A monoclinic polymorph of cysteamine hydro­chloride

Ahmad, S.; Shaheen, M.A.; Stoeckli-Evans, H.

doi:10.1107/S1600536809053008

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o134

doi:10.1107/S1600536809053008

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A monoclinic polymorph of cysteamine hydrochloride

Saeed Ahmad,^a Muhammad Ashraf Shaheen ^b and Helen Stoeckli-Evans ^c ^*

^aDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan, ^bDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^cInstitute of Physics, University of Neuchâtel, rue Emile Atgand 11, CH-2009 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

(Received 8 December 2009; accepted 9 December 2009; online 12 December 2009)

The title compound (systematic name: 2-mercaptoethanaminium chloride), C₂H₈NS⁺·Cl⁻, the hydrochloride salt of cysteamine, in contrast to the previously reported triclinic polymorph [Kim et al. (2002 ). Polyhedron, 21, 225–228], crystallized in the monoclinic crystal system. In the crystal, the cysteaminium cations are linked to the chloride anions via one S—H⋯Cl and three N—H⋯Cl hydrogen bonds. Two-dimensional slab-like networks are formed, which are stacked in [100]. This arrangement is similar to that observed in the triclinic polymorph.

Related literature

For the structure of the triclinic polymorph, see: Kim et al. (2002).

Experimental

Crystal data

C₂H₈NS⁺·Cl⁻
M_r = 113.60
Monoclinic, P 2₁ /c
a = 7.7441 (4) Å
b = 8.4931 (5) Å
c = 8.7126 (5) Å
β = 101.962 (4)°
V = 560.60 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 173 K
0.40 × 0.40 × 0.40 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2009 ) T_min = 0.738, T_max = 0.860
10581 measured reflections
1506 independent reflections
1426 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.10
1506 reflections
79 parameters
All H-atom parameters refined
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
S1—H1S⋯Cl1ⁱ	1.21 (3)	2.69 (3)	3.8003 (5)	152 (2)
N1—H1AN⋯Cl1ⁱⁱ	0.89 (3)	2.31 (3)	3.1485 (13)	159 (2)
N1—H1BN⋯Cl1ⁱⁱⁱ	0.89 (2)	2.44 (2)	3.2563 (14)	152 (2)
N1—H1CN⋯Cl1	0.90 (3)	2.26 (3)	3.1437 (13)	169 (2)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053008/is2503sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053008/is2503Isup2.hkl

checkCIF report

Comment top

The crystal structure of the triclinic polymorph, (I), of the title compound has been reported previously (Kim et al., 2002). Those crystals were prepared by recrystallization of cysteamine hydrochloride from hot alchohols, such as n-butanol, 2-propanol or n-propanol.

The stucture of the monoclinic polymorph, (II), is illustrated in Fig. 1, and the geometrical parameters are available in the Supplementary Information and the archived CIF. Here the crystalline sample received from the producers was used without further recrystallization. In contrast to (I), that crystallized with two independent molecules per asymmetric unit, polymorph (II) crystallized with one independent molecule per asymmetric unit. The conformation of the cation (i.e. torsion angle S—C—C—N) is similar in the two polymorphs: 61.49 (16)° in (II), and -60.28 and 60.65° in (I).

In the crystal of (II) the cysteaminium cations are linked to the chloride anions, via one S—H···Cl and three N—H···Cl hydrogen bonds (Table 1). Two-dimensional slab-like networks are formed, which stack in the [100] direction (Fig. 2). A similar hydrogen-bonded slab-like arrangement was also observed in the crystal structure of the triclinic polymorph (I), see Fig. 3.

Related literature top

For the structure of the triclinic polymorph, see: Kim et al. (2002).

Experimental top

The sample used, supplied by Alfa Aesar (A Johnson Matthey Company) USA, consisted of colourless block-like crystals. A small piece of a large crystal was used for data collection.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with the displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view, along the b axis, of the crystal packing of the title compound. The S—H···Cl and N—H···Cl hydrogen bonds are shown as dotted cyan lines (see Table 1 for details).
	Fig. 3. A view, along the a axis, of the crystal packing in the triclinic polymorph of the title compound (Kim et al., 2002). The S—H···Cl and N—H···Cl hydrogen bonds are shown as dotted cyan lines.

2-mercaptoethanaminium chloride top

Crystal data top

C₂H₈NS⁺·Cl⁻	F(000) = 240
M_r = 113.60	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15168 reflections
a = 7.7441 (4) Å	θ = 2.4–29.5°
b = 8.4931 (5) Å	µ = 0.90 mm⁻¹
c = 8.7126 (5) Å	T = 173 K
β = 101.962 (4)°	Block, colourless
V = 560.60 (5) Å³	0.40 × 0.40 × 0.40 mm
Z = 4

Data collection top

Stoe IPDS-2 diffractometer	1506 independent reflections
Radiation source: fine-focus sealed tube	1426 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
ϕ and ω scans	θ_max = 29.2°, θ_min = 2.7°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2009)	h = −10→10
T_min = 0.738, T_max = 0.860	k = −11→11
10581 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	All H-atom parameters refined
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0466P)² + 0.1619P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
1506 reflections	Δρ_max = 0.30 e Å⁻³
79 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (9)

Crystal data top

C₂H₈NS⁺·Cl⁻	V = 560.60 (5) Å³
M_r = 113.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7441 (4) Å	µ = 0.90 mm⁻¹
b = 8.4931 (5) Å	T = 173 K
c = 8.7126 (5) Å	0.40 × 0.40 × 0.40 mm
β = 101.962 (4)°

Data collection top

Stoe IPDS-2 diffractometer	1506 independent reflections
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2009)	1426 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.860	R_int = 0.072
10581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.088	All H-atom parameters refined
S = 1.10	Δρ_max = 0.30 e Å⁻³
1506 reflections	Δρ_min = −0.36 e Å⁻³
79 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 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
S1	0.85152 (6)	0.67255 (4)	0.96395 (5)	0.0370 (1)
N1	0.83799 (17)	0.42811 (15)	0.67906 (15)	0.0288 (3)
C1	0.6807 (2)	0.53275 (19)	0.87903 (17)	0.0327 (4)
C2	0.67171 (19)	0.4989 (2)	0.70672 (17)	0.0326 (4)
Cl1	0.77972 (4)	0.40823 (4)	0.31160 (4)	0.0290 (1)
H1AN	0.853 (3)	0.335 (3)	0.726 (3)	0.045 (6)*
H1A	0.711 (3)	0.439 (3)	0.942 (3)	0.038 (5)*
H1B	0.570 (3)	0.572 (3)	0.894 (3)	0.045 (6)*
H1S	0.795 (3)	0.783 (3)	0.881 (3)	0.060 (7)*
H1BN	0.935 (3)	0.485 (3)	0.714 (3)	0.044 (6)*
H2A	0.652 (3)	0.597 (2)	0.644 (2)	0.033 (5)*
H2B	0.575 (3)	0.428 (3)	0.668 (3)	0.055 (7)*
H1CN	0.834 (3)	0.414 (3)	0.576 (3)	0.047 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0457 (3)	0.0318 (2)	0.0344 (2)	−0.0024 (1)	0.0107 (2)	−0.0034 (1)
N1	0.0285 (6)	0.0321 (6)	0.0256 (6)	−0.0013 (4)	0.0053 (4)	0.0005 (5)
C1	0.0301 (7)	0.0407 (8)	0.0284 (7)	0.0010 (6)	0.0083 (5)	0.0038 (6)
C2	0.0273 (6)	0.0432 (8)	0.0265 (6)	0.0019 (6)	0.0041 (5)	0.0032 (6)
Cl1	0.0289 (2)	0.0307 (2)	0.0268 (2)	0.0011 (1)	0.0046 (1)	−0.0016 (1)

Geometric parameters (Å, º) top

S1—C1	1.8170 (16)	C1—C2	1.516 (2)
S1—H1S	1.21 (3)	C1—H1A	0.97 (3)
N1—C2	1.485 (2)	C1—H1B	0.95 (2)
N1—H1BN	0.89 (2)	C2—H2A	0.991 (17)
N1—H1AN	0.89 (3)	C2—H2B	0.97 (2)
N1—H1CN	0.90 (3)

C1—S1—H1S	96.9 (12)	S1—C1—H1B	108.4 (15)
H1AN—N1—H1CN	108 (2)	C2—C1—H1A	111.2 (15)
H1BN—N1—H1CN	105 (2)	C2—C1—H1B	110.1 (15)
C2—N1—H1AN	108.7 (16)	H1A—C1—H1B	109 (2)
C2—N1—H1BN	115.0 (16)	N1—C2—H2A	106.9 (13)
C2—N1—H1CN	111.4 (15)	N1—C2—H2B	109.1 (15)
H1AN—N1—H1BN	108 (2)	C1—C2—H2A	110.9 (10)
S1—C1—C2	114.04 (11)	C1—C2—H2B	109.7 (15)
N1—C2—C1	111.96 (12)	H2A—C2—H2B	108 (2)
S1—C1—H1A	103.7 (15)

S1—C1—C2—N1	61.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
S1—H1S···Cl1ⁱ	1.21 (3)	2.69 (3)	3.8003 (5)	152 (2)
N1—H1AN···Cl1ⁱⁱ	0.89 (3)	2.31 (3)	3.1485 (13)	159 (2)
N1—H1BN···Cl1ⁱⁱⁱ	0.89 (2)	2.44 (2)	3.2563 (14)	152 (2)
N1—H1CN···Cl1	0.90 (3)	2.26 (3)	3.1437 (13)	169 (2)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂H₈NS⁺·Cl⁻
M_r	113.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.7441 (4), 8.4931 (5), 8.7126 (5)
β (°)	101.962 (4)
V (Å³)	560.60 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.40 × 0.40 × 0.40

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE; Stoe & Cie, 2009)
T_min, T_max	0.738, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	10581, 1506, 1426
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.10
No. of reflections	1506
No. of parameters	79
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.36

Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
S1—H1S···Cl1ⁱ	1.21 (3)	2.69 (3)	3.8003 (5)	152 (2)
N1—H1AN···Cl1ⁱⁱ	0.89 (3)	2.31 (3)	3.1485 (13)	159 (2)
N1—H1BN···Cl1ⁱⁱⁱ	0.89 (2)	2.44 (2)	3.2563 (14)	152 (2)
N1—H1CN···Cl1	0.90 (3)	2.26 (3)	3.1437 (13)	169 (2)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+1.

Acknowledgements

HSE is grateful to the XRD Application LAB, Microsystems Technology Division, Swiss Center for Electronics and Microtechnology, Neuchâtel, for access to the X-ray diffraction equipment.

References

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