |
O1—C4—C10—C5 | −7.2 (3) | C6"'—C1"'—C2"'—C3"' | 0.1 (3) |
N3—C4—C10—C5 | 174.40 (17) | C4'—C1"'—C2"'—C3"' | −177.95 (16) |
O1—C4—C10—C9 | 168.34 (18) | C1"'—C2"'—C3"'—C4"' | 0.4 (3) |
N3—C4—C10—C9 | −10.1 (3) | C1"'—C2"'—C3"'—C7"' | −178.81 (17) |
C4'—N3'—C2'—N3 | −176.67 (16) | C2"'—C3"'—C4"'—C5"' | 0.0 (3) |
C4'—N3'—C2'—S1' | 0.3 (2) | C7"'—C3"'—C4"'—C5"' | 179.19 (17) |
C4—N3—C2'—N3' | −177.08 (16) | C2"'—C3"'—C4"'—C8"' | −178.90 (18) |
C2—N3—C2'—N3' | 18.1 (2) | C7"'—C3"'—C4"'—C8"' | 0.3 (3) |
C4—N3—C2'—S1' | 6.1 (2) | C3"'—C4"'—C5"'—C6"' | −0.9 (3) |
C2—N3—C2'—S1' | −158.71 (13) | C8"'—C4"'—C5"'—C6"' | 178.01 (18) |
C5'—S1'—C2'—N3' | −0.85 (15) | C4"'—C5"'—C6"'—C1"' | 1.4 (3) |
C5'—S1'—C2'—N3 | 176.09 (16) | C2"'—C1"'—C6"'—C5"' | −1.0 (3) |
C2'—N3'—C4'—C5' | 0.6 (2) | C4'—C1"'—C6"'—C5"' | 177.07 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2"B···O1i | 0.84 (3) | 1.93 (3) | 2.7682 (18) | 173 (3) |
N1—H1A···O2 | 0.80 (2) | 2.42 (2) | 2.885 (2) | 118.4 (18) |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C25H21N3O2S |
Mr | 427.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 8.9439 (9), 11.5231 (12), 12.0135 (12) |
α, β, γ (°) | 63.663 (3), 68.248 (3), 75.966 (3) |
V (Å3) | 1026.06 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.42 × 0.32 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986) |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.926, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6303, 4545, 3162 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.116, 0.96 |
No. of reflections | 4545 |
No. of parameters | 294 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.32 |
Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1995), SAINT, SHELXTL/PC (Siemens, 1994), SHELXL97 (Sheldrick, 1997), SHELXTL/PC.
S1'—C5' | 1.716 (2) | S1'—C2' | 1.7308 (17) |
C5'—S1'—C2' | 87.98 (9) | ||
C2'—N3—C4—O1 | 3.6 (3) | N3—C2—C1"—C6" | 4.6 (2) |
C2—N3—C4—O1 | 167.90 (16) | C5'—C4'—C1"'—C2"' | 32.2 (3) |
C4—N3—C2'—S1' | 6.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2"B···O1i | 0.84 (3) | 1.93 (3) | 2.7682 (18) | 173 (3) |
N1—H1A···O2 | 0.80 (2) | 2.42 (2) | 2.885 (2) | 118.4 (18) |
Symmetry code: (i) x+1, y, z. |
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4-(1H)-Quinazolinones, commonly known as benzpyrimidinones, form an important class of heterocyclic compounds. Some of them either occur as quinazoline alkaloids (Mohrle & Gundlack, 1970; Baker & McEvoy, 1995) or their precursors (Brown, 1984). In addition, numerous synthetic quinazolinone derivatives are known which exhibit diverse antihistamic (Graham, 1960), diuretic (Cohen et al., 1960), hypnotic (Chappel & Seeman, 1963) and anti-inflammatory (Saravanan et al., 1998) biological activities.
In view of the multifaceted pharmacological behaviour of this class of heterocyclic compounds, an attempt was made to synthesize some new 2,3-disubstituted-benzpyrimidones, containing three different biodynamic moieties. For this purpose, synthesis of the title compound, (IV), was anticipated starting from the key intermediate (III) which in turn might be obtained by condensing 2-amino-4-(3,4-dimethylphenyl)thiazole, (I), with N-(2-hydrpoxybenzylidine)-anthranilic acid, (II), in the presence of phosphorus oxychloride. When this reaction was carried out, (IV) was obtained directly, rather than the expected amide (III). The direct formation of (IV) might be explained on the basis that the condensation and cyclization take place in a concerted manner with the final stage involving the facile nucleophilic attack of the amidic nitrogen on the benzylidene carbon. Crystals of (IV) were recrystallized from a mixture of DMF-C2H5OH and its structure was finally confirmed by single-crystal X-ray diffraction. \sch
The molecular structure of the title compound is illustrated in Fig. 1. The bond lengths and angles are largely unremarkable, although the C5'-S1'-C2' bond angle of 87.98 (9)° is perhaps slightly narrower than expected; a survey of the Cambridge Structural Database (Allen & Kennard, 1993) for 1,3-thiazol rings gave a mean (based upon 1906 observations) value of 90.79 (5)° for this angle. The thiazole ring is flat (r.m.s. deviation 0.005 Å) and is inclined at an angle of 32.7 (1)° to the plane of the attached phenyl group. The 1,3-diaza ring, containing an sp3 carbon atom (i.e. C2), is non-planar with Cremer-Pople puckering parameters (Cremer & Pople, 1975) of QT = 0.418 (2) Å, θ = 61.9 (3)° and ϕ = 44.9 (3)°; the only axial substituent attached to this ring is the hydroxyphenyl group which is inclined at an angle of 86.1 (1)° with respect to the best plane through the diaza ring (r.m.s. deviation 0.0171 Å).
The intramolecular O1···S1' contact of 2.6138 (14) Å is short in comparison to the sum of the van der Waals radii for O and S (3.32 Å): it arises from the planarity of the O1═C4—N3—C2'—S1' unit (see the appropriate torsion angles in Table 1), an arrangement which minimizes the O···S separation. This planarity is anticipated on the basis of resonance theory which predicts partial double bond character in the N3—C4 and N3–C2' bonds, resulting in restricted rotation about these linkages.
Infinite one-dimensional chains are formed via hydrogen bonding between hydroxyl groups (O2—H) and ketonic O atoms (O1) in the a direction; these O.·O distances of 2.7682 (18) Å are significantly shorter than the sum of the oxygen van der Waals radii (3.04 Å; Bondi, 1964). A weaker intra-molecular hydrogen-bonding interaction between the N1 hydrogen atom and the O2 atom is also present.