organic compounds
7-Benzyl-3-(4-fluorophenyl)-2-propylamino-5,6,7,8-tetrahydropyrido[4′,3′:4,5]thieno[2,3-d]pyrimidin-4(3H)-one
aHubei Key Laboratory of Natural Products Research and Development, China Three Gorges University, Yichang 443002, People's Republic of China, and bCollege of Chemistry and Life Science, China Three Gorges University, Yichang 443002, People's Republic of China
*Correspondence e-mail: chenhong3736@sina.com
In the title compound, C25H25FN4OS, the thienopyrimidine fused-ring system is close to planar (r.m.s. deviation = 0.0089 Å), with a maximum deviation of 0.0261 (17) Å for the N atom adjacent to the benzene ring. This thienopyrimidine fused-ring system forms dihedral angles of 64.73 (3) and 81.56 (5)° with the adjacent benzyl and fluorophenyl rings, respectively. Intermolecular N—H⋯F and C—H⋯F hydrogen bonding, as well as C—F⋯π interactions [F⋯centroid = 3.449 (3) Å; C—F⋯centroid = 91.87 (15)°], help to stabilize the crystal structure.
Related literature
For the biological and pharmaceutical properties of compounds containing the fused thienopyrimidine system, see: Amr et al. (2010); Huang et al. (2009); Mavrova et al. (2010). For similar crystal structures, see: Xie et al. (2008); Chen et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812010318/gw2115sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812010318/gw2115Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812010318/gw2115Isup3.cml
1-fluoro-4-isocyanatobenzene (2 mmol) under nitrogen atmosphere was added to a solution of iminophosphorane (2 mmol) in anhydrous CH2Cl2 (10 ml) at room temperature. When the reaction mixture was left unstirred for 12 h at 273–278 k, iminophosphorane was consumed (TLC monitored). The solvent was removed under reduced pressure and ether/petroleum ether (volume ratio 1:2, 20 ml) was added to precipitate triphenylphosphine oxide. Removal of the solvent gave carbodiimide, which was used directly without further purification. Propan-1-amine (2 mmol) was added to the solution of carbodiimide in anhydrous dichloromethane (10 ml). After the reaction mixture was left unstirred for 5–6 h, the solvent was removed and anhydrous EtOH (10 ml) with several drops of EtONa (in EtOH) was added to the mixture. The mixture was stirred for another 6–8 h at room temperature. The solution was condensed and the residual was recrystallized from EtOH to give the expected title compound as white crystals, 0.832 g (87%), M.p. 431–432 K; 1H NMR (CDCl3, 600 MHz) δ: 7.37–7.25 (m, 9H, Ar—H), 4.06 (br, 1H, NH), 3.72 (s, 2H, Ar—CH2), 3.59 (s, 2H, NCH2-thiophene), 3.31 (m, 2H, NHCH2), 2.98 (t, J = 5.1 Hz, 2H, NCH2CH2), 2.82 (t, J = 5.1 Hz, 2H, NCH2CH2), 1.50–1.48 (m, 2H, CH2CH3), 0.84 (t, J = 6.6 Hz, 3H, CH2CH3); IR (KBr) v: 3373 (N—H), 1673 (C=O), 1540, 1378, 696 cm-1; EI—MS m/z (%): 448 (M+, 15), 357 (16), 329 (100), 287 (26), 91 (72). Anal. calcd for C25H25FN4OS: C 66.94, H 5.62, N 12.49; found: C 66.71, H 5.50, N 12.23.
All H atoms were positioned geometrically [C—H = 0.93, 0.96, 0.97 Å and N—H = 0.86 Å] and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N).
Derivatives of heterocycles containing the thienopyrimidine system have proved to show significant antifungal, antibacterical, anticonvulsant and angiotensin antagonistic activities (Amr et al. 2010; Huang et al. 2009; Mavrova et al. 2010). Recently, we have focused on the synthesis of fused heterocyclic systems containing thienopyrimidine via aza-wittig reaction under mild conditions. Some X-ray crystal structures of fused pyrimidinone derivatives have been reported (Chen et al., 2011; Xie et al., 2008). The title compound has potential use as a precursor for obtaining bioactive molecules with fluorescence properties. Herein, we report its
(Fig. 1).In the π interactions (C20—F1···Cg1 with Cg1 centroids of the C17—C18—C19—C20—C21 ring), helps to stabilize the crystal structure.
of the title compound, C25H25FN4OS, the thienopyrimidine fused-ring system is close to coplanar (r.m.s deviation = 0.0089 Å) with a maximum deviation of -0.0261 (17) Å for atom N(3). This ring system forms diherdral angles of 64.73 (3) and 81.56 (5)° with the adjacent 6-membered rings C1—C6 and C17—C22, respectively. Most bond lengths in the system fell in the range of single and double bonds, for example, the bond lengths of C(9)—C(10), C(13)—C(14) and C(16)—O(1) were in accordance with the double bond distances. Intermolecular N—H···F (N4—H4A···F1i with symmetry code: (i) 3/2 - x, y, -z) and C—H···F hydrogen bonding (C24—H24B···F1i and C25—H25A···F1i), as well as C—F···For the biological and pharmaceutical properties of compounds containing the fused thienopyrimidine system, see: Amr et al. (2010); Huang et al. (2009); Mavrova et al. (2010). For similar crystal structures, see: Xie et al. (2008); Chen et al. (2011).
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of the title compound with 50% probability displacement ellipsoids. | |
Fig. 2. Reaction scheme. |
C25H25FN4OS | F(000) = 3776 |
Mr = 448.55 | Dx = 1.331 Mg m−3 |
Orthorhombic, Ibca | Melting point: 432 K |
Hall symbol: -I 2b 2c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.921 (7) Å | θ = 2.2–27.5° |
b = 18.427 (7) Å | µ = 0.18 mm−1 |
c = 27.114 (10) Å | T = 296 K |
V = 8954 (6) Å3 | Block, white |
Z = 16 | 0.26 × 0.25 × 0.23 mm |
Bruker SMART CCD diffractometer | 5152 independent reflections |
Radiation source: fine-focus sealed tube | 4234 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.107 |
CCD Profile fitting scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→23 |
Tmin = 0.955, Tmax = 0.960 | k = −23→23 |
46089 measured reflections | l = −35→35 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.194 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.090P)2 + 9.9439P] where P = (Fo2 + 2Fc2)/3 |
5152 reflections | (Δ/σ)max = 0.001 |
290 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C25H25FN4OS | V = 8954 (6) Å3 |
Mr = 448.55 | Z = 16 |
Orthorhombic, Ibca | Mo Kα radiation |
a = 17.921 (7) Å | µ = 0.18 mm−1 |
b = 18.427 (7) Å | T = 296 K |
c = 27.114 (10) Å | 0.26 × 0.25 × 0.23 mm |
Bruker SMART CCD diffractometer | 5152 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4234 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.960 | Rint = 0.107 |
46089 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.194 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.58 e Å−3 |
5152 reflections | Δρmin = −0.30 e Å−3 |
290 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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.87109 (4) | 0.17415 (4) | 0.30237 (2) | 0.0591 (2) | |
C1 | 0.46974 (17) | 0.04644 (18) | 0.32327 (13) | 0.0698 (8) | |
H1 | 0.4418 | 0.0066 | 0.3132 | 0.084* | |
C2 | 0.50154 (17) | 0.09137 (18) | 0.28892 (11) | 0.0674 (8) | |
H2 | 0.4948 | 0.0820 | 0.2555 | 0.081* | |
C3 | 0.54325 (15) | 0.15022 (16) | 0.30340 (10) | 0.0571 (6) | |
H3 | 0.5640 | 0.1805 | 0.2796 | 0.068* | |
C4 | 0.55497 (13) | 0.16516 (14) | 0.35321 (9) | 0.0496 (6) | |
C5 | 0.52218 (15) | 0.11933 (16) | 0.38753 (10) | 0.0587 (7) | |
H5 | 0.5290 | 0.1282 | 0.4210 | 0.070* | |
C6 | 0.47947 (17) | 0.06071 (18) | 0.37275 (12) | 0.0673 (8) | |
H6 | 0.4573 | 0.0309 | 0.3962 | 0.081* | |
C7 | 0.60106 (14) | 0.22989 (15) | 0.36911 (11) | 0.0583 (7) | |
H7A | 0.5969 | 0.2669 | 0.3438 | 0.070* | |
H7B | 0.5792 | 0.2495 | 0.3990 | 0.070* | |
C8 | 0.72121 (13) | 0.19589 (15) | 0.33405 (10) | 0.0530 (6) | |
H8A | 0.7181 | 0.2345 | 0.3098 | 0.064* | |
H8B | 0.6990 | 0.1526 | 0.3200 | 0.064* | |
C9 | 0.80136 (13) | 0.18162 (14) | 0.34679 (9) | 0.0495 (6) | |
C10 | 0.82718 (13) | 0.17246 (13) | 0.39342 (9) | 0.0452 (5) | |
C11 | 0.77549 (13) | 0.17373 (15) | 0.43661 (9) | 0.0522 (6) | |
H11A | 0.7811 | 0.2191 | 0.4543 | 0.063* | |
H11B | 0.7877 | 0.1343 | 0.4589 | 0.063* | |
C12 | 0.69484 (14) | 0.16574 (15) | 0.41885 (9) | 0.0520 (6) | |
H12A | 0.6863 | 0.1165 | 0.4076 | 0.062* | |
H12B | 0.6608 | 0.1756 | 0.4458 | 0.062* | |
C13 | 0.90652 (12) | 0.16038 (12) | 0.39418 (9) | 0.0452 (5) | |
C14 | 0.93774 (13) | 0.15967 (14) | 0.34782 (9) | 0.0492 (6) | |
C15 | 1.05433 (13) | 0.13502 (14) | 0.37363 (9) | 0.0513 (6) | |
C16 | 0.95394 (12) | 0.14756 (13) | 0.43557 (9) | 0.0445 (5) | |
C17 | 1.07929 (12) | 0.11374 (13) | 0.46200 (9) | 0.0444 (5) | |
C18 | 1.11037 (14) | 0.16664 (13) | 0.49144 (10) | 0.0507 (6) | |
H18 | 1.0994 | 0.2153 | 0.4859 | 0.061* | |
C19 | 1.15808 (14) | 0.14701 (16) | 0.52937 (10) | 0.0574 (6) | |
H19 | 1.1794 | 0.1819 | 0.5498 | 0.069* | |
C20 | 1.17280 (15) | 0.07522 (17) | 0.53586 (10) | 0.0605 (7) | |
C21 | 1.14149 (17) | 0.02195 (16) | 0.50825 (13) | 0.0688 (8) | |
H21 | 1.1518 | −0.0266 | 0.5147 | 0.083* | |
C22 | 1.09393 (16) | 0.04143 (14) | 0.47039 (12) | 0.0615 (7) | |
H22 | 1.0720 | 0.0060 | 0.4507 | 0.074* | |
C23 | 1.15905 (18) | 0.1213 (2) | 0.31582 (13) | 0.0810 (10) | |
H23A | 1.1625 | 0.1710 | 0.3043 | 0.097* | |
H23B | 1.1256 | 0.0955 | 0.2938 | 0.097* | |
C24 | 1.2338 (2) | 0.0875 (2) | 0.31314 (14) | 0.0900 (11) | |
H24A | 1.2548 | 0.0963 | 0.2807 | 0.108* | |
H24B | 1.2662 | 0.1104 | 0.3372 | 0.108* | |
C25 | 1.2322 (3) | 0.0086 (2) | 0.32243 (17) | 0.1213 (17) | |
H25A | 1.2107 | −0.0005 | 0.3542 | 0.182* | |
H25B | 1.2822 | −0.0102 | 0.3216 | 0.182* | |
H25C | 1.2028 | −0.0149 | 0.2975 | 0.182* | |
N1 | 0.68111 (11) | 0.21671 (11) | 0.37846 (8) | 0.0519 (5) | |
N2 | 1.01070 (11) | 0.14831 (13) | 0.33586 (8) | 0.0560 (5) | |
N3 | 1.02934 (10) | 0.13358 (11) | 0.42237 (7) | 0.0471 (5) | |
N4 | 1.12699 (12) | 0.12111 (16) | 0.36574 (9) | 0.0667 (7) | |
H4A | 1.1554 | 0.1119 | 0.3905 | 0.080* | |
O1 | 0.93579 (10) | 0.14699 (11) | 0.47917 (6) | 0.0568 (5) | |
F1 | 1.22046 (12) | 0.05586 (13) | 0.57255 (7) | 0.0979 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0455 (4) | 0.0870 (5) | 0.0447 (4) | 0.0112 (3) | −0.0047 (3) | 0.0065 (3) |
C1 | 0.0575 (16) | 0.0736 (19) | 0.078 (2) | −0.0005 (14) | −0.0060 (15) | −0.0112 (16) |
C2 | 0.0616 (16) | 0.090 (2) | 0.0500 (15) | 0.0039 (16) | −0.0082 (13) | −0.0146 (14) |
C3 | 0.0490 (13) | 0.0763 (17) | 0.0460 (13) | 0.0092 (12) | −0.0013 (11) | 0.0003 (12) |
C4 | 0.0362 (11) | 0.0627 (14) | 0.0499 (13) | 0.0181 (10) | −0.0067 (10) | −0.0054 (11) |
C5 | 0.0524 (14) | 0.0802 (18) | 0.0435 (13) | 0.0193 (13) | −0.0041 (11) | −0.0007 (12) |
C6 | 0.0564 (16) | 0.0786 (19) | 0.0668 (18) | 0.0092 (14) | 0.0029 (14) | 0.0103 (15) |
C7 | 0.0418 (12) | 0.0654 (16) | 0.0677 (17) | 0.0201 (12) | −0.0108 (12) | −0.0123 (13) |
C8 | 0.0432 (12) | 0.0642 (15) | 0.0516 (14) | 0.0114 (11) | −0.0092 (11) | 0.0023 (11) |
C9 | 0.0403 (12) | 0.0592 (14) | 0.0489 (13) | 0.0082 (10) | −0.0050 (10) | 0.0013 (11) |
C10 | 0.0392 (11) | 0.0506 (12) | 0.0457 (12) | 0.0101 (9) | −0.0050 (9) | −0.0048 (10) |
C11 | 0.0420 (12) | 0.0700 (16) | 0.0447 (13) | 0.0140 (11) | −0.0056 (10) | −0.0060 (11) |
C12 | 0.0425 (12) | 0.0669 (15) | 0.0465 (13) | 0.0120 (11) | −0.0024 (10) | −0.0080 (11) |
C13 | 0.0380 (11) | 0.0518 (12) | 0.0457 (12) | 0.0073 (9) | −0.0039 (9) | −0.0040 (10) |
C14 | 0.0401 (11) | 0.0596 (14) | 0.0478 (13) | 0.0083 (10) | −0.0062 (10) | 0.0014 (11) |
C15 | 0.0398 (12) | 0.0647 (15) | 0.0493 (13) | 0.0093 (11) | 0.0002 (10) | −0.0035 (11) |
C16 | 0.0363 (11) | 0.0488 (12) | 0.0484 (13) | 0.0071 (9) | −0.0037 (9) | −0.0081 (10) |
C17 | 0.0348 (10) | 0.0525 (13) | 0.0458 (12) | 0.0037 (9) | −0.0066 (9) | −0.0040 (10) |
C18 | 0.0453 (12) | 0.0495 (13) | 0.0572 (15) | 0.0005 (10) | −0.0047 (11) | −0.0053 (11) |
C19 | 0.0449 (13) | 0.0731 (17) | 0.0542 (15) | −0.0050 (12) | −0.0077 (11) | −0.0152 (13) |
C20 | 0.0452 (13) | 0.088 (2) | 0.0485 (14) | 0.0082 (13) | −0.0105 (11) | 0.0052 (13) |
C21 | 0.0661 (17) | 0.0546 (15) | 0.086 (2) | 0.0117 (13) | −0.0186 (16) | 0.0080 (15) |
C22 | 0.0564 (15) | 0.0500 (14) | 0.0780 (19) | 0.0051 (12) | −0.0196 (14) | −0.0104 (13) |
C23 | 0.0612 (18) | 0.112 (3) | 0.070 (2) | 0.0229 (18) | 0.0134 (16) | 0.0164 (19) |
C24 | 0.083 (2) | 0.121 (3) | 0.066 (2) | 0.025 (2) | 0.0101 (18) | 0.0016 (19) |
C25 | 0.179 (5) | 0.092 (3) | 0.094 (3) | 0.036 (3) | −0.002 (3) | −0.014 (2) |
N1 | 0.0415 (10) | 0.0570 (12) | 0.0572 (12) | 0.0142 (9) | −0.0088 (9) | −0.0070 (9) |
N2 | 0.0419 (10) | 0.0796 (15) | 0.0465 (11) | 0.0110 (10) | −0.0011 (9) | 0.0005 (10) |
N3 | 0.0370 (9) | 0.0595 (12) | 0.0448 (10) | 0.0102 (8) | −0.0067 (8) | −0.0066 (9) |
N4 | 0.0412 (11) | 0.1052 (19) | 0.0538 (13) | 0.0170 (12) | −0.0007 (9) | 0.0013 (13) |
O1 | 0.0460 (9) | 0.0815 (13) | 0.0428 (9) | 0.0111 (9) | −0.0057 (7) | −0.0078 (8) |
F1 | 0.0855 (13) | 0.1396 (19) | 0.0686 (12) | 0.0214 (13) | −0.0338 (10) | 0.0128 (11) |
S1—C14 | 1.737 (2) | C13—C16 | 1.427 (3) |
S1—C9 | 1.741 (3) | C14—N2 | 1.363 (3) |
C1—C2 | 1.370 (5) | C15—N2 | 1.312 (3) |
C1—C6 | 1.378 (5) | C15—N4 | 1.344 (3) |
C1—H1 | 0.9300 | C15—N3 | 1.395 (3) |
C2—C3 | 1.374 (4) | C16—O1 | 1.226 (3) |
C2—H2 | 0.9300 | C16—N3 | 1.421 (3) |
C3—C4 | 1.394 (4) | C17—C18 | 1.377 (3) |
C3—H3 | 0.9300 | C17—C22 | 1.377 (3) |
C4—C5 | 1.387 (4) | C17—N3 | 1.446 (3) |
C4—C7 | 1.513 (4) | C18—C19 | 1.385 (4) |
C5—C6 | 1.383 (4) | C18—H18 | 0.9300 |
C5—H5 | 0.9300 | C19—C20 | 1.360 (4) |
C6—H6 | 0.9300 | C19—H19 | 0.9300 |
C7—N1 | 1.477 (3) | C20—F1 | 1.359 (3) |
C7—H7A | 0.9700 | C20—C21 | 1.356 (4) |
C7—H7B | 0.9700 | C21—C22 | 1.382 (4) |
C8—N1 | 1.454 (3) | C21—H21 | 0.9300 |
C8—C9 | 1.501 (3) | C22—H22 | 0.9300 |
C8—H8A | 0.9700 | C23—N4 | 1.471 (4) |
C8—H8B | 0.9700 | C23—C24 | 1.479 (5) |
C9—C10 | 1.357 (3) | C23—H23A | 0.9700 |
C10—C13 | 1.439 (3) | C23—H23B | 0.9700 |
C10—C11 | 1.493 (3) | C24—C25 | 1.476 (6) |
C11—C12 | 1.531 (3) | C24—H24A | 0.9700 |
C11—H11A | 0.9700 | C24—H24B | 0.9700 |
C11—H11B | 0.9700 | C25—H25A | 0.9600 |
C12—N1 | 1.464 (3) | C25—H25B | 0.9600 |
C12—H12A | 0.9700 | C25—H25C | 0.9600 |
C12—H12B | 0.9700 | N4—H4A | 0.8600 |
C13—C14 | 1.376 (3) | ||
C14—S1—C9 | 90.85 (12) | C13—C14—S1 | 111.54 (18) |
C2—C1—C6 | 119.6 (3) | N2—C15—N4 | 119.3 (2) |
C2—C1—H1 | 120.2 | N2—C15—N3 | 123.5 (2) |
C6—C1—H1 | 120.2 | N4—C15—N3 | 117.3 (2) |
C3—C2—C1 | 120.6 (3) | O1—C16—N3 | 119.6 (2) |
C3—C2—H2 | 119.7 | O1—C16—C13 | 127.0 (2) |
C1—C2—H2 | 119.7 | N3—C16—C13 | 113.5 (2) |
C2—C3—C4 | 121.0 (3) | C18—C17—C22 | 120.8 (2) |
C2—C3—H3 | 119.5 | C18—C17—N3 | 120.1 (2) |
C4—C3—H3 | 119.5 | C22—C17—N3 | 119.0 (2) |
C5—C4—C3 | 117.8 (3) | C17—C18—C19 | 119.7 (2) |
C5—C4—C7 | 121.3 (2) | C17—C18—H18 | 120.2 |
C3—C4—C7 | 120.9 (3) | C19—C18—H18 | 120.2 |
C6—C5—C4 | 121.0 (3) | C20—C19—C18 | 118.0 (2) |
C6—C5—H5 | 119.5 | C20—C19—H19 | 121.0 |
C4—C5—H5 | 119.5 | C18—C19—H19 | 121.0 |
C1—C6—C5 | 120.1 (3) | F1—C20—C21 | 118.3 (3) |
C1—C6—H6 | 120.0 | F1—C20—C19 | 118.2 (3) |
C5—C6—H6 | 120.0 | C21—C20—C19 | 123.5 (2) |
N1—C7—C4 | 116.7 (2) | C20—C21—C22 | 118.5 (3) |
N1—C7—H7A | 108.1 | C20—C21—H21 | 120.7 |
C4—C7—H7A | 108.1 | C22—C21—H21 | 120.7 |
N1—C7—H7B | 108.1 | C21—C22—C17 | 119.5 (2) |
C4—C7—H7B | 108.1 | C21—C22—H22 | 120.3 |
H7A—C7—H7B | 107.3 | C17—C22—H22 | 120.3 |
N1—C8—C9 | 109.2 (2) | N4—C23—C24 | 113.5 (3) |
N1—C8—H8A | 109.8 | N4—C23—H23A | 108.9 |
C9—C8—H8A | 109.8 | C24—C23—H23A | 108.9 |
N1—C8—H8B | 109.8 | N4—C23—H23B | 108.9 |
C9—C8—H8B | 109.8 | C24—C23—H23B | 108.9 |
H8A—C8—H8B | 108.3 | H23A—C23—H23B | 107.7 |
C10—C9—C8 | 124.2 (2) | C25—C24—C23 | 112.9 (4) |
C10—C9—S1 | 112.95 (18) | C25—C24—H24A | 109.0 |
C8—C9—S1 | 122.80 (18) | C23—C24—H24A | 109.0 |
C9—C10—C13 | 111.7 (2) | C25—C24—H24B | 109.0 |
C9—C10—C11 | 121.1 (2) | C23—C24—H24B | 109.0 |
C13—C10—C11 | 127.2 (2) | H24A—C24—H24B | 107.8 |
C10—C11—C12 | 109.7 (2) | C24—C25—H25A | 109.5 |
C10—C11—H11A | 109.7 | C24—C25—H25B | 109.5 |
C12—C11—H11A | 109.7 | H25A—C25—H25B | 109.5 |
C10—C11—H11B | 109.7 | C24—C25—H25C | 109.5 |
C12—C11—H11B | 109.7 | H25A—C25—H25C | 109.5 |
H11A—C11—H11B | 108.2 | H25B—C25—H25C | 109.5 |
N1—C12—C11 | 109.4 (2) | C8—N1—C12 | 111.55 (19) |
N1—C12—H12A | 109.8 | C8—N1—C7 | 112.4 (2) |
C11—C12—H12A | 109.8 | C12—N1—C7 | 113.4 (2) |
N1—C12—H12B | 109.8 | C15—N2—C14 | 114.5 (2) |
C11—C12—H12B | 109.8 | C15—N3—C16 | 122.68 (19) |
H12A—C12—H12B | 108.2 | C15—N3—C17 | 120.66 (19) |
C14—C13—C16 | 118.3 (2) | C16—N3—C17 | 116.58 (19) |
C14—C13—C10 | 113.0 (2) | C15—N4—C23 | 121.6 (2) |
C16—C13—C10 | 128.7 (2) | C15—N4—H4A | 119.2 |
N2—C14—C13 | 127.5 (2) | C23—N4—H4A | 119.2 |
N2—C14—S1 | 120.96 (19) | ||
C6—C1—C2—C3 | 0.3 (5) | N3—C17—C18—C19 | 179.9 (2) |
C1—C2—C3—C4 | 0.8 (4) | C17—C18—C19—C20 | 0.4 (4) |
C2—C3—C4—C5 | −1.0 (4) | C18—C19—C20—F1 | 179.0 (2) |
C2—C3—C4—C7 | 179.9 (2) | C18—C19—C20—C21 | −2.2 (5) |
C3—C4—C5—C6 | 0.2 (4) | F1—C20—C21—C22 | −179.0 (3) |
C7—C4—C5—C6 | 179.3 (2) | C19—C20—C21—C22 | 2.2 (5) |
C2—C1—C6—C5 | −1.1 (4) | C20—C21—C22—C17 | −0.5 (5) |
C4—C5—C6—C1 | 0.9 (4) | C18—C17—C22—C21 | −1.2 (4) |
C5—C4—C7—N1 | 87.2 (3) | N3—C17—C22—C21 | −179.9 (3) |
C3—C4—C7—N1 | −93.7 (3) | N4—C23—C24—C25 | 67.6 (5) |
N1—C8—C9—C10 | 14.6 (4) | C9—C8—N1—C12 | −49.8 (3) |
N1—C8—C9—S1 | −166.08 (19) | C9—C8—N1—C7 | −178.5 (2) |
C14—S1—C9—C10 | −0.9 (2) | C11—C12—N1—C8 | 69.8 (3) |
C14—S1—C9—C8 | 179.7 (2) | C11—C12—N1—C7 | −162.1 (2) |
C8—C9—C10—C13 | −179.4 (2) | C4—C7—N1—C8 | 65.3 (3) |
S1—C9—C10—C13 | 1.3 (3) | C4—C7—N1—C12 | −62.4 (3) |
C8—C9—C10—C11 | 2.0 (4) | N4—C15—N2—C14 | 178.2 (3) |
S1—C9—C10—C11 | −177.38 (19) | N3—C15—N2—C14 | −1.0 (4) |
C9—C10—C11—C12 | 15.1 (3) | C13—C14—N2—C15 | 1.7 (4) |
C13—C10—C11—C12 | −163.3 (2) | S1—C14—N2—C15 | −177.2 (2) |
C10—C11—C12—N1 | −48.8 (3) | N2—C15—N3—C16 | −0.9 (4) |
C9—C10—C13—C14 | −1.0 (3) | N4—C15—N3—C16 | 179.8 (2) |
C11—C10—C13—C14 | 177.5 (2) | N2—C15—N3—C17 | 175.8 (2) |
C9—C10—C13—C16 | −179.1 (2) | N4—C15—N3—C17 | −3.5 (4) |
C11—C10—C13—C16 | −0.5 (4) | O1—C16—N3—C15 | −178.5 (2) |
C16—C13—C14—N2 | −0.4 (4) | C13—C16—N3—C15 | 2.2 (3) |
C10—C13—C14—N2 | −178.7 (2) | O1—C16—N3—C17 | 4.7 (3) |
C16—C13—C14—S1 | 178.59 (18) | C13—C16—N3—C17 | −174.7 (2) |
C10—C13—C14—S1 | 0.3 (3) | C18—C17—N3—C15 | 101.6 (3) |
C9—S1—C14—N2 | 179.4 (2) | C22—C17—N3—C15 | −79.7 (3) |
C9—S1—C14—C13 | 0.3 (2) | C18—C17—N3—C16 | −81.5 (3) |
C14—C13—C16—O1 | 179.2 (2) | C22—C17—N3—C16 | 97.2 (3) |
C10—C13—C16—O1 | −2.8 (4) | N2—C15—N4—C23 | 0.8 (5) |
C14—C13—C16—N3 | −1.5 (3) | N3—C15—N4—C23 | −180.0 (3) |
C10—C13—C16—N3 | 176.5 (2) | C24—C23—N4—C15 | −165.6 (3) |
C22—C17—C18—C19 | 1.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24B···F1i | 0.97 | 2.66 | 3.258 (5) | 121 |
C25—H25A···F1i | 0.96 | 2.56 | 3.096 (5) | 116 |
N4—H4A···F1i | 0.86 | 2.65 | 3.423 (3) | 151 |
Symmetry code: (i) −x+5/2, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H25FN4OS |
Mr | 448.55 |
Crystal system, space group | Orthorhombic, Ibca |
Temperature (K) | 296 |
a, b, c (Å) | 17.921 (7), 18.427 (7), 27.114 (10) |
V (Å3) | 8954 (6) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.26 × 0.25 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.955, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 46089, 5152, 4234 |
Rint | 0.107 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.194, 1.05 |
No. of reflections | 5152 |
No. of parameters | 290 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.30 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24B···F1i | 0.97 | 2.66 | 3.258 (5) | 120.6 |
C25—H25A···F1i | 0.96 | 2.56 | 3.096 (5) | 115.6 |
N4—H4A···F1i | 0.86 | 2.65 | 3.423 (3) | 150.5 |
Symmetry code: (i) −x+5/2, y, −z+1. |
Acknowledgements
This work was supported financially by the National Natural Science Foundation of China (project No. 21102084), the Key Project of Hubei Provincial Department of Education, China (project No. D20091301) and the Doctoral Start-up Foundation of China Three Gorges University (project No. KJ2009B004).
References
Amr, A. E. G., Sherif, M. H., Assy, M. G., Al-Omar, M. A. & Ragab, I. (2010). Eur. J. Med. Chem. 45, 5935–5942. Web of Science CrossRef CAS PubMed Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, H., Hu, H.-J., Yan, K. & Dai, Q.-H. (2011). Acta Cryst. E67, o2228. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, N. Y., Liang, Y. J., Ding, M. W., Fu, L. W. & He, H. W. (2009). Bioorg. Med. Chem. Lett. 19, 831–833. Web of Science CrossRef PubMed CAS Google Scholar
Mavrova, A. T., Vuchev, D., Anichina, K. & Vassilev, N. (2010). Eur. J. Med. Chem. 45, 5856–5861. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, H., Meng, S.-M., Fan, Y.-Q. & Guo, Y. (2008). Acta Cryst. E64, o2434. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Derivatives of heterocycles containing the thienopyrimidine system have proved to show significant antifungal, antibacterical, anticonvulsant and angiotensin antagonistic activities (Amr et al. 2010; Huang et al. 2009; Mavrova et al. 2010). Recently, we have focused on the synthesis of fused heterocyclic systems containing thienopyrimidine via aza-wittig reaction under mild conditions. Some X-ray crystal structures of fused pyrimidinone derivatives have been reported (Chen et al., 2011; Xie et al., 2008). The title compound has potential use as a precursor for obtaining bioactive molecules with fluorescence properties. Herein, we report its crystal structure (Fig. 1).
In the crystal structure of the title compound, C25H25FN4OS, the thienopyrimidine fused-ring system is close to coplanar (r.m.s deviation = 0.0089 Å) with a maximum deviation of -0.0261 (17) Å for atom N(3). This ring system forms diherdral angles of 64.73 (3) and 81.56 (5)° with the adjacent 6-membered rings C1—C6 and C17—C22, respectively. Most bond lengths in the system fell in the range of single and double bonds, for example, the bond lengths of C(9)—C(10), C(13)—C(14) and C(16)—O(1) were in accordance with the double bond distances. Intermolecular N—H···F (N4—H4A···F1i with symmetry code: (i) 3/2 - x, y, -z) and C—H···F hydrogen bonding (C24—H24B···F1i and C25—H25A···F1i), as well as C—F···π interactions (C20—F1···Cg1 with Cg1 centroids of the C17—C18—C19—C20—C21 ring), helps to stabilize the crystal structure.