N-(2,6-Dimethyl­anilino)-5,6-dihydro-4H-1,3-thia­zin-3-ium chloride monohydrate

Veidis, M.V.; Orola, L.; Arajs, R.

doi:10.1107/S160053680801372X

organic compounds

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Volume 64| Part 6| June 2008| Page o1062

doi:10.1107/S160053680801372X

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N-(2,6-Dimethylanilino)-5,6-dihydro-4H-1,3-thiazin-3-ium chloride monohydrate

Mikelis V. Veidis,^a ^* Liana Orola ^a and Reinis Arajs ^a

^aUniversity of Latvia, Kr. Valdemara 48, Riga, LV 1013, Latvia
^*Correspondence e-mail: veidis@lu.lv

(Received 22 April 2008; accepted 8 May 2008; online 10 May 2008)

In the title compound, alternatively called xylazine hydrochloride monohydrate, C₁₂H₁₇N₂S⁺·Cl⁻·H₂O, the six-membered thiazine ring is in a half-chair conformation. In the crystal structure, six component centrosymmetric clusters are formed via intermolecular O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds involving xylazine cations, chloride anions and water molecules.

Related literature

For related literature see: Carpy et al. (1979 ); Kalman et al. (1977 ).

Experimental

Crystal data

C₁₂H₁₇N₂S⁺·Cl⁻·H₂O
M_r = 274.81
Monoclinic, P 2₁ /c
a = 13.4546 (2) Å
b = 8.6547 (1) Å
c = 12.7732 (2) Å
β = 109.210 (2)°
V = 1404.56 (4) Å³
Z = 4
Cu Kα radiation
μ = 3.69 mm⁻¹
T = 100 K
0.44 × 0.25 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: numerical (de Meulenaer & Tompa, 1965 ) T_min = 0.30, T_max = 0.61
19046 measured reflections
2747 independent reflections
2509 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.01
2509 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O17	0.87	1.97	2.815 (2)	163
O17—H171⋯Cl16ⁱ	0.82	2.36	3.158 (1)	164
N7—H7⋯Cl16ⁱ	0.87	2.37	3.204 (1)	162
O17—H172⋯Cl16ⁱⁱ	0.83	2.35	3.171 (1)	173
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801372X/lh2620sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801372X/lh2620Isup2.hkl

checkCIF report

Comment top

Xylazine hydrochloride monohydrate is a pharmaceutical used in veterinary medicine as an anesthetic. The substance is an alpha2-agonist with sedative, analgesic, and muscle relaxing properties.

The crystal structure of the title compound has been determined at 100 K. The structure is depicted in Fig. 1. The phenyl ring forms a dihedral angle of 83.24 (14)° with the plane defined by S1, C6 and N5 of the thiazine ring. The six-member thiazine ring assumes the half-chair conformation.

Hydrogen atoms are bonded to both nitrogen atoms forming a cation. Both hydrogen atoms participate in hydrogen bonding. The two xylazine moieties are held together through an extended H-bond network involving the nitrogen, oxygen, and chlorine anions. In the crystal structure, centrosymmetric clusters are formed by N—H···O—H···Cl···H—N hydrogen bond sequence between the two xylazine moieties.

There are H-bonds which do not join the xylazine moities between oxygen and chlorine (Fig. 2). These may impart additional rigidity in the cluster. As a result of Cl···H—O hydrogen bonding a parallelogram is formed by the Cl—O—Cl—O atoms.

The hydrogen bond lengths are given in the Table 1.

Related literature top

For related literature see: Carpy et al. (1979); Kalman et al. (1977).

Experimental top

The title compound was supplied by Grindeks Company. For crystal structure determination suitable crystals were grown by slow evaporation of an ethanol (96%) solution at room temperature.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The molecular structure of the title compound with thermal ellipsoids drawn at the 50% probability level.
	Fig. 2. Intermolecular hydrogen bond formation (dashed lines) in the title compound.

N-(2,6-Dimethylanilino)-5,6-dihydro-4H-1,3-thiazin-3-ium chloride monohydrate top

Crystal data top

C₁₂H₁₇N₂S⁺·Cl⁻·H₂O	F(000) = 584
M_r = 274.81	D_x = 1.300 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 19046 reflections
a = 13.4546 (2) Å	θ = 3.5–74.6°
b = 8.6547 (1) Å	µ = 3.69 mm⁻¹
c = 12.7732 (2) Å	T = 100 K
β = 109.210 (2)°	Prism, white
V = 1404.56 (4) Å³	0.44 × 0.25 × 0.14 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer	2747 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2509 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 74.6°, θ_min = 3.5°
Absorption correction: numerical (de Meulenaer & Tompa, 1965)	h = −16→16
T_min = 0.30, T_max = 0.61	k = −10→10
19046 measured reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	W = [weight][1-(δF/6σF)²]²
wR(F²) = 0.088	(Δ/σ)_max = 0.000294
S = 1.02	Δρ_max = 0.43 e Å⁻³
2509 reflections	Δρ_min = −0.33 e Å⁻³
154 parameters

Crystal data top

C₁₂H₁₇N₂S⁺·Cl⁻·H₂O	V = 1404.56 (4) Å³
M_r = 274.81	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.4546 (2) Å	µ = 3.69 mm⁻¹
b = 8.6547 (1) Å	T = 100 K
c = 12.7732 (2) Å	0.44 × 0.25 × 0.14 mm
β = 109.210 (2)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	2747 independent reflections
Absorption correction: numerical (de Meulenaer & Tompa, 1965)	2509 reflections with I > 2.0σ(I)
T_min = 0.30, T_max = 0.61	R_int = 0.029
19046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.02	Δρ_max = 0.43 e Å⁻³
2509 reflections	Δρ_min = −0.33 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.72343 (3)	0.06408 (5)	0.19253 (3)	0.0234
C2	0.79732 (14)	−0.11421 (19)	0.19970 (14)	0.0244
C3	0.90751 (14)	−0.0827 (2)	0.19854 (14)	0.0252
C4	0.90283 (13)	−0.0099 (2)	0.08935 (14)	0.0244
N5	0.84522 (11)	0.13793 (17)	0.06888 (12)	0.0225
C6	0.76970 (12)	0.17936 (19)	0.10687 (13)	0.0199
N7	0.72435 (11)	0.31807 (16)	0.08222 (11)	0.0217
C8	0.65460 (13)	0.37922 (18)	0.13689 (14)	0.0210
C9	0.69975 (13)	0.4718 (2)	0.23077 (14)	0.0224
C10	0.63438 (14)	0.5346 (2)	0.28445 (15)	0.0278
C11	0.52719 (15)	0.5046 (2)	0.24466 (17)	0.0319
C12	0.48404 (14)	0.4128 (2)	0.15214 (17)	0.0300
C13	0.54694 (13)	0.3482 (2)	0.09525 (15)	0.0255
C14	0.49879 (15)	0.2481 (2)	−0.00495 (16)	0.0319
C15	0.81647 (13)	0.4980 (2)	0.27462 (14)	0.0249
Cl16	0.18401 (3)	0.10294 (5)	0.51765 (3)	0.0238
O17	0.94136 (9)	0.31268 (14)	−0.05720 (10)	0.0272
H21	0.8012	−0.1644	0.2678	0.0280*
H31	0.9450	−0.1803	0.2067	0.0276*
H32	0.9432	−0.0145	0.2573	0.0277*
H41	0.9748	0.0101	0.0908	0.0289*
H42	0.8694	−0.0804	0.0300	0.0289*
H141	0.4312	0.2885	−0.0488	0.0475*
H142	0.5426	0.2414	−0.0510	0.0467*
H143	0.4889	0.1450	0.0189	0.0475*
H151	0.8332	0.5724	0.3339	0.0357*
H152	0.8415	0.5357	0.2174	0.0356*
H153	0.8515	0.4017	0.3030	0.0359*
H171	0.9124	0.3966	−0.0570	0.0391*
H172	1.0056	0.3286	−0.0335	0.0395*
H22	0.7604	−0.1794	0.1379	0.0278*
H5	0.8667	0.2066	0.0318	0.0267*
H7	0.7466	0.3812	0.0417	0.0250*
H10	0.6635	0.5960	0.3474	0.0320*
H11	0.4838	0.5483	0.2825	0.0362*
H12	0.4111	0.3933	0.1255	0.0341*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0236 (2)	0.0216 (2)	0.0306 (2)	0.00450 (15)	0.01642 (17)	0.00271 (14)
C2	0.0292 (9)	0.0208 (8)	0.0269 (8)	0.0023 (6)	0.0143 (7)	0.0055 (6)
C3	0.0257 (8)	0.0265 (8)	0.0251 (8)	−0.0001 (7)	0.0109 (7)	0.0059 (7)
C4	0.0227 (8)	0.0262 (9)	0.0274 (8)	−0.0012 (7)	0.0127 (7)	0.0037 (6)
N5	0.0227 (7)	0.0222 (7)	0.0268 (7)	0.0015 (5)	0.0137 (5)	0.0004 (5)
C6	0.0186 (7)	0.0218 (8)	0.0203 (7)	−0.0012 (6)	0.0076 (6)	−0.0019 (6)
N7	0.0237 (7)	0.0206 (7)	0.0245 (7)	0.0018 (5)	0.0130 (6)	0.0002 (5)
C8	0.0203 (7)	0.0193 (8)	0.0258 (8)	0.0046 (6)	0.0107 (6)	0.0032 (6)
C9	0.0225 (8)	0.0204 (8)	0.0258 (8)	0.0035 (6)	0.0103 (7)	0.0035 (6)
C10	0.0297 (9)	0.0274 (8)	0.0296 (9)	−0.0003 (7)	0.0140 (7)	0.0043 (7)
C11	0.0274 (9)	0.0319 (10)	0.0432 (10)	0.0024 (8)	0.0209 (8)	0.0065 (7)
C12	0.0181 (8)	0.0290 (9)	0.0442 (11)	0.0072 (8)	0.0121 (7)	0.0020 (7)
C13	0.0221 (8)	0.0218 (8)	0.0319 (9)	0.0052 (7)	0.0078 (7)	0.0008 (6)
C14	0.0264 (8)	0.0263 (9)	0.0382 (10)	0.0001 (8)	0.0042 (7)	−0.0029 (7)
C15	0.0224 (8)	0.0254 (9)	0.0259 (8)	0.0012 (7)	0.0065 (7)	0.0007 (6)
Cl16	0.0232 (2)	0.0239 (2)	0.0266 (2)	0.00033 (14)	0.01150 (16)	0.00127 (14)
O17	0.0244 (6)	0.0248 (6)	0.0351 (7)	−0.0025 (5)	0.0135 (5)	−0.0028 (5)

Geometric parameters (Å, º) top

S1—C2	1.8215 (17)	C9—C10	1.391 (2)
S1—C6	1.7403 (16)	C9—C15	1.501 (2)
C2—C3	1.512 (2)	C10—C11	1.387 (3)
C2—H21	0.959	C10—H10	0.936
C2—H22	0.964	C11—C12	1.383 (3)
C3—C4	1.513 (2)	C11—H11	0.950
C3—H31	0.971	C12—C13	1.401 (3)
C3—H32	0.952	C12—H12	0.942
C4—N5	1.474 (2)	C13—C14	1.504 (3)
C4—H41	0.977	C14—H141	0.964
C4—H42	0.961	C14—H142	0.961
N5—C6	1.312 (2)	C14—H143	0.966
N5—H5	0.866	C15—H151	0.963
C6—N7	1.336 (2)	C15—H152	0.957
N7—C8	1.442 (2)	C15—H153	0.967
N7—H7	0.870	O17—H171	0.825
C8—C9	1.404 (2)	O17—H172	0.829
C8—C13	1.395 (2)

C2—S1—C6	102.42 (8)	C9—C8—C13	122.61 (15)
S1—C2—C3	111.57 (12)	C8—C9—C10	118.55 (16)
S1—C2—H21	107.2	C8—C9—C15	120.71 (15)
C3—C2—H21	109.3	C10—C9—C15	120.71 (16)
S1—C2—H22	109.2	C9—C10—C11	119.76 (17)
C3—C2—H22	109.9	C9—C10—H10	119.4
H21—C2—H22	109.7	C11—C10—H10	120.8
C2—C3—C4	109.91 (14)	C10—C11—C12	120.93 (16)
C2—C3—H31	108.6	C10—C11—H11	118.6
C4—C3—H31	108.9	C12—C11—H11	120.5
C2—C3—H32	110.3	C11—C12—C13	121.14 (16)
C4—C3—H32	109.0	C11—C12—H12	120.4
H31—C3—H32	110.2	C13—C12—H12	118.5
C3—C4—N5	112.65 (13)	C12—C13—C8	117.01 (16)
C3—C4—H41	108.4	C12—C13—C14	120.45 (16)
N5—C4—H41	108.0	C8—C13—C14	122.53 (16)
C3—C4—H42	109.2	C13—C14—H141	110.2
N5—C4—H42	109.1	C13—C14—H142	112.1
H41—C4—H42	109.3	H141—C14—H142	108.5
C4—N5—C6	126.70 (14)	C13—C14—H143	109.2
C4—N5—H5	116.2	H141—C14—H143	108.5
C6—N5—H5	116.9	H142—C14—H143	108.3
S1—C6—N5	123.83 (13)	C9—C15—H151	109.9
S1—C6—N7	115.66 (12)	C9—C15—H152	110.8
N5—C6—N7	120.50 (15)	H151—C15—H152	108.8
C6—N7—C8	122.35 (13)	C9—C15—H153	109.3
C6—N7—H7	118.9	H151—C15—H153	108.8
C8—N7—H7	117.6	H152—C15—H153	109.3
N7—C8—C9	117.10 (14)	H171—O17—H172	106.9
N7—C8—C13	120.28 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O17	0.87	1.97	2.815 (2)	163
O17—H171···Cl16ⁱ	0.82	2.36	3.158 (1)	164
N7—H7···Cl16ⁱ	0.87	2.37	3.204 (1)	162
O17—H172···Cl16ⁱⁱ	0.83	2.35	3.171 (1)	173

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇N₂S⁺·Cl⁻·H₂O
M_r	274.81
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.4546 (2), 8.6547 (1), 12.7732 (2)
β (°)	109.210 (2)
V (Å³)	1404.56 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.69
Crystal size (mm)	0.44 × 0.25 × 0.14

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	Numerical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.30, 0.61
No. of measured, independent and observed [I > 2.0σ(I)] reflections	19046, 2747, 2509
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.02
No. of reflections	2509
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O17	0.87	1.97	2.815 (2)	163
O17—H171···Cl16ⁱ	0.82	2.36	3.158 (1)	164
N7—H7···Cl16ⁱ	0.87	2.37	3.204 (1)	162
O17—H172···Cl16ⁱⁱ	0.83	2.35	3.171 (1)	173

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

Acknowledgements

We thank Oxford Diffraction Ltd for the low-temperature data collection and reduction. Cooperation of the University of Cincinnati Crystallography Centre and the Latvia Institute of Organic Synthesis is acknowledged. Financial aid was provided by Latvia Science Council grant 05.1737.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Carpy, A., Gadret, M. & Leger, J. M. (1979). Acta Cryst. B35, 994–996. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kalman, A., Argay, G., Ribar, B. & Toldy, L. (1977). Tetrahedron Lett. 18, 4241–4244. CSD CrossRef Google Scholar
Meulenaer, J. de & Tompa, H. (1965). Acta Cryst. A19, 1014–1018. Google Scholar
Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1062

doi:10.1107/S160053680801372X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-(2,6-Di­methyl­anilino)-5,6-di­hydro-4H-1,3-thia­zin-3-ium chloride monohydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

N-(2,6-Dimethylanilino)-5,6-dihydro-4H-1,3-thiazin-3-ium chloride monohydrate