organic compounds
1-[(4-Chlorophenyl)(phenyl)methyl]piperazine-1,4-diium bis(trichloroacetate)–trichloroacetic acid (1/1)
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
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 QT = 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
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536812034794/fj2574sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034794/fj2574Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812034794/fj2574Isup3.cml
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).
The hydroxyl H atom appeared in a difference map and was positioned geometrically and refined by using a riding model [O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O)]. The disordered H1C atom attached to C11 was refined with a restrained distance C—H = 0.93 (6) Å and Uiso(H) = 1.2Ueq(C). The rest H atoms bonded to C atoms were located geometrically, with C—H = 0.93–0.98 Å, and refined by using a riding model, with 1.2Ueq(C). The occupancies of the disordered chlorine atoms in three trichloroacetic acid moieties refined to 0.59 (3), 0.41 (3) [for Cl1A,B–Cl3A,B]; 0.503 (12), 0.417 (12) [for Cl4A,B–Cl6A,B] and 0.653 (12), 0.347 (12) [for Cl7A,B–Cl9A,B]. The chlorine atom in the 1-[(4-chlorophenyl)(phenyl)methyl]piperazinediium moiety is disordered on the two-symmetric C atoms of the two benzene rings with refined site-occupation factors of 0.915 (3), 0.085 (3). The disorder was refined using the commands DFIX and EADP.
Data collection: APEX2 (Bruker, 2004); cell
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).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. |
C17H21ClN22+·2C2Cl3O2−·C2HCl3O2 | Z = 2 |
Mr = 776.93 | F(000) = 784 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII CCD diffractometer | 7039 independent reflections |
Radiation source: fine-focus sealed tube | 5186 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 27.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −11→12 |
Tmin = 0.790, Tmax = 0.875 | k = −16→11 |
10010 measured reflections | l = −16→17 |
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(Fo2) + (0.0496P)2 + 0.7913P] where P = (Fo2 + 2Fc2)/3 |
7039 reflections | (Δ/σ)max = 0.001 |
468 parameters | Δρmax = 0.40 e Å−3 |
38 restraints | Δρmin = −0.33 e Å−3 |
C17H21ClN22+·2C2Cl3O2−·C2HCl3O2 | γ = 77.169 (3)° |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 7039 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5186 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.875 | Rint = 0.012 |
10010 measured reflections |
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 | Δρmax = 0.40 e Å−3 |
7039 reflections | Δρmin = −0.33 e Å−3 |
468 parameters |
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. |
x | y | z | Uiso*/Ueq | 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* |
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) |
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) |
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···O2iv | 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···Cl7Av | 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 |
Mr | 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) |
Tmin, Tmax | 0.790, 0.875 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10010, 7039, 5186 |
Rint | 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 |
Δρmax, Δρmin (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).
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···O2iv | 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···Cl7Av | 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
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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.
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.