4-(4-Chloro­phen­yl)-4-hy­droxy­piperidinium maleate maleic acid solvate

Jasinski, J.P.; Pek, A.E.; Siddaraju, B.P.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536810026917

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2012-o2013

https://doi.org/10.1107/S1600536810026917

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4-(4-Chlorophenyl)-4-hydroxypiperidinium maleate maleic acid solvate

Jerry P. Jasinski,^a ^* Albert E. Pek,^a B. P. Siddaraju,^b H. S. Yathirajan ^c and B. Narayana ^d

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Studies in Chemistry, V.V Puram College of Science, Bangalore 560 004, India, ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^dDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 4 July 2010; accepted 7 July 2010; online 14 July 2010)

In the cation of the title compound, C₁₁H₁₅ClNO⁺·C₄H₃O₄⁻·C₄H₄O₄, the dihedral angle between the mean planes of the chlorine-substituted aromatic ring and the 4-hydroxypiperidinium ring (C–C–C–C–C–N) is 61.9 (8)°. Intramolecular O—H⋯O and intermolecular O—H⋯O and N—H⋯O hydrogen bonding, as well as weak π-stacking interactions [centroid–centroid distance = 3.646 (5) Å] help to establish the packing.

Related literature

For the synthesis and biological activity of uncondensed cyclic derivatives of piperidine, see: Vartanyan (1984 ). For related structures, see: James & Williams (1974 ); Bertolasi et al. (1980 ); Dawson et al. (1986 ); Vyas et al. (1999 ); Kiang et al. (2003 ); Trask et al. (2005 ); Mohamed et al. (2009 ); Dutkiewicz et al. (2010 ); Fun et al. (2010 ); Jasinski et al. (2010 ). For bond-length data, see: Allen et al. (1987 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₅ClNO⁺·C₄H₃O₄⁻·C₄H₄O₄
M_r = 443.83
Monoclinic, C 2/c
a = 19.282 (7) Å
b = 7.867 (3) Å
c = 25.115 (9) Å
β = 91.545 (5)°
V = 3808 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.52 × 0.41 × 0.39 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.878, T_max = 0.907
18187 measured reflections
5841 independent reflections
5194 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.03
5841 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1C—H1C⋯O2Bⁱ	0.82	1.97	2.7852 (13)	171
O1A—H2A⋯O1Bⁱⁱ	0.90 (2)	1.68 (2)	2.5546 (13)	162 (2)
N1C—H13C⋯O3Bⁱⁱⁱ	0.890 (17)	1.954 (18)	2.8328 (14)	168.6 (16)
N1C—H14C⋯O2A^iv	0.887 (17)	2.087 (17)	2.9144 (15)	154.9 (15)
O4A—H1A⋯O3A	0.91 (2)	1.65 (2)	2.5531 (13)	173.7 (19)
O3B—H1B⋯O4B	1.18 (2)	1.23 (2)	2.4108 (12)	177 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810026917/wm2372sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810026917/wm2372Isup2.hkl

checkCIF report

Comment top

4-(4-Chlorophenyl)-4-hydroxypiperidine is used as an intermediate for the synthesis of pharmaceuticals such as haloperidol (a neuroleptic drug used to treat patients with psychotic illnesses, extreme agitation, or Tourette's syndrome) and loperamide which is a synthetic piperidine derivative and a drug effective against diarrhea resulting from gastroenteritis or inflammatory bowel disease. A review on the synthesis and biological activity of uncondensed cyclic derivatives of piperidine is reported (Vartanyan, 1984). A study of the structural chemistry of maleic acid and related substances arises from the fact that these systems possess short but highly strained hydrogen bonds (James & Williams, 1974). The crystal structures of maleic acid (James & Williams, 1974), carbinoxamine maleate (Bertolasi et al., 1980), [2-(2,2-dicyclohexylethyl) piperidine] maleate (Dawson et al., 1986), domeperidone maleate (Vyas et al., 1999), enalapril maleate (Kiang et al., 2003), 1:1 co-crystal of caffeine with maleic acid (Trask et al., 2005), 4-dimethylaminopyridinium maleate (Mohamed et al., 2009), 4-(4-chlorophenyl)piperidin-4-ol (Dutkiewicz et al., 2010), bis[4-(4-chlorophenyl)-4-hydroxypiperidinium] dipicrate dimethyl sulfoxide solvate (Fun et al., 2010) and trimipraminium maleate (Jasinski et al., 2010) have been reported. In view of the importance of salts of piperidines, this paper reports the crystal structure of the title compound, C₁₁H₁₅Cl N O⁺, C₄H₃O₄^-, C₄H₄O₄.

The asymmetric unit of the title compound (Fig.1) contains one 4-(4-chlorophenyl)-4-hydroxypiperidinium cation, one maleate anion, and one maleic acid molecule. The protonated 4-hydroxypiperidinium cation is in a chair conformation (puckering parameters Q, θ, and φ = 0.576 (2) Å, 179.0 (8)° and 159.955 (0)°, respectively; (Cremer & Pople, 1975). For an ideal chair θ has a value of 0 or 180°). Bond distances and angles are in normal ranges (Allen et al., 1987). The dihedral angle between the mean planes of the piperidinium ring in the cation (C7C/C8C/C9C/C10C/C11C/N1C) and the benzene ring (C1—C6) is 61.9 (8)°. Strong intramolecular O—H···O and intermolecular O—H···O, N—H···O hydrogen bonding interactions (Table 1, Fig. 2) dominate the crystal packing which leads to the formation of chains along [010]. In addition, weak π-stacking intermolecular interactions occur between symmetry related benzene rings (Table 2) which also influence the crystal packing.

Related literature top

For the synthesis and biological activity of uncondensed cyclic derivatives of piperidine, see: Vartanyan, (1984). For a study of the structural chemistry of maleic acid and related substances, see: James & Williams (1974). For related structures, see: James & Williams (1974); Bertolasi et al. (1980); Dawson et al. (1986); Vyas et al. (1999); Kiang et al. (2003); Trask et al. (2005); Mohamed et al. (2009); Dutkiewicz et al. (2010); Fun et al. (2010); Jasinski et al. (2010). For bond-length data, see: Allen et al. (1987). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

4-(4-chlorophenyl)-piperidin-4-ol (2.2 g, 0.01 mol) and maleic acid (1.16 g, 0.01 mol) were dissolved in 20 ml of methanol. The mixture was stirred for 30 minutes at 333 K. Then the solution was kept aside for 3 days at room temperature. Yellow crystals were obtained (m.p: 381–383 K) by slow evaporation of methanol solution.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structures of the C₁₁H₁₅ClNO⁺, C₄H₃O₄^- and C₄H₄O₄ entities, showing the atom labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound C₁₁H₁₅ClNO⁺, C₄H₃O₄^-, C₄H₄O₄, viewed down [100].

4-(4-Chlorophenyl)-4-hydroxypiperidinium maleate maleic acid solvate top

Crystal data top

C₁₁H₁₅ClNO⁺·C₄H₃O₄⁻·C₄H₄O₄	F(000) = 1856
M_r = 443.83	D_x = 1.548 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8484 reflections
a = 19.282 (7) Å	θ = 2.6–31.3°
b = 7.867 (3) Å	µ = 0.26 mm⁻¹
c = 25.115 (9) Å	T = 100 K
β = 91.545 (5)°	Block, yellow
V = 3808 (2) Å³	0.52 × 0.41 × 0.39 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	5841 independent reflections
Radiation source: fine-focus sealed tube	5194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 31.3°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −27→27
T_min = 0.878, T_max = 0.907	k = −11→11
18187 measured reflections	l = −35→35

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0463P)² + 3.2429P] where P = (F_o² + 2F_c²)/3
5841 reflections	(Δ/σ)_max = 0.001
292 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₁H₁₅ClNO⁺·C₄H₃O₄⁻·C₄H₄O₄	V = 3808 (2) Å³
M_r = 443.83	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.282 (7) Å	µ = 0.26 mm⁻¹
b = 7.867 (3) Å	T = 100 K
c = 25.115 (9) Å	0.52 × 0.41 × 0.39 mm
β = 91.545 (5)°

Data collection top

Bruker APEXII CCD diffractometer	5841 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5194 reflections with I > 2σ(I)
T_min = 0.878, T_max = 0.907	R_int = 0.021
18187 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.48 e Å⁻³
5841 reflections	Δρ_min = −0.23 e Å⁻³
292 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.480203 (14)	0.66435 (4)	0.161617 (11)	0.02088 (7)
O4B	0.16691 (4)	0.58804 (10)	0.50337 (3)	0.01619 (15)
O3B	0.22900 (4)	0.66101 (10)	0.42453 (3)	0.01604 (15)
C5B	0.20779 (5)	0.56565 (13)	0.38519 (4)	0.01359 (18)
C4B	0.14848 (6)	0.44620 (14)	0.39300 (4)	0.01543 (19)
H4B	0.1353	0.3844	0.3628	0.019*
C2B	0.11909 (5)	0.47937 (13)	0.49149 (4)	0.01414 (19)
C3B	0.11113 (6)	0.41304 (14)	0.43602 (4)	0.01520 (19)
H3B	0.0747	0.3371	0.4304	0.018*
O3A	0.46151 (4)	0.35880 (11)	0.96021 (3)	0.01793 (16)
C2A	0.44308 (6)	0.35385 (13)	1.00654 (4)	0.01452 (19)
C3A	0.38419 (6)	0.45056 (14)	1.02827 (4)	0.0163 (2)
H3A	0.3766	0.4349	1.0644	0.020*
C5A	0.33654 (6)	0.61984 (14)	0.94690 (4)	0.01610 (19)
C4A	0.34039 (6)	0.55740 (14)	1.00297 (4)	0.0162 (2)
H4A	0.3060	0.6007	1.0244	0.019*
O1A	0.47414 (4)	0.26101 (10)	1.04317 (3)	0.01712 (16)
O2A	0.29197 (4)	0.72438 (11)	0.93499 (3)	0.02023 (17)
O1B	0.07936 (4)	0.42630 (10)	0.52580 (3)	0.01788 (16)
O2B	0.23403 (4)	0.57247 (10)	0.34108 (3)	0.01693 (16)
C4C	0.37887 (5)	0.24201 (13)	0.25343 (4)	0.01180 (18)
C1C	0.44091 (5)	0.50191 (14)	0.19706 (4)	0.01430 (19)
C6C	0.39980 (5)	0.54258 (13)	0.23944 (4)	0.01428 (19)
H6C	0.3928	0.6554	0.2490	0.017*
C5C	0.36902 (5)	0.41155 (13)	0.26767 (4)	0.01336 (18)
H5C	0.3415	0.4374	0.2964	0.016*
C3C	0.42116 (5)	0.20613 (14)	0.21058 (4)	0.01490 (19)
H3C	0.4287	0.0936	0.2010	0.018*
C2C	0.45221 (6)	0.33510 (14)	0.18203 (4)	0.0161 (2)
H2C	0.4800	0.3100	0.1534	0.019*
O1C	0.33643 (4)	−0.04881 (10)	0.24944 (3)	0.01551 (15)
H1C	0.3122	−0.0211	0.2235	0.023*
C10C	0.39685 (5)	0.03445 (13)	0.32796 (4)	0.01363 (18)
H10A	0.4395	−0.0037	0.3123	0.016*
H10B	0.4080	0.1291	0.3514	0.016*
C8C	0.27733 (5)	0.14407 (13)	0.30800 (4)	0.01358 (18)
H8C1	0.2841	0.2427	0.3307	0.016*
H8C2	0.2444	0.1744	0.2797	0.016*
C7C	0.34665 (5)	0.09495 (13)	0.28369 (4)	0.01154 (17)
C9C	0.36671 (5)	−0.10930 (14)	0.36035 (4)	0.01464 (19)
H9C1	0.3594	−0.2083	0.3379	0.018*
H9C2	0.3989	−0.1401	0.3891	0.018*
C11C	0.24805 (5)	−0.00126 (14)	0.34043 (4)	0.01492 (19)
H11A	0.2054	0.0348	0.3566	0.018*
H11B	0.2374	−0.0968	0.3172	0.018*
N1C	0.29935 (5)	−0.05450 (12)	0.38279 (3)	0.01394 (17)
O4A	0.38012 (5)	0.56565 (12)	0.91126 (3)	0.02079 (17)
H13C	0.2810 (9)	−0.142 (2)	0.3999 (7)	0.026 (4)*
H14C	0.3072 (8)	0.031 (2)	0.4050 (7)	0.024 (4)*
H1A	0.4103 (10)	0.490 (3)	0.9264 (8)	0.042 (5)*
H2A	0.5113 (11)	0.206 (3)	1.0307 (8)	0.049 (6)*
H1B	0.1992 (12)	0.629 (3)	0.4638 (9)	0.059 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01862 (13)	0.02183 (14)	0.02233 (13)	−0.00193 (9)	0.00295 (9)	0.01083 (10)
O4B	0.0190 (4)	0.0170 (4)	0.0125 (3)	−0.0050 (3)	−0.0001 (3)	−0.0003 (3)
O3B	0.0197 (4)	0.0149 (4)	0.0136 (3)	−0.0050 (3)	0.0016 (3)	−0.0013 (3)
C5B	0.0153 (4)	0.0120 (4)	0.0134 (4)	0.0008 (3)	−0.0006 (3)	0.0011 (3)
C4B	0.0185 (5)	0.0139 (5)	0.0138 (4)	−0.0022 (4)	−0.0015 (4)	−0.0018 (3)
C2B	0.0158 (5)	0.0126 (4)	0.0139 (4)	−0.0002 (4)	−0.0009 (3)	0.0011 (3)
C3B	0.0172 (5)	0.0140 (5)	0.0143 (4)	−0.0022 (4)	−0.0017 (4)	−0.0009 (3)
O3A	0.0202 (4)	0.0188 (4)	0.0150 (3)	0.0024 (3)	0.0031 (3)	0.0004 (3)
C2A	0.0154 (5)	0.0122 (4)	0.0160 (4)	−0.0015 (3)	0.0007 (3)	−0.0003 (3)
C3A	0.0191 (5)	0.0153 (5)	0.0146 (4)	0.0008 (4)	0.0027 (4)	0.0000 (4)
C5A	0.0168 (5)	0.0136 (5)	0.0178 (5)	−0.0020 (4)	−0.0011 (4)	0.0008 (4)
C4A	0.0171 (5)	0.0145 (5)	0.0170 (5)	0.0005 (4)	0.0022 (4)	−0.0005 (4)
O1A	0.0181 (4)	0.0173 (4)	0.0159 (3)	0.0041 (3)	0.0010 (3)	0.0013 (3)
O2A	0.0195 (4)	0.0164 (4)	0.0246 (4)	0.0012 (3)	−0.0029 (3)	0.0038 (3)
O1B	0.0198 (4)	0.0188 (4)	0.0151 (3)	−0.0042 (3)	0.0025 (3)	0.0011 (3)
O2B	0.0191 (4)	0.0187 (4)	0.0131 (3)	−0.0003 (3)	0.0019 (3)	0.0003 (3)
C4C	0.0123 (4)	0.0121 (4)	0.0110 (4)	−0.0001 (3)	−0.0002 (3)	0.0005 (3)
C1C	0.0122 (4)	0.0171 (5)	0.0136 (4)	−0.0018 (4)	−0.0003 (3)	0.0057 (4)
C6C	0.0151 (4)	0.0124 (4)	0.0154 (4)	−0.0006 (4)	0.0004 (3)	0.0013 (3)
C5C	0.0152 (4)	0.0129 (4)	0.0122 (4)	−0.0001 (3)	0.0023 (3)	−0.0003 (3)
C3C	0.0155 (5)	0.0144 (5)	0.0149 (4)	0.0006 (4)	0.0018 (3)	−0.0003 (4)
C2C	0.0158 (5)	0.0197 (5)	0.0128 (4)	0.0010 (4)	0.0035 (3)	0.0013 (4)
O1C	0.0234 (4)	0.0113 (3)	0.0117 (3)	−0.0010 (3)	−0.0014 (3)	−0.0015 (3)
C10C	0.0133 (4)	0.0147 (5)	0.0129 (4)	0.0004 (3)	0.0004 (3)	0.0017 (3)
C8C	0.0133 (4)	0.0128 (4)	0.0147 (4)	0.0006 (3)	0.0014 (3)	0.0030 (3)
C7C	0.0139 (4)	0.0100 (4)	0.0107 (4)	−0.0004 (3)	0.0006 (3)	−0.0003 (3)
C9C	0.0161 (5)	0.0143 (5)	0.0135 (4)	0.0015 (4)	0.0005 (3)	0.0019 (3)
C11C	0.0133 (4)	0.0160 (5)	0.0154 (4)	−0.0015 (4)	0.0002 (3)	0.0033 (4)
N1C	0.0172 (4)	0.0136 (4)	0.0110 (4)	−0.0017 (3)	0.0011 (3)	0.0011 (3)
O4A	0.0230 (4)	0.0236 (4)	0.0157 (4)	0.0043 (3)	0.0010 (3)	0.0026 (3)

Geometric parameters (Å, º) top

Cl1—C1C	1.7424 (11)	C1C—C2C	1.3844 (16)
O4B—C2B	1.2865 (13)	C6C—C5C	1.3929 (14)
O4B—H1B	1.23 (2)	C6C—H6C	0.9300
O3B—C5B	1.2978 (13)	C5C—H5C	0.9300
O3B—H1B	1.18 (2)	C3C—C2C	1.3876 (15)
C5B—O2B	1.2315 (13)	C3C—H3C	0.9300
C5B—C4B	1.4972 (15)	C2C—H2C	0.9300
C4B—C3B	1.3403 (15)	O1C—C7C	1.4314 (12)
C4B—H4B	0.9300	O1C—H1C	0.8200
C2B—O1B	1.2408 (13)	C10C—C9C	1.5178 (15)
C2B—C3B	1.4917 (15)	C10C—C7C	1.5301 (15)
C3B—H3B	0.9300	C10C—H10A	0.9700
O3A—C2A	1.2265 (13)	C10C—H10B	0.9700
C2A—O1A	1.3072 (13)	C8C—C11C	1.5212 (15)
C2A—C3A	1.4830 (15)	C8C—C7C	1.5339 (15)
C3A—C4A	1.3396 (16)	C8C—H8C1	0.9700
C3A—H3A	0.9300	C8C—H8C2	0.9700
C5A—O2A	1.2209 (14)	C9C—N1C	1.4932 (14)
C5A—O4A	1.3153 (14)	C9C—H9C1	0.9700
C5A—C4A	1.4912 (16)	C9C—H9C2	0.9700
C4A—H4A	0.9300	C11C—N1C	1.4930 (14)
O1A—H2A	0.90 (2)	C11C—H11A	0.9700
C4C—C5C	1.3952 (15)	C11C—H11B	0.9700
C4C—C3C	1.3965 (14)	N1C—H13C	0.890 (17)
C4C—C7C	1.5255 (14)	N1C—H14C	0.887 (17)
C1C—C6C	1.3816 (15)	O4A—H1A	0.91 (2)

C2B—O4B—H1B	111.1 (10)	C1C—C2C—C3C	118.61 (10)
C5B—O3B—H1B	111.1 (11)	C1C—C2C—H2C	120.7
O2B—C5B—O3B	122.07 (10)	C3C—C2C—H2C	120.7
O2B—C5B—C4B	118.62 (9)	C7C—O1C—H1C	109.5
O3B—C5B—C4B	119.30 (9)	C9C—C10C—C7C	112.16 (9)
C3B—C4B—C5B	131.05 (10)	C9C—C10C—H10A	109.2
C3B—C4B—H4B	114.5	C7C—C10C—H10A	109.2
C5B—C4B—H4B	114.5	C9C—C10C—H10B	109.2
O1B—C2B—O4B	120.98 (10)	C7C—C10C—H10B	109.2
O1B—C2B—C3B	118.74 (10)	H10A—C10C—H10B	107.9
O4B—C2B—C3B	120.28 (9)	C11C—C8C—C7C	111.33 (9)
C4B—C3B—C2B	129.85 (10)	C11C—C8C—H8C1	109.4
C4B—C3B—H3B	115.1	C7C—C8C—H8C1	109.4
C2B—C3B—H3B	115.1	C11C—C8C—H8C2	109.4
O3A—C2A—O1A	123.13 (10)	C7C—C8C—H8C2	109.4
O3A—C2A—C3A	125.25 (10)	H8C1—C8C—H8C2	108.0
O1A—C2A—C3A	111.63 (9)	O1C—C7C—C4C	110.55 (8)
C4A—C3A—C2A	128.80 (10)	O1C—C7C—C10C	105.37 (8)
C4A—C3A—H3A	115.6	C4C—C7C—C10C	109.86 (8)
C2A—C3A—H3A	115.6	O1C—C7C—C8C	109.32 (8)
O2A—C5A—O4A	120.67 (10)	C4C—C7C—C8C	112.22 (8)
O2A—C5A—C4A	118.03 (10)	C10C—C7C—C8C	109.28 (8)
O4A—C5A—C4A	121.29 (10)	N1C—C9C—C10C	109.67 (9)
C3A—C4A—C5A	132.01 (10)	N1C—C9C—H9C1	109.7
C3A—C4A—H4A	114.0	C10C—C9C—H9C1	109.7
C5A—C4A—H4A	114.0	N1C—C9C—H9C2	109.7
C2A—O1A—H2A	112.2 (13)	C10C—C9C—H9C2	109.7
C5C—C4C—C3C	118.49 (9)	H9C1—C9C—H9C2	108.2
C5C—C4C—C7C	122.50 (9)	N1C—C11C—C8C	110.12 (9)
C3C—C4C—C7C	118.99 (9)	N1C—C11C—H11A	109.6
C6C—C1C—C2C	121.83 (9)	C8C—C11C—H11A	109.6
C6C—C1C—Cl1	119.35 (9)	N1C—C11C—H11B	109.6
C2C—C1C—Cl1	118.82 (8)	C8C—C11C—H11B	109.6
C1C—C6C—C5C	118.81 (10)	H11A—C11C—H11B	108.1
C1C—C6C—H6C	120.6	C11C—N1C—C9C	112.23 (8)
C5C—C6C—H6C	120.6	C11C—N1C—H13C	107.2 (11)
C6C—C5C—C4C	120.95 (9)	C9C—N1C—H13C	108.7 (11)
C6C—C5C—H5C	119.5	C11C—N1C—H14C	109.4 (11)
C4C—C5C—H5C	119.5	C9C—N1C—H14C	108.7 (10)
C2C—C3C—C4C	121.30 (10)	H13C—N1C—H14C	110.6 (15)
C2C—C3C—H3C	119.3	C5A—O4A—H1A	110.0 (12)
C4C—C3C—H3C	119.3

O2B—C5B—C4B—C3B	179.66 (11)	Cl1—C1C—C2C—C3C	179.61 (8)
O3B—C5B—C4B—C3B	−1.76 (18)	C4C—C3C—C2C—C1C	0.45 (16)
C5B—C4B—C3B—C2B	−3.5 (2)	C5C—C4C—C7C—O1C	152.93 (9)
O1B—C2B—C3B—C4B	−177.70 (11)	C3C—C4C—C7C—O1C	−28.58 (13)
O4B—C2B—C3B—C4B	1.50 (18)	C5C—C4C—C7C—C10C	−91.18 (12)
O3A—C2A—C3A—C4A	0.66 (19)	C3C—C4C—C7C—C10C	87.30 (11)
O1A—C2A—C3A—C4A	−179.62 (11)	C5C—C4C—C7C—C8C	30.61 (13)
C2A—C3A—C4A—C5A	−2.4 (2)	C3C—C4C—C7C—C8C	−150.91 (9)
O2A—C5A—C4A—C3A	−176.96 (12)	C9C—C10C—C7C—O1C	−62.30 (10)
O4A—C5A—C4A—C3A	2.41 (19)	C9C—C10C—C7C—C4C	178.59 (8)
C2C—C1C—C6C—C5C	0.00 (16)	C9C—C10C—C7C—C8C	55.07 (11)
Cl1—C1C—C6C—C5C	−179.61 (8)	C11C—C8C—C7C—O1C	60.01 (11)
C1C—C6C—C5C—C4C	−0.44 (16)	C11C—C8C—C7C—C4C	−176.97 (8)
C3C—C4C—C5C—C6C	0.87 (15)	C11C—C8C—C7C—C10C	−54.84 (11)
C7C—C4C—C5C—C6C	179.36 (9)	C7C—C10C—C9C—N1C	−56.43 (11)
C5C—C4C—C3C—C2C	−0.88 (16)	C7C—C8C—C11C—N1C	56.71 (11)
C7C—C4C—C3C—C2C	−179.42 (9)	C8C—C11C—N1C—C9C	−58.48 (11)
C6C—C1C—C2C—C3C	0.00 (16)	C10C—C9C—N1C—C11C	57.97 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1C—H1C···O2Bⁱ	0.82	1.97	2.7852 (13)	171
O1A—H2A···O1Bⁱⁱ	0.90 (2)	1.68 (2)	2.5546 (13)	162 (2)
N1C—H13C···O3Bⁱⁱⁱ	0.890 (17)	1.954 (18)	2.8328 (14)	168.6 (16)
N1C—H14C···O2A^iv	0.887 (17)	2.087 (17)	2.9144 (15)	154.9 (15)
O4A—H1A···O3A	0.91 (2)	1.65 (2)	2.5531 (13)	173.7 (19)
O3B—H1B···O4B	1.18 (2)	1.23 (2)	2.4108 (12)	177 (2)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅ClNO⁺·C₄H₃O₄⁻·C₄H₄O₄
M_r	443.83
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	19.282 (7), 7.867 (3), 25.115 (9)
β (°)	91.545 (5)
V (Å³)	3808 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.52 × 0.41 × 0.39

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.878, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	18187, 5841, 5194
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.731

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.03
No. of reflections	5841
No. of parameters	292
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.23

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1C—H1C···O2Bⁱ	0.82	1.97	2.7852 (13)	170.7
O1A—H2A···O1Bⁱⁱ	0.90 (2)	1.68 (2)	2.5546 (13)	162 (2)
N1C—H13C···O3Bⁱⁱⁱ	0.890 (17)	1.954 (18)	2.8328 (14)	168.6 (16)
N1C—H14C···O2A^iv	0.887 (17)	2.087 (17)	2.9144 (15)	154.9 (15)
O4A—H1A···O3A	0.91 (2)	1.65 (2)	2.5531 (13)	173.7 (19)
O3B—H1B···O4B	1.18 (2)	1.23 (2)	2.4108 (12)	177 (2)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y+1, z−1/2.

Cg···Cg interactions (Å) top

Cg2 is the centroid of the C1–C6 ring.

CgX···CgY	Cg···Cg	CgX···Perp	CgY···Perp
Cg2···Cg2ⁱ	3.646 (5)	-3.460 (6)	-3.460 (6)

Symmetry code: (i) -x ,y, 1/2-z.

Acknowledgements

JPJ thanks Dr Matthias Zeller and the YSU Department of Chemistry for their assistance with the data collection. The diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491, and by YSU. BPS thanks R. L. Fine Chem, Bangalore for a gift sample of 4-(4-chlorophenyl)piperidin-4-ol. HSY thanks the University of Mysore for research facilities and for sabbatical leave.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bertolasi, V., Borea, P. A., Gilli, G. & Sacerdoti, M. (1980). Acta Cryst. B36, 2287–2291. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Dawson, B. M., Katz, H. & Glusker, J. P. (1986). Acta Cryst. C42, 67–71. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Dutkiewicz, G., Siddaraju, B. P., Yathirajan, H. S., Siddegowda, M. S. & Kubicki, M. (2010). Acta Cryst. E66, o562. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Hemamalini, M., Siddaraju, B. P., Yathirajan, H. S. & Narayana, B. (2010). Acta Cryst. E66, o682–o683. CSD CrossRef CAS IUCr Journals Google Scholar
James, M. N. G. & Williams, G. J. B. (1974). Acta Cryst. B30, 1249–1257. CSD CrossRef IUCr Journals Web of Science Google Scholar
Jasinski, J. P., Butcher, R. J., Hakim Al-Arique, Q. N. M., Yathirajan, H. S. & Narayana, B. (2010). Acta Cryst. E66, o366–o367. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kiang, Y. H., Huq, A., Stephens, P. W. & Xu, W. (2003). J. Pharm. Sci. 92, 1844–1853. Web of Science CSD CrossRef PubMed CAS Google Scholar
Mohamed, S., Tocher, D. A., Vickers, M., Karamertzanis, P. G. & Price, S. L. (2009). Cryst. Growth Des. 9, 2881–2889. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Trask, A. V., Motherwell, S. W. D. & Jones, W. (2005). Cryst. Growth Des. 5, 1013–1021. Web of Science CSD CrossRef CAS Google Scholar
Vartanyan, R. S. (1984). Pharm. Chem. J. 18, 736–749. CrossRef Google Scholar
Vyas, K., Moses Babu, J. & Om Reddy, G. (1999). Acta Cryst. C55, IUC9900104. CrossRef IUCr Journals Google Scholar