Crystal structure of the adduct (4-chloro-phen-yl)(4-hy-droxy-piperidin-1-yl)methanone-(4-chloro-phen-yl)(piperidin-1-yl)methanone (0.75/0.25).

In the title compound, 0.75C12H14ClNO2·0.25C12H14ClNO, which is an adduct comprising 0.75 4-hy-droxy-piperidin-1-yl or 0.25 4-piperidin-1-yl substituents on a common (4-chloro-phen-yl)methanone component; the dihedral angles between the benzene ring and the two piperidine rings are 51.6 (3) and 89.5 (7)°, respectively. The hy-droxy-piperidine ring is in a bis-ectional oriention (bi) with the phenyl ring. In the crystal, inter-molecular O-H⋯O hydrogen bonds between the hy-droxy-piperidine group and the keto O atom lead to the formation of chains extending along the c- axis direction.

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 ▸).

Experimental

Crystal data

0.75C12H14ClNO2·0.25C12H14ClNO

M = 235.69

Orthorhombic,

a = 24.312 (4) Å

b = 6.1628 (10) Å

c = 7.9654 (11) Å

V = 1193.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.930, T max = 0.941

17321 measured reflections

2356 independent reflections

1539 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.144

S = 1.02

2356 reflections

200 parameters

121 restraints

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack x determined using 583 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)

Absolute structure parameter: 0.03 (3)

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: 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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015020265/zs2348sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015020265/zs2348Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015020265/zs2348Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015020265/zs2348fig1.tif

The mol­ecular structure of the major (73%) 4-hy­droxy­piperidin-1-yl substituted component of the title adduct, showing atom numbering, with displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015020265/zs2348fig2.tif

The mol­ecular structure of the minor (25%) piperidin-1-yl substituted component of the title adduct, showing atom numbering, with displacement ellipsoids drawn at the 30% probability level. The bonds for the minor-occupancy piperidinyl group are shown as dashed lines

Click here for additional data file.

. DOI: 10.1107/S2056989015020265/zs2348fig3.tif

The packing of the mol­ecules in the crystal structure. The dashed lines indicate the O—H⋯O hydrogen bonds and weak inter-chain C—H⋯Cl inter­actions.

CCDC reference: 1433393

Additional supporting information: crystallographic information; 3D view; checkCIF report

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)

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

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O2H2AO1i	0.82	2.05	2.693(7)	135

Symmetry code: (i) .