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Acta Cryst. (2008). E64, o670    [ doi:10.1107/S1600536808000573 ]

7-Chloro-4-(2,5-dichlorophenyl)-1-phenyl-1H-thiochromeno[2,3-b]pyridine-2,5(3H,4H)-dione

L.-R. Wen, C. Ji, J.-H. Sun and H.-Y. Xie

Abstract top

In the crystal structure of the title compound, C24H14Cl3NO2S, the tetrahydropyridine ring adopts a half-chair conformation and both pendant benzene rings are oriented nearly perpendicular to the thiochromeno[2,3-b]pyridine system.

Comment top

N, S-containing heterocycles shows a wide range of biological activities Ingall et al.,1996). For example, the thiochromones (Wang et al.,2006) as important structural motifs exhibit interesting biological properties and have been tested and applied as drugs (Quaglia et al., 2002). In a continuation of our study of structure-activity, we report here the crystal structure of the title compound,(I), which was synthesized from 3-(2,5- dichlorophenyl)-3-oxo-N-phenylpropanethioamide.

The thiopyran ring is almost planar and the 4H-pyridine ring adpots a half-chair conformation. Both benzene rings are oriented nearly perpendicular to the to the thiochromeno[2,3-b]pyridine ring. The bond length C11—O2(1.21 Å) is shorter than C7—O1(1.24 Å), which might be due to the strong electron withdrawing effect of the nitrogen atom in the pyridine ring.

The interest in the N, S-containing heterocycles has been significantly surged since a wide range of biological activities have been identified (Ingall et al.,1996). For example, the thiochromones (Wang et al.,2006) as important structural motifs exhibit interesting biological properties and have been tested and applied as drugs (Quaglia et al., 2002). In a continuation of our study of structure-activity, we report here the crystal structure of the title compound.

Related literature top

For related literature, see: Ingall et al. (1996), Wang et al. (2006); Quaglia et al. (2002).

Experimental top

3-(2,5-dichlorophenyl)-3-oxo-N-phenylpropanethioamide (1 mmol), 2,5-dichlorobenzaldehyde (1 mmol), (2,2-dimethyl-1,3-dioxane-4,6-dione) (1 mmol) and triethylamine (0.5 mmol)were refluxed in anhydrous alcohol for 8 h. The precipitate was filtered off and dissolved in THF. On slow evaporation of the solvent crystals of the title compound has formed (m.p.498 K).

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93, 0.97 or 0.98 A%, and refined using a riding model with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound (I) with labeling and displacement ellipsoids drawn at the 50% probability level.
7-Chloro-4-(2,5-dichlorophenyl)-1-phenyl-1H- thiochromeno[2,3-b]pyridine-2,5(3H,4H)-dione top
Crystal data top
C24H14Cl3NO2SF000 = 992
Mr = 486.77Dx = 1.491 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2857 reflections
a = 13.624 (5) Åθ = 2.3–23.4º
b = 13.474 (5) ŵ = 0.54 mm−1
c = 11.861 (4) ÅT = 294 (2) K
β = 95.042 (6)ºPrism, yellow
V = 2168.9 (14) Å30.18 × 0.12 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4426 independent reflections
Radiation source: fine-focus sealed tube2650 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
T = 294(2) Kθmax = 26.5º
φ and ω scansθmin = 1050º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→17
Tmin = 0.909, Tmax = 0.948k = −13→16
12228 measured reflectionsl = −14→14
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0479P)2 + 0.2323P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.043(Δ/σ)max = 0.001
wR(F2) = 0.112Δρmax = 0.28 e Å−3
S = 0.99Δρmin = −0.26 e Å−3
4426 reflectionsExtinction correction: none
280 parameters
Crystal data top
C24H14Cl3NO2SV = 2168.9 (14) Å3
Mr = 486.77Z = 4
Monoclinic, P21/cMo Kα
a = 13.624 (5) ŵ = 0.54 mm−1
b = 13.474 (5) ÅT = 294 (2) K
c = 11.861 (4) Å0.18 × 0.12 × 0.10 mm
β = 95.042 (6)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4426 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2650 reflections with I > 2σ(I)
Tmin = 0.909, Tmax = 0.948Rint = 0.049
12228 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043280 parameters
wR(F2) = 0.112H-atom parameters constrained
S = 0.99Δρmax = 0.28 e Å−3
4426 reflectionsΔρmin = −0.26 e Å−3
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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.90221 (5)0.18709 (5)0.44648 (6)0.04544 (19)
Cl11.15911 (7)0.38600 (6)0.09743 (8)0.0852 (3)
Cl20.73863 (7)0.67908 (6)0.56211 (8)0.0848 (3)
Cl30.48232 (6)0.37484 (7)0.27266 (7)0.0859 (3)
O10.92297 (13)0.51190 (12)0.38778 (15)0.0534 (5)
O20.66915 (15)0.28572 (14)0.71540 (16)0.0633 (6)
N10.76934 (14)0.25141 (14)0.57736 (16)0.0395 (5)
C10.97544 (16)0.24922 (17)0.3549 (2)0.0388 (6)
C21.03240 (18)0.18948 (19)0.2898 (2)0.0505 (7)
H21.03270.12110.30040.061*
C31.0880 (2)0.2301 (2)0.2103 (2)0.0581 (8)
H31.12460.18960.16630.070*
C41.08877 (19)0.3324 (2)0.1967 (2)0.0524 (7)
C51.03478 (18)0.39236 (19)0.2611 (2)0.0464 (6)
H51.03660.46080.25110.056*
C60.97697 (16)0.35243 (17)0.3415 (2)0.0370 (6)
C70.91855 (17)0.42134 (18)0.4054 (2)0.0387 (6)
C80.85216 (17)0.38283 (17)0.4844 (2)0.0362 (6)
C90.79469 (17)0.45849 (17)0.5447 (2)0.0408 (6)
H90.83730.51660.55830.049*
C100.77372 (19)0.41789 (18)0.6606 (2)0.0470 (7)
H10A0.83460.41750.70970.056*
H10B0.72810.46210.69400.056*
C110.73121 (19)0.31487 (19)0.6559 (2)0.0450 (6)
C120.83881 (16)0.28430 (17)0.50370 (19)0.0357 (6)
C130.73107 (17)0.15033 (17)0.56871 (19)0.0365 (6)
C140.7620 (2)0.0818 (2)0.6502 (2)0.0540 (7)
H140.80820.09930.70930.065*
C150.7234 (2)−0.0139 (2)0.6432 (3)0.0646 (8)
H150.7440−0.06080.69780.077*
C160.6561 (2)−0.0390 (2)0.5570 (3)0.0654 (9)
H160.6301−0.10290.55280.079*
C170.6263 (2)0.0299 (2)0.4760 (3)0.0656 (9)
H170.58060.01210.41670.079*
C180.6631 (2)0.1252 (2)0.4812 (2)0.0533 (7)
H180.64220.17160.42630.064*
C190.70135 (18)0.49370 (19)0.4760 (2)0.0430 (6)
C200.6704 (2)0.5922 (2)0.4790 (2)0.0545 (7)
C210.5847 (3)0.6240 (2)0.4178 (3)0.0715 (9)
H210.56630.69040.42040.086*
C220.5269 (2)0.5584 (3)0.3538 (3)0.0687 (9)
H220.46920.57960.31320.082*
C230.55580 (19)0.4603 (2)0.3506 (2)0.0548 (7)
C240.64242 (18)0.4289 (2)0.4096 (2)0.0480 (7)
H240.66140.36290.40450.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0490 (4)0.0304 (3)0.0585 (4)−0.0002 (3)0.0140 (3)0.0006 (3)
Cl10.0958 (6)0.0721 (6)0.0966 (6)−0.0206 (5)0.0581 (5)−0.0068 (5)
Cl20.0883 (6)0.0413 (4)0.1249 (8)0.0078 (4)0.0104 (6)−0.0151 (5)
Cl30.0627 (5)0.1131 (8)0.0772 (6)0.0090 (5)−0.0198 (4)−0.0077 (5)
O10.0648 (12)0.0295 (10)0.0678 (12)0.0001 (8)0.0161 (10)0.0042 (9)
O20.0759 (14)0.0576 (13)0.0610 (12)−0.0091 (10)0.0315 (11)−0.0065 (10)
N10.0441 (12)0.0354 (11)0.0394 (11)−0.0040 (10)0.0067 (10)−0.0026 (9)
C10.0323 (13)0.0371 (14)0.0466 (15)−0.0055 (11)0.0021 (11)−0.0025 (12)
C20.0500 (16)0.0335 (14)0.0698 (18)−0.0063 (12)0.0161 (14)−0.0092 (14)
C30.0531 (17)0.0519 (18)0.073 (2)−0.0066 (14)0.0274 (15)−0.0147 (15)
C40.0494 (17)0.0490 (17)0.0612 (18)−0.0118 (13)0.0181 (14)−0.0051 (14)
C50.0436 (15)0.0381 (14)0.0581 (16)−0.0082 (12)0.0075 (13)0.0000 (13)
C60.0302 (13)0.0336 (13)0.0465 (14)−0.0036 (11)−0.0005 (11)−0.0006 (12)
C70.0369 (14)0.0339 (14)0.0444 (15)−0.0034 (11)−0.0022 (12)−0.0012 (12)
C80.0353 (13)0.0316 (13)0.0408 (14)0.0005 (11)−0.0017 (11)−0.0026 (11)
C90.0417 (14)0.0347 (14)0.0457 (15)−0.0015 (11)0.0024 (12)−0.0029 (12)
C100.0558 (16)0.0411 (15)0.0438 (15)−0.0003 (13)0.0022 (13)−0.0073 (12)
C110.0522 (16)0.0462 (16)0.0355 (14)0.0019 (13)−0.0014 (13)−0.0021 (13)
C120.0336 (13)0.0368 (13)0.0360 (13)−0.0020 (11)−0.0004 (11)−0.0014 (11)
C130.0360 (13)0.0373 (13)0.0372 (14)−0.0044 (11)0.0083 (11)−0.0002 (11)
C140.0525 (17)0.0521 (17)0.0558 (17)−0.0012 (14)−0.0050 (14)0.0090 (15)
C150.072 (2)0.0414 (17)0.082 (2)0.0038 (15)0.0182 (19)0.0161 (16)
C160.069 (2)0.0457 (18)0.087 (2)−0.0152 (16)0.0352 (19)−0.0166 (18)
C170.066 (2)0.070 (2)0.061 (2)−0.0267 (17)0.0071 (16)−0.0144 (18)
C180.0604 (18)0.0563 (18)0.0424 (16)−0.0108 (15)−0.0004 (14)0.0055 (14)
C190.0424 (15)0.0423 (15)0.0458 (15)0.0057 (12)0.0120 (13)0.0036 (13)
C200.0566 (18)0.0454 (16)0.0632 (18)0.0124 (14)0.0155 (15)0.0031 (14)
C210.079 (2)0.057 (2)0.081 (2)0.0328 (18)0.019 (2)0.0087 (18)
C220.058 (2)0.088 (3)0.061 (2)0.0302 (19)0.0091 (16)0.0115 (19)
C230.0449 (16)0.073 (2)0.0468 (16)0.0085 (15)0.0052 (13)0.0046 (15)
C240.0444 (16)0.0506 (16)0.0495 (16)0.0099 (13)0.0063 (13)0.0027 (14)
Geometric parameters (Å, °) top
S1—C121.739 (2)C9—H90.9800
S1—C11.751 (2)C10—C111.503 (3)
Cl1—C41.739 (3)C10—H10A0.9700
Cl2—C201.744 (3)C10—H10B0.9700
Cl3—C231.737 (3)C13—C181.371 (3)
O1—C71.240 (3)C13—C141.376 (3)
O2—C111.213 (3)C14—C151.393 (4)
N1—C111.398 (3)C14—H140.9300
N1—C121.414 (3)C15—C161.355 (4)
N1—C131.459 (3)C15—H150.9300
C1—C21.397 (3)C16—C171.372 (4)
C1—C61.400 (3)C16—H160.9300
C2—C31.374 (3)C17—C181.377 (4)
C2—H20.9300C17—H170.9300
C3—C41.389 (4)C18—H180.9300
C3—H30.9300C19—C241.384 (3)
C4—C51.370 (3)C19—C201.395 (3)
C5—C61.397 (3)C20—C211.387 (4)
C5—H50.9300C21—C221.368 (4)
C6—C71.475 (3)C21—H210.9300
C7—C81.454 (3)C22—C231.382 (4)
C8—C121.362 (3)C22—H220.9300
C8—C91.504 (3)C23—C241.384 (3)
C9—C191.525 (3)C24—H240.9300
C9—C101.530 (3)
C12—S1—C1102.22 (11)O2—C11—C10124.3 (2)
C11—N1—C12121.9 (2)N1—C11—C10115.2 (2)
C11—N1—C13117.80 (19)C8—C12—N1121.0 (2)
C12—N1—C13120.23 (19)C8—C12—S1126.18 (19)
C2—C1—C6119.7 (2)N1—C12—S1112.79 (16)
C2—C1—S1116.23 (18)C18—C13—C14120.7 (2)
C6—C1—S1124.06 (19)C18—C13—N1119.8 (2)
C3—C2—C1121.1 (2)C14—C13—N1119.4 (2)
C3—C2—H2119.4C13—C14—C15119.2 (3)
C1—C2—H2119.4C13—C14—H14120.4
C2—C3—C4119.0 (3)C15—C14—H14120.4
C2—C3—H3120.5C16—C15—C14120.2 (3)
C4—C3—H3120.5C16—C15—H15119.9
C5—C4—C3120.7 (2)C14—C15—H15119.9
C5—C4—Cl1119.2 (2)C15—C16—C17119.8 (3)
C3—C4—Cl1120.1 (2)C15—C16—H16120.1
C4—C5—C6121.1 (2)C17—C16—H16120.1
C4—C5—H5119.5C16—C17—C18121.1 (3)
C6—C5—H5119.4C16—C17—H17119.5
C5—C6—C1118.3 (2)C18—C17—H17119.5
C5—C6—C7118.1 (2)C13—C18—C17118.9 (3)
C1—C6—C7123.6 (2)C13—C18—H18120.6
O1—C7—C8120.1 (2)C17—C18—H18120.6
O1—C7—C6119.8 (2)C24—C19—C20117.0 (2)
C8—C7—C6120.0 (2)C24—C19—C9121.5 (2)
C12—C8—C7123.8 (2)C20—C19—C9121.5 (2)
C12—C8—C9119.9 (2)C21—C20—C19121.5 (3)
C7—C8—C9116.4 (2)C21—C20—Cl2118.1 (2)
C8—C9—C19113.64 (19)C19—C20—Cl2120.4 (2)
C8—C9—C10109.34 (19)C22—C21—C20120.5 (3)
C19—C9—C10112.3 (2)C22—C21—H21119.8
C8—C9—H9107.1C20—C21—H21119.8
C19—C9—H9107.1C21—C22—C23118.9 (3)
C10—C9—H9107.1C21—C22—H22120.6
C11—C10—C9113.5 (2)C23—C22—H22120.6
C11—C10—H10A108.9C22—C23—C24120.7 (3)
C9—C10—H10A108.9C22—C23—Cl3119.8 (2)
C11—C10—H10B108.9C24—C23—Cl3119.5 (2)
C9—C10—H10B108.9C23—C24—C19121.4 (3)
H10A—C10—H10B107.7C23—C24—H24119.3
O2—C11—N1120.6 (2)C19—C24—H24119.3
C12—S1—C1—C2−176.43 (19)C7—C8—C12—S14.3 (3)
C12—S1—C1—C61.4 (2)C9—C8—C12—S1−177.11 (17)
C6—C1—C2—C3−1.8 (4)C11—N1—C12—C8−17.6 (3)
S1—C1—C2—C3176.1 (2)C13—N1—C12—C8158.9 (2)
C1—C2—C3—C41.3 (4)C11—N1—C12—S1161.51 (17)
C2—C3—C4—C5−0.2 (4)C13—N1—C12—S1−22.0 (3)
C2—C3—C4—Cl1179.6 (2)C1—S1—C12—C8−4.3 (2)
C3—C4—C5—C6−0.5 (4)C1—S1—C12—N1176.67 (16)
Cl1—C4—C5—C6179.76 (19)C11—N1—C13—C18101.9 (3)
C4—C5—C6—C10.0 (4)C12—N1—C13—C18−74.8 (3)
C4—C5—C6—C7−178.2 (2)C11—N1—C13—C14−76.6 (3)
C2—C1—C6—C51.1 (3)C12—N1—C13—C14106.7 (3)
S1—C1—C6—C5−176.60 (18)C18—C13—C14—C15−0.1 (4)
C2—C1—C6—C7179.3 (2)N1—C13—C14—C15178.4 (2)
S1—C1—C6—C71.5 (3)C13—C14—C15—C16−0.1 (4)
C5—C6—C7—O1−1.0 (3)C14—C15—C16—C170.5 (4)
C1—C6—C7—O1−179.1 (2)C15—C16—C17—C18−0.7 (4)
C5—C6—C7—C8175.8 (2)C14—C13—C18—C17−0.1 (4)
C1—C6—C7—C8−2.3 (3)N1—C13—C18—C17−178.6 (2)
O1—C7—C8—C12176.1 (2)C16—C17—C18—C130.5 (4)
C6—C7—C8—C12−0.7 (3)C8—C9—C19—C2438.9 (3)
O1—C7—C8—C9−2.5 (3)C10—C9—C19—C24−85.8 (3)
C6—C7—C8—C9−179.3 (2)C8—C9—C19—C20−142.5 (2)
C12—C8—C9—C19−95.5 (3)C10—C9—C19—C2092.8 (3)
C7—C8—C9—C1983.2 (3)C24—C19—C20—C21−0.3 (4)
C12—C8—C9—C1030.8 (3)C9—C19—C20—C21−179.0 (2)
C7—C8—C9—C10−150.5 (2)C24—C19—C20—Cl2178.93 (19)
C8—C9—C10—C11−49.6 (3)C9—C19—C20—Cl20.3 (3)
C19—C9—C10—C1177.5 (3)C19—C20—C21—C221.1 (4)
C12—N1—C11—O2177.4 (2)Cl2—C20—C21—C22−178.2 (2)
C13—N1—C11—O20.8 (3)C20—C21—C22—C23−0.5 (5)
C12—N1—C11—C10−3.4 (3)C21—C22—C23—C24−1.0 (4)
C13—N1—C11—C10180.0 (2)C21—C22—C23—Cl3178.5 (2)
C9—C10—C11—O2−143.4 (3)C22—C23—C24—C191.8 (4)
C9—C10—C11—N137.4 (3)Cl3—C23—C24—C19−177.65 (19)
C7—C8—C12—N1−176.7 (2)C20—C19—C24—C23−1.1 (4)
C9—C8—C12—N11.9 (3)C9—C19—C24—C23177.5 (2)
Table 1
Selected geometric parameters (Å) top
S1—C121.739 (2)C8—C91.504 (3)
S1—C11.751 (2)C9—C101.530 (3)
O2—C111.213 (3)C10—C111.503 (3)
N1—C111.398 (3)
Acknowledgements top

The authors are very grateful for financial support by the National Natural Science Foundation of China (No. 20572057), the Natural Science Foundation of Shandong Province (No. Y2006B11) and the Doctoral Foundation of Qingdao University of Science and Technology.

references
References top

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Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Ingall, A. H. (1996). InComprehensive Heterocyclic Chemistry II,Vol. 5, p 501. Oxford: Pergamon.

Quaglia, W., Pigini, M., Piergentili, A., Giannella, M., Leonardi, A. & Melchiorre, C. (2002). J. Med. Chem. 45, 1633–1643. Check date – was 2000 in text

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, W., Li, H., Wang, J. & Zu, L. S. (2006). J. Am. Chem. Soc. 128, 10354–10355.