1-[(4-Chloro­phen­yl)(phen­yl)meth­yl]piperazine-1,4-diium bis­(trichloro­acetate)–trichloro­acetic acid (1/1)

Song, Y.; Chidan Kumar, C.S.; Akkurt, M.; Chandraju, S.; Li, H.

doi:10.1107/S1600536812034794

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages o2695-o2696

doi:10.1107/S1600536812034794

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1-[(4-Chlorophenyl)(phenyl)methyl]piperazine-1,4-diium bis(trichloroacetate)–trichloroacetic acid (1/1)

Yanxi Song,^a C. S. Chidan Kumar,^b Mehmet Akkurt,^c S. Chandraju ^d and Hongqi Li ^e ^*

^aSchool of Environmental Science and Engineering, Donghua University, Shanghai 201620, People's Republic of China, ^bDepartment of Chemistry, Alva's Institute of Engineering & Technology, Shobhavana Campus, Mijar, Moodbidri 574 225, South Canara District, Karnataka, India, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^dDepartment of Sugar Technology, University of Mysore, Sir. M.V. PG Center, Tubinakere 571 402, India, and ^eKey Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, People's Republic of China
^*Correspondence e-mail: hongqili@dhu.edu.cn

(Received 17 June 2012; accepted 6 August 2012; online 11 August 2012)

In the title salt adduct, C₁₇H₂₁ClN₂²⁺·2C₂Cl₃O₂⁻·C₂HCl₃O₂, the Cl atom of the dication is disordered over two positions in a 0.915 (3):0.085 (3) ratio. The Cl atoms in the trichloroacetate anions and trichloroacetic acid molecule are also disordered, with refined site-occupation factors of 0.59 (3):0.41 (3), 0.503 (12):0.417 (12) and 0.653 (12):0.347 (12). The piperazine ring adopts a chair conformation, with puckering parameters Q_T = 0.587 (3) Å, θ = 2.6 (2) and Φ 334 (6)°. In the crystal, neighbouring molecules are linked by N—H⋯O, O—H⋯O, N—H⋯Cl, C—H⋯O and C—H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For the biological activity of piperazine derivatives, see: Dinsmore et al. (2002 ); Berkheij et al. (2005 ); Humle & Cherrier (1999 ); Campbell et al. (1973 ). For related structures, see: Jasinski et al. (2011 ); Song et al. (2012 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₇H₂₁ClN₂²⁺·2C₂Cl₃O₂⁻·C₂HCl₃O₂
M_r = 776.93
Triclinic, $[P \overline 1]$
a = 9.746 (2) Å
b = 13.096 (3) Å
c = 13.725 (3) Å
α = 88.317 (3)°
β = 73.127 (3)°
γ = 77.169 (3)°
V = 1633.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 293 K
0.27 × 0.22 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004) T_min = 0.790, T_max = 0.875
10010 measured reflections
7039 independent reflections
5186 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.125
S = 1.04
7039 reflections
468 parameters
38 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.91	1.78	2.685 (3)	172
O1—H1B⋯O6ⁱ	0.82	1.74	2.560 (4)	178
N2—H2A⋯Cl6Bⁱⁱ	0.90	2.74	3.299 (5)	121
N2—H2A⋯O4ⁱⁱ	0.90	1.84	2.716 (3)	162
N2—H2B⋯O5ⁱⁱⁱ	0.90	1.84	2.710 (3)	161
C7—H7⋯O2^iv	0.98	2.47	3.435 (4)	167
C9—H9⋯O3	0.93	2.39	3.270 (3)	157
C14—H14B⋯O6ⁱⁱⁱ	0.97	2.42	3.323 (4)	156
C15—H15B⋯Cl7A^v	0.97	2.79	3.526 (5)	133
Symmetry codes: (i) x, y, z+1; (ii) -x+2, -y, -z; (iii) -x+1, -y+1, -z; (iv) -x+1, -y+1, -z+1; (v) -x+2, -y+1, -z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812034794/fj2574sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034794/fj2574Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812034794/fj2574Isup3.cml

checkCIF report

Comment top

The piperazine nucleus is capable of binding to multiple receptors with high affinity and therefore piperazine has been classified as a privileged structure (Dinsmore et al., 2002). They are found in biologically active compounds across a number of different therapeutic areas (Berkheij et al., 2005) such as antifungal, antibacterial, antimalarial, antipsychotic, antidepressant and antitumour activity against colon, prostate, breast, lung and leukemia tumors (Humle & Cherrier, 1999). 1-Benzylpiperazine was originally synthesized as a potential antihelminthic (Campbell et al., 1973) and these derivatives were found to possess excellent pharmacological activities such as vasodilator, hypotensive, antiviral activity and cerebral blood flow increasing actions, broad pharmacological action on central nerves system (CNS), especially on dopaminergic neurotransmission. In the course of our studies on the salts of piperazines (Jasinski et al., 2011; Song et al., 2012) and in view of the importance of piperazines, the paper reports the crystal and molecular structure of the title salt.

The piperazine ring in the title compound adopts a chair conformation [puckering parameters (Cremer & Pople, 1975) QT = 0.587 (3) Å, θ = 2.6 (2)° and Φ 334 (6)°]. In the crystal, molecules are connected via N—H···O, O—H···O, N—H···C, C—H···O and C—H···C hydrogen bonds forming a three dimensional network (Table 1, Fig. 2). Furthermore, C—H···π interactions help to contribute to the stabilization of the structure.

Related literature top

For the biological activity of piperazine derivatives, see: Dinsmore et al. (2002); Berkheij et al. (2005); Humle & Cherrier (1999); Campbell et al. (1973). For related structures, see: Jasinski et al. (2011); Song et al. (2012). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

1-((4-Chlorophenyl)(phenyl)methyl)piperazine (2.88 g, 0.01 mol) was dissolved in 10 ml of methanol and trichloroacetic acid (4.89 g, 0.03 mol) was also dissolved in 10 ml of methanol. Both the solutions were mixed and stirred in a beaker over a magnetic plate at 333 K for 30 minutes. The mixture was kept aside for a day at room temperature. The title compound was obtained by the slow evaporation of methanol (m.p: 409 K-411 K).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the molecule of the title compound. Displacement ellipsoids are drawn at the 30% probability level and H atoms are omitted for clarity.
	Fig. 2. View of the packing and hydroegen bonding diagrams of the title compound along the a axis. H atoms not involved in hydrogen bonding have been omitted for clarity. Only major components of the disorder parts are shown.

1-[(4-Chlorophenyl)(phenyl)methyl]piperazine-1,4-diium bis(trichloroacetate)– trichloroacetic acid (1/1) top

Crystal data top

C₁₇H₂₁ClN₂²⁺·2C₂Cl₃O₂⁻·C₂HCl₃O₂	Z = 2
M_r = 776.93	F(000) = 784
Triclinic, P1	D_x = 1.580 Mg m⁻³
Hall symbol: -P 1	Melting point = 409–411 K
a = 9.746 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.096 (3) Å	Cell parameters from 3555 reflections
c = 13.725 (3) Å	θ = 2.2–26.9°
α = 88.317 (3)°	µ = 0.89 mm⁻¹
β = 73.127 (3)°	T = 293 K
γ = 77.169 (3)°	Plate, colourless
V = 1633.3 (6) Å³	0.27 × 0.22 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	7039 independent reflections
Radiation source: fine-focus sealed tube	5186 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
ϕ and ω scans	θ_max = 27.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→12
T_min = 0.790, T_max = 0.875	k = −16→11
10010 measured reflections	l = −16→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0496P)² + 0.7913P] where P = (F_o² + 2F_c²)/3
7039 reflections	(Δ/σ)_max = 0.001
468 parameters	Δρ_max = 0.40 e Å⁻³
38 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₇H₂₁ClN₂²⁺·2C₂Cl₃O₂⁻·C₂HCl₃O₂	γ = 77.169 (3)°
M_r = 776.93	V = 1633.3 (6) Å³
Triclinic, P1	Z = 2
a = 9.746 (2) Å	Mo Kα radiation
b = 13.096 (3) Å	µ = 0.89 mm⁻¹
c = 13.725 (3) Å	T = 293 K
α = 88.317 (3)°	0.27 × 0.22 × 0.15 mm
β = 73.127 (3)°

Data collection top

Bruker APEXII CCD diffractometer	7039 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	5186 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.875	R_int = 0.012
10010 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	38 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.40 e Å⁻³
7039 reflections	Δρ_min = −0.33 e Å⁻³
468 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	Occ. (<1)
Cl1C	0.31840 (14)	0.07626 (8)	0.67451 (7)	0.1062 (4)	0.915 (3)
N1	0.66237 (18)	0.23191 (14)	0.21015 (13)	0.0366 (5)
N2	0.7247 (2)	0.14402 (17)	0.00697 (14)	0.0500 (6)
C1	0.3636 (3)	0.2436 (2)	0.42747 (18)	0.0496 (8)
C2	0.3041 (3)	0.1922 (2)	0.5133 (2)	0.0623 (10)
C3	0.3952 (4)	0.1382 (2)	0.5661 (2)	0.0614 (9)
C4	0.5441 (4)	0.1344 (2)	0.5345 (2)	0.0672 (10)
C5	0.6024 (3)	0.1857 (2)	0.4488 (2)	0.0545 (8)
C6	0.5126 (2)	0.24114 (17)	0.39409 (16)	0.0391 (6)
C7	0.5689 (2)	0.30362 (17)	0.30255 (16)	0.0386 (6)
C8	0.6491 (3)	0.38233 (17)	0.32521 (16)	0.0417 (7)
C9	0.7969 (3)	0.3582 (2)	0.3198 (2)	0.0544 (8)
C10	0.8610 (3)	0.4331 (2)	0.3469 (2)	0.0643 (10)
C11	0.7786 (4)	0.5318 (3)	0.3801 (2)	0.0690 (11)
C12	0.6326 (4)	0.5560 (2)	0.3859 (2)	0.0671 (10)
C13	0.5666 (3)	0.48247 (19)	0.35811 (19)	0.0532 (8)
C14	0.7043 (3)	0.2947 (2)	0.11745 (17)	0.0472 (8)
C15	0.8003 (3)	0.2238 (2)	0.02683 (18)	0.0555 (9)
C16	0.6808 (3)	0.08220 (19)	0.09830 (18)	0.0478 (8)
C17	0.5831 (2)	0.15348 (18)	0.18780 (17)	0.0416 (7)
Cl1D	0.8762 (17)	0.5906 (10)	0.4249 (12)	0.123 (6)	0.085 (3)
Cl1B	0.6717 (5)	0.2921 (6)	0.7725 (6)	0.0945 (12)	0.59 (3)
Cl2B	0.9718 (4)	0.2936 (7)	0.7561 (5)	0.0923 (13)	0.59 (3)
Cl3B	0.8561 (7)	0.3498 (10)	0.5860 (4)	0.129 (2)	0.59 (3)
O1	0.7348 (4)	0.46222 (19)	0.8666 (2)	0.0975 (10)
O2	0.7545 (3)	0.5423 (2)	0.7197 (2)	0.1045 (11)
C18	0.7641 (3)	0.4663 (3)	0.7690 (3)	0.0725 (11)
C19	0.8137 (3)	0.3552 (3)	0.7202 (2)	0.0700 (10)
Cl1A	0.6634 (9)	0.2930 (7)	0.7508 (14)	0.121 (3)	0.41 (3)
Cl2A	0.9600 (10)	0.2728 (12)	0.7519 (6)	0.116 (2)	0.41 (3)
Cl3A	0.8603 (7)	0.3771 (15)	0.5911 (6)	0.104 (3)	0.41 (3)
Cl4B	1.1554 (7)	0.1768 (5)	0.2833 (10)	0.163 (3)	0.503 (12)
Cl5B	1.0936 (7)	−0.0153 (9)	0.3672 (4)	0.146 (3)	0.503 (12)
Cl6B	1.3218 (4)	−0.0180 (4)	0.1815 (4)	0.0598 (10)	0.503 (12)
O3	0.90549 (18)	0.11171 (14)	0.24280 (14)	0.0588 (6)
O4	1.05566 (19)	−0.00573 (16)	0.12532 (14)	0.0631 (7)
C20	1.0244 (2)	0.05258 (18)	0.19980 (17)	0.0406 (7)
C21	1.1464 (3)	0.0551 (2)	0.25207 (19)	0.0537 (8)
Cl4A	1.1704 (3)	0.1899 (2)	0.2413 (3)	0.0618 (8)	0.497 (12)
Cl5A	1.0917 (8)	0.0294 (5)	0.3806 (3)	0.1017 (17)	0.497 (12)
Cl6A	1.3180 (5)	−0.0238 (5)	0.1946 (6)	0.0861 (16)	0.497 (12)
Cl7A	0.8144 (3)	0.8071 (2)	0.0564 (3)	0.0937 (8)	0.653 (12)
Cl8A	0.7410 (4)	0.6177 (5)	0.1419 (3)	0.1097 (12)	0.653 (12)
Cl9A	0.9218 (3)	0.6188 (3)	−0.0657 (2)	0.0773 (8)	0.653 (12)
O5	0.5411 (2)	0.79751 (16)	0.02795 (15)	0.0696 (7)
O6	0.6096 (3)	0.6471 (2)	−0.0567 (2)	0.1044 (13)
C22	0.6253 (3)	0.7137 (2)	−0.0029 (2)	0.0565 (9)
C23	0.7680 (3)	0.6882 (2)	0.0312 (2)	0.0588 (9)
Cl7B	0.7846 (14)	0.7855 (7)	0.1020 (12)	0.155 (4)	0.347 (12)
Cl8B	0.7349 (10)	0.5792 (8)	0.1111 (9)	0.134 (3)	0.347 (12)
Cl9B	0.9191 (8)	0.6431 (10)	−0.0692 (6)	0.141 (3)	0.347 (12)
H1	0.30230	0.28060	0.39140	0.0590*
H1A	0.74610	0.19660	0.22360	0.0440*
H1C	0.812 (7)	0.587 (4)	0.400 (5)	0.1680*	0.915 (3)
H2	0.20380	0.19420	0.53480	0.0750*
H2A	0.78510	0.10080	−0.04520	0.0600*
H2B	0.64430	0.17580	−0.01100	0.0600*
H4	0.60480	0.09750	0.57100	0.0810*
H5	0.70280	0.18320	0.42730	0.0650*
H7	0.48250	0.34370	0.28470	0.0460*
H9	0.85350	0.29140	0.29790	0.0650*
H10	0.96050	0.41640	0.34260	0.0770*
H12	0.57670	0.62280	0.40870	0.0810*
H13	0.46750	0.50020	0.36150	0.0640*
H14A	0.75700	0.34490	0.13060	0.0570*
H14B	0.61620	0.33320	0.10230	0.0570*
H15A	0.82360	0.26550	−0.03280	0.0670*
H15B	0.89180	0.18940	0.03990	0.0670*
H16A	0.76800	0.04370	0.11480	0.0570*
H16B	0.62870	0.03200	0.08420	0.0570*
H17A	0.49400	0.18980	0.17250	0.0500*
H17B	0.55550	0.11210	0.24720	0.0500*
H1D	0.35640	0.10400	0.62340	0.1680*	0.085 (3)
H1B	0.69470	0.52090	0.89260	0.1460*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1C	0.1343 (10)	0.0734 (6)	0.0679 (6)	−0.0027 (6)	0.0188 (6)	0.0294 (5)
N1	0.0324 (9)	0.0402 (10)	0.0346 (9)	−0.0041 (7)	−0.0085 (7)	−0.0037 (8)
N2	0.0382 (10)	0.0655 (13)	0.0387 (10)	0.0035 (9)	−0.0094 (8)	−0.0153 (10)
C1	0.0481 (13)	0.0562 (15)	0.0428 (13)	−0.0120 (11)	−0.0102 (11)	−0.0012 (11)
C2	0.0619 (17)	0.0661 (18)	0.0532 (16)	−0.0233 (14)	−0.0007 (13)	−0.0032 (14)
C3	0.082 (2)	0.0423 (14)	0.0446 (14)	−0.0083 (13)	0.0010 (13)	0.0017 (11)
C4	0.080 (2)	0.0580 (17)	0.0522 (16)	0.0059 (15)	−0.0186 (15)	0.0086 (13)
C5	0.0497 (14)	0.0539 (15)	0.0510 (14)	0.0012 (11)	−0.0103 (11)	0.0011 (12)
C6	0.0423 (11)	0.0369 (11)	0.0340 (11)	−0.0053 (9)	−0.0068 (9)	−0.0072 (9)
C7	0.0366 (11)	0.0367 (11)	0.0367 (11)	0.0004 (9)	−0.0075 (9)	−0.0056 (9)
C8	0.0485 (13)	0.0367 (12)	0.0354 (11)	−0.0076 (10)	−0.0065 (9)	−0.0036 (9)
C9	0.0510 (14)	0.0475 (14)	0.0624 (16)	−0.0082 (11)	−0.0136 (12)	−0.0141 (12)
C10	0.0616 (17)	0.0729 (19)	0.0616 (17)	−0.0269 (15)	−0.0128 (14)	−0.0095 (15)
C11	0.088 (2)	0.0628 (19)	0.0562 (17)	−0.0337 (17)	−0.0069 (15)	−0.0114 (14)
C12	0.092 (2)	0.0397 (14)	0.0586 (17)	−0.0133 (14)	−0.0047 (15)	−0.0111 (12)
C13	0.0621 (15)	0.0418 (13)	0.0460 (14)	−0.0038 (11)	−0.0060 (12)	−0.0042 (11)
C14	0.0481 (13)	0.0535 (14)	0.0389 (12)	−0.0147 (11)	−0.0083 (10)	0.0018 (11)
C15	0.0471 (14)	0.0763 (18)	0.0388 (13)	−0.0162 (13)	−0.0034 (11)	−0.0066 (12)
C16	0.0431 (12)	0.0468 (13)	0.0516 (14)	−0.0019 (10)	−0.0155 (11)	−0.0127 (11)
C17	0.0404 (11)	0.0413 (12)	0.0419 (12)	−0.0070 (9)	−0.0110 (9)	−0.0054 (10)
Cl1D	0.138 (13)	0.084 (8)	0.122 (11)	−0.057 (8)	0.028 (9)	−0.043 (8)
Cl1B	0.087 (2)	0.092 (2)	0.103 (2)	−0.0406 (17)	−0.0098 (14)	0.0010 (15)
Cl2B	0.0502 (18)	0.125 (3)	0.080 (2)	0.010 (2)	−0.0111 (14)	0.039 (2)
Cl3B	0.166 (5)	0.130 (4)	0.0581 (17)	0.026 (3)	−0.0279 (19)	0.0032 (17)
O1	0.128 (2)	0.0724 (16)	0.0876 (18)	−0.0050 (15)	−0.0374 (16)	0.0014 (13)
O2	0.1013 (19)	0.0807 (17)	0.136 (2)	−0.0134 (14)	−0.0510 (17)	0.0464 (17)
C18	0.0613 (18)	0.073 (2)	0.089 (2)	−0.0147 (15)	−0.0330 (17)	0.0250 (18)
C19	0.0590 (17)	0.078 (2)	0.0604 (17)	0.0002 (15)	−0.0106 (14)	0.0138 (15)
Cl1A	0.121 (4)	0.069 (3)	0.162 (8)	−0.018 (3)	−0.027 (4)	−0.015 (3)
Cl2A	0.114 (5)	0.116 (4)	0.061 (3)	0.062 (4)	−0.003 (3)	0.007 (3)
Cl3A	0.083 (3)	0.146 (7)	0.064 (3)	0.000 (3)	−0.0147 (18)	0.027 (3)
Cl4B	0.124 (3)	0.115 (3)	0.274 (7)	0.028 (2)	−0.125 (4)	−0.117 (3)
Cl5B	0.096 (3)	0.252 (8)	0.0563 (17)	0.034 (4)	−0.0272 (15)	0.028 (3)
Cl6B	0.0251 (13)	0.075 (2)	0.0773 (16)	−0.0025 (13)	−0.0156 (11)	−0.0275 (15)
O3	0.0395 (9)	0.0604 (11)	0.0696 (12)	0.0093 (8)	−0.0186 (8)	−0.0206 (9)
O4	0.0446 (9)	0.0845 (14)	0.0543 (11)	0.0062 (9)	−0.0178 (8)	−0.0291 (10)
C20	0.0333 (11)	0.0433 (12)	0.0435 (12)	−0.0024 (9)	−0.0130 (9)	−0.0005 (10)
C21	0.0441 (13)	0.0605 (16)	0.0550 (15)	0.0020 (11)	−0.0213 (11)	−0.0107 (12)
Cl4A	0.0429 (12)	0.0478 (11)	0.0974 (18)	−0.0109 (7)	−0.0229 (11)	−0.0082 (12)
Cl5A	0.102 (3)	0.165 (4)	0.0475 (15)	−0.038 (3)	−0.0323 (15)	0.0251 (18)
Cl6A	0.060 (2)	0.075 (2)	0.121 (4)	0.0152 (18)	−0.045 (2)	−0.003 (2)
Cl7A	0.0516 (10)	0.0767 (12)	0.146 (2)	−0.0045 (8)	−0.0225 (13)	−0.0295 (13)
Cl8A	0.0871 (13)	0.160 (3)	0.0825 (15)	−0.0239 (17)	−0.0334 (12)	0.0591 (18)
Cl9A	0.0466 (12)	0.0750 (12)	0.0865 (15)	0.0172 (9)	−0.0047 (9)	−0.0106 (9)
O5	0.0487 (10)	0.0748 (13)	0.0735 (13)	0.0149 (10)	−0.0203 (9)	−0.0066 (11)
O6	0.0810 (16)	0.0876 (17)	0.154 (3)	0.0089 (13)	−0.0651 (17)	−0.0407 (17)
C22	0.0419 (13)	0.0611 (17)	0.0591 (16)	0.0008 (12)	−0.0131 (12)	0.0056 (13)
C23	0.0454 (14)	0.0588 (16)	0.0644 (17)	0.0045 (12)	−0.0164 (12)	0.0032 (13)
Cl7B	0.156 (7)	0.118 (5)	0.214 (9)	0.051 (4)	−0.144 (6)	−0.083 (5)
Cl8B	0.139 (4)	0.125 (5)	0.112 (5)	0.020 (3)	−0.039 (3)	0.058 (4)
Cl9B	0.053 (3)	0.189 (7)	0.167 (6)	−0.035 (4)	0.000 (3)	−0.060 (5)

Geometric parameters (Å, º) top

Cl1C—C3	1.728 (3)	C2—C3	1.370 (4)
Cl1D—C11	1.603 (17)	C3—C4	1.379 (6)
Cl1A—C19	1.772 (11)	C4—C5	1.376 (4)
Cl1B—C19	1.735 (7)	C5—C6	1.387 (4)
Cl2A—C19	1.742 (13)	C6—C7	1.513 (3)
Cl2B—C19	1.770 (7)	C7—C8	1.513 (3)
Cl3A—C19	1.729 (9)	C8—C9	1.385 (4)
Cl3B—C19	1.767 (6)	C8—C13	1.388 (3)
Cl4A—C21	1.828 (4)	C9—C10	1.385 (4)
Cl4B—C21	1.690 (8)	C10—C11	1.373 (5)
Cl5A—C21	1.735 (5)	C11—C12	1.366 (6)
Cl5B—C21	1.807 (8)	C12—C13	1.388 (4)
Cl6A—C21	1.732 (7)	C14—C15	1.514 (3)
Cl6B—C21	1.773 (6)	C16—C17	1.510 (3)
Cl7A—C23	1.784 (4)	C1—H1	0.9300
Cl7B—C23	1.688 (13)	C2—H2	0.9300
Cl8A—C23	1.739 (5)	C3—H1D	0.9200
Cl8B—C23	1.803 (11)	C4—H4	0.9300
Cl9A—C23	1.775 (4)	C5—H5	0.9300
Cl9B—C23	1.703 (9)	C7—H7	0.9800
O1—C18	1.288 (5)	C9—H9	0.9300
O2—C18	1.189 (5)	C10—H10	0.9300
O1—H1B	0.8200	C11—H1C	0.93 (6)
O3—C20	1.234 (3)	C12—H12	0.9300
O4—C20	1.218 (3)	C13—H13	0.9300
O5—C22	1.218 (3)	C14—H14B	0.9700
O6—C22	1.222 (4)	C14—H14A	0.9700
N1—C17	1.502 (3)	C15—H15B	0.9700
N1—C14	1.499 (3)	C15—H15A	0.9700
N1—C7	1.530 (3)	C16—H16A	0.9700
N2—C16	1.481 (3)	C16—H16B	0.9700
N2—C15	1.478 (4)	C17—H17B	0.9700
N1—H1A	0.9100	C17—H17A	0.9700
N2—H2B	0.9000	C18—C19	1.535 (5)
N2—H2A	0.9000	C20—C21	1.563 (4)
C1—C2	1.381 (4)	C22—C23	1.558 (4)
C1—C6	1.383 (4)

C18—O1—H1B	110.00	C15—C14—H14A	109.00
C7—N1—C17	111.81 (16)	C15—C14—H14B	110.00
C14—N1—C17	108.77 (17)	N1—C14—H14B	110.00
C7—N1—C14	110.75 (17)	H14A—C14—H14B	108.00
C15—N2—C16	111.02 (19)	N2—C15—H15B	110.00
C17—N1—H1A	109.00	C14—C15—H15A	109.00
C7—N1—H1A	108.00	C14—C15—H15B	110.00
C14—N1—H1A	108.00	H15A—C15—H15B	108.00
C16—N2—H2A	109.00	N2—C15—H15A	110.00
C16—N2—H2B	109.00	N2—C16—H16B	110.00
H2A—N2—H2B	108.00	C17—C16—H16A	110.00
C15—N2—H2B	109.00	N2—C16—H16A	110.00
C15—N2—H2A	109.00	H16A—C16—H16B	108.00
C2—C1—C6	121.3 (3)	C17—C16—H16B	110.00
C1—C2—C3	119.0 (3)	N1—C17—H17A	110.00
C2—C3—C4	121.0 (3)	N1—C17—H17B	110.00
Cl1C—C3—C4	120.7 (2)	C16—C17—H17B	110.00
Cl1C—C3—C2	118.3 (3)	H17A—C17—H17B	108.00
C3—C4—C5	119.6 (3)	C16—C17—H17A	110.00
C4—C5—C6	120.5 (3)	O1—C18—C19	110.2 (3)
C1—C6—C5	118.6 (2)	O2—C18—C19	122.1 (3)
C1—C6—C7	118.4 (2)	O1—C18—O2	127.6 (4)
C5—C6—C7	123.0 (2)	Cl1B—C19—Cl2B	110.1 (4)
N1—C7—C6	111.45 (17)	Cl1B—C19—Cl3B	109.5 (4)
C6—C7—C8	112.71 (17)	Cl2B—C19—Cl3B	109.3 (4)
N1—C7—C8	111.75 (17)	Cl2B—C19—C18	106.4 (3)
C7—C8—C9	123.6 (2)	Cl1B—C19—C18	106.7 (3)
C9—C8—C13	119.0 (2)	Cl1A—C19—C18	109.9 (5)
C7—C8—C13	117.3 (3)	Cl2A—C19—C18	116.1 (5)
C8—C9—C10	120.3 (2)	Cl3A—C19—C18	103.2 (7)
C9—C10—C11	120.4 (3)	Cl1A—C19—Cl2A	108.3 (6)
Cl1D—C11—C12	131.9 (6)	Cl1A—C19—Cl3A	108.3 (7)
Cl1D—C11—C10	107.6 (6)	Cl2A—C19—Cl3A	110.7 (5)
C10—C11—C12	119.5 (3)	Cl3B—C19—C18	114.8 (5)
C11—C12—C13	121.0 (3)	O3—C20—O4	128.7 (2)
C8—C13—C12	119.8 (3)	O3—C20—C21	113.0 (2)
N1—C14—C15	110.6 (2)	O4—C20—C21	118.3 (2)
N2—C15—C14	110.7 (2)	Cl4B—C21—Cl5B	109.1 (5)
N2—C16—C17	110.42 (19)	Cl4B—C21—Cl6B	111.0 (4)
N1—C17—C16	110.10 (19)	Cl4B—C21—C20	114.3 (3)
C2—C1—H1	119.00	Cl5B—C21—Cl6B	105.5 (4)
C6—C1—H1	119.00	Cl5B—C21—C20	103.6 (3)
C3—C2—H2	121.00	Cl6B—C21—C20	112.6 (2)
C1—C2—H2	120.00	Cl4A—C21—C20	104.9 (2)
C2—C3—H1D	119.00	Cl5A—C21—C20	112.1 (3)
C4—C3—H1D	120.00	Cl6A—C21—C20	115.9 (3)
C5—C4—H4	120.00	Cl4A—C21—Cl5A	107.8 (3)
C3—C4—H4	120.00	Cl4A—C21—Cl6A	106.1 (3)
C4—C5—H5	120.00	Cl5A—C21—Cl6A	109.6 (4)
C6—C5—H5	120.00	O5—C22—O6	127.3 (3)
N1—C7—H7	107.00	O5—C22—C23	116.3 (2)
C6—C7—H7	107.00	O6—C22—C23	116.5 (3)
C8—C7—H7	107.00	Cl7A—C23—Cl8A	108.5 (3)
C10—C9—H9	120.00	Cl7A—C23—Cl9A	105.8 (2)
C8—C9—H9	120.00	Cl7A—C23—C22	109.7 (2)
C9—C10—H10	120.00	Cl8A—C23—Cl9A	110.3 (3)
C11—C10—H10	120.00	Cl8A—C23—C22	110.3 (2)
C12—C11—H1C	114 (4)	Cl9A—C23—C22	112.1 (2)
C10—C11—H1C	127 (4)	Cl7B—C23—C22	113.7 (5)
C11—C12—H12	119.00	Cl8B—C23—C22	100.1 (4)
C13—C12—H12	120.00	Cl9B—C23—C22	111.2 (3)
C12—C13—H13	120.00	Cl7B—C23—Cl8B	108.9 (6)
C8—C13—H13	120.00	Cl7B—C23—Cl9B	114.1 (6)
N1—C14—H14A	110.00	Cl8B—C23—Cl9B	107.7 (6)

C17—N1—C14—C15	−58.3 (3)	C9—C8—C13—C12	−0.7 (4)
C14—N1—C7—C8	−58.7 (2)	C7—C8—C13—C12	176.1 (2)
C17—N1—C7—C8	179.79 (17)	C13—C8—C9—C10	0.0 (4)
C14—N1—C17—C16	59.2 (2)	C7—C8—C9—C10	−176.6 (2)
C14—N1—C7—C6	174.17 (19)	C8—C9—C10—C11	0.5 (4)
C7—N1—C17—C16	−178.22 (18)	C9—C10—C11—C12	−0.3 (4)
C7—N1—C14—C15	178.4 (2)	C10—C11—C12—C13	−0.4 (4)
C17—N1—C7—C6	52.7 (2)	C11—C12—C13—C8	0.9 (4)
C16—N2—C15—C14	−56.4 (3)	N1—C14—C15—N2	57.3 (3)
C15—N2—C16—C17	57.4 (3)	N2—C16—C17—N1	−59.0 (3)
C2—C1—C6—C7	−177.0 (2)	O1—C18—C19—Cl1B	58.1 (4)
C6—C1—C2—C3	0.2 (4)	O1—C18—C19—Cl2B	−59.4 (4)
C2—C1—C6—C5	−0.1 (4)	O1—C18—C19—Cl3B	179.6 (4)
C1—C2—C3—Cl1C	178.9 (2)	O2—C18—C19—Cl1B	−121.0 (4)
C1—C2—C3—C4	−0.2 (4)	O2—C18—C19—Cl2B	121.5 (4)
Cl1C—C3—C4—C5	−179.0 (2)	O2—C18—C19—Cl3B	0.4 (5)
C2—C3—C4—C5	0.1 (4)	O3—C20—C21—Cl4B	−45.2 (5)
C3—C4—C5—C6	0.0 (4)	O3—C20—C21—Cl5B	73.4 (4)
C4—C5—C6—C1	−0.1 (4)	O3—C20—C21—Cl6B	−173.0 (2)
C4—C5—C6—C7	176.8 (2)	O4—C20—C21—Cl4B	135.6 (5)
C5—C6—C7—C8	−54.2 (3)	O4—C20—C21—Cl5B	−105.8 (4)
C1—C6—C7—C8	122.6 (2)	O4—C20—C21—Cl6B	7.7 (3)
C5—C6—C7—N1	72.4 (3)	O5—C22—C23—Cl7A	−26.7 (3)
C1—C6—C7—N1	−110.8 (2)	O5—C22—C23—Cl8A	92.7 (3)
C6—C7—C8—C9	85.5 (3)	O5—C22—C23—Cl9A	−144.0 (2)
N1—C7—C8—C9	−40.9 (3)	O6—C22—C23—Cl7A	154.0 (3)
N1—C7—C8—C13	142.5 (2)	O6—C22—C23—Cl8A	−86.7 (3)
C6—C7—C8—C13	−91.1 (2)	O6—C22—C23—Cl9A	36.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.91	1.78	2.685 (3)	172
O1—H1B···O6ⁱ	0.82	1.74	2.560 (4)	178
N2—H2A···Cl6Bⁱⁱ	0.90	2.74	3.299 (5)	121
N2—H2A···O4ⁱⁱ	0.90	1.84	2.716 (3)	162
N2—H2B···O5ⁱⁱⁱ	0.90	1.84	2.710 (3)	161
C7—H7···O2^iv	0.98	2.47	3.435 (4)	167
C9—H9···O3	0.93	2.39	3.270 (3)	157
C14—H14B···O6ⁱⁱⁱ	0.97	2.42	3.323 (4)	156
C15—H15B···Cl7A^v	0.97	2.79	3.526 (5)	133

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₁ClN₂²⁺·2C₂Cl₃O₂⁻·C₂HCl₃O₂
M_r	776.93
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.746 (2), 13.096 (3), 13.725 (3)
α, β, γ (°)	88.317 (3), 73.127 (3), 77.169 (3)
V (Å³)	1633.3 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.27 × 0.22 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.790, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	10010, 7039, 5186
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 1.04
No. of reflections	7039
No. of parameters	468
No. of restraints	38
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.91	1.78	2.685 (3)	172
O1—H1B···O6ⁱ	0.82	1.74	2.560 (4)	178
N2—H2A···Cl6Bⁱⁱ	0.90	2.74	3.299 (5)	121
N2—H2A···O4ⁱⁱ	0.90	1.84	2.716 (3)	162
N2—H2B···O5ⁱⁱⁱ	0.90	1.84	2.710 (3)	161
C7—H7···O2^iv	0.98	2.47	3.435 (4)	167
C9—H9···O3	0.93	2.39	3.270 (3)	157
C14—H14B···O6ⁱⁱⁱ	0.97	2.42	3.323 (4)	156
C15—H15B···Cl7A^v	0.97	2.79	3.526 (5)	133

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

Acknowledgements

This work was supported in part by the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research. YS and HL acknowledge financial support by the Fundamental Research Funds for the Central Universities.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Berkheij, M., van der Sluis, L., Sewing, C., den Boer, D. J., Terpstra, J. W., Heimstra, H., Bakker, W. I. I., van den Hoogen Band, A. & van Maarseveen, J. H. (2005). Tetrahedron, 46, 2369–2371. CrossRef CAS Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Campbell, H., Cline, W., Evans, M., Lloyd, J. & Peck, A. W. (1973). Eur. J. Clin. Pharmacol. 6, 170–176. CrossRef CAS PubMed Web of Science Google Scholar
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Jasinski, J. P., Butcher, R. J., Siddegowda, M. S., Yathirajan, H. S. & Chidan Kumar, C. S. (2011). Acta Cryst. E67, o500–o501. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 68| Part 9| September 2012| Pages o2695-o2696

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-[(4-Chloro­phen­yl)(phen­yl)meth­yl]piperazine-1,4-diium bis­­(tri­chloro­acetate)–tri­chloro­acetic acid (1/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-[(4-Chlorophenyl)(phenyl)methyl]piperazine-1,4-diium bis(trichloroacetate)–trichloroacetic acid (1/1)