organic compounds
of the adduct (4-chlorophenyl)(4-hydroxypiperidin-1-yl)methanone–(4-chlorophenyl)(piperidin-1-yl)methanone (0.75/0.25)
aPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India, bDepartment of Chemistry, Madras Christian College, Chennai-59, India, cSCRI, Anna Hospital Campus, Chennai-106, Tamilnadu, India, and dAnna Siddha Medical College, Chennai-106, Tamilnadu, India
*Correspondence e-mail: guqmc@yahoo.com
In the title compound, 0.75C12H14ClNO2·0.25C12H14ClNO, which is an adduct comprising 0.75 4-hydroxypiperidin-1-yl or 0.25 4-piperidin-1-yl substituents on a common (4-chlorophenyl)methanone component; the dihedral angles between the benzene ring and the two piperidine rings are 51.6 (3) and 89.5 (7)°, respectively. The hydroxypiperidine ring is in a bisectional oriention (bi) with the phenyl ring. In the crystal, intermolecular O—H⋯O hydrogen bonds between the hydroxypiperidine group and the keto O atom lead to the formation of chains extending along the c- axis direction.
Keywords: crystal structure; adduct; piperidine derivative; hydrogen bonding.
CCDC reference: 1433393
1. Related literature
For the synthesis, see: Revathi et al. (2015). For the biological activity of piperidine derivatives, see: Ramalingan et al. (2004); Sargent & May (1970); Rubiralta et al. (1991). For related structures, see: Revathi et al. (2015); Prathebha et al. (2015).
2. Experimental
2.1. Crystal data
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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: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL2014.
Supporting information
CCDC reference: 1433393
https://doi.org/10.1107/S2056989015020265/zs2348sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015020265/zs2348Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015020265/zs2348Isup3.cml
The title compound was synthesized by utilizing a reported procedure (Revathi et al., 2015). In a 250 ml round-bottomed flask, 130 ml of ethylmethylketone was added to 4-hydroxypiperidiene (0.04 mol) and stirred well. Triethylamine (0.04 mol) was then added and the mixture was stirred for 10 min. 4-Chlorobenzoyl chloride (0.04 mol) was added and the reaction mixture was stirred at room temperature for about 2 hr. A white precipitate of triethylammonium chloride was produced, which was filtered and the filtrate was evaporated to obtain the crude product, crystallization from ethylmethylketone gave colourless block-like crystals of the unexpected title adduct (yield: 88%).
H atoms were positioned geometrically and treated as riding on their parent atoms and refined with, C—H distances of 0.93–0.98 Å, an O—H distance of 0.82 Å, with Uiso(H)= 1.5 Ueq(C-methyl), Uiso(H)= 1.2Ueq(C,O) for other H atoms. The value of the
parameter (Parsons et al., 2013), although of no relevance for the present structure was determined as 0.03 (3) using 583 quotients [(I+)-(I-)]/[(I+)+(I-)].Piperidine is very important pharmacophore because of its presence in numerous
pharmaceuticals, agrochemicals and as synthetic intermediates. Biologically active with substituted piperidine ring systems have been targeted for their total or partial synthesis (Ramalingan et al., 2004). Piperidines are known to have CNS depressant action at low dosage levels and stimulant activity with increased dosages. In addition, the nucleus also possesses analgesic, ganglionic blocking and anesthetic properties as well (Sargent & May, 1970; Rubiralta et al., 1991).In the title compound, 0.75(C12H14NO2Cl) . 0.25(C12H14NOCl), which is an adduct comprising 0.75(4-hydroxypiperidin-1-yl) or 0.25(4-piperidin-1-yl) substituents on a common (4-chlorophenyl)methanone component, the dihedral angles between the benzene ring and the two piperidine rings defined by N1–C12 and N1'–C12' are 51.6 (3) and 89.5 (7)°, respectively (Figs. 1, 2). The C—C distances in the hydroxypiperidine ring and the benzene ring are in the range [1.472 (9)–1.529 (8)Å and 1.346 (7)–1.390 (8)Å], respectively and are in good agreement with literature values (Allen et al., 1987). The C—N distances are in the range [1.346 (7)Å - 1.465 (7)Å] and are in good agreement with values in a similar reported structure (Revathi et al., 2015). The C—O distance [1.223 (6)Å] indicates double bond character and is comparable with the value reported previously (Prathebha et al., 2015). The hydroxypiperdine ring is in a bisectional oriention (bi) with the phenyl ring. The sum of the bond angle around the N1 atom is [359.9 (5)°], showing sp2
of the atoms. The torsion angle C8—N1—C7—O1 [12.3 (10)°], indicates that the keto group is in a +syn-periplanar (+sp) orientation with the hydroxy piperidine ring. The hydroxypiperidine ring adopts a chair conformation with puckering parameters of q2 = 0.029Å, phi2 = -173.57° q3 = -0.555Å, QT = 0.555Å and theta2 = 176.95°.In the crystal, molecules are linked by O2—H···O1i hydrogen bonds (Table 1), forming one-dimensional chains extending along c (Fig. 3). Present also are very weak inter-chain C12'—H···Cl1ii interactions [3.63 (2) Å]. For symmetry code (ii) -x + 3/2, -y + 1, z - 1.
For the synthesis, see: Revathi et al. (2015). For the biological activity of piperidine derivatives, see: Ramalingan et al. (2004); Sargent & May (1970); Rubiralta et al. (1991). For related structures, see: Revathi et al. (2015); Prathebha et al. (2015).
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: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).0.75C12H14ClNO2·0.25C12H14ClNO | Dx = 1.312 Mg m−3 |
Mr = 235.69 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 3452 reflections |
a = 24.312 (4) Å | θ = 2.8–23.2° |
b = 6.1628 (10) Å | µ = 0.30 mm−1 |
c = 7.9654 (11) Å | T = 293 K |
V = 1193.5 (3) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.20 × 0.20 mm |
F(000) = 496 |
Bruker Kappa APEXII CCD diffractometer | 1539 reflections with I > 2σ(I) |
Radiation source: Sealed tube | Rint = 0.031 |
ω and φ scan | θmax = 26.1°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −30→30 |
Tmin = 0.930, Tmax = 0.941 | k = −7→7 |
17321 measured reflections | l = −9→9 |
2356 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0664P)2 + 0.3379P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2356 reflections | Δρmax = 0.31 e Å−3 |
200 parameters | Δρmin = −0.22 e Å−3 |
121 restraints | Absolute structure: Flack x determined using 583 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (3) |
0.75C12H14ClNO2·0.25C12H14ClNO | V = 1193.5 (3) Å3 |
Mr = 235.69 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 24.312 (4) Å | µ = 0.30 mm−1 |
b = 6.1628 (10) Å | T = 293 K |
c = 7.9654 (11) Å | 0.25 × 0.20 × 0.20 mm |
Bruker Kappa APEXII CCD diffractometer | 2356 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1539 reflections with I > 2σ(I) |
Tmin = 0.930, Tmax = 0.941 | Rint = 0.031 |
17321 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.144 | Δρmax = 0.31 e Å−3 |
S = 1.02 | Δρmin = −0.22 e Å−3 |
2356 reflections | Absolute structure: Flack x determined using 583 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
200 parameters | Absolute structure parameter: 0.03 (3) |
121 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.73230 (19) | 0.1884 (8) | 0.7580 (6) | 0.0743 (13) | |
C2 | 0.7397 (2) | 0.3762 (10) | 0.6747 (8) | 0.0909 (16) | |
H2 | 0.7748 | 0.4191 | 0.6416 | 0.109* | |
C3 | 0.6943 (2) | 0.5050 (9) | 0.6390 (7) | 0.0832 (15) | |
H3 | 0.6991 | 0.6353 | 0.5819 | 0.100* | |
C4 | 0.64254 (19) | 0.4423 (8) | 0.6867 (5) | 0.0656 (12) | |
C5 | 0.63637 (19) | 0.2510 (8) | 0.7729 (8) | 0.0811 (14) | |
H5 | 0.6016 | 0.2076 | 0.8082 | 0.097* | |
C6 | 0.6815 (2) | 0.1230 (8) | 0.8074 (8) | 0.0890 (16) | |
H6 | 0.6771 | −0.0076 | 0.8643 | 0.107* | |
C7 | 0.5944 (2) | 0.5838 (9) | 0.6575 (6) | 0.0773 (14) | |
C8 | 0.5243 (3) | 0.7357 (12) | 0.4730 (9) | 0.0749 (18) | 0.75 |
H8A | 0.5155 | 0.8165 | 0.5739 | 0.090* | 0.75 |
H8B | 0.4918 | 0.6565 | 0.4381 | 0.090* | 0.75 |
C9 | 0.5419 (3) | 0.8877 (11) | 0.3372 (9) | 0.0681 (17) | 0.75 |
H9A | 0.5727 | 0.9741 | 0.3766 | 0.082* | 0.75 |
H9B | 0.5119 | 0.9855 | 0.3109 | 0.082* | 0.75 |
C10 | 0.5587 (3) | 0.7668 (13) | 0.1804 (9) | 0.0711 (19) | 0.75 |
H10 | 0.5263 | 0.6897 | 0.1375 | 0.085* | 0.75 |
C11 | 0.6028 (3) | 0.5988 (12) | 0.2233 (8) | 0.0690 (16) | 0.75 |
H11A | 0.6102 | 0.5109 | 0.1249 | 0.083* | 0.75 |
H11B | 0.6365 | 0.6732 | 0.2537 | 0.083* | 0.75 |
C12 | 0.5859 (3) | 0.4567 (10) | 0.3627 (8) | 0.0640 (14) | 0.75 |
H12A | 0.5554 | 0.3660 | 0.3269 | 0.077* | 0.75 |
H12B | 0.6162 | 0.3627 | 0.3935 | 0.077* | 0.75 |
N1 | 0.5694 (2) | 0.5841 (9) | 0.5067 (6) | 0.0659 (14) | 0.75 |
O2 | 0.5746 (2) | 0.8993 (9) | 0.0685 (7) | 0.0870 (14) | 0.75 |
H2A | 0.5924 | 0.8339 | −0.0030 | 0.105 (17)* | 0.75 |
C8' | 0.5628 (8) | 0.863 (3) | 0.454 (3) | 0.069 (4) | 0.25 |
H8'1 | 0.5850 | 0.9758 | 0.4031 | 0.083* | 0.25 |
H8'2 | 0.5466 | 0.9203 | 0.5556 | 0.083* | 0.25 |
C9' | 0.5169 (8) | 0.795 (4) | 0.331 (2) | 0.072 (5) | 0.25 |
H9'1 | 0.4939 | 0.9210 | 0.3107 | 0.087* | 0.25 |
H9'2 | 0.4942 | 0.6872 | 0.3865 | 0.087* | 0.25 |
C10' | 0.5350 (9) | 0.703 (4) | 0.160 (2) | 0.077 (6) | 0.25 |
H10A | 0.5559 | 0.8073 | 0.0953 | 0.093* | 0.25 |
H10B | 0.5040 | 0.6510 | 0.0946 | 0.093* | 0.25 |
C11' | 0.5714 (8) | 0.515 (3) | 0.226 (3) | 0.069 (5) | 0.25 |
H11C | 0.5475 | 0.4128 | 0.2838 | 0.082* | 0.25 |
H11D | 0.5864 | 0.4396 | 0.1295 | 0.082* | 0.25 |
C12' | 0.6196 (7) | 0.568 (3) | 0.345 (2) | 0.057 (4) | 0.25 |
H12C | 0.6383 | 0.4350 | 0.3775 | 0.069* | 0.25 |
H12D | 0.6458 | 0.6610 | 0.2887 | 0.069* | 0.25 |
N1' | 0.5977 (6) | 0.677 (2) | 0.4953 (15) | 0.053 (3) | 0.25 |
O1 | 0.57385 (17) | 0.6828 (7) | 0.7749 (5) | 0.1119 (14) | |
Cl1 | 0.78823 (7) | 0.0274 (3) | 0.7998 (3) | 0.1274 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.067 (3) | 0.080 (3) | 0.076 (3) | 0.011 (2) | −0.016 (2) | −0.004 (3) |
C2 | 0.070 (3) | 0.098 (4) | 0.104 (4) | −0.010 (3) | 0.001 (3) | 0.003 (4) |
C3 | 0.091 (4) | 0.076 (3) | 0.083 (4) | −0.003 (3) | −0.002 (3) | 0.018 (3) |
C4 | 0.073 (3) | 0.071 (3) | 0.053 (2) | 0.012 (2) | 0.002 (2) | 0.010 (2) |
C5 | 0.066 (3) | 0.080 (3) | 0.097 (3) | 0.007 (3) | 0.011 (3) | 0.019 (3) |
C6 | 0.092 (4) | 0.072 (3) | 0.103 (4) | 0.017 (3) | 0.001 (3) | 0.023 (3) |
C7 | 0.090 (3) | 0.082 (3) | 0.061 (2) | 0.029 (3) | 0.005 (2) | 0.006 (2) |
C8 | 0.074 (4) | 0.076 (4) | 0.075 (4) | 0.031 (3) | 0.005 (3) | 0.011 (3) |
C9 | 0.080 (5) | 0.057 (3) | 0.068 (4) | 0.018 (3) | −0.012 (3) | 0.004 (3) |
C10 | 0.067 (4) | 0.081 (4) | 0.066 (3) | 0.020 (3) | −0.018 (3) | −0.003 (3) |
C11 | 0.067 (4) | 0.082 (4) | 0.058 (4) | 0.020 (3) | −0.004 (3) | −0.004 (3) |
C12 | 0.063 (3) | 0.056 (3) | 0.074 (3) | 0.017 (3) | −0.010 (3) | −0.008 (3) |
N1 | 0.072 (3) | 0.064 (3) | 0.062 (3) | 0.023 (3) | −0.001 (2) | 0.006 (2) |
O2 | 0.097 (4) | 0.088 (3) | 0.076 (3) | 0.017 (3) | 0.004 (3) | 0.004 (3) |
C8' | 0.079 (9) | 0.064 (8) | 0.064 (9) | 0.032 (7) | −0.003 (8) | −0.001 (6) |
C9' | 0.067 (9) | 0.080 (12) | 0.071 (9) | 0.034 (8) | −0.001 (7) | −0.007 (9) |
C10' | 0.057 (11) | 0.085 (12) | 0.090 (9) | 0.012 (9) | 0.012 (7) | −0.020 (8) |
C11' | 0.054 (8) | 0.079 (10) | 0.073 (9) | 0.006 (7) | 0.002 (7) | −0.023 (7) |
C12' | 0.050 (7) | 0.059 (9) | 0.062 (7) | 0.009 (7) | 0.001 (6) | −0.008 (6) |
N1' | 0.051 (7) | 0.052 (6) | 0.055 (4) | 0.012 (5) | −0.004 (4) | −0.004 (4) |
O1 | 0.121 (3) | 0.147 (3) | 0.067 (2) | 0.057 (3) | 0.008 (2) | −0.004 (3) |
Cl1 | 0.0952 (10) | 0.1290 (13) | 0.1579 (17) | 0.0462 (9) | −0.0304 (12) | −0.0134 (14) |
C1—C2 | 1.346 (7) | C10—H10 | 0.9800 |
C1—C6 | 1.358 (7) | C11—C12 | 1.472 (9) |
C1—Cl1 | 1.716 (5) | C11—H11A | 0.9700 |
C2—C3 | 1.390 (8) | C11—H11B | 0.9700 |
C2—H2 | 0.9300 | C12—N1 | 1.447 (8) |
C3—C4 | 1.370 (7) | C12—H12A | 0.9700 |
C3—H3 | 0.9300 | C12—H12B | 0.9700 |
C4—C5 | 1.373 (7) | O2—H2A | 0.8200 |
C4—C7 | 1.478 (7) | C8'—N1' | 1.460 (16) |
C5—C6 | 1.378 (6) | C8'—C9' | 1.54 (2) |
C5—H5 | 0.9300 | C8'—H8'1 | 0.9700 |
C6—H6 | 0.9300 | C8'—H8'2 | 0.9700 |
C7—O1 | 1.223 (6) | C9'—C10' | 1.540 (12) |
C7—N1 | 1.346 (7) | C9'—H9'1 | 0.9700 |
C7—N1' | 1.417 (13) | C9'—H9'2 | 0.9700 |
C8—N1 | 1.465 (7) | C10'—C11' | 1.552 (12) |
C8—C9 | 1.494 (9) | C10'—H10A | 0.9700 |
C8—H8A | 0.9700 | C10'—H10B | 0.9700 |
C8—H8B | 0.9700 | C11'—C12' | 1.542 (19) |
C9—C10 | 1.510 (9) | C11'—H11C | 0.9700 |
C9—H9A | 0.9700 | C11'—H11D | 0.9700 |
C9—H9B | 0.9700 | C12'—N1' | 1.474 (16) |
C10—O2 | 1.269 (9) | C12'—H12C | 0.9700 |
C10—C11 | 1.529 (8) | C12'—H12D | 0.9700 |
C2—C1—C6 | 121.4 (5) | C10—C11—H11B | 109.2 |
C2—C1—Cl1 | 119.1 (4) | H11A—C11—H11B | 107.9 |
C6—C1—Cl1 | 119.5 (4) | N1—C12—C11 | 110.6 (5) |
C1—C2—C3 | 119.0 (5) | N1—C12—H12A | 109.5 |
C1—C2—H2 | 120.5 | C11—C12—H12A | 109.5 |
C3—C2—H2 | 120.5 | N1—C12—H12B | 109.5 |
C4—C3—C2 | 120.8 (5) | C11—C12—H12B | 109.5 |
C4—C3—H3 | 119.6 | H12A—C12—H12B | 108.1 |
C2—C3—H3 | 119.6 | C7—N1—C12 | 125.6 (5) |
C3—C4—C5 | 118.8 (4) | C7—N1—C8 | 120.2 (5) |
C3—C4—C7 | 121.1 (4) | C12—N1—C8 | 114.1 (5) |
C5—C4—C7 | 119.9 (4) | C10—O2—H2A | 109.5 |
C4—C5—C6 | 120.3 (5) | N1'—C8'—C9' | 110.8 (15) |
C4—C5—H5 | 119.9 | N1'—C8'—H8'1 | 109.5 |
C6—C5—H5 | 119.9 | C9'—C8'—H8'1 | 109.5 |
C1—C6—C5 | 119.7 (5) | N1'—C8'—H8'2 | 109.5 |
C1—C6—H6 | 120.1 | C9'—C8'—H8'2 | 109.5 |
C5—C6—H6 | 120.1 | H8'1—C8'—H8'2 | 108.1 |
O1—C7—N1 | 119.8 (5) | C8'—C9'—C10' | 116.9 (17) |
O1—C7—N1' | 121.2 (6) | C8'—C9'—H9'1 | 108.1 |
O1—C7—C4 | 119.8 (4) | C10'—C9'—H9'1 | 108.1 |
N1—C7—C4 | 119.9 (5) | C8'—C9'—H9'2 | 108.1 |
N1'—C7—C4 | 109.8 (6) | C10'—C9'—H9'2 | 108.1 |
N1—C8—C9 | 108.5 (6) | H9'1—C9'—H9'2 | 107.3 |
N1—C8—H8A | 110.0 | C9'—C10'—C11' | 98.0 (15) |
C9—C8—H8A | 110.0 | C9'—C10'—H10A | 112.2 |
N1—C8—H8B | 110.0 | C11'—C10'—H10A | 112.2 |
C9—C8—H8B | 110.0 | C9'—C10'—H10B | 112.2 |
H8A—C8—H8B | 108.4 | C11'—C10'—H10B | 112.2 |
C8—C9—C10 | 111.5 (6) | H10A—C10'—H10B | 109.8 |
C8—C9—H9A | 109.3 | C12'—C11'—C10' | 118.9 (17) |
C10—C9—H9A | 109.3 | C12'—C11'—H11C | 107.6 |
C8—C9—H9B | 109.3 | C10'—C11'—H11C | 107.6 |
C10—C9—H9B | 109.3 | C12'—C11'—H11D | 107.6 |
H9A—C9—H9B | 108.0 | C10'—C11'—H11D | 107.6 |
O2—C10—C9 | 110.2 (6) | H11C—C11'—H11D | 107.0 |
O2—C10—C11 | 112.2 (6) | N1'—C12'—C11' | 108.7 (13) |
C9—C10—C11 | 109.8 (5) | N1'—C12'—H12C | 109.9 |
O2—C10—H10 | 108.2 | C11'—C12'—H12C | 109.9 |
C9—C10—H10 | 108.2 | N1'—C12'—H12D | 109.9 |
C11—C10—H10 | 108.2 | C11'—C12'—H12D | 109.9 |
C12—C11—C10 | 112.0 (6) | H12C—C12'—H12D | 108.3 |
C12—C11—H11A | 109.2 | C7—N1'—C8' | 119.5 (12) |
C10—C11—H11A | 109.2 | C7—N1'—C12' | 125.0 (12) |
C12—C11—H11B | 109.2 | C8'—N1'—C12' | 112.7 (13) |
C6—C1—C2—C3 | 0.0 (8) | C10—C11—C12—N1 | −53.4 (9) |
Cl1—C1—C2—C3 | 179.1 (5) | O1—C7—N1—C12 | −173.2 (6) |
C1—C2—C3—C4 | −0.3 (8) | C4—C7—N1—C12 | −1.0 (10) |
C2—C3—C4—C5 | 0.9 (8) | O1—C7—N1—C8 | 12.3 (10) |
C2—C3—C4—C7 | 176.6 (5) | C4—C7—N1—C8 | −175.4 (6) |
C3—C4—C5—C6 | −1.3 (8) | C11—C12—N1—C7 | −116.7 (7) |
C7—C4—C5—C6 | −177.0 (5) | C11—C12—N1—C8 | 58.0 (9) |
C2—C1—C6—C5 | −0.3 (9) | C9—C8—N1—C7 | 115.9 (7) |
Cl1—C1—C6—C5 | −179.5 (5) | C9—C8—N1—C12 | −59.2 (9) |
C4—C5—C6—C1 | 1.0 (9) | N1'—C8'—C9'—C10' | −60 (3) |
C3—C4—C7—O1 | −104.8 (7) | C8'—C9'—C10'—C11' | 56 (2) |
C5—C4—C7—O1 | 70.8 (7) | C9'—C10'—C11'—C12' | −57 (2) |
C3—C4—C7—N1 | 82.9 (7) | C10'—C11'—C12'—N1' | 59 (2) |
C5—C4—C7—N1 | −101.4 (6) | O1—C7—N1'—C8' | −18.1 (18) |
C3—C4—C7—N1' | 42.4 (9) | C4—C7—N1'—C8' | −164.8 (13) |
C5—C4—C7—N1' | −142.0 (8) | O1—C7—N1'—C12' | −177.3 (12) |
N1—C8—C9—C10 | 56.9 (9) | C4—C7—N1'—C12' | 36.0 (17) |
C8—C9—C10—O2 | −178.5 (7) | C9'—C8'—N1'—C7 | −108.1 (19) |
C8—C9—C10—C11 | −54.4 (9) | C9'—C8'—N1'—C12' | 54 (2) |
O2—C10—C11—C12 | 175.3 (7) | C11'—C12'—N1'—C7 | 108.5 (19) |
C9—C10—C11—C12 | 52.4 (9) | C11'—C12'—N1'—C8' | −52 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.82 | 2.05 | 2.693 (7) | 135 |
C12′—H12D···Cl1ii | 0.97 | 2.77 | 3.63 (2) | 148 |
Symmetry codes: (i) x, y, z−1; (ii) −x+3/2, y+1, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.82 | 2.05 | 2.693 (7) | 135 |
Symmetry code: (i) x, y, z−1. |
Acknowledgements
The authors thank DST–FIST, sponsored Central Instrumentation Facility, Queen Mary's College (A), Chennai-4, for the computing facility and SAIF, IIT, Madras, for the X-ray data collection facility.
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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.
Piperidine is very important pharmacophore because of its presence in numerous alkaloids, pharmaceuticals, agrochemicals and as synthetic intermediates. Biologically active alkaloids with substituted piperidine ring systems have been targeted for their total or partial synthesis (Ramalingan et al., 2004). Piperidines are known to have CNS depressant action at low dosage levels and stimulant activity with increased dosages. In addition, the nucleus also possesses analgesic, ganglionic blocking and anesthetic properties as well (Sargent & May, 1970; Rubiralta et al., 1991).
In the title compound, 0.75(C12H14NO2Cl) . 0.25(C12H14NOCl), which is an adduct comprising 0.75(4-hydroxypiperidin-1-yl) or 0.25(4-piperidin-1-yl) substituents on a common (4-chlorophenyl)methanone component, the dihedral angles between the benzene ring and the two piperidine rings defined by N1–C12 and N1'–C12' are 51.6 (3) and 89.5 (7)°, respectively (Figs. 1, 2). The C—C distances in the hydroxypiperidine ring and the benzene ring are in the range [1.472 (9)–1.529 (8)Å and 1.346 (7)–1.390 (8)Å], respectively and are in good agreement with literature values (Allen et al., 1987). The C—N distances are in the range [1.346 (7)Å - 1.465 (7)Å] and are in good agreement with values in a similar reported structure (Revathi et al., 2015). The C—O distance [1.223 (6)Å] indicates double bond character and is comparable with the value reported previously (Prathebha et al., 2015). The hydroxypiperdine ring is in a bisectional oriention (bi) with the phenyl ring. The sum of the bond angle around the N1 atom is [359.9 (5)°], showing sp2 hybridization of the atoms. The torsion angle C8—N1—C7—O1 [12.3 (10)°], indicates that the keto group is in a +syn-periplanar (+sp) orientation with the hydroxy piperidine ring. The hydroxypiperidine ring adopts a chair conformation with puckering parameters of q2 = 0.029Å, phi2 = -173.57° q3 = -0.555Å, QT = 0.555Å and theta2 = 176.95°.
In the crystal, molecules are linked by O2—H···O1i hydrogen bonds (Table 1), forming one-dimensional chains extending along c (Fig. 3). Present also are very weak inter-chain C12'—H···Cl1ii interactions [3.63 (2) Å]. For symmetry code (ii) -x + 3/2, -y + 1, z - 1.