Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011303059X/sk3519sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011303059X/sk3519Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S010827011303059X/sk3519Isup3.cml |
CCDC reference: 970789
We report here the molecular and supramolecular structure of the title compound (9E)-9-benzylidene-2-methylsulfanyl-5-phenyl-6,7,8,9-tetrahydropyrimido[4,5-b]quinolin-4(3H)-one, (I) (Fig. 1), which we compare with the related reduced compound, (II) (see Scheme 1; Becerra et al., 2010). Compounds containing a pyrimidoquinoline framework have attracted considerable interest in recent years because of the wide range of biological activity which they can exhibit. For example, compounds of this type have been found to exhibit antibacterial activity against Escherischia coli and Pseudomonas aeruginosa (Selvi et al., 2006) and antifungal activity against Candida albicans and Candida gabrata (El-Gazzar et al., 2008), as well as acting as potent inhibitors of Ehrlich Ascites Carconoma (EAC) cells (Alqasoumi et al., 2010), in addition to potential antimalarial activity (Joshi & Viswanathan, 2006). During our studies on the use of bis-arylidene derivatives for the synthesis of a range of heterocyclic frameworks (Becerra et al., 2010; Insuasty et al., 2008, 2013a,b), pyrimido[4,5-b]quinolines have proved to be interesting targets because of their structural resemblance to benzopteridine derivatives. The title compound, (I), is an example of this class and it was prepared by mild oxidation, using p-chloranil (2,3,5,6-tetrachloro-1,4-benzoquinone), of the corresponding 5,6,7,8,9,10-hexahydro derivative [cf. compound (II)], which had itself been prepared by the acid-catalysed condensation reaction between (2E,6E)-2,6-dibenzylidenecyclohexanone and 6-amino-2-methylsulfanylpyrimidin-4(3H)-one (cf. Becerra et al., 2010).
A mixture of (9E)-9-benzylidene-2-methylsulfanyl-5-phenyl-5,6,7,8,9,10-hexahydropyrimido[4,5-b]quinolin-4(3H)-one (1 mmol) and p-chloranil (1 mmol) in chloroform (20 ml) was heated under reflux for 4 h. The mixture was then cooled to ambient temperature, and the resulting solid product (I) was collected by filtration and then purified by column chromatography on silica gel using dichloromethane–ethanol (30:1 v/v) as eluant. Yellow crystals of compound (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, of a solution in ethanol–dimethylsulfoxide (1:1 v/v) [yield 30%, m.p. 559 K (with decomposition)]. MS (EI, 70 eV) m/z (%): 411 (54) (M+), 410 (98), 397 (31), 396 (100). Analysis found: C 72.9, H 5.2, N 10.2, S 7.7%; C25H21N3OS requires C 73.0, H 5.1, N 10.2, S 7.8%.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were permitted to ride in geometrically idealized positions, with C—H distances of 0.95 (aromatic and alkenic), 0.98 (CH3) or 0.99 Å (CH2) and with Uiso(H) = kUeq(C) where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. The H atom bonded to atom N3 was permitted to ride at the position located in a difference map, with Uiso(H) = 1.2Ueq(N), giving the N—H distance shown in Table 3. Five low-angle reflections, 110, 101, 011, 111 and 002, which had been wholly or partially attenuated by the beam-stop, were omitted from the final refinements.
The title compound, (I), and the 5,6,7,8,9,10-hexahydro derivative, (II), both crystallize in the space group P1 with Z' = 1; the unit-cell vectors for (I) and (II) are reasonably similar, but give slightly different unit-cell volumes as expected from the different molecular compositions (Hofmann, 2002). The compounds are not isostructural since, as noted below, the hydrogen-bonded assembly of the molecules in (I) and (II) is completely different; in addition, the molecules of compound (I) are only conformationally chiral, whereas those of compound (II) are configurationally chiral.
For the fused carbocyclic ring, the ring-puckering parameters (Cremer & Pople, 1975) calculated for the atom sequence C5A—C6—C7—C8—C9—C9A are Q = 0.500 (2) Å, θ = 52.6 (2)° and ϕ = 132.5 (3)°, corresponding closely to an envelope conformation where the ring is folded across the line C6···C8: the idealized values of the ring-puckering angles for this conformation are θ = 54.7° and ϕ = (60k)°, where k represents an integer (Boeyens, 1978). The reminder of the molecular conformation can be specified in terms of just three torsional angles (Table 2) defining the orientation of the peripheral substituents with respect to the adjacent ring system. For comparison, the corresponding torsional angles in the R enantiomer of compound (II) are, respectively, 1.6 (2), -84.5 (3) and -23.7 (4)°, indicating a fairly close conformational similarity between (I) and (II). The dihedral angles between the pyridine ring in compound (I) and the two aryl rings (C51—56) and (C91–C96) are 74.14 (9) and 54.97 (9)°, respectively. The molecules of compound (I) thus exhibit no internal symmetry and they are thus, as noted above, conformationally chiral, although the centrosymmetric space group confirms that equal numbers of the two conformational enantiomers are present. Within the pyridine ring of compound (I), the bond lengths (Table 2) indicate typical heteroaromatic delocalization. The remaining bond distances in (I) show no unusual values: in particular there is no metrical evidence for the type of electronic polarization observed in the molecule of compound (II) (Becerra et al., 2010).
The molecules of compound (I) are linked by an inversion-related pair of almost linear N—H···O hydrogen bonds (Table 3) to form a cyclic centrosymmetric dimer (Fig. 2) characterized by an R22(8) (Bernstein et al., 1995) motif. The only short direction-specific contact between adjacent dimers is a C—H···π(arene) interaction involving one of the C—H bonds of the methyl group (Table 3). This contact is not to be regarded as structurally significant, firstly because the methyl group is likely to be undergoing very rapid rotation about the C21—S21 bond (Riddell & Rogerson, 1996, 1997), and secondly because the H···(ring centroid) distance is long while the C—H···(ring centroid) angle is only 138° (cf. Wood et al., 2009). Hence, the supramolecular assembly in (I) can be regarded as finite or zero-dimensional. By contrast, the supramolecular assembly in (II) is two-dimensional, taking the form of bilayers comprising inversion-related pairs of sheets, built from a combination of two C—H···O hydrogen bonds and two C—H···π(arene) hydrogen bonds. Within the bilayer, each component sheet contains just one enantiomeric form as the molecules comprising the sheet are all related by simple translations (Becerra et al., 2010).
Data collection: COLLECT (Hooft, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C25H21N3OS | Z = 2 |
Mr = 411.52 | F(000) = 432 |
Triclinic, P1 | Dx = 1.343 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2168 (16) Å | Cell parameters from 4669 reflections |
b = 9.7617 (18) Å | θ = 3.7–27.5° |
c = 12.6839 (17) Å | µ = 0.18 mm−1 |
α = 77.688 (16)° | T = 120 K |
β = 75.951 (11)° | Block, yellow |
γ = 68.117 (13)° | 0.34 × 0.30 × 0.28 mm |
V = 1017.7 (3) Å3 |
Bruker–Nonius KappaCCD diffractometer | 4669 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 3311 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.7° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.821, Tmax = 0.950 | l = −16→16 |
28315 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0342P)2 + 0.6598P] where P = (Fo2 + 2Fc2)/3 |
4669 reflections | (Δ/σ)max = 0.001 |
272 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C25H21N3OS | γ = 68.117 (13)° |
Mr = 411.52 | V = 1017.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2168 (16) Å | Mo Kα radiation |
b = 9.7617 (18) Å | µ = 0.18 mm−1 |
c = 12.6839 (17) Å | T = 120 K |
α = 77.688 (16)° | 0.34 × 0.30 × 0.28 mm |
β = 75.951 (11)° |
Bruker–Nonius KappaCCD diffractometer | 4669 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3311 reflections with I > 2σ(I) |
Tmin = 0.821, Tmax = 0.950 | Rint = 0.065 |
28315 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.34 e Å−3 |
4669 reflections | Δρmin = −0.31 e Å−3 |
272 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.69387 (18) | 0.28333 (17) | 0.47393 (13) | 0.0200 (3) | |
C2 | 0.8019 (2) | 0.2844 (2) | 0.52232 (15) | 0.0203 (4) | |
N3 | 0.86286 (19) | 0.39788 (18) | 0.50421 (13) | 0.0229 (4) | |
H3 | 0.9424 | 0.3896 | 0.5348 | 0.027* | |
C4 | 0.8170 (2) | 0.5234 (2) | 0.42981 (15) | 0.0214 (4) | |
O4 | 0.88394 (17) | 0.61698 (16) | 0.41202 (12) | 0.0297 (3) | |
C4A | 0.6921 (2) | 0.5301 (2) | 0.37473 (15) | 0.0184 (4) | |
C5 | 0.6308 (2) | 0.6503 (2) | 0.29529 (15) | 0.0185 (4) | |
C5A | 0.5252 (2) | 0.6393 (2) | 0.23719 (15) | 0.0182 (4) | |
C6 | 0.4605 (2) | 0.7611 (2) | 0.14729 (16) | 0.0223 (4) | |
H6A | 0.5448 | 0.8017 | 0.1059 | 0.027* | |
H6B | 0.3715 | 0.8431 | 0.1808 | 0.027* | |
C7 | 0.4021 (2) | 0.7043 (2) | 0.06845 (16) | 0.0244 (4) | |
H7A | 0.4934 | 0.6329 | 0.0266 | 0.029* | |
H7B | 0.3506 | 0.7887 | 0.0156 | 0.029* | |
C8 | 0.2833 (2) | 0.6276 (2) | 0.13201 (17) | 0.0244 (4) | |
H8A | 0.1915 | 0.6995 | 0.1731 | 0.029* | |
H8B | 0.2436 | 0.5938 | 0.0799 | 0.029* | |
C9 | 0.3602 (2) | 0.4955 (2) | 0.21102 (15) | 0.0202 (4) | |
C9A | 0.4776 (2) | 0.5115 (2) | 0.26666 (15) | 0.0180 (4) | |
N10 | 0.53123 (18) | 0.40011 (17) | 0.34554 (13) | 0.0192 (3) | |
C10A | 0.6393 (2) | 0.4068 (2) | 0.39696 (15) | 0.0188 (4) | |
S21 | 0.88995 (6) | 0.13658 (6) | 0.61849 (4) | 0.02601 (14) | |
C21 | 0.8091 (2) | −0.0012 (2) | 0.60934 (18) | 0.0283 (5) | |
H21A | 0.8117 | −0.0041 | 0.5321 | 0.042* | |
H21B | 0.6989 | 0.0245 | 0.6488 | 0.042* | |
H21C | 0.8725 | −0.0992 | 0.6421 | 0.042* | |
C51 | 0.6735 (2) | 0.7885 (2) | 0.27651 (15) | 0.0187 (4) | |
C52 | 0.6090 (2) | 0.8855 (2) | 0.35568 (16) | 0.0224 (4) | |
H52 | 0.5392 | 0.8631 | 0.4201 | 0.027* | |
C53 | 0.6460 (2) | 1.0142 (2) | 0.34097 (16) | 0.0246 (4) | |
H53 | 0.6002 | 1.0804 | 0.3946 | 0.030* | |
C54 | 0.7500 (2) | 1.0467 (2) | 0.24794 (17) | 0.0260 (4) | |
H54 | 0.7761 | 1.1346 | 0.2379 | 0.031* | |
C55 | 0.8155 (2) | 0.9498 (2) | 0.16989 (17) | 0.0263 (4) | |
H55 | 0.8875 | 0.9712 | 0.1065 | 0.032* | |
C56 | 0.7769 (2) | 0.8219 (2) | 0.18364 (16) | 0.0226 (4) | |
H56 | 0.8214 | 0.7569 | 0.1292 | 0.027* | |
C97 | 0.3365 (2) | 0.3642 (2) | 0.22874 (15) | 0.0216 (4) | |
H97 | 0.3965 | 0.2872 | 0.2769 | 0.026* | |
C91 | 0.2268 (2) | 0.3271 (2) | 0.18121 (15) | 0.0211 (4) | |
C92 | 0.0693 (2) | 0.4207 (2) | 0.17904 (17) | 0.0259 (4) | |
H92 | 0.0309 | 0.5127 | 0.2075 | 0.031* | |
C93 | −0.0314 (2) | 0.3800 (2) | 0.13561 (17) | 0.0276 (5) | |
H93 | −0.1379 | 0.4446 | 0.1345 | 0.033* | |
C94 | 0.0228 (2) | 0.2458 (2) | 0.09391 (16) | 0.0268 (5) | |
H94 | −0.0457 | 0.2190 | 0.0634 | 0.032* | |
C95 | 0.1780 (3) | 0.1511 (2) | 0.09714 (16) | 0.0261 (4) | |
H95 | 0.2153 | 0.0585 | 0.0696 | 0.031* | |
C96 | 0.2789 (2) | 0.1908 (2) | 0.14029 (16) | 0.0230 (4) | |
H96 | 0.3847 | 0.1249 | 0.1422 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0203 (8) | 0.0213 (8) | 0.0190 (8) | −0.0078 (7) | −0.0047 (7) | −0.0011 (6) |
C2 | 0.0186 (9) | 0.0204 (10) | 0.0183 (9) | −0.0038 (8) | −0.0021 (8) | −0.0017 (7) |
N3 | 0.0217 (8) | 0.0253 (9) | 0.0253 (9) | −0.0097 (7) | −0.0111 (7) | 0.0003 (7) |
C4 | 0.0199 (9) | 0.0222 (10) | 0.0218 (10) | −0.0064 (8) | −0.0045 (8) | −0.0031 (8) |
O4 | 0.0293 (8) | 0.0269 (8) | 0.0402 (9) | −0.0149 (6) | −0.0180 (7) | 0.0039 (6) |
C4A | 0.0161 (9) | 0.0208 (10) | 0.0178 (9) | −0.0055 (7) | −0.0008 (7) | −0.0057 (7) |
C5 | 0.0168 (9) | 0.0199 (9) | 0.0185 (9) | −0.0060 (7) | −0.0005 (7) | −0.0051 (7) |
C5A | 0.0163 (9) | 0.0176 (9) | 0.0191 (9) | −0.0038 (7) | −0.0016 (7) | −0.0046 (7) |
C6 | 0.0248 (10) | 0.0197 (10) | 0.0236 (10) | −0.0076 (8) | −0.0084 (8) | −0.0011 (8) |
C7 | 0.0312 (11) | 0.0220 (10) | 0.0225 (10) | −0.0093 (8) | −0.0121 (9) | 0.0007 (8) |
C8 | 0.0262 (10) | 0.0212 (10) | 0.0295 (11) | −0.0082 (8) | −0.0127 (9) | −0.0023 (8) |
C9 | 0.0185 (9) | 0.0205 (10) | 0.0214 (10) | −0.0054 (8) | −0.0037 (8) | −0.0044 (8) |
C9A | 0.0173 (9) | 0.0177 (9) | 0.0180 (9) | −0.0048 (7) | −0.0027 (7) | −0.0033 (7) |
N10 | 0.0192 (8) | 0.0185 (8) | 0.0208 (8) | −0.0061 (6) | −0.0047 (6) | −0.0038 (6) |
C10A | 0.0165 (9) | 0.0198 (10) | 0.0182 (9) | −0.0046 (7) | −0.0015 (7) | −0.0034 (7) |
S21 | 0.0242 (3) | 0.0277 (3) | 0.0246 (3) | −0.0076 (2) | −0.0097 (2) | 0.0037 (2) |
C21 | 0.0273 (11) | 0.0243 (11) | 0.0294 (11) | −0.0070 (9) | −0.0068 (9) | 0.0031 (9) |
C51 | 0.0180 (9) | 0.0176 (9) | 0.0212 (9) | −0.0052 (7) | −0.0086 (8) | −0.0001 (7) |
C52 | 0.0203 (9) | 0.0244 (10) | 0.0223 (10) | −0.0060 (8) | −0.0053 (8) | −0.0038 (8) |
C53 | 0.0263 (10) | 0.0229 (10) | 0.0257 (11) | −0.0059 (8) | −0.0074 (8) | −0.0071 (8) |
C54 | 0.0305 (11) | 0.0191 (10) | 0.0327 (11) | −0.0113 (8) | −0.0109 (9) | −0.0009 (8) |
C55 | 0.0279 (11) | 0.0265 (11) | 0.0250 (10) | −0.0126 (9) | −0.0015 (8) | −0.0019 (8) |
C56 | 0.0225 (10) | 0.0232 (10) | 0.0217 (10) | −0.0069 (8) | −0.0026 (8) | −0.0052 (8) |
C97 | 0.0226 (10) | 0.0214 (10) | 0.0209 (10) | −0.0069 (8) | −0.0064 (8) | −0.0013 (8) |
C91 | 0.0249 (10) | 0.0222 (10) | 0.0188 (9) | −0.0114 (8) | −0.0046 (8) | −0.0007 (8) |
C92 | 0.0257 (10) | 0.0279 (11) | 0.0259 (10) | −0.0097 (9) | −0.0036 (8) | −0.0074 (9) |
C93 | 0.0207 (10) | 0.0345 (12) | 0.0298 (11) | −0.0096 (9) | −0.0046 (8) | −0.0081 (9) |
C94 | 0.0313 (11) | 0.0331 (12) | 0.0232 (10) | −0.0189 (9) | −0.0074 (9) | −0.0012 (9) |
C95 | 0.0367 (12) | 0.0213 (10) | 0.0242 (10) | −0.0121 (9) | −0.0093 (9) | −0.0029 (8) |
C96 | 0.0266 (10) | 0.0207 (10) | 0.0220 (10) | −0.0090 (8) | −0.0070 (8) | 0.0010 (8) |
N1—C2 | 1.294 (2) | C21—H21A | 0.9800 |
N1—C10A | 1.394 (2) | C21—H21B | 0.9800 |
C2—N3 | 1.374 (2) | C21—H21C | 0.9800 |
C2—S21 | 1.7567 (19) | C51—C56 | 1.387 (3) |
N3—C4 | 1.373 (2) | C51—C52 | 1.399 (3) |
N3—H3 | 0.8801 | C52—C53 | 1.385 (3) |
C4—O4 | 1.237 (2) | C52—H52 | 0.9500 |
C4—C4A | 1.461 (3) | C53—C54 | 1.389 (3) |
N10—C10A | 1.343 (2) | C53—H53 | 0.9500 |
C10A—C4A | 1.410 (3) | C54—C55 | 1.387 (3) |
C4A—C5 | 1.411 (3) | C54—H54 | 0.9500 |
C5—C5A | 1.400 (3) | C55—C56 | 1.388 (3) |
C5—C51 | 1.498 (3) | C55—H55 | 0.9500 |
C5A—C9A | 1.422 (3) | C56—H56 | 0.9500 |
C5A—C6 | 1.514 (3) | C97—C91 | 1.476 (3) |
C6—C7 | 1.522 (3) | C97—H97 | 0.9500 |
C6—H6A | 0.9900 | C91—C92 | 1.401 (3) |
C6—H6B | 0.9900 | C91—C96 | 1.402 (3) |
C7—C8 | 1.527 (3) | C92—C93 | 1.392 (3) |
C7—H7A | 0.9900 | C92—H92 | 0.9500 |
C7—H7B | 0.9900 | C93—C94 | 1.387 (3) |
C8—C9 | 1.511 (3) | C93—H93 | 0.9500 |
C8—H8A | 0.9900 | C94—C95 | 1.389 (3) |
C8—H8B | 0.9900 | C94—H94 | 0.9500 |
C9—C97 | 1.342 (3) | C95—C96 | 1.386 (3) |
C9—C9A | 1.495 (3) | C95—H95 | 0.9500 |
C9A—N10 | 1.343 (2) | C96—H96 | 0.9500 |
S21—C21 | 1.799 (2) | ||
C2—N1—C10A | 116.22 (16) | C2—S21—C21 | 101.51 (9) |
N1—C2—N3 | 124.83 (17) | S21—C21—H21A | 109.5 |
N1—C2—S21 | 123.03 (15) | S21—C21—H21B | 109.5 |
N3—C2—S21 | 112.13 (13) | H21A—C21—H21B | 109.5 |
C4—N3—C2 | 123.11 (16) | S21—C21—H21C | 109.5 |
C4—N3—H3 | 115.3 | H21A—C21—H21C | 109.5 |
C2—N3—H3 | 121.2 | H21B—C21—H21C | 109.5 |
O4—C4—N3 | 119.98 (17) | C56—C51—C52 | 119.05 (17) |
O4—C4—C4A | 125.54 (17) | C56—C51—C5 | 121.94 (17) |
N3—C4—C4A | 114.44 (16) | C52—C51—C5 | 119.00 (17) |
C10A—C4A—C5 | 119.23 (16) | C53—C52—C51 | 120.51 (18) |
C10A—C4A—C4 | 118.26 (16) | C53—C52—H52 | 119.7 |
C5—C4A—C4 | 122.36 (17) | C51—C52—H52 | 119.7 |
C5A—C5—C4A | 118.46 (17) | C52—C53—C54 | 120.12 (19) |
C5A—C5—C51 | 120.91 (16) | C52—C53—H53 | 119.9 |
C4A—C5—C51 | 120.59 (16) | C54—C53—H53 | 119.9 |
C5—C5A—C9A | 117.98 (16) | C55—C54—C53 | 119.47 (18) |
C5—C5A—C6 | 121.32 (16) | C55—C54—H54 | 120.3 |
C9A—C5A—C6 | 120.69 (16) | C53—C54—H54 | 120.3 |
C5A—C6—C7 | 111.98 (16) | C54—C55—C56 | 120.54 (19) |
C5A—C6—H6A | 109.2 | C54—C55—H55 | 119.7 |
C7—C6—H6A | 109.2 | C56—C55—H55 | 119.7 |
C5A—C6—H6B | 109.2 | C51—C56—C55 | 120.29 (19) |
C7—C6—H6B | 109.2 | C51—C56—H56 | 119.9 |
H6A—C6—H6B | 107.9 | C55—C56—H56 | 119.9 |
C6—C7—C8 | 110.10 (16) | C9—C97—C91 | 126.78 (17) |
C6—C7—H7A | 109.6 | C9—C97—H97 | 116.6 |
C8—C7—H7A | 109.6 | C91—C97—H97 | 116.6 |
C6—C7—H7B | 109.6 | C92—C91—C96 | 118.20 (17) |
C8—C7—H7B | 109.6 | C92—C91—C97 | 122.42 (18) |
H7A—C7—H7B | 108.2 | C96—C91—C97 | 119.33 (17) |
C9—C8—C7 | 110.73 (16) | C93—C92—C91 | 120.64 (19) |
C9—C8—H8A | 109.5 | C93—C92—H92 | 119.7 |
C7—C8—H8A | 109.5 | C91—C92—H92 | 119.7 |
C9—C8—H8B | 109.5 | C94—C93—C92 | 120.41 (19) |
C7—C8—H8B | 109.5 | C94—C93—H93 | 119.8 |
H8A—C8—H8B | 108.1 | C92—C93—H93 | 119.8 |
C97—C9—C9A | 118.93 (17) | C93—C94—C95 | 119.46 (18) |
C97—C9—C8 | 124.17 (17) | C93—C94—H94 | 120.3 |
C9A—C9—C8 | 116.78 (16) | C95—C94—H94 | 120.3 |
N10—C9A—C5A | 123.25 (16) | C96—C95—C94 | 120.43 (19) |
N10—C9A—C9 | 115.97 (16) | C96—C95—H95 | 119.8 |
C5A—C9A—C9 | 120.77 (16) | C94—C95—H95 | 119.8 |
C9A—N10—C10A | 118.69 (16) | C95—C96—C91 | 120.84 (18) |
N10—C10A—N1 | 114.79 (16) | C95—C96—H96 | 119.6 |
N10—C10A—C4A | 122.22 (17) | C91—C96—H96 | 119.6 |
N1—C10A—C4A | 122.99 (16) | ||
C10A—N1—C2—N3 | 1.0 (3) | C9A—N10—C10A—N1 | −177.11 (16) |
C10A—N1—C2—S21 | −177.95 (14) | C9A—N10—C10A—C4A | 3.3 (3) |
N1—C2—N3—C4 | −1.3 (3) | C2—N1—C10A—N10 | 177.87 (17) |
S21—C2—N3—C4 | 177.72 (15) | C2—N1—C10A—C4A | −2.5 (3) |
C2—N3—C4—O4 | −175.20 (18) | C5—C4A—C10A—N10 | −0.5 (3) |
C2—N3—C4—C4A | 2.8 (3) | C4—C4A—C10A—N10 | −176.30 (17) |
O4—C4—C4A—C10A | 173.84 (19) | C5—C4A—C10A—N1 | 179.87 (17) |
N3—C4—C4A—C10A | −4.0 (3) | C4—C4A—C10A—N1 | 4.1 (3) |
O4—C4—C4A—C5 | −1.8 (3) | N1—C2—S21—C21 | 7.03 (19) |
N3—C4—C4A—C5 | −179.62 (17) | N3—C2—S21—C21 | −172.05 (14) |
C10A—C4A—C5—C5A | −3.2 (3) | C5A—C5—C51—C56 | −75.2 (2) |
C4—C4A—C5—C5A | 172.40 (17) | C4A—C5—C51—C56 | 106.9 (2) |
C10A—C4A—C5—C51 | 174.73 (17) | C5A—C5—C51—C52 | 105.7 (2) |
C4—C4A—C5—C51 | −9.7 (3) | C4A—C5—C51—C52 | −72.2 (2) |
C4A—C5—C5A—C9A | 4.0 (3) | C56—C51—C52—C53 | 0.8 (3) |
C51—C5—C5A—C9A | −173.86 (17) | C5—C51—C52—C53 | 179.97 (17) |
C4A—C5—C5A—C6 | −177.27 (17) | C51—C52—C53—C54 | −1.1 (3) |
C51—C5—C5A—C6 | 4.8 (3) | C52—C53—C54—C55 | 0.4 (3) |
C5—C5A—C6—C7 | 158.42 (18) | C53—C54—C55—C56 | 0.6 (3) |
C9A—C5A—C6—C7 | −22.9 (3) | C52—C51—C56—C55 | 0.1 (3) |
C5A—C6—C7—C8 | 53.5 (2) | C5—C51—C56—C55 | −179.02 (17) |
C6—C7—C8—C9 | −60.9 (2) | C54—C55—C56—C51 | −0.8 (3) |
C7—C8—C9—C97 | −139.0 (2) | C9A—C9—C97—C91 | −179.76 (18) |
C7—C8—C9—C9A | 37.0 (2) | C8—C9—C97—C91 | −3.9 (3) |
C5—C5A—C9A—N10 | −1.4 (3) | C9—C97—C91—C92 | −46.8 (3) |
C6—C5A—C9A—N10 | 179.91 (17) | C9—C97—C91—C96 | 135.7 (2) |
C5—C5A—C9A—C9 | 177.57 (17) | C96—C91—C92—C93 | −1.1 (3) |
C6—C5A—C9A—C9 | −1.1 (3) | C97—C91—C92—C93 | −178.58 (18) |
C97—C9—C9A—N10 | −11.1 (3) | C91—C92—C93—C94 | 0.1 (3) |
C8—C9—C9A—N10 | 172.76 (17) | C92—C93—C94—C95 | 0.9 (3) |
C97—C9—C9A—C5A | 169.91 (18) | C93—C94—C95—C96 | −0.9 (3) |
C8—C9—C9A—C5A | −6.3 (3) | C94—C95—C96—C91 | −0.1 (3) |
C5A—C9A—N10—C10A | −2.3 (3) | C92—C91—C96—C95 | 1.1 (3) |
C9—C9A—N10—C10A | 178.69 (16) | C97—C91—C96—C95 | 178.68 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.88 | 1.86 | 2.735 (3) | 175 |
C21—H21C···Cg1ii | 0.98 | 2.99 | 3.777 (2) | 138 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H21N3OS |
Mr | 411.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 9.2168 (16), 9.7617 (18), 12.6839 (17) |
α, β, γ (°) | 77.688 (16), 75.951 (11), 68.117 (13) |
V (Å3) | 1017.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.34 × 0.30 × 0.28 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.821, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28315, 4669, 3311 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.107, 1.06 |
No. of reflections | 4669 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.31 |
Computer programs: COLLECT (Hooft, 1998), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
N10—C10A | 1.343 (2) | C5—C5A | 1.400 (3) |
C10A—C4A | 1.410 (3) | C5A—C9A | 1.422 (3) |
C4A—C5 | 1.411 (3) | C9A—N10 | 1.343 (2) |
N1—C2—S21—C21 | 7.03 (19) | C9—C97—C91—C92 | −46.8 (3) |
C4A—C5—C51—C52 | −72.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4i | 0.88 | 1.86 | 2.735 (3) | 175 |
C21—H21C···Cg1ii | 0.98 | 2.99 | 3.777 (2) | 138 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y, −z+1. |