Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101004036/gd1131sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004036/gd1131IIIsup2.hkl |
CCDC reference: 166989
4-Chloro-2-(prop-2'-ynyloxy)aniline was arylated with 3-chloroiodobenzene under palladium-copper catalysis in triethylamine (Kundu et al., 2001). This was converted to the corresponding tosylate with tosyl chloride in presence of pyridine in dichloromethane. The tosylate was then cyclized with CuI in the presence of K2CO3 and tetrabutylammonium bromide in acetonitrile by refluxing at 353 K to yield the title compound, (III), m.p. 428 K. Single crystals suitable for X-ray analysis were obtained from CHCl3/petroleum ether (b.p. 333–353 K) (1:3) by slow crystallization.
H atoms were included in calculated positions with C—H 0.93 to 0.97 Å. The hydrogen atoms bonded to C22 (the p-methyl group) were disordered over two sets of sites, rotated with respect to one another by 60 °. They were modelled using the AFIX 123 command, and assigned occupancies of 0.5 each.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1995); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.
C22H17Cl2NO3S | Z = 2 |
Mr = 446.33 | F(000) = 460 |
Triclinic, P1 | Dx = 1.479 Mg m−3 |
a = 10.899 (5) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 12.211 (4) Å | Cell parameters from 20 reflections |
c = 7.775 (3) Å | θ = 6.8–8.2° |
α = 102.23 (2)° | µ = 0.45 mm−1 |
β = 92.21 (3)° | T = 296 K |
γ = 96.64 (3)° | Block, colourless |
V = 1002.4 (6) Å3 | 0.40 × 0.37 × 0.37 mm |
Rigaku AFC5R diffractometer | 3158 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.018 |
Graphite monochromator | θmax = 27.6°, θmin = 1.7° |
ω–2θ scans | h = 0→14 |
Absorption correction: ψ scans (north et al., 1968) ? | k = −15→15 |
Tmin = 0.800, Tmax = 0.846 | l = −10→10 |
4862 measured reflections | 3 standard reflections every 150 reflections |
4619 independent reflections | intensity decay: 0.3% |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.09 | Calculated w = 1/[σ2(Fo2) + (0.0422P)2 + 0.3626P] where P = (Fo2 + 2Fc2)/3 |
4619 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C22H17Cl2NO3S | γ = 96.64 (3)° |
Mr = 446.33 | V = 1002.4 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.899 (5) Å | Mo Kα radiation |
b = 12.211 (4) Å | µ = 0.45 mm−1 |
c = 7.775 (3) Å | T = 296 K |
α = 102.23 (2)° | 0.40 × 0.37 × 0.37 mm |
β = 92.21 (3)° |
Rigaku AFC5R diffractometer | 3158 reflections with I > 2σ(I) |
Absorption correction: ψ scans (north et al., 1968) ? | Rint = 0.018 |
Tmin = 0.800, Tmax = 0.846 | 3 standard reflections every 150 reflections |
4862 measured reflections | intensity decay: 0.3% |
4619 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.33 e Å−3 |
4619 reflections | Δρmin = −0.22 e Å−3 |
262 parameters |
Experimental. The scan width was (1.15 + 0.30tanθ)° with an ω scan speed of 10° per minute (up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
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. Table of Least-Squares Planes —————————— ————– Plane number 1 ————— Atoms Defining Plane Distance C(1) (1) -0.0174 C(2) (1) 0.0206 C(3) (1) -0.0061 C(4) (1) -0.0115 C(5) (1) 0.0142 C(6) (1) 0.0002 Mean deviation from plane is 0.0117 angstroms Chi-squared: 0.0 ————– Plane number 2 ————— Atoms Defining Plane Distance O(1) (1) -0.0016 N(1) (1) 0.0014 C(1) (1) -0.0031 C(6) (1) 0.0032 Additional Atoms Distance C(7) (1) -0.3713 C(8) (1) 0.3256 Mean deviation from plane is 0.0023 angstroms Chi-squared: 0.0 Dihedral angles between least-squares planes plane plane angle 2 1 2.22 |
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 | Occ. (<1) | |
Cl1 | 0.60753 (9) | 0.47686 (8) | 0.28836 (13) | 0.0776 (3) | |
Cl2 | 0.16901 (8) | 1.25696 (7) | −0.16951 (11) | 0.0661 (2) | |
S1 | 0.26517 (6) | 0.92383 (5) | 0.51062 (8) | 0.03593 (16) | |
O1 | 0.22911 (16) | 0.63114 (14) | 0.1063 (2) | 0.0470 (5) | |
O2 | 0.37269 (16) | 0.94479 (15) | 0.6270 (2) | 0.0478 (5) | |
O3 | 0.20554 (17) | 1.01453 (14) | 0.4742 (2) | 0.0478 (5) | |
N1 | 0.30633 (17) | 0.85392 (16) | 0.3145 (2) | 0.0338 (4) | |
C1 | 0.3788 (2) | 0.7624 (2) | 0.3124 (3) | 0.0346 (5) | |
C2 | 0.4938 (2) | 0.7797 (2) | 0.4019 (3) | 0.0416 (6) | |
H2 | 0.5246 | 0.8515 | 0.4662 | 0.050* | |
C3 | 0.5632 (3) | 0.6920 (2) | 0.3971 (4) | 0.0495 (7) | |
H3 | 0.6390 | 0.7035 | 0.4617 | 0.059* | |
C4 | 0.5198 (3) | 0.5879 (2) | 0.2963 (4) | 0.0484 (7) | |
C5 | 0.4092 (3) | 0.5688 (2) | 0.1995 (4) | 0.0468 (6) | |
H5 | 0.3824 | 0.4980 | 0.1285 | 0.056* | |
C6 | 0.3373 (2) | 0.6562 (2) | 0.2081 (3) | 0.0381 (6) | |
C7 | 0.1435 (2) | 0.7123 (2) | 0.1472 (3) | 0.0404 (6) | |
H7A | 0.1034 | 0.7033 | 0.2535 | 0.049* | |
H7B | 0.0801 | 0.6998 | 0.0516 | 0.049* | |
C8 | 0.2104 (2) | 0.8296 (2) | 0.1736 (3) | 0.0356 (5) | |
C9 | 0.1884 (2) | 0.8997 (2) | 0.0715 (3) | 0.0386 (6) | |
H9 | 0.1207 | 0.8739 | −0.0093 | 0.046* | |
C10 | 0.2513 (2) | 1.0107 (2) | 0.0623 (3) | 0.0372 (5) | |
C11 | 0.1902 (2) | 1.0758 (2) | −0.0310 (3) | 0.0403 (6) | |
H11 | 0.1099 | 1.0502 | −0.0793 | 0.048* | |
C12 | 0.2479 (2) | 1.1778 (2) | −0.0521 (3) | 0.0422 (6) | |
C13 | 0.3669 (3) | 1.2175 (2) | 0.0145 (4) | 0.0522 (7) | |
H13 | 0.4053 | 1.2863 | −0.0018 | 0.063* | |
C14 | 0.4282 (3) | 1.1528 (3) | 0.1060 (4) | 0.0563 (8) | |
H14 | 0.5091 | 1.1783 | 0.1517 | 0.068* | |
C15 | 0.3716 (2) | 1.0514 (2) | 0.1309 (4) | 0.0481 (7) | |
H15 | 0.4143 | 1.0094 | 0.1942 | 0.058* | |
C16 | 0.1555 (2) | 0.8288 (2) | 0.5823 (3) | 0.0358 (5) | |
C17 | 0.0320 (2) | 0.8437 (2) | 0.5768 (3) | 0.0453 (6) | |
H17 | 0.0071 | 0.9064 | 0.5418 | 0.054* | |
C18 | −0.0539 (3) | 0.7655 (3) | 0.6232 (4) | 0.0526 (7) | |
H18 | −0.1368 | 0.7768 | 0.6219 | 0.063* | |
C19 | −0.0195 (3) | 0.6704 (2) | 0.6717 (4) | 0.0522 (7) | |
C20 | 0.1046 (3) | 0.6577 (2) | 0.6780 (4) | 0.0517 (7) | |
H20 | 0.1293 | 0.5947 | 0.7125 | 0.062* | |
C21 | 0.1931 (2) | 0.7359 (2) | 0.6345 (3) | 0.0431 (6) | |
H21 | 0.2765 | 0.7263 | 0.6403 | 0.052* | |
C22 | −0.1147 (4) | 0.5833 (3) | 0.7161 (5) | 0.0831 (12) | |
H22A | −0.0744 | 0.5235 | 0.7466 | 0.125* | 0.50 |
H22B | −0.1721 | 0.5531 | 0.6160 | 0.125* | 0.50 |
H22C | −0.1583 | 0.6176 | 0.8141 | 0.125* | 0.50 |
H22D | −0.1955 | 0.6060 | 0.7046 | 0.125* | 0.50 |
H22E | −0.0977 | 0.5764 | 0.8351 | 0.125* | 0.50 |
H22F | −0.1116 | 0.5119 | 0.6370 | 0.125* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0802 (6) | 0.0717 (6) | 0.0954 (7) | 0.0454 (5) | 0.0147 (5) | 0.0299 (5) |
Cl2 | 0.0673 (5) | 0.0728 (5) | 0.0754 (5) | 0.0307 (4) | 0.0108 (4) | 0.0417 (4) |
S1 | 0.0397 (3) | 0.0328 (3) | 0.0349 (3) | 0.0061 (3) | 0.0009 (3) | 0.0058 (2) |
O1 | 0.0453 (11) | 0.0366 (10) | 0.0537 (11) | 0.0043 (8) | −0.0033 (9) | −0.0005 (8) |
O2 | 0.0449 (10) | 0.0533 (11) | 0.0392 (10) | 0.0009 (9) | −0.0043 (8) | 0.0006 (8) |
O3 | 0.0615 (12) | 0.0342 (10) | 0.0505 (11) | 0.0148 (9) | 0.0063 (9) | 0.0107 (8) |
N1 | 0.0347 (11) | 0.0344 (10) | 0.0321 (10) | 0.0043 (8) | −0.0003 (8) | 0.0077 (8) |
C1 | 0.0356 (13) | 0.0365 (13) | 0.0342 (13) | 0.0063 (10) | 0.0082 (10) | 0.0113 (10) |
C2 | 0.0358 (14) | 0.0444 (14) | 0.0444 (14) | 0.0051 (11) | 0.0026 (11) | 0.0092 (11) |
C3 | 0.0390 (14) | 0.0642 (19) | 0.0507 (16) | 0.0160 (13) | 0.0040 (12) | 0.0192 (14) |
C4 | 0.0517 (17) | 0.0487 (16) | 0.0538 (17) | 0.0222 (13) | 0.0170 (14) | 0.0203 (13) |
C5 | 0.0529 (17) | 0.0361 (14) | 0.0538 (16) | 0.0093 (12) | 0.0123 (14) | 0.0115 (12) |
C6 | 0.0358 (13) | 0.0389 (14) | 0.0399 (14) | 0.0029 (11) | 0.0073 (11) | 0.0093 (11) |
C7 | 0.0353 (13) | 0.0433 (14) | 0.0409 (14) | 0.0025 (11) | 0.0000 (11) | 0.0069 (11) |
C8 | 0.0337 (13) | 0.0378 (13) | 0.0339 (13) | 0.0062 (10) | 0.0005 (10) | 0.0041 (10) |
C9 | 0.0370 (13) | 0.0442 (14) | 0.0333 (13) | 0.0071 (11) | −0.0029 (10) | 0.0057 (11) |
C10 | 0.0402 (14) | 0.0404 (13) | 0.0320 (12) | 0.0081 (11) | 0.0001 (11) | 0.0087 (10) |
C11 | 0.0369 (14) | 0.0508 (16) | 0.0359 (13) | 0.0120 (12) | 0.0028 (11) | 0.0116 (11) |
C12 | 0.0494 (16) | 0.0447 (15) | 0.0378 (14) | 0.0181 (12) | 0.0062 (12) | 0.0140 (11) |
C13 | 0.0614 (19) | 0.0454 (16) | 0.0508 (17) | 0.0009 (14) | 0.0037 (14) | 0.0161 (13) |
C14 | 0.0495 (17) | 0.0598 (19) | 0.0596 (18) | −0.0067 (14) | −0.0101 (14) | 0.0231 (15) |
C15 | 0.0453 (16) | 0.0561 (17) | 0.0463 (16) | 0.0050 (13) | −0.0074 (12) | 0.0214 (13) |
C16 | 0.0416 (14) | 0.0355 (13) | 0.0298 (12) | 0.0062 (10) | 0.0020 (10) | 0.0056 (10) |
C17 | 0.0424 (15) | 0.0506 (16) | 0.0455 (15) | 0.0108 (13) | 0.0011 (12) | 0.0140 (12) |
C18 | 0.0390 (15) | 0.0651 (19) | 0.0503 (17) | 0.0011 (14) | 0.0026 (13) | 0.0080 (14) |
C19 | 0.0633 (19) | 0.0462 (16) | 0.0400 (15) | −0.0085 (14) | 0.0113 (14) | 0.0007 (12) |
C20 | 0.074 (2) | 0.0388 (15) | 0.0466 (16) | 0.0104 (14) | 0.0147 (15) | 0.0144 (12) |
C21 | 0.0475 (15) | 0.0439 (15) | 0.0417 (14) | 0.0149 (12) | 0.0070 (12) | 0.0120 (12) |
C22 | 0.092 (3) | 0.072 (2) | 0.073 (2) | −0.025 (2) | 0.027 (2) | 0.0044 (19) |
Cl1—C4 | 1.740 (3) | C10—C15 | 1.390 (4) |
Cl2—C12 | 1.735 (3) | C11—C12 | 1.374 (4) |
S1—O2 | 1.4169 (19) | C11—H11 | 0.9300 |
S1—O3 | 1.4191 (18) | C12—C13 | 1.372 (4) |
S1—N1 | 1.687 (2) | C13—C14 | 1.378 (4) |
S1—C16 | 1.758 (3) | C13—H13 | 0.9300 |
O1—C6 | 1.361 (3) | C14—C15 | 1.373 (4) |
O1—C7 | 1.434 (3) | C14—H14 | 0.9300 |
N1—C1 | 1.439 (3) | C15—H15 | 0.9300 |
N1—C8 | 1.443 (3) | C16—C17 | 1.379 (3) |
C1—C2 | 1.382 (3) | C16—C21 | 1.382 (3) |
C1—C6 | 1.391 (3) | C17—C18 | 1.373 (4) |
C2—C3 | 1.377 (3) | C17—H17 | 0.9300 |
C2—H2 | 0.9300 | C18—C19 | 1.380 (4) |
C3—C4 | 1.365 (4) | C18—H18 | 0.9300 |
C3—H3 | 0.9300 | C19—C20 | 1.380 (4) |
C4—C5 | 1.365 (4) | C19—C22 | 1.502 (4) |
C5—C6 | 1.387 (3) | C20—C21 | 1.380 (4) |
C5—H5 | 0.9300 | C20—H20 | 0.9300 |
C7—C8 | 1.499 (3) | C21—H21 | 0.9300 |
C7—H7A | 0.9700 | C22—H22A | 0.9600 |
C7—H7B | 0.9700 | C22—H22B | 0.9600 |
C8—C9 | 1.320 (3) | C22—H22C | 0.9600 |
C9—C10 | 1.464 (3) | C22—H22D | 0.9600 |
C9—H9 | 0.9300 | C22—H22E | 0.9600 |
C10—C11 | 1.389 (3) | C22—H22F | 0.9600 |
O2—S1—O3 | 120.68 (12) | C12—C13—C14 | 118.3 (3) |
O2—S1—N1 | 106.29 (11) | C12—C13—H13 | 120.8 |
O3—S1—N1 | 105.86 (10) | C14—C13—H13 | 120.8 |
O2—S1—C16 | 108.54 (12) | C15—C14—C13 | 121.0 (3) |
O3—S1—C16 | 108.71 (12) | C15—C14—H14 | 119.5 |
N1—S1—C16 | 105.79 (11) | C13—C14—H14 | 119.5 |
C6—O1—C7 | 114.86 (19) | C14—C15—C10 | 120.7 (2) |
C1—N1—C8 | 112.98 (18) | C14—C15—H15 | 119.7 |
C1—N1—S1 | 118.36 (15) | C10—C15—H15 | 119.7 |
C8—N1—S1 | 115.05 (15) | C17—C16—C21 | 120.4 (2) |
C2—C1—C6 | 118.8 (2) | C17—C16—S1 | 120.01 (19) |
C2—C1—N1 | 121.2 (2) | C21—C16—S1 | 119.46 (19) |
C6—C1—N1 | 119.8 (2) | C18—C17—C16 | 119.7 (3) |
C3—C2—C1 | 120.8 (3) | C18—C17—H17 | 120.2 |
C3—C2—H2 | 119.6 | C16—C17—H17 | 120.2 |
C1—C2—H2 | 119.6 | C17—C18—C19 | 121.3 (3) |
C4—C3—C2 | 119.3 (3) | C17—C18—H18 | 119.4 |
C4—C3—H3 | 120.4 | C19—C18—H18 | 119.4 |
C2—C3—H3 | 120.4 | C18—C19—C20 | 118.1 (3) |
C3—C4—C5 | 121.6 (2) | C18—C19—C22 | 120.9 (3) |
C3—C4—Cl1 | 119.6 (2) | C20—C19—C22 | 121.0 (3) |
C5—C4—Cl1 | 118.9 (2) | C19—C20—C21 | 121.8 (3) |
C4—C5—C6 | 119.3 (3) | C19—C20—H20 | 119.1 |
C4—C5—H5 | 120.4 | C21—C20—H20 | 119.1 |
C6—C5—H5 | 120.4 | C20—C21—C16 | 118.7 (2) |
O1—C6—C5 | 115.9 (2) | C20—C21—H21 | 120.6 |
O1—C6—C1 | 124.0 (2) | C16—C21—H21 | 120.6 |
C5—C6—C1 | 120.1 (2) | C19—C22—H22A | 109.5 |
O1—C7—C8 | 109.9 (2) | C19—C22—H22B | 109.5 |
O1—C7—H7A | 109.7 | H22A—C22—H22B | 109.5 |
C8—C7—H7A | 109.7 | C19—C22—H22C | 109.5 |
O1—C7—H7B | 109.7 | H22A—C22—H22C | 109.5 |
C8—C7—H7B | 109.7 | H22B—C22—H22C | 109.5 |
H7A—C7—H7B | 108.2 | C19—C22—H22D | 109.5 |
C9—C8—N1 | 124.1 (2) | H22A—C22—H22D | 141.1 |
C9—C8—C7 | 123.2 (2) | H22B—C22—H22D | 56.3 |
N1—C8—C7 | 112.6 (2) | H22C—C22—H22D | 56.3 |
C8—C9—C10 | 131.6 (2) | C19—C22—H22E | 109.5 |
C8—C9—H9 | 114.2 | H22A—C22—H22E | 56.3 |
C10—C9—H9 | 114.2 | H22B—C22—H22E | 141.1 |
C11—C10—C15 | 118.2 (2) | H22C—C22—H22E | 56.3 |
C11—C10—C9 | 117.9 (2) | H22D—C22—H22E | 109.5 |
C15—C10—C9 | 123.8 (2) | C19—C22—H22F | 109.5 |
C12—C11—C10 | 120.2 (2) | H22A—C22—H22F | 56.3 |
C12—C11—H11 | 119.9 | H22B—C22—H22F | 56.3 |
C10—C11—H11 | 119.9 | H22C—C22—H22F | 141.1 |
C13—C12—C11 | 121.6 (2) | H22D—C22—H22F | 109.5 |
C13—C12—Cl2 | 119.3 (2) | H22E—C22—H22F | 109.5 |
C11—C12—Cl2 | 119.1 (2) | ||
O2—S1—N1—C1 | 45.3 (2) | O1—C7—C8—N1 | −59.4 (3) |
O3—S1—N1—C1 | 174.74 (17) | N1—C8—C9—C10 | 3.4 (4) |
C16—S1—N1—C1 | −69.99 (19) | C7—C8—C9—C10 | −172.3 (2) |
O2—S1—N1—C8 | −176.83 (16) | C8—C9—C10—C11 | −165.4 (3) |
O3—S1—N1—C8 | −47.36 (19) | C8—C9—C10—C15 | 19.2 (4) |
C16—S1—N1—C8 | 67.90 (18) | C15—C10—C11—C12 | −0.7 (4) |
C8—N1—C1—C2 | 161.6 (2) | C9—C10—C11—C12 | −176.3 (2) |
S1—N1—C1—C2 | −59.7 (3) | C10—C11—C12—C13 | 1.2 (4) |
C8—N1—C1—C6 | −13.5 (3) | C10—C11—C12—Cl2 | 179.95 (18) |
S1—N1—C1—C6 | 125.2 (2) | C11—C12—C13—C14 | −0.7 (4) |
C6—C1—C2—C3 | −3.9 (4) | Cl2—C12—C13—C14 | −179.5 (2) |
N1—C1—C2—C3 | −179.1 (2) | C12—C13—C14—C15 | −0.3 (5) |
C1—C2—C3—C4 | 2.8 (4) | C13—C14—C15—C10 | 0.7 (5) |
C2—C3—C4—C5 | 0.3 (4) | C11—C10—C15—C14 | −0.3 (4) |
C2—C3—C4—Cl1 | 179.6 (2) | C9—C10—C15—C14 | 175.1 (3) |
C3—C4—C5—C6 | −2.1 (4) | O2—S1—C16—C17 | 139.9 (2) |
Cl1—C4—C5—C6 | 178.56 (19) | O3—S1—C16—C17 | 6.9 (2) |
C7—O1—C6—C5 | 166.0 (2) | N1—S1—C16—C17 | −106.4 (2) |
C7—O1—C6—C1 | −15.8 (3) | O2—S1—C16—C21 | −43.7 (2) |
C4—C5—C6—O1 | 179.2 (2) | O3—S1—C16—C21 | −176.70 (19) |
C4—C5—C6—C1 | 0.9 (4) | N1—S1—C16—C21 | 70.0 (2) |
C2—C1—C6—O1 | −176.1 (2) | C21—C16—C17—C18 | −0.1 (4) |
N1—C1—C6—O1 | −0.9 (4) | S1—C16—C17—C18 | 176.2 (2) |
C2—C1—C6—C5 | 2.0 (4) | C16—C17—C18—C19 | −1.5 (4) |
N1—C1—C6—C5 | 177.2 (2) | C17—C18—C19—C20 | 2.1 (4) |
C6—O1—C7—C8 | 44.2 (3) | C17—C18—C19—C22 | −177.8 (3) |
C1—N1—C8—C9 | −133.0 (2) | C18—C19—C20—C21 | −1.1 (4) |
S1—N1—C8—C9 | 86.9 (3) | C22—C19—C20—C21 | 178.8 (3) |
C1—N1—C8—C7 | 43.1 (3) | C19—C20—C21—C16 | −0.4 (4) |
S1—N1—C8—C7 | −97.1 (2) | C17—C16—C21—C20 | 1.1 (4) |
O1—C7—C8—C9 | 116.7 (3) | S1—C16—C21—C20 | −175.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C22H17Cl2NO3S |
Mr | 446.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.899 (5), 12.211 (4), 7.775 (3) |
α, β, γ (°) | 102.23 (2), 92.21 (3), 96.64 (3) |
V (Å3) | 1002.4 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.40 × 0.37 × 0.37 |
Data collection | |
Diffractometer | Rigaku AFC5R diffractometer |
Absorption correction | ψ scans (North et al., 1968) |
Tmin, Tmax | 0.800, 0.846 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4862, 4619, 3158 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.118, 1.09 |
No. of reflections | 4619 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.22 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1995), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1995), SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), TEXSAN.
The 3,4-dihydro-2H-1,4-Benzoxazine, (I), structure has been the integral part of many naturally occurring substances (Sainsbury, 1984). Also, various benzoxazine derivatives have shown interesting pharmacological activities, e.g. anticancer (Sugimoto et al., 1990; Zhen et al., 1989), antiemetic (Fukuda et al., 1991), antitubercular (Hirata et al., 1995) and antirheumatic properties (Matsuoka et al., 1997). \sch
As a continuation of our studies on the synthesis of heterocyclic structures of biological importance (Nandi & Kundu, 2000; Chaudhuri & Kundu, 2000), we have recently reported the synthesis and X-ray structure determination of (Z)—N-benzyl-2,3-dihydro-2- (2-methoxybenzylidene)-4H-1,4-benzoxazine, (II) (Maiti et al., 1999). In the present paper, we describe the synthesis and X-ray structure determination of a 3-alkylidene benzoxazine, namely, (Z)-7-chloro-3-[(3-chlorophenyl)methylidene]-4-p-tosyl-3,4-dihydro- 2H-1,4-benzoxazine, (III).
The geometric parameters determined for (III) show some similarities to those found in (II) (Maiti et al., 1999); the heterocyclic ring adopts a half boat conformation and the planar part of the heterocyclic ring (atoms O1, N1, C6, and C8) forms a dihedral angle with the fused phenyl ring A of 10.2 (2)°, with C1 and C7 on opposite sides of the best plane by 0.085 (3) and 0.611 (4) Å, respectively. This dihedral angle is however somewhat larger than that in (II), which is 4.70 (6)°. A shortening of bond length of atoms adjacent to the phenyl rings A and B due to conjugation, is seen which is particularly marked for the bond-length O1—C6 of 1.361 (3) Å [compared with 1.434 (3) for O1—C7]. The effect of conjugation is less evident for the bond lengths to N1 which are 1.439 (3) and 1.443 (3) Å for N1—C1 and N1—C8, respectively, although these values are still significantly shorter than the N—C single bond length of 1.48 Å (Allen et al.. 1987). The dihedral angles A/B, A/C and B/C are 42.18 (9), 52.49 (8) and 26.9 (1)°, respectively. The geometric parameters of the p-tosyl group and of the chlorophenyl group are within normal bounds, with the p-tosyl group angled away from the 3-chlorophenyl derivative reducing steric hindrance.