organic compounds
4-(3-Chlorophenyl)-1-(3-chloropropyl)piperazin-1-ium chloride redetermined at 100 K
aSchool of Studies in Chemistry, Jiwaji University, Gwalior 474 011, India, and bDepartment of Chemistry, Howard University, Washington DC 20059, USA
*Correspondence e-mail: sksrivas7@yahoo.com
The 13H19Cl2N2+·Cl−, has been reported previously [Homrighausen & Krause Bauer (2002). Acta Cryst. E58, o1395–o1396] based on room-temperature data, where it was found to contain a disordered chloropropyl group. We now present the structure at 100 K in which the chloropropyl group is ordered. The piperazine ring adopts a chair conformation with the exocyclic N—C bonds in equatorial orientations. The dihedral angle between the piperazine ring (all atoms) and the benzene ring is 28.47 (5)°. The chloropropyl group has an extended conformation [N—C—C—C = −177.25 (8) ° and C—C—C—Cl = 174.23 (7)°]. In the crystal, charge-assisted N—H⋯Cl hydrogen bonds link the cation and anion into ion pairs. Numerous weak C—H⋯Cl interactions link the ion pairs into a three-dimensional network. Short Cl⋯Cl contacts [3.2419 (4) Å] are also observed.
of the title salt, CCCDC reference: 1450257
Structure description
The title compound C13H19Cl2N2+Cl− belongs to a class of 5-HT1 (5-hydroxytryptamine1) subtype serotonin receptor ligands (Okamoto et al., 1993; Verdonk et al., 1992; Dalpiaz et al., 1996). The structure of the title compound (Fig. 1) has been previously reported (Homrighausen & Krause Bauer, 2002) but was collected at 296 K and contained a disordered chloropropyl group. This redetermination at 100 K shows that the chloropropyl group is ordered. In the crystal, charge-assisted N—H⋯Cl hydrogen bonds and C—H⋯Cl secondary interactions occur (Table 1 and Fig. 2), resulting in a three-dimensional supramolecular architecture.
Synthesis and crystallization
The title compound was obtained from Sigma Aldrich and crystals suitable for a single-crystal X-ray diffraction study were obtained by dissolving the title compound in ethanol and allowing the solvent to evaporate slowly at room temperature.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1450257
https://doi.org/10.1107/S2414314616001681/hb4012sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001681/hb4012Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314616001681/hb4012Isup3.cml
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C13H19Cl2N2+·Cl− | F(000) = 648 |
Mr = 309.65 | Dx = 1.412 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.9608 (9) Å | Cell parameters from 9973 reflections |
b = 9.5199 (8) Å | θ = 2.6–31.8° |
c = 14.0262 (11) Å | µ = 0.61 mm−1 |
β = 95.398 (1)° | T = 100 K |
V = 1457.1 (2) Å3 | Block, colourless |
Z = 4 | 0.55 × 0.32 × 0.30 mm |
Bruker APEXII diffractometer | 4407 reflections with I > 2σ(I) |
ω scans | Rint = 0.025 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 32.1°, θmin = 2.6° |
Tmin = 0.610, Tmax = 0.746 | h = −16→16 |
32810 measured reflections | k = −14→14 |
4808 independent reflections | l = −20→20 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.537P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
4808 reflections | Δρmax = 0.69 e Å−3 |
167 parameters | Δρmin = −0.33 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.19355 (2) | 0.41129 (3) | 0.74761 (2) | 0.02408 (7) | |
Cl2 | 0.89868 (2) | 0.06195 (3) | 0.56586 (2) | 0.02604 (7) | |
Cl3 | 0.45091 (2) | 0.23674 (3) | 0.38594 (2) | 0.01897 (6) | |
N1 | 0.23210 (7) | 0.38855 (8) | 0.62774 (6) | 0.01511 (15) | |
N2 | 0.44985 (7) | 0.22760 (8) | 0.60415 (6) | 0.01394 (14) | |
H2N | 0.4481 (13) | 0.2217 (15) | 0.5379 (11) | 0.016 (3)* | |
C1 | 0.12197 (9) | 0.46460 (10) | 0.62867 (7) | 0.01423 (16) | |
C2 | 0.02649 (9) | 0.40667 (10) | 0.67638 (7) | 0.01616 (17) | |
H2A | 0.0346 | 0.3152 | 0.7033 | 0.019* | |
C3 | −0.07914 (9) | 0.48363 (10) | 0.68387 (7) | 0.01700 (17) | |
C4 | −0.09634 (10) | 0.61775 (11) | 0.64557 (8) | 0.01990 (19) | |
H4A | −0.1700 | 0.6685 | 0.6509 | 0.024* | |
C5 | −0.00117 (10) | 0.67422 (11) | 0.59915 (8) | 0.02107 (19) | |
H5A | −0.0097 | 0.7662 | 0.5731 | 0.025* | |
C6 | 0.10650 (10) | 0.59958 (10) | 0.58970 (7) | 0.01782 (18) | |
H6A | 0.1695 | 0.6404 | 0.5567 | 0.021* | |
C7 | 0.33718 (9) | 0.45553 (10) | 0.58992 (7) | 0.01646 (17) | |
H7A | 0.3409 | 0.5558 | 0.6088 | 0.020* | |
H7B | 0.3285 | 0.4504 | 0.5191 | 0.020* | |
C8 | 0.45436 (9) | 0.38120 (10) | 0.62920 (7) | 0.01595 (17) | |
H8A | 0.5254 | 0.4252 | 0.6023 | 0.019* | |
H8B | 0.4654 | 0.3920 | 0.6997 | 0.019* | |
C9 | 0.33685 (9) | 0.16198 (10) | 0.63727 (7) | 0.01506 (16) | |
H9A | 0.3424 | 0.1627 | 0.7081 | 0.018* | |
H9B | 0.3309 | 0.0630 | 0.6156 | 0.018* | |
C10 | 0.22316 (9) | 0.24111 (10) | 0.59790 (7) | 0.01574 (17) | |
H10A | 0.2145 | 0.2354 | 0.5271 | 0.019* | |
H10B | 0.1498 | 0.1978 | 0.6218 | 0.019* | |
C11 | 0.56026 (9) | 0.14857 (11) | 0.64726 (7) | 0.01708 (17) | |
H11A | 0.5382 | 0.0484 | 0.6537 | 0.020* | |
H11B | 0.5840 | 0.1856 | 0.7123 | 0.020* | |
C12 | 0.66940 (9) | 0.15917 (11) | 0.58844 (7) | 0.01750 (17) | |
H12A | 0.6965 | 0.2581 | 0.5850 | 0.021* | |
H12B | 0.6468 | 0.1250 | 0.5225 | 0.021* | |
C13 | 0.77155 (9) | 0.06936 (11) | 0.63720 (8) | 0.01945 (18) | |
H13A | 0.7406 | −0.0268 | 0.6469 | 0.023* | |
H13B | 0.7987 | 0.1095 | 0.7008 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.01963 (12) | 0.02193 (12) | 0.03227 (14) | 0.00122 (8) | 0.01077 (10) | −0.00347 (9) |
Cl2 | 0.01862 (12) | 0.02468 (13) | 0.03645 (15) | 0.00401 (9) | 0.01116 (10) | 0.00181 (10) |
Cl3 | 0.02473 (12) | 0.02111 (12) | 0.01101 (10) | −0.00293 (8) | 0.00141 (8) | 0.00052 (7) |
N1 | 0.0135 (3) | 0.0116 (3) | 0.0205 (4) | 0.0004 (3) | 0.0030 (3) | 0.0001 (3) |
N2 | 0.0142 (3) | 0.0143 (3) | 0.0136 (3) | 0.0015 (3) | 0.0030 (3) | 0.0010 (3) |
C1 | 0.0152 (4) | 0.0133 (4) | 0.0140 (4) | 0.0014 (3) | 0.0002 (3) | −0.0016 (3) |
C2 | 0.0162 (4) | 0.0148 (4) | 0.0176 (4) | 0.0015 (3) | 0.0023 (3) | −0.0006 (3) |
C3 | 0.0160 (4) | 0.0173 (4) | 0.0178 (4) | 0.0009 (3) | 0.0023 (3) | −0.0037 (3) |
C4 | 0.0196 (4) | 0.0188 (4) | 0.0209 (4) | 0.0062 (3) | 0.0002 (3) | −0.0022 (3) |
C5 | 0.0239 (5) | 0.0166 (4) | 0.0225 (5) | 0.0051 (4) | 0.0008 (4) | 0.0021 (3) |
C6 | 0.0200 (4) | 0.0154 (4) | 0.0179 (4) | 0.0014 (3) | 0.0012 (3) | 0.0022 (3) |
C7 | 0.0152 (4) | 0.0136 (4) | 0.0208 (4) | −0.0006 (3) | 0.0026 (3) | 0.0019 (3) |
C8 | 0.0149 (4) | 0.0141 (4) | 0.0189 (4) | −0.0006 (3) | 0.0018 (3) | −0.0005 (3) |
C9 | 0.0152 (4) | 0.0134 (4) | 0.0171 (4) | 0.0001 (3) | 0.0044 (3) | 0.0010 (3) |
C10 | 0.0150 (4) | 0.0127 (4) | 0.0196 (4) | −0.0002 (3) | 0.0018 (3) | −0.0013 (3) |
C11 | 0.0158 (4) | 0.0193 (4) | 0.0165 (4) | 0.0044 (3) | 0.0032 (3) | 0.0036 (3) |
C12 | 0.0158 (4) | 0.0215 (4) | 0.0156 (4) | 0.0032 (3) | 0.0035 (3) | 0.0020 (3) |
C13 | 0.0165 (4) | 0.0207 (4) | 0.0216 (5) | 0.0042 (3) | 0.0045 (3) | 0.0028 (3) |
Cl1—C3 | 1.7485 (11) | C7—C8 | 1.5234 (13) |
Cl2—C13 | 1.7918 (11) | C7—H7A | 0.9900 |
N1—C1 | 1.4087 (12) | C7—H7B | 0.9900 |
N1—C7 | 1.4592 (12) | C8—H8A | 0.9900 |
N1—C10 | 1.4654 (12) | C8—H8B | 0.9900 |
N2—C9 | 1.4995 (12) | C9—C10 | 1.5151 (13) |
N2—C11 | 1.5029 (12) | C9—H9A | 0.9900 |
N2—C8 | 1.5037 (12) | C9—H9B | 0.9900 |
N2—H2N | 0.929 (15) | C10—H10A | 0.9900 |
C1—C6 | 1.4005 (13) | C10—H10B | 0.9900 |
C1—C2 | 1.4067 (14) | C11—C12 | 1.5191 (14) |
C2—C3 | 1.3824 (13) | C11—H11A | 0.9900 |
C2—H2A | 0.9500 | C11—H11B | 0.9900 |
C3—C4 | 1.3912 (14) | C12—C13 | 1.5193 (14) |
C4—C5 | 1.3888 (16) | C12—H12A | 0.9900 |
C4—H4A | 0.9500 | C12—H12B | 0.9900 |
C5—C6 | 1.3945 (14) | C13—H13A | 0.9900 |
C5—H5A | 0.9500 | C13—H13B | 0.9900 |
C6—H6A | 0.9500 | ||
C1—N1—C7 | 119.02 (8) | C7—C8—H8A | 109.4 |
C1—N1—C10 | 117.42 (8) | N2—C8—H8B | 109.4 |
C7—N1—C10 | 110.40 (8) | C7—C8—H8B | 109.4 |
C9—N2—C11 | 108.92 (7) | H8A—C8—H8B | 108.0 |
C9—N2—C8 | 110.04 (7) | N2—C9—C10 | 110.79 (7) |
C11—N2—C8 | 112.66 (8) | N2—C9—H9A | 109.5 |
C9—N2—H2N | 110.1 (9) | C10—C9—H9A | 109.5 |
C11—N2—H2N | 108.2 (9) | N2—C9—H9B | 109.5 |
C8—N2—H2N | 106.8 (9) | C10—C9—H9B | 109.5 |
C6—C1—C2 | 118.50 (9) | H9A—C9—H9B | 108.1 |
C6—C1—N1 | 122.71 (9) | N1—C10—C9 | 109.97 (8) |
C2—C1—N1 | 118.65 (8) | N1—C10—H10A | 109.7 |
C3—C2—C1 | 119.62 (9) | C9—C10—H10A | 109.7 |
C3—C2—H2A | 120.2 | N1—C10—H10B | 109.7 |
C1—C2—H2A | 120.2 | C9—C10—H10B | 109.7 |
C2—C3—C4 | 122.76 (9) | H10A—C10—H10B | 108.2 |
C2—C3—Cl1 | 118.44 (8) | N2—C11—C12 | 113.18 (8) |
C4—C3—Cl1 | 118.77 (8) | N2—C11—H11A | 108.9 |
C5—C4—C3 | 117.12 (9) | C12—C11—H11A | 108.9 |
C5—C4—H4A | 121.4 | N2—C11—H11B | 108.9 |
C3—C4—H4A | 121.4 | C12—C11—H11B | 108.9 |
C4—C5—C6 | 121.80 (10) | H11A—C11—H11B | 107.8 |
C4—C5—H5A | 119.1 | C11—C12—C13 | 107.62 (8) |
C6—C5—H5A | 119.1 | C11—C12—H12A | 110.2 |
C5—C6—C1 | 120.20 (10) | C13—C12—H12A | 110.2 |
C5—C6—H6A | 119.9 | C11—C12—H12B | 110.2 |
C1—C6—H6A | 119.9 | C13—C12—H12B | 110.2 |
N1—C7—C8 | 109.46 (8) | H12A—C12—H12B | 108.5 |
N1—C7—H7A | 109.8 | C12—C13—Cl2 | 110.47 (7) |
C8—C7—H7A | 109.8 | C12—C13—H13A | 109.6 |
N1—C7—H7B | 109.8 | Cl2—C13—H13A | 109.6 |
C8—C7—H7B | 109.8 | C12—C13—H13B | 109.6 |
H7A—C7—H7B | 108.2 | Cl2—C13—H13B | 109.6 |
N2—C8—C7 | 111.04 (8) | H13A—C13—H13B | 108.1 |
N2—C8—H8A | 109.4 | ||
C7—N1—C1—C6 | 3.76 (14) | C1—N1—C7—C8 | 158.63 (8) |
C10—N1—C1—C6 | −133.72 (10) | C10—N1—C7—C8 | −61.16 (10) |
C7—N1—C1—C2 | −171.80 (9) | C9—N2—C8—C7 | −54.39 (10) |
C10—N1—C1—C2 | 50.72 (12) | C11—N2—C8—C7 | −176.15 (8) |
C6—C1—C2—C3 | −0.17 (14) | N1—C7—C8—N2 | 57.77 (10) |
N1—C1—C2—C3 | 175.57 (9) | C11—N2—C9—C10 | 178.29 (8) |
C1—C2—C3—C4 | 0.26 (15) | C8—N2—C9—C10 | 54.33 (10) |
C1—C2—C3—Cl1 | −177.57 (7) | C1—N1—C10—C9 | −157.53 (8) |
C2—C3—C4—C5 | −0.65 (15) | C7—N1—C10—C9 | 61.56 (10) |
Cl1—C3—C4—C5 | 177.17 (8) | N2—C9—C10—N1 | −57.91 (10) |
C3—C4—C5—C6 | 0.98 (16) | C9—N2—C11—C12 | 154.36 (8) |
C4—C5—C6—C1 | −0.93 (16) | C8—N2—C11—C12 | −83.25 (10) |
C2—C1—C6—C5 | 0.50 (14) | N2—C11—C12—C13 | −177.25 (8) |
N1—C1—C6—C5 | −175.06 (9) | C11—C12—C13—Cl2 | 174.23 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl3 | 0.929 (15) | 2.139 (15) | 3.0629 (9) | 172.4 (13) |
C8—H8B···Cl3i | 0.99 | 2.90 | 3.7757 (10) | 147 |
C9—H9A···Cl3i | 0.99 | 2.83 | 3.7200 (10) | 150 |
C11—H11A···Cl3ii | 0.99 | 2.78 | 3.6981 (11) | 155 |
C12—H12A···Cl1iii | 0.99 | 2.87 | 3.5172 (11) | 123 |
C12—H12B···Cl3 | 0.99 | 2.94 | 3.6149 (10) | 126 |
C13—H13A···Cl3ii | 0.99 | 2.90 | 3.7940 (11) | 150 |
C13—H13B···Cl1iii | 0.99 | 2.95 | 3.6095 (12) | 125 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) x+1, y, z. |
Acknowledgements
RJB wishes to acknowledge NSF award 1205608, Partnership for Reduced Dimensional Materials, for partial funding of this research. The authors wish to acknowledge the assistance of Dr Matthias Zeller in the collection of the diffraction data and NSF Grant CHE 0087210, Ohio Board of Regents Grant CAP-491, and Youngstown State University for funds to purchase the X-ray diffractometer.
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