organic compounds
Ethyl 2-[2-(2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazin-1-yl]-4-methyl-1,3-thiazole-5-carboxylate dimethylformamide monosolvate
aDepartment of Chemistry, Annamalai University, Annamalainagar 608 002, Chidambaram, Tamil Nadu, India
*Correspondence e-mail: jothiichem@gmail.com
In the title molecule, C27H30N4O2S·C3H7NO, the fused piperidine and cyclohexane rings adopt a twin chair conformation and the phenyl groups occupy equatorial sites. The phenyl rings make a dihedral angle of 40.74 (2)°. In the crystal, the dimethylformamide solvent molecule is connected to the main molecule by an N—H⋯O hydrogen bond. An additional N—H⋯O hydrogen bond connects molecules into chains along [100]. Pairs of weak C—H⋯O hydrogen bonds connect inversion-related chains. The ethyl group was refined as disordered over two sets of sites with an occupancy ratio of 0.660 (17):0.340 (17).
CCDC reference: 956569
Related literature
For the biological activity of related structures, see: Ramachandran et al. (2009); Hutchinson et al. (2002); Bondock et al. (2007). For bicyclic compounds, see: Jeyaraman & Avila (1981).
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2004); cell APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 956569
https://doi.org/10.1107/S1600536813033540/lh5671sup1.cif
contains datablocks I, 1. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033540/lh5671Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813033540/lh5671Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S1600536813033540/lh5671Isup4.cml
To a boiling solution of the bicyclic thiosemicarbazone (0.01 mol) in ethanolic–chloroform (1:1 / v:v), ethyl-2-chloroacetoacetate(0.01 mol), sodium acetate trihydrate (0.02 mol) and a few drops of acetic acid were added and refluxed for about 5–6 h. After the completion of reaction, excess of solvent was removed under reduced pressure and poured into water. After work–up, the solid was separated and purified by
using benzene–ethyl acetate (9:1 / v:v) as on neutral alumina. Colourless crystals were grown by slow evaporation method using dimethylformamide as the solvent.H atoms bonded to C atoms were included in calculated positions with C—H = 0.93-0.98Å and included in the
with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). H atoms bonded to N atoms were refined independently with isotropic displacment parameters.Thiazoles are an interesting unit in medicinal chemistry and are responsible for numerous pharmacological and biological properties (Hutchinson et al. 2002; Bondock et al., 2007; Ramachandran et al., 2009). This has piqued our interest in the synthesis of thiazole containing compounds. The importance of bicyclic compounds as intermediates in the synthesis of a several physiologically active compounds have been reviewed by Jeyaraman & Avila (1981). Moreover, these bridged bicyclic compounds exhibit twin chair, chair–boat or twin boat conformations and possess interesting stereochemistries. In order to investigate the change in
of the piperidine and cyclohexane rings, the X-ray of the title compound was carried out. The six–membered heterocyclic piperidine ring (Fig. 1) adopts the expected chair conformation. The two phenyl rings form a dihedral angle of 40.74 (2)°. In the crystal the dimethylformamide solvent molecule is connected to the main molecule by an N—H···O hydrogen bond. An additional N—H···O hydrogen bond connects molecules into chains along [100] (Fig. 2). Weak C—H···O hydrogen bonds connect pairs of inversion related chains. The ethyl group was refined as disordered over two sets of sites with a 0.660 (17): 0.340 (17) ratio of occupancies.For the biological activity of related structures, see: Ramachandran et al. (2009); Hutchinson et al. (2002); Bondock et al. (2007). For bicyclic compounds, see: Jeyaraman & Avila (1981).
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. | |
Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines. |
C27H30N4O2S·C3H7NO | F(000) = 1168 |
Mr = 547.71 | Dx = 1.235 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6962 reflections |
a = 12.700 (5) Å | θ = 2.1–22.4° |
b = 19.427 (5) Å | µ = 0.15 mm−1 |
c = 13.203 (5) Å | T = 293 K |
β = 115.249 (5)° | Block, colourless |
V = 2946.3 (18) Å3 | 0.35 × 0.35 × 0.30 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 5179 independent reflections |
Radiation source: fine-focus sealed tube | 3606 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω and φ sacn scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −15→15 |
Tmin = 0.937, Tmax = 0.965 | k = −20→23 |
25815 measured reflections | l = −15→15 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0579P)2 + 2.3626P] where P = (Fo2 + 2Fc2)/3 |
5179 reflections | (Δ/σ)max = 0.001 |
379 parameters | Δρmax = 0.56 e Å−3 |
40 restraints | Δρmin = −0.37 e Å−3 |
C27H30N4O2S·C3H7NO | V = 2946.3 (18) Å3 |
Mr = 547.71 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.700 (5) Å | µ = 0.15 mm−1 |
b = 19.427 (5) Å | T = 293 K |
c = 13.203 (5) Å | 0.35 × 0.35 × 0.30 mm |
β = 115.249 (5)° |
Bruker Kappa APEXII CCD diffractometer | 5179 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3606 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.965 | Rint = 0.032 |
25815 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 40 restraints |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.56 e Å−3 |
5179 reflections | Δρmin = −0.37 e Å−3 |
379 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 | Occ. (<1) | |
C1 | 0.0735 (2) | 0.24044 (14) | 0.5466 (2) | 0.0499 (7) | |
C2 | 0.0996 (3) | 0.27051 (16) | 0.6495 (3) | 0.0647 (8) | |
H2 | 0.0572 | 0.2579 | 0.6892 | 0.078* | |
C3 | 0.1867 (3) | 0.31863 (18) | 0.6946 (3) | 0.0815 (11) | |
H3 | 0.2018 | 0.3387 | 0.7634 | 0.098* | |
C4 | 0.2508 (3) | 0.33680 (19) | 0.6382 (4) | 0.0891 (12) | |
H4 | 0.3109 | 0.3686 | 0.6690 | 0.107* | |
C5 | 0.2264 (3) | 0.3081 (2) | 0.5363 (4) | 0.0902 (12) | |
H5 | 0.2692 | 0.3211 | 0.4972 | 0.108* | |
C6 | 0.1386 (3) | 0.25983 (18) | 0.4907 (3) | 0.0706 (9) | |
H6 | 0.1234 | 0.2403 | 0.4215 | 0.085* | |
C7 | −0.0232 (2) | 0.18797 (13) | 0.5011 (2) | 0.0450 (6) | |
H7 | −0.0184 | 0.1591 | 0.5638 | 0.054* | |
C8 | −0.0971 (2) | 0.08953 (13) | 0.3738 (2) | 0.0445 (6) | |
H8 | −0.0939 | 0.0613 | 0.4365 | 0.053* | |
C9 | −0.0710 (2) | 0.04318 (13) | 0.2953 (2) | 0.0452 (6) | |
C10 | −0.0280 (2) | 0.06844 (15) | 0.2225 (2) | 0.0546 (7) | |
H10 | −0.0154 | 0.1155 | 0.2208 | 0.066* | |
C11 | −0.0035 (3) | 0.02520 (19) | 0.1523 (3) | 0.0673 (9) | |
H11 | 0.0247 | 0.0434 | 0.1036 | 0.081* | |
C12 | −0.0204 (3) | −0.0437 (2) | 0.1539 (3) | 0.0750 (10) | |
H12 | −0.0027 | −0.0727 | 0.1073 | 0.090* | |
C13 | −0.0633 (3) | −0.07009 (17) | 0.2242 (3) | 0.0743 (10) | |
H13 | −0.0757 | −0.1172 | 0.2248 | 0.089* | |
C14 | −0.0887 (3) | −0.02709 (15) | 0.2951 (3) | 0.0613 (8) | |
H14 | −0.1180 | −0.0458 | 0.3427 | 0.074* | |
C15 | −0.2198 (2) | 0.12259 (15) | 0.3180 (2) | 0.0490 (7) | |
H15 | −0.2783 | 0.0858 | 0.2944 | 0.059* | |
C16 | −0.2341 (2) | 0.16510 (14) | 0.4064 (2) | 0.0472 (6) | |
C17 | −0.1453 (2) | 0.22093 (14) | 0.4488 (2) | 0.0495 (7) | |
H17 | −0.1569 | 0.2461 | 0.5076 | 0.059* | |
C18 | −0.1687 (3) | 0.27046 (16) | 0.3508 (3) | 0.0626 (8) | |
H18A | −0.2426 | 0.2933 | 0.3319 | 0.075* | |
H18B | −0.1086 | 0.3055 | 0.3749 | 0.075* | |
C19 | −0.1718 (3) | 0.23575 (17) | 0.2467 (3) | 0.0665 (9) | |
H19A | −0.0928 | 0.2250 | 0.2583 | 0.080* | |
H19B | −0.2043 | 0.2675 | 0.1841 | 0.080* | |
C20 | −0.2433 (2) | 0.17010 (17) | 0.2176 (2) | 0.0625 (8) | |
H20A | −0.2274 | 0.1449 | 0.1623 | 0.075* | |
H20B | −0.3252 | 0.1823 | 0.1837 | 0.075* | |
C21 | −0.4752 (2) | 0.10489 (15) | 0.4414 (2) | 0.0518 (7) | |
C22 | −0.6309 (2) | 0.06611 (18) | 0.4541 (3) | 0.0641 (9) | |
C23 | −0.5903 (3) | 0.10747 (18) | 0.5450 (3) | 0.0670 (9) | |
C24 | −0.6432 (4) | 0.1188 (2) | 0.6213 (4) | 0.0859 (12) | |
C27 | −0.7378 (3) | 0.0215 (2) | 0.4136 (4) | 0.0902 (12) | |
H27A | −0.7461 | −0.0024 | 0.3470 | 0.135* | |
H27B | −0.8051 | 0.0498 | 0.3974 | 0.135* | |
H27C | −0.7305 | −0.0113 | 0.4706 | 0.135* | |
C28 | −0.7208 (4) | −0.0655 (2) | 0.1020 (4) | 0.1106 (15) | |
H28A | −0.7792 | −0.0754 | 0.0281 | 0.166* | |
H28B | −0.7567 | −0.0450 | 0.1455 | 0.166* | |
H28C | −0.6827 | −0.1074 | 0.1371 | 0.166* | |
C29 | −0.6557 (3) | 0.0071 (2) | −0.0138 (3) | 0.0943 (12) | |
H29C | −0.6091 | 0.0475 | −0.0054 | 0.141* | |
H29A | −0.7365 | 0.0185 | −0.0551 | 0.141* | |
H29B | −0.6344 | −0.0275 | −0.0534 | 0.141* | |
C30 | −0.5483 (3) | 0.00313 (18) | 0.1851 (3) | 0.0675 (8) | |
H30 | −0.5396 | −0.0152 | 0.2533 | 0.081* | |
N1 | −0.00799 (18) | 0.14310 (11) | 0.41935 (18) | 0.0453 (5) | |
N2 | −0.31082 (18) | 0.16070 (12) | 0.44462 (18) | 0.0512 (6) | |
N3 | −0.39631 (19) | 0.11185 (14) | 0.3983 (2) | 0.0567 (6) | |
N4 | −0.56551 (19) | 0.06438 (13) | 0.3952 (2) | 0.0583 (6) | |
N5 | −0.6363 (2) | −0.01846 (13) | 0.0948 (2) | 0.0637 (7) | |
O1 | −0.7381 (2) | 0.09901 (17) | 0.6088 (3) | 0.1174 (11) | |
O2 | −0.5722 (3) | 0.15330 (17) | 0.7104 (2) | 0.1002 (9) | |
O3 | −0.4768 (2) | 0.04548 (16) | 0.1866 (2) | 0.0917 (8) | |
S1 | −0.46094 (7) | 0.14717 (5) | 0.56068 (7) | 0.0648 (3) | |
C25 | −0.588 (2) | 0.1963 (16) | 0.8026 (13) | 0.120 (6) | 0.340 (17) |
H25A | −0.5743 | 0.2446 | 0.7939 | 0.144* | 0.340 (17) |
H25B | −0.6672 | 0.1914 | 0.7946 | 0.144* | 0.340 (17) |
C26 | −0.5059 (18) | 0.1725 (11) | 0.9147 (13) | 0.091 (5) | 0.340 (17) |
H26A | −0.5358 | 0.1840 | 0.9682 | 0.137* | 0.340 (17) |
H26B | −0.4319 | 0.1945 | 0.9354 | 0.137* | 0.340 (17) |
H26C | −0.4965 | 0.1235 | 0.9135 | 0.137* | 0.340 (17) |
C25' | −0.6228 (7) | 0.1578 (6) | 0.7918 (6) | 0.085 (2) | 0.660 (17) |
H25C | −0.6998 | 0.1783 | 0.7589 | 0.103* | 0.660 (17) |
H25D | −0.6268 | 0.1130 | 0.8225 | 0.103* | 0.660 (17) |
C26' | −0.5381 (12) | 0.2028 (9) | 0.8765 (14) | 0.140 (5) | 0.660 (17) |
H26D | −0.5628 | 0.2118 | 0.9345 | 0.210* | 0.660 (17) |
H26E | −0.5326 | 0.2455 | 0.8423 | 0.210* | 0.660 (17) |
H26F | −0.4633 | 0.1808 | 0.9081 | 0.210* | 0.660 (17) |
H1A | 0.0570 (18) | 0.1231 (13) | 0.451 (2) | 0.051 (8)* | |
H3A | −0.415 (2) | 0.0916 (13) | 0.3356 (17) | 0.051 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0418 (14) | 0.0513 (16) | 0.0553 (16) | −0.0015 (12) | 0.0194 (12) | −0.0048 (13) |
C2 | 0.0544 (17) | 0.070 (2) | 0.073 (2) | −0.0053 (15) | 0.0304 (16) | −0.0243 (17) |
C3 | 0.064 (2) | 0.075 (2) | 0.096 (3) | −0.0101 (18) | 0.026 (2) | −0.040 (2) |
C4 | 0.065 (2) | 0.070 (2) | 0.118 (3) | −0.0231 (18) | 0.025 (2) | −0.023 (2) |
C5 | 0.078 (2) | 0.093 (3) | 0.107 (3) | −0.034 (2) | 0.047 (2) | −0.001 (2) |
C6 | 0.069 (2) | 0.080 (2) | 0.068 (2) | −0.0245 (17) | 0.0339 (17) | −0.0077 (17) |
C7 | 0.0438 (14) | 0.0508 (15) | 0.0434 (14) | −0.0053 (12) | 0.0215 (12) | −0.0018 (12) |
C8 | 0.0411 (13) | 0.0510 (15) | 0.0436 (14) | −0.0048 (12) | 0.0203 (11) | −0.0011 (12) |
C9 | 0.0353 (13) | 0.0489 (16) | 0.0490 (15) | −0.0025 (11) | 0.0158 (11) | −0.0046 (12) |
C10 | 0.0482 (16) | 0.0595 (17) | 0.0653 (18) | −0.0076 (13) | 0.0331 (14) | −0.0098 (15) |
C11 | 0.0583 (18) | 0.083 (2) | 0.072 (2) | 0.0003 (16) | 0.0382 (17) | −0.0126 (18) |
C12 | 0.077 (2) | 0.079 (3) | 0.070 (2) | 0.0138 (19) | 0.0332 (19) | −0.0153 (19) |
C13 | 0.091 (2) | 0.0468 (18) | 0.071 (2) | 0.0058 (17) | 0.0211 (19) | −0.0102 (16) |
C14 | 0.0672 (19) | 0.0564 (18) | 0.0578 (18) | −0.0036 (15) | 0.0242 (15) | 0.0037 (15) |
C15 | 0.0359 (13) | 0.0662 (18) | 0.0490 (15) | −0.0060 (12) | 0.0220 (12) | −0.0080 (13) |
C16 | 0.0380 (13) | 0.0634 (17) | 0.0438 (14) | 0.0022 (12) | 0.0210 (12) | −0.0036 (13) |
C17 | 0.0449 (14) | 0.0598 (17) | 0.0525 (16) | −0.0029 (13) | 0.0290 (13) | −0.0102 (13) |
C18 | 0.0561 (17) | 0.0620 (19) | 0.075 (2) | 0.0106 (15) | 0.0330 (16) | 0.0056 (16) |
C19 | 0.0674 (19) | 0.078 (2) | 0.0617 (19) | 0.0187 (17) | 0.0348 (16) | 0.0212 (17) |
C20 | 0.0484 (16) | 0.093 (2) | 0.0455 (16) | 0.0174 (16) | 0.0193 (13) | −0.0005 (16) |
C21 | 0.0392 (14) | 0.0680 (18) | 0.0523 (16) | 0.0086 (13) | 0.0235 (13) | 0.0115 (14) |
C22 | 0.0426 (16) | 0.077 (2) | 0.080 (2) | 0.0187 (15) | 0.0330 (16) | 0.0376 (19) |
C23 | 0.0543 (18) | 0.085 (2) | 0.079 (2) | 0.0233 (17) | 0.0450 (17) | 0.037 (2) |
C24 | 0.080 (3) | 0.114 (3) | 0.086 (3) | 0.041 (2) | 0.057 (2) | 0.050 (2) |
C27 | 0.0486 (18) | 0.098 (3) | 0.130 (3) | 0.0033 (18) | 0.044 (2) | 0.033 (2) |
C28 | 0.109 (3) | 0.117 (3) | 0.105 (3) | −0.050 (3) | 0.045 (3) | −0.007 (3) |
C29 | 0.074 (2) | 0.134 (4) | 0.063 (2) | −0.019 (2) | 0.0183 (18) | 0.007 (2) |
C30 | 0.061 (2) | 0.078 (2) | 0.060 (2) | 0.0036 (18) | 0.0231 (17) | −0.0044 (17) |
N1 | 0.0351 (11) | 0.0515 (13) | 0.0495 (13) | −0.0012 (10) | 0.0182 (10) | −0.0055 (11) |
N2 | 0.0390 (12) | 0.0712 (15) | 0.0486 (13) | −0.0025 (11) | 0.0238 (10) | −0.0022 (12) |
N3 | 0.0427 (13) | 0.0850 (18) | 0.0492 (14) | −0.0094 (12) | 0.0262 (11) | −0.0104 (13) |
N4 | 0.0361 (12) | 0.0736 (16) | 0.0659 (15) | 0.0040 (11) | 0.0224 (11) | 0.0138 (13) |
N5 | 0.0546 (15) | 0.0708 (17) | 0.0600 (16) | −0.0065 (13) | 0.0190 (13) | −0.0008 (13) |
O1 | 0.0866 (19) | 0.164 (3) | 0.145 (3) | 0.0323 (19) | 0.0910 (19) | 0.058 (2) |
O2 | 0.096 (2) | 0.148 (3) | 0.0854 (18) | 0.0435 (19) | 0.0665 (17) | 0.0204 (18) |
O3 | 0.0672 (15) | 0.135 (2) | 0.0749 (16) | −0.0336 (16) | 0.0326 (13) | −0.0304 (15) |
S1 | 0.0582 (5) | 0.0880 (6) | 0.0615 (5) | 0.0065 (4) | 0.0383 (4) | 0.0060 (4) |
C25 | 0.119 (13) | 0.152 (14) | 0.117 (11) | 0.027 (11) | 0.077 (10) | −0.002 (12) |
C26 | 0.121 (11) | 0.099 (11) | 0.079 (8) | 0.025 (8) | 0.067 (8) | −0.005 (7) |
C25' | 0.096 (5) | 0.096 (6) | 0.099 (4) | −0.001 (4) | 0.075 (4) | −0.009 (4) |
C26' | 0.133 (11) | 0.165 (11) | 0.147 (12) | −0.027 (9) | 0.083 (10) | −0.078 (9) |
C1—C6 | 1.375 (4) | C20—H20A | 0.9700 |
C1—C2 | 1.383 (4) | C20—H20B | 0.9700 |
C1—C7 | 1.509 (4) | C21—N4 | 1.308 (4) |
C2—C3 | 1.375 (4) | C21—N3 | 1.354 (3) |
C2—H2 | 0.9300 | C21—S1 | 1.716 (3) |
C3—C4 | 1.364 (5) | C22—C23 | 1.351 (5) |
C3—H3 | 0.9300 | C22—N4 | 1.358 (4) |
C4—C5 | 1.364 (5) | C22—C27 | 1.503 (5) |
C4—H4 | 0.9300 | C23—C24 | 1.445 (5) |
C5—C6 | 1.383 (5) | C23—S1 | 1.746 (3) |
C5—H5 | 0.9300 | C24—O1 | 1.208 (5) |
C6—H6 | 0.9300 | C24—O2 | 1.320 (5) |
C7—N1 | 1.462 (3) | C27—H27A | 0.9600 |
C7—C17 | 1.542 (4) | C27—H27B | 0.9600 |
C7—H7 | 0.9800 | C27—H27C | 0.9600 |
C8—N1 | 1.464 (3) | C28—N5 | 1.443 (4) |
C8—C9 | 1.512 (4) | C28—H28A | 0.9600 |
C8—C15 | 1.551 (4) | C28—H28B | 0.9600 |
C8—H8 | 0.9800 | C28—H28C | 0.9600 |
C9—C10 | 1.382 (4) | C29—N5 | 1.435 (4) |
C9—C14 | 1.383 (4) | C29—H29C | 0.9600 |
C10—C11 | 1.381 (4) | C29—H29A | 0.9600 |
C10—H10 | 0.9300 | C29—H29B | 0.9600 |
C11—C12 | 1.357 (5) | C30—O3 | 1.219 (4) |
C11—H11 | 0.9300 | C30—N5 | 1.308 (4) |
C12—C13 | 1.361 (5) | C30—H30 | 0.9300 |
C12—H12 | 0.9300 | N1—H1A | 0.844 (17) |
C13—C14 | 1.392 (4) | N2—N3 | 1.374 (3) |
C13—H13 | 0.9300 | N3—H3A | 0.853 (17) |
C14—H14 | 0.9300 | O2—C25' | 1.472 (6) |
C15—C16 | 1.502 (4) | O2—C25 | 1.559 (15) |
C15—C20 | 1.536 (4) | C25—C26 | 1.474 (16) |
C15—H15 | 0.9800 | C25—H25A | 0.9700 |
C16—N2 | 1.277 (3) | C25—H25B | 0.9700 |
C16—C17 | 1.491 (4) | C26—H26A | 0.9600 |
C17—C18 | 1.536 (4) | C26—H26B | 0.9600 |
C17—H17 | 0.9800 | C26—H26C | 0.9600 |
C18—C19 | 1.517 (4) | C25'—C26' | 1.465 (11) |
C18—H18A | 0.9700 | C25'—H25C | 0.9700 |
C18—H18B | 0.9700 | C25'—H25D | 0.9700 |
C19—C20 | 1.517 (4) | C26'—H26D | 0.9600 |
C19—H19A | 0.9700 | C26'—H26E | 0.9600 |
C19—H19B | 0.9700 | C26'—H26F | 0.9600 |
C6—C1—C2 | 117.7 (3) | C19—C20—H20A | 108.7 |
C6—C1—C7 | 123.0 (3) | C15—C20—H20A | 108.7 |
C2—C1—C7 | 119.3 (2) | C19—C20—H20B | 108.7 |
C3—C2—C1 | 121.6 (3) | C15—C20—H20B | 108.7 |
C3—C2—H2 | 119.2 | H20A—C20—H20B | 107.6 |
C1—C2—H2 | 119.2 | N4—C21—N3 | 121.6 (3) |
C4—C3—C2 | 119.8 (3) | N4—C21—S1 | 116.3 (2) |
C4—C3—H3 | 120.1 | N3—C21—S1 | 122.1 (2) |
C2—C3—H3 | 120.1 | C23—C22—N4 | 115.4 (3) |
C3—C4—C5 | 119.7 (3) | C23—C22—C27 | 127.1 (3) |
C3—C4—H4 | 120.1 | N4—C22—C27 | 117.5 (3) |
C5—C4—H4 | 120.1 | C22—C23—C24 | 126.5 (3) |
C4—C5—C6 | 120.6 (4) | C22—C23—S1 | 110.6 (2) |
C4—C5—H5 | 119.7 | C24—C23—S1 | 122.9 (3) |
C6—C5—H5 | 119.7 | O1—C24—O2 | 123.1 (4) |
C1—C6—C5 | 120.6 (3) | O1—C24—C23 | 126.1 (5) |
C1—C6—H6 | 119.7 | O2—C24—C23 | 110.8 (4) |
C5—C6—H6 | 119.7 | C22—C27—H27A | 109.5 |
N1—C7—C1 | 110.8 (2) | C22—C27—H27B | 109.5 |
N1—C7—C17 | 110.0 (2) | H27A—C27—H27B | 109.5 |
C1—C7—C17 | 112.9 (2) | C22—C27—H27C | 109.5 |
N1—C7—H7 | 107.6 | H27A—C27—H27C | 109.5 |
C1—C7—H7 | 107.6 | H27B—C27—H27C | 109.5 |
C17—C7—H7 | 107.6 | N5—C28—H28A | 109.5 |
N1—C8—C9 | 110.3 (2) | N5—C28—H28B | 109.5 |
N1—C8—C15 | 110.2 (2) | H28A—C28—H28B | 109.5 |
C9—C8—C15 | 113.0 (2) | N5—C28—H28C | 109.5 |
N1—C8—H8 | 107.7 | H28A—C28—H28C | 109.5 |
C9—C8—H8 | 107.7 | H28B—C28—H28C | 109.5 |
C15—C8—H8 | 107.7 | N5—C29—H29C | 109.5 |
C10—C9—C14 | 117.5 (3) | N5—C29—H29A | 109.5 |
C10—C9—C8 | 122.1 (2) | H29C—C29—H29A | 109.5 |
C14—C9—C8 | 120.4 (2) | N5—C29—H29B | 109.5 |
C11—C10—C9 | 121.3 (3) | H29C—C29—H29B | 109.5 |
C11—C10—H10 | 119.4 | H29A—C29—H29B | 109.5 |
C9—C10—H10 | 119.4 | O3—C30—N5 | 124.9 (3) |
C12—C11—C10 | 120.5 (3) | O3—C30—H30 | 117.6 |
C12—C11—H11 | 119.8 | N5—C30—H30 | 117.6 |
C10—C11—H11 | 119.8 | C7—N1—C8 | 113.88 (19) |
C11—C12—C13 | 119.6 (3) | C7—N1—H1A | 108.3 (19) |
C11—C12—H12 | 120.2 | C8—N1—H1A | 107.3 (19) |
C13—C12—H12 | 120.2 | C16—N2—N3 | 117.5 (2) |
C12—C13—C14 | 120.5 (3) | C21—N3—N2 | 117.9 (2) |
C12—C13—H13 | 119.7 | C21—N3—H3A | 114.5 (19) |
C14—C13—H13 | 119.7 | N2—N3—H3A | 126.0 (19) |
C9—C14—C13 | 120.6 (3) | C21—N4—C22 | 110.3 (3) |
C9—C14—H14 | 119.7 | C30—N5—C29 | 121.0 (3) |
C13—C14—H14 | 119.7 | C30—N5—C28 | 120.9 (3) |
C16—C15—C20 | 107.2 (2) | C29—N5—C28 | 118.0 (3) |
C16—C15—C8 | 106.8 (2) | C24—O2—C25' | 109.6 (4) |
C20—C15—C8 | 116.4 (2) | C24—O2—C25 | 134.6 (12) |
C16—C15—H15 | 108.7 | C21—S1—C23 | 87.38 (16) |
C20—C15—H15 | 108.7 | C26—C25—O2 | 110.1 (13) |
C8—C15—H15 | 108.7 | C26—C25—H25A | 109.6 |
N2—C16—C17 | 118.8 (2) | O2—C25—H25A | 109.6 |
N2—C16—C15 | 129.5 (2) | C26—C25—H25B | 109.6 |
C17—C16—C15 | 111.7 (2) | O2—C25—H25B | 109.6 |
C16—C17—C18 | 107.2 (2) | H25A—C25—H25B | 108.1 |
C16—C17—C7 | 108.7 (2) | C25—C26—H26A | 109.5 |
C18—C17—C7 | 115.7 (2) | C25—C26—H26B | 109.5 |
C16—C17—H17 | 108.4 | H26A—C26—H26B | 109.5 |
C18—C17—H17 | 108.4 | C25—C26—H26C | 109.5 |
C7—C17—H17 | 108.4 | H26A—C26—H26C | 109.5 |
C19—C18—C17 | 114.0 (2) | H26B—C26—H26C | 109.5 |
C19—C18—H18A | 108.8 | C26'—C25'—O2 | 100.7 (9) |
C17—C18—H18A | 108.8 | C26'—C25'—H25C | 111.6 |
C19—C18—H18B | 108.8 | O2—C25'—H25C | 111.6 |
C17—C18—H18B | 108.8 | C26'—C25'—H25D | 111.6 |
H18A—C18—H18B | 107.7 | O2—C25'—H25D | 111.6 |
C18—C19—C20 | 112.6 (2) | H25C—C25'—H25D | 109.4 |
C18—C19—H19A | 109.1 | C25'—C26'—H26D | 109.5 |
C20—C19—H19A | 109.1 | C25'—C26'—H26E | 109.5 |
C18—C19—H19B | 109.1 | H26D—C26'—H26E | 109.5 |
C20—C19—H19B | 109.1 | C25'—C26'—H26F | 109.5 |
H19A—C19—H19B | 107.8 | H26D—C26'—H26F | 109.5 |
C19—C20—C15 | 114.3 (2) | H26E—C26'—H26F | 109.5 |
C6—C1—C2—C3 | 0.6 (5) | C7—C17—C18—C19 | 66.9 (3) |
C7—C1—C2—C3 | −179.9 (3) | C17—C18—C19—C20 | 45.7 (3) |
C1—C2—C3—C4 | −1.1 (5) | C18—C19—C20—C15 | −45.1 (3) |
C2—C3—C4—C5 | 1.3 (6) | C16—C15—C20—C19 | 53.1 (3) |
C3—C4—C5—C6 | −1.1 (6) | C8—C15—C20—C19 | −66.4 (3) |
C2—C1—C6—C5 | −0.4 (5) | N4—C22—C23—C24 | 179.7 (3) |
C7—C1—C6—C5 | −179.9 (3) | C27—C22—C23—C24 | −1.6 (5) |
C4—C5—C6—C1 | 0.7 (6) | N4—C22—C23—S1 | −0.4 (3) |
C6—C1—C7—N1 | 22.4 (4) | C27—C22—C23—S1 | 178.2 (3) |
C2—C1—C7—N1 | −157.1 (3) | C22—C23—C24—O1 | −8.7 (6) |
C6—C1—C7—C17 | −101.5 (3) | S1—C23—C24—O1 | 171.5 (3) |
C2—C1—C7—C17 | 79.0 (3) | C22—C23—C24—O2 | 170.0 (3) |
N1—C8—C9—C10 | −39.0 (3) | S1—C23—C24—O2 | −9.8 (4) |
C15—C8—C9—C10 | 84.8 (3) | C1—C7—N1—C8 | 178.4 (2) |
N1—C8—C9—C14 | 140.4 (3) | C17—C7—N1—C8 | −56.0 (3) |
C15—C8—C9—C14 | −95.8 (3) | C9—C8—N1—C7 | −176.8 (2) |
C14—C9—C10—C11 | −0.1 (4) | C15—C8—N1—C7 | 57.7 (3) |
C8—C9—C10—C11 | 179.3 (3) | C17—C16—N2—N3 | 175.5 (2) |
C9—C10—C11—C12 | −0.5 (5) | C15—C16—N2—N3 | −2.0 (4) |
C10—C11—C12—C13 | 0.9 (5) | N4—C21—N3—N2 | 173.3 (2) |
C11—C12—C13—C14 | −0.7 (5) | S1—C21—N3—N2 | −8.0 (4) |
C10—C9—C14—C13 | 0.4 (4) | C16—N2—N3—C21 | 177.3 (3) |
C8—C9—C14—C13 | −179.1 (3) | N3—C21—N4—C22 | 179.8 (3) |
C12—C13—C14—C9 | 0.0 (5) | S1—C21—N4—C22 | 1.0 (3) |
N1—C8—C15—C16 | −57.6 (3) | C23—C22—N4—C21 | −0.3 (4) |
C9—C8—C15—C16 | 178.4 (2) | C27—C22—N4—C21 | −179.1 (3) |
N1—C8—C15—C20 | 62.0 (3) | O3—C30—N5—C29 | 0.1 (5) |
C9—C8—C15—C20 | −61.9 (3) | O3—C30—N5—C28 | −176.0 (4) |
C20—C15—C16—N2 | 113.4 (3) | O1—C24—O2—C25' | 4.6 (6) |
C8—C15—C16—N2 | −121.2 (3) | C23—C24—O2—C25' | −174.1 (5) |
C20—C15—C16—C17 | −64.3 (3) | O1—C24—O2—C25 | −20.2 (15) |
C8—C15—C16—C17 | 61.1 (3) | C23—C24—O2—C25 | 161.0 (14) |
N2—C16—C17—C18 | −113.0 (3) | N4—C21—S1—C23 | −1.0 (2) |
C15—C16—C17—C18 | 65.0 (3) | N3—C21—S1—C23 | −179.8 (3) |
N2—C16—C17—C7 | 121.3 (3) | C22—C23—S1—C21 | 0.8 (2) |
C15—C16—C17—C7 | −60.7 (3) | C24—C23—S1—C21 | −179.4 (3) |
N1—C7—C17—C16 | 55.5 (3) | C24—O2—C25—C26 | 128.4 (18) |
C1—C7—C17—C16 | 179.9 (2) | C25'—O2—C25—C26 | 81 (3) |
N1—C7—C17—C18 | −65.1 (3) | C24—O2—C25'—C26' | −174.6 (10) |
C1—C7—C17—C18 | 59.3 (3) | C25—O2—C25'—C26' | −28.6 (14) |
C16—C17—C18—C19 | −54.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.93 | 2.41 | 3.284 (4) | 156 |
N1—H1A···O1ii | 0.84 (2) | 2.59 (2) | 3.380 (4) | 157 (2) |
N3—H3A···O3 | 0.85 (2) | 1.99 (2) | 2.843 (4) | 173 (3) |
Symmetry codes: (i) −x−1, −y, −z+1; (ii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.93 | 2.41 | 3.284 (4) | 156 |
N1—H1A···O1ii | 0.844 (17) | 2.59 (2) | 3.380 (4) | 157 (2) |
N3—H3A···O3 | 0.853 (17) | 1.993 (18) | 2.843 (4) | 173 (3) |
Symmetry codes: (i) −x−1, −y, −z+1; (ii) x+1, y, z. |
Acknowledgements
SJ is thankful to the Council of Scientific and Industrial Research (CSIR), New Delhi, India, for the award of a Senior Research Fellowship through research grant No. 01/2454/11/EMR-II. The authors are thankful to the SAIF, IIT Madras, for the data collection.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Thiazoles are an interesting unit in medicinal chemistry and are responsible for numerous pharmacological and biological properties (Hutchinson et al. 2002; Bondock et al., 2007; Ramachandran et al., 2009). This has piqued our interest in the synthesis of thiazole containing compounds. The importance of bicyclic compounds as intermediates in the synthesis of a several physiologically active compounds have been reviewed by Jeyaraman & Avila (1981). Moreover, these bridged bicyclic compounds exhibit twin chair, chair–boat or twin boat conformations and possess interesting stereochemistries. In order to investigate the change in molecular conformation of the piperidine and cyclohexane rings, the X-ray structure determination of the title compound was carried out. The six–membered heterocyclic piperidine ring (Fig. 1) adopts the expected chair conformation. The two phenyl rings form a dihedral angle of 40.74 (2)°. In the crystal the dimethylformamide solvent molecule is connected to the main molecule by an N—H···O hydrogen bond. An additional N—H···O hydrogen bond connects molecules into chains along [100] (Fig. 2). Weak C—H···O hydrogen bonds connect pairs of inversion related chains. The ethyl group was refined as disordered over two sets of sites with a 0.660 (17): 0.340 (17) ratio of occupancies.