4-(Methyl­sulfon­yl)piperazin-1-ium chloride

Fun, H.-K.; Yeap, C.S.; Chidan Kumar, C.S.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536810001224

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages o361-o362

https://doi.org/10.1107/S1600536810001224

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4-(Methylsulfonyl)piperazin-1-ium chloride

Hoong-Kun Fun,^a ^*‡ Chin Sing Yeap,^a § C. S. Chidan Kumar,^b H. S. Yathirajan ^b and B. Narayana ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 10 January 2010; accepted 10 January 2010; online 16 January 2010)

In the title molecular salt, C₅H₁₃N₂O₂S⁺·Cl⁻, the complete cation is generated by crystallographic mirror symmetry, with both N atoms, the S atom and one C atom lying on the reflecting plane. The chloride ion also lies on the mirror plane. The piperazinium ring adopts a chair conformation and the N—S bond adopts an equatorial orientation. In the crystal structure, the component ions are linked into a three-dimensional framework by intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds.

Related literature

For medicinal background to piperazine derivatives, see: Dinsmore & Beshore (2002 ); Berkheij et al. (2005 ); Humle & Cherrier (1999 ). For related structures, see: Bart et al. (1978 ); Girisha et al. (2008 ); Homrighausen & Krause Bauer (2002 ); Jin et al. (2007 ); Kubo et al. (2007 ); Parkin et al. (2004 ); Shen et al. (2006 ), Wang et al. (2006 ). For ring conformations, see: Cremer & Pople (1975 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₅H₁₃N₂O₂S⁺·Cl⁻
M_r = 200.68
Monoclinic, P 2₁ /m
a = 6.0231 (1) Å
b = 9.1097 (2) Å
c = 7.9852 (2) Å
β = 100.700 (1)°
V = 430.52 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 100 K
0.36 × 0.32 × 0.05 mm

Data collection

Bruker APEX Duo CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.801, T_max = 0.968
10626 measured reflections
2790 independent reflections
2419 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.072
S = 1.10
2790 reflections
87 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯Cl1ⁱ	0.92 (2)	2.40 (2)	3.1341 (8)	137 (1)
N1—H2N1⋯Cl1ⁱⁱ	0.93 (2)	2.19 (2)	3.0966 (8)	164 (1)
C1—H1A⋯Cl1ⁱⁱⁱ	0.953 (12)	2.700 (12)	3.5251 (6)	145.2 (9)
C3—H3A⋯Cl1	0.94 (2)	2.65 (2)	3.5487 (10)	160 (2)
Symmetry codes: (i) x+1, y, z-1; (ii) x, y, z-1; (iii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001224/hb5306sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001224/hb5306Isup2.hkl

checkCIF report

Comment top

Piperazines are among the most important building blocks in today's drug discovery. The piperazine nucleus is capable of binding to multiple receptors with high affinity and therefore piperazine has been classified as a privileged structure (Dinsmore & Beshore, 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). The piperazines are a broad class of chemical compounds, many with important pharmacological properties, which contain a core piperazine functional group. 1-(Methylsulfonyl)piperazine is an important intermediate in synthetic organic chemistry, mainly used as a pharmaceutical intermediate.

The crystal structures of trans-2,5-dimethylpiperazine dihydrochloride (Bart et al., 1978), 1-(3-chlorophenyl)-4-(3-chloropropyl)piperazinium chloride (Homrighausen & Krause Bauer, 2002), piperazine (Parkin et al., 2004), 2,2'-(piperazine-1,4-diium-1,4-diyl)diacetate dehydrate (Shen et al., 2006), 1,4-bis(chloroacetyl)piperazine (Wang et al., 2006), 1,4-bis(1-naphthylmethyl) piperazine (Kubo et al., 2007), 1,4-bis(4-chlorobenzo-yl)piperazine (Jin et al., 2007) and 1-benzhydryl-4-(4-chlorophenylsulfonyl) piperazine (Girisha et al., 2008) have been reported. In view of the importance of the title compound, this paper reports its crystal structure.

The asymmetric unit of the title compound contains one-half of a cation and half of a cloride anion (Fig. 1). The Cl1, S1, N1, N2, and C3 atoms are lying on a mirror plane. The piperazinium ring adopts a chair conformation with puckering amplitude Q = 0.5680 (7) Å, θ = 179.90 (7)°, φ = 180 (7)° (Cremer & Pople, 1975). In the crystal structure (Fig. 2), the molecules are linked into a three-dimensional framework by intermolecular hydrogen bonds (Table 1).

Related literature top

For medicinal background to piperazine derivatives, see: Dinsmore & Beshore (2002); Berkheij et al. (2005); Humle & Cherrier (1999). For related structures, see: Bart et al. (1978); Girisha et al. (2008); Homrighausen & Krause Bauer (2002); Jin et al. (2007); Kubo et al. (2007); Parkin et al. (2004); Shen et al. (2006), Wang et al. (2006). For ring conformations, see: Cremer & Pople (1975). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine Chem., Bangalore, India. The compound was used without further purification. Colourless plates of (I) were obtained from slow evaporation of a methanol solution (m.p.: 489–492 K).

Structure description top

For medicinal background to piperazine derivatives, see: Dinsmore & Beshore (2002); Berkheij et al. (2005); Humle & Cherrier (1999). For related structures, see: Bart et al. (1978); Girisha et al. (2008); Homrighausen & Krause Bauer (2002); Jin et al. (2007); Kubo et al. (2007); Parkin et al. (2004); Shen et al. (2006), Wang et al. (2006). For ring conformations, see: Cremer & Pople (1975). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with 50% probability ellipsoids for the non-H atoms. Atoms with suffix A are generated by the symmetry operation (x, 1/2 - y, z).
	Fig. 2. The crystal packing of (I), viewed down the a axis, showing the hydrogen-bonded (dashed lines) three-dimensional framework.

4-(Methylsulfonyl)piperazin-1-ium chloride top

Crystal data top

C₅H₁₃N₂O₂S⁺·Cl⁻	F(000) = 212
M_r = 200.68	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 4890 reflections
a = 6.0231 (1) Å	θ = 3.4–40.1°
b = 9.1097 (2) Å	µ = 0.64 mm⁻¹
c = 7.9852 (2) Å	T = 100 K
β = 100.700 (1)°	Plate, colourless
V = 430.52 (2) Å³	0.36 × 0.32 × 0.05 mm
Z = 2

Data collection top

Bruker APEX Duo CCD diffractometer	2790 independent reflections
Radiation source: fine-focus sealed tube	2419 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 40.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.801, T_max = 0.968	k = −14→16
10626 measured reflections	l = −14→14

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0335P)² + 0.0922P] where P = (F_o² + 2F_c²)/3
2790 reflections	(Δ/σ)_max = 0.001
87 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₅H₁₃N₂O₂S⁺·Cl⁻	V = 430.52 (2) Å³
M_r = 200.68	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 6.0231 (1) Å	µ = 0.64 mm⁻¹
b = 9.1097 (2) Å	T = 100 K
c = 7.9852 (2) Å	0.36 × 0.32 × 0.05 mm
β = 100.700 (1)°

Data collection top

Bruker APEX Duo CCD diffractometer	2790 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2419 reflections with I > 2σ(I)
T_min = 0.801, T_max = 0.968	R_int = 0.022
10626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.49 e Å⁻³
2790 reflections	Δρ_min = −0.40 e Å⁻³
87 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.30674 (3)	0.2500	0.93448 (3)	0.01195 (5)
S1	0.69091 (3)	0.2500	0.56598 (2)	0.00951 (5)
N1	0.82854 (12)	0.2500	0.03611 (9)	0.01007 (11)
N2	0.79320 (12)	0.2500	0.38830 (9)	0.00974 (11)
O1	0.75935 (9)	0.11396 (6)	0.65235 (6)	0.01498 (9)
C1	0.87784 (10)	0.11522 (7)	0.14202 (8)	0.01165 (9)
C2	0.74465 (10)	0.11465 (7)	0.28537 (8)	0.01168 (9)
C3	0.39411 (15)	0.2500	0.50705 (12)	0.01332 (13)
H1A	0.8351 (18)	0.0315 (13)	0.0719 (14)	0.012 (2)*
H1B	1.040 (2)	0.1186 (13)	0.1845 (16)	0.016 (3)*
H2A	0.583 (2)	0.1017 (14)	0.2371 (15)	0.018 (3)*
H2B	0.789 (2)	0.0335 (16)	0.3554 (17)	0.027 (3)*
H3A	0.331 (3)	0.2500	0.606 (2)	0.019 (4)*
H3B	0.350 (2)	0.3381 (15)	0.4460 (16)	0.025 (3)*
H1N1	0.914 (3)	0.2500	−0.048 (2)	0.019 (4)*
H2N1	0.677 (3)	0.2500	−0.017 (2)	0.021 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.00886 (7)	0.01261 (8)	0.01485 (9)	0.000	0.00346 (6)	0.000
S1	0.01110 (8)	0.01033 (8)	0.00696 (8)	0.000	0.00128 (6)	0.000
N1	0.0098 (2)	0.0115 (3)	0.0095 (3)	0.000	0.00316 (19)	0.000
N2	0.0126 (2)	0.0084 (2)	0.0087 (2)	0.000	0.0032 (2)	0.000
O1	0.01874 (19)	0.01499 (19)	0.01109 (18)	0.00356 (16)	0.00245 (15)	0.00480 (15)
C1	0.0148 (2)	0.00900 (19)	0.0122 (2)	0.00097 (17)	0.00547 (17)	−0.00041 (17)
C2	0.0162 (2)	0.0083 (2)	0.0117 (2)	−0.00109 (16)	0.00571 (17)	−0.00060 (16)
C3	0.0115 (3)	0.0166 (3)	0.0121 (3)	0.000	0.0027 (2)	0.000

Geometric parameters (Å, º) top

S1—O1ⁱ	1.4408 (5)	N2—C2ⁱ	1.4806 (7)
S1—O1	1.4408 (5)	C1—C2	1.5148 (8)
S1—N2	1.6484 (7)	C1—H1A	0.953 (11)
S1—C3	1.7621 (9)	C1—H1B	0.976 (12)
N1—C1	1.4892 (7)	C2—H2A	0.983 (13)
N1—C1ⁱ	1.4892 (7)	C2—H2B	0.935 (14)
N1—H1N1	0.920 (17)	C3—H3A	0.941 (18)
N1—H2N1	0.933 (19)	C3—H3B	0.951 (14)
N2—C2	1.4806 (7)

O1ⁱ—S1—O1	118.67 (4)	N1—C1—C2	110.75 (5)
O1ⁱ—S1—N2	107.01 (2)	N1—C1—H1A	108.8 (7)
O1—S1—N2	107.01 (2)	C2—C1—H1A	108.5 (6)
O1ⁱ—S1—C3	108.28 (3)	N1—C1—H1B	104.6 (7)
O1—S1—C3	108.29 (3)	C2—C1—H1B	112.1 (7)
N2—S1—C3	107.03 (4)	H1A—C1—H1B	112.0 (9)
C1—N1—C1ⁱ	111.07 (7)	N2—C2—C1	109.81 (5)
C1—N1—H1N1	109.7 (5)	N2—C2—H2A	113.4 (7)
C1ⁱ—N1—H1N1	109.7 (5)	C1—C2—H2A	109.1 (7)
C1—N1—H2N1	109.5 (5)	N2—C2—H2B	108.7 (8)
C1ⁱ—N1—H2N1	109.5 (5)	C1—C2—H2B	108.7 (7)
H1N1—N1—H2N1	107.3 (15)	H2A—C2—H2B	107.1 (10)
C2—N2—C2ⁱ	112.77 (7)	S1—C3—H3A	108.9 (11)
C2—N2—S1	114.27 (4)	S1—C3—H3B	108.1 (8)
C2ⁱ—N2—S1	114.27 (4)	H3A—C3—H3B	108.3 (9)

O1ⁱ—S1—N2—C2	178.10 (5)	C3—S1—N2—C2ⁱ	66.00 (5)
O1—S1—N2—C2	49.91 (6)	C1ⁱ—N1—C1—C2	56.95 (8)
C3—S1—N2—C2	−65.99 (5)	C2ⁱ—N2—C2—C1	56.73 (8)
O1ⁱ—S1—N2—C2ⁱ	−49.91 (6)	S1—N2—C2—C1	−170.56 (4)
O1—S1—N2—C2ⁱ	−178.10 (5)	N1—C1—C2—N2	−55.89 (7)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···Cl1ⁱⁱ	0.92 (2)	2.40 (2)	3.1341 (8)	137 (1)
N1—H2N1···Cl1ⁱⁱⁱ	0.93 (2)	2.19 (2)	3.0966 (8)	164 (1)
C1—H1A···Cl1^iv	0.953 (12)	2.700 (12)	3.5251 (6)	145.2 (9)
C3—H3A···Cl1	0.94 (2)	2.65 (2)	3.5487 (10)	160 (2)

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

Experimental details

Crystal data
Chemical formula	C₅H₁₃N₂O₂S⁺·Cl⁻
M_r	200.68
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	100
a, b, c (Å)	6.0231 (1), 9.1097 (2), 7.9852 (2)
β (°)	100.700 (1)
V (Å³)	430.52 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.36 × 0.32 × 0.05

Data collection
Diffractometer	Bruker APEX Duo CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.801, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	10626, 2790, 2419
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.906

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.072, 1.10
No. of reflections	2790
No. of parameters	87
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.40

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···Cl1ⁱ	0.919 (17)	2.395 (18)	3.1341 (8)	137.4 (14)
N1—H2N1···Cl1ⁱⁱ	0.932 (18)	2.192 (18)	3.0966 (8)	163.5 (14)
C1—H1A···Cl1ⁱⁱⁱ	0.953 (12)	2.700 (12)	3.5251 (6)	145.2 (9)
C3—H3A···Cl1	0.938 (17)	2.654 (16)	3.5487 (10)	159.6 (15)

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5523-2009.

Acknowledgements

HKF thanks Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CSY thanks USM for the award of a USM Fellowship. CSC thanks University of Mysore for research facilities.

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