4-(3-Chloro­phen­yl)-1-(3-chloro­prop­yl)piperazin-1-ium chloride redetermined at 100 K

Bhat, M.A.; Srivastava, S.K.; Sharma, P.; Chopra, A.; Butcher, R.J.

doi:10.1107/S2414314616001681

organic compounds

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ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160168

https://doi.org/10.1107/S2414314616001681

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4-(3-Chlorophenyl)-1-(3-chloropropyl)piperazin-1-ium chloride redetermined at 100 K

Muzzaffar Ahmad Bhat,^a Sanjay K. Srivastava,^a ^* Pooja Sharma,^a Ambika Chopra ^a and Ray J. Butcher ^b

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 January 2016; accepted 27 January 2016; online 6 February 2016)

The crystal structure of the title salt, C₁₃H₁₉Cl₂N₂⁺·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.

Keywords: crystal structure; 5-HT1 serotonin receptor ligands; piperazinium salts; disorder.

CCDC 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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) x+1, y, z.

Figure 1
Diagram of C₁₃H₁₉Cl₂N₂⁺Cl⁻, with hydrogen bonds shown as dashed lines. Atomic displacement parameters are shown at the 30% probability level.

Figure 2
Packing daigram viewed along the a axis, showing the extensive network of N—H⋯Cl hydrogen bonds and C—H⋯Cl secondary interactions (indicated by dashed lines).

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₉Cl₂N₂⁺·Cl⁻
M_r	309.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.9608 (9), 9.5199 (8), 14.0262 (11)
β (°)	95.398 (1)
V (Å³)	1457.1 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.61
Crystal size (mm)	0.55 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.610, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	32810, 4808, 4407
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.748

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.08
No. of reflections	4808
No. of parameters	167
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.33
Computer programs: APEX2 (Bruker, 2005 ), SAINT (Bruker, 2002 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1450257

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001681/hb4012sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

4-(3-Chlorophenyl)-1-(3-chloropropyl)piperazin-1-ium chloride top

Crystal data top

C₁₃H₁₉Cl₂N₂⁺·Cl⁻	F(000) = 648
M_r = 309.65	D_x = 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

Data collection top

Bruker APEXII diffractometer	4407 reflections with I > 2σ(I)
ω scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 32.1°, θ_min = 2.6°
T_min = 0.610, T_max = 0.746	h = −16→16
32810 measured reflections	k = −14→14
4808 independent reflections	l = −20→20

Refinement top

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(F_o²) + (0.0462P)² + 0.537P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
4808 reflections	Δρ_max = 0.69 e Å⁻³
167 parameters	Δρ_min = −0.33 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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