Tris(2-hydroxy­ethyl)ammonium 1,3-benzo­thia­zole-2-thiol­ate

Zhu, J.-Q.; Fang, H.-C.; Chen, B.-Y.; Feng, M.-S.; Li, J.-N.

doi:10.1107/S160053680902248X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1640

doi:10.1107/S160053680902248X

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Tris(2-hydroxyethyl)ammonium 1,3-benzothiazole-2-thiolate

Ji-Qin Zhu,^a Hua-Cai Fang,^a Bi-Yun Chen,^a Mao-Song Feng ^a and Jing-Ning Li ^a ^*

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: ypcai8@yahoo.com

(Received 21 May 2009; accepted 12 June 2009; online 20 June 2009)

In the title compound, C₆H₁₆NO₃⁺·C₇H₄NS₂⁻, the cations and anions are connected by O—H⋯N and O—H⋯S hydrogen bonding. Weak C—H⋯O hydrogen bonding between adjacent cations helps to stabilize the crystal structure.

Related literature

For related structures, see Bethge et al. (2008 ); Siracusa et al. (2008 ); Solar et al. (2008 ); Varlamov et al. (2005 ).

Experimental

Crystal data

C₆H₁₆NO₃⁺·C₇H₄NS₂⁻
M_r = 316.43
Monoclinic, P 2₁ /c
a = 16.496 (2) Å
b = 5.7184 (8) Å
c = 17.462 (3) Å
β = 111.524 (2)°
V = 1532.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 296 K
0.56 × 0.38 × 0.23 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.803, T_max = 0.921
7572 measured reflections
2827 independent reflections
2185 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.04
2827 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.96	2.770 (2)	168
O2—H2⋯S2ⁱ	0.82	2.43	3.2258 (17)	165
O3—H3⋯S2	0.82	2.35	3.1621 (16)	169
C8—H8A⋯O1ⁱⁱ	0.97	2.50	3.385 (3)	151
C10—H10B⋯O3ⁱⁱⁱ	0.97	2.47	3.425 (3)	167
Symmetry codes: (i) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902248X/xu2531sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902248X/xu2531Isup2.hkl

checkCIF report

Comment top

Some related compounds involving the 2-mercaptobenzothiazole and its derivatives has reported previously (Varlamov et al., 2005; Solar et al., 2008; Siracusa et al. 2008; Bethge et al., 2008). The crystal structure of the title compound consists of tris(2-hydroxyethyl)ammonium cations and benzothiazole-2-thiolate anions (Fig. 1). The cations and anions are connected by O—H···N and O—H···S hydrogen bonding (Table 1).

Related literature top

For related structures, see Bethge et al. (2008); Siracusa et al. (2008); Solar et al. (2008); Varlamov et al. (2005).

Experimental top

A mixture of benzothiazole (335 mg, 2 mmol), triethanolamine (0.4 ml and 3 mmol) in ethyl acetate (20 ml) was refluxed for 20 h. The resultant yellow solution was delaminated into two layers at room temperature and then filtered. Single crystals suitable for X-ray diffraction were obtained in two day by slow diffusion of diethyl ether into a dilute solution of the title complex in ethyl acetate. The elemental analysis; calculated for C₁₃H₂₀N₂O₃S₂: C 49.37, H 6.33, N 8.86%; found: C 49.31, H 6.38, N 8.82%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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).

Figures top

Fig. 1. The structure of the title compound with 50% probability displacement ellipsoids.

Tris(2-hydroxyethyl)ammonium 1,3-benzothiazole-2-thiolate top

Crystal data top

C₆H₁₆NO₃⁺·C₇H₄NS₂⁻	F(000) = 672
M_r = 316.43	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 236 reflections
a = 16.496 (2) Å	θ = 2.4–25.5°
b = 5.7184 (8) Å	µ = 0.36 mm⁻¹
c = 17.462 (3) Å	T = 296 K
β = 111.524 (2)°	Block, colorless
V = 1532.3 (4) Å³	0.56 × 0.38 × 0.23 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	2827 independent reflections
Radiation source: fine-focus sealed tube	2185 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
T_min = 0.803, T_max = 0.921	k = −6→6
7572 measured reflections	l = −20→21

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0394P)² + 0.2793P] where P = (F_o² + 2F_c²)/3
2827 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₆H₁₆NO₃⁺·C₇H₄NS₂⁻	V = 1532.3 (4) Å³
M_r = 316.43	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.496 (2) Å	µ = 0.36 mm⁻¹
b = 5.7184 (8) Å	T = 296 K
c = 17.462 (3) Å	0.56 × 0.38 × 0.23 mm
β = 111.524 (2)°

Data collection top

Bruker SMART area-detector diffractometer	2827 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2185 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.921	R_int = 0.034
7572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
2827 reflections	Δρ_min = −0.16 e Å⁻³
185 parameters

Special details top

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
C1	0.26675 (13)	1.1324 (4)	0.12815 (11)	0.0361 (5)
C2	0.39268 (13)	0.8624 (4)	0.15930 (11)	0.0347 (5)
C3	0.39516 (12)	1.0658 (3)	0.11586 (11)	0.0347 (5)
C4	0.46629 (14)	1.1048 (4)	0.09259 (13)	0.0459 (5)
H4	0.4692	1.2382	0.0632	0.055*
C5	0.53229 (15)	0.9413 (5)	0.11398 (14)	0.0521 (6)
H5	0.5803	0.9667	0.0992	0.062*
C6	0.52890 (15)	0.7410 (4)	0.15671 (13)	0.0498 (6)
H6	0.5743	0.6335	0.1699	0.060*
C7	0.45902 (14)	0.6983 (4)	0.18000 (12)	0.0445 (5)
H7	0.4565	0.5634	0.2088	0.053*
C8	0.25776 (13)	0.6974 (4)	0.44442 (12)	0.0412 (5)
H8A	0.2820	0.5472	0.4383	0.049*
H8B	0.2541	0.7025	0.4986	0.049*
C9	0.31648 (14)	0.8890 (4)	0.43727 (13)	0.0451 (5)
H9A	0.3726	0.8760	0.4819	0.054*
H9B	0.3257	0.8727	0.3858	0.054*
C10	0.09961 (15)	0.6154 (4)	0.40603 (14)	0.0501 (6)
H10A	0.1175	0.4593	0.4272	0.060*
H10B	0.0458	0.6019	0.3585	0.060*
C11	0.08354 (14)	0.7592 (4)	0.47092 (14)	0.0485 (6)
H11A	0.0323	0.7022	0.4798	0.058*
H11B	0.1330	0.7479	0.5224	0.058*
C12	0.16366 (15)	0.6302 (4)	0.29797 (12)	0.0477 (6)
H12A	0.1524	0.4633	0.2951	0.057*
H12B	0.2190	0.6556	0.2916	0.057*
C13	0.09228 (15)	0.7522 (5)	0.22968 (13)	0.0537 (6)
H13A	0.0969	0.7155	0.1772	0.064*
H13B	0.0359	0.6984	0.2282	0.064*
N1	0.32350 (11)	1.2134 (3)	0.09787 (10)	0.0371 (4)
N2	0.16844 (9)	0.7219 (3)	0.38008 (9)	0.0318 (4)
H2A	0.1569	0.8778	0.3736	0.038*
O1	0.28024 (11)	1.1097 (3)	0.44019 (9)	0.0515 (4)
H1	0.2898	1.1449	0.4882	0.077*
O2	0.07100 (11)	0.9936 (3)	0.44415 (9)	0.0581 (4)
H2	0.0927	1.0808	0.4837	0.087*
O3	0.09930 (10)	0.9968 (3)	0.24292 (9)	0.0533 (4)
H3	0.1244	1.0551	0.2148	0.080*
S1	0.29720 (3)	0.86166 (10)	0.17920 (3)	0.04177 (18)
S2	0.16918 (4)	1.25406 (11)	0.11908 (4)	0.04881 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0443 (12)	0.0320 (12)	0.0297 (10)	−0.0048 (9)	0.0107 (9)	−0.0028 (9)
C2	0.0382 (11)	0.0340 (12)	0.0270 (9)	−0.0052 (9)	0.0063 (8)	−0.0007 (9)
C3	0.0405 (11)	0.0326 (11)	0.0289 (9)	−0.0054 (9)	0.0103 (8)	−0.0021 (9)
C4	0.0496 (13)	0.0463 (15)	0.0453 (12)	−0.0018 (11)	0.0215 (10)	0.0073 (11)
C5	0.0451 (13)	0.0620 (17)	0.0543 (14)	−0.0008 (11)	0.0245 (11)	−0.0012 (12)
C6	0.0465 (13)	0.0513 (16)	0.0478 (13)	0.0115 (11)	0.0128 (11)	−0.0004 (11)
C7	0.0509 (13)	0.0388 (13)	0.0379 (11)	0.0017 (10)	0.0094 (10)	0.0031 (10)
C8	0.0392 (12)	0.0404 (13)	0.0411 (11)	0.0054 (9)	0.0114 (9)	0.0034 (10)
C9	0.0449 (12)	0.0458 (14)	0.0457 (12)	−0.0063 (10)	0.0181 (10)	−0.0091 (11)
C10	0.0506 (13)	0.0500 (15)	0.0526 (13)	−0.0124 (11)	0.0225 (11)	−0.0010 (11)
C11	0.0449 (13)	0.0574 (16)	0.0485 (13)	−0.0021 (11)	0.0234 (11)	0.0049 (12)
C12	0.0649 (15)	0.0422 (14)	0.0375 (11)	0.0001 (11)	0.0204 (11)	−0.0070 (10)
C13	0.0533 (14)	0.0671 (18)	0.0342 (11)	−0.0093 (12)	0.0082 (10)	0.0001 (11)
N1	0.0436 (10)	0.0307 (10)	0.0375 (9)	−0.0019 (8)	0.0154 (8)	0.0030 (7)
N2	0.0351 (9)	0.0275 (9)	0.0319 (8)	0.0001 (7)	0.0110 (7)	0.0011 (7)
O1	0.0690 (10)	0.0380 (10)	0.0454 (8)	−0.0041 (8)	0.0186 (8)	−0.0074 (7)
O2	0.0705 (11)	0.0570 (12)	0.0490 (9)	0.0164 (9)	0.0244 (8)	0.0038 (8)
O3	0.0591 (10)	0.0590 (12)	0.0462 (9)	0.0122 (8)	0.0244 (7)	0.0144 (8)
S1	0.0457 (3)	0.0401 (3)	0.0402 (3)	−0.0032 (2)	0.0166 (2)	0.0092 (2)
S2	0.0518 (4)	0.0470 (4)	0.0536 (4)	0.0074 (3)	0.0263 (3)	0.0074 (3)

Geometric parameters (Å, º) top

C1—N1	1.317 (2)	C9—H9A	0.9700
C1—S2	1.707 (2)	C9—H9B	0.9700
C1—S1	1.765 (2)	C10—N2	1.497 (2)
C2—C7	1.385 (3)	C10—C11	1.500 (3)
C2—C3	1.398 (3)	C10—H10A	0.9700
C2—S1	1.733 (2)	C10—H10B	0.9700
C3—N1	1.391 (2)	C11—O2	1.410 (3)
C3—C4	1.393 (3)	C11—H11A	0.9700
C4—C5	1.379 (3)	C11—H11B	0.9700
C4—H4	0.9300	C12—N2	1.501 (2)
C5—C6	1.379 (3)	C12—C13	1.505 (3)
C5—H5	0.9300	C12—H12A	0.9700
C6—C7	1.378 (3)	C12—H12B	0.9700
C6—H6	0.9300	C13—O3	1.415 (3)
C7—H7	0.9300	C13—H13A	0.9700
C8—N2	1.496 (2)	C13—H13B	0.9700
C8—C9	1.497 (3)	N2—H2A	0.9100
C8—H8A	0.9700	O1—H1	0.8200
C8—H8B	0.9700	O2—H2	0.8200
C9—O1	1.405 (3)	O3—H3	0.8200

N1—C1—S2	127.19 (16)	N2—C10—H10A	109.3
N1—C1—S1	113.51 (15)	C11—C10—H10A	109.3
S2—C1—S1	119.24 (11)	N2—C10—H10B	109.3
C7—C2—C3	121.86 (19)	C11—C10—H10B	109.3
C7—C2—S1	129.44 (16)	H10A—C10—H10B	107.9
C3—C2—S1	108.70 (15)	O2—C11—C10	108.40 (17)
N1—C3—C4	125.02 (18)	O2—C11—H11A	110.0
N1—C3—C2	115.84 (17)	C10—C11—H11A	110.0
C4—C3—C2	119.13 (19)	O2—C11—H11B	110.0
C5—C4—C3	118.6 (2)	C10—C11—H11B	110.0
C5—C4—H4	120.7	H11A—C11—H11B	108.4
C3—C4—H4	120.7	N2—C12—C13	110.28 (18)
C4—C5—C6	121.7 (2)	N2—C12—H12A	109.6
C4—C5—H5	119.2	C13—C12—H12A	109.6
C6—C5—H5	119.2	N2—C12—H12B	109.6
C7—C6—C5	120.7 (2)	C13—C12—H12B	109.6
C7—C6—H6	119.6	H12A—C12—H12B	108.1
C5—C6—H6	119.6	O3—C13—C12	109.59 (18)
C6—C7—C2	118.0 (2)	O3—C13—H13A	109.8
C6—C7—H7	121.0	C12—C13—H13A	109.8
C2—C7—H7	121.0	O3—C13—H13B	109.8
N2—C8—C9	110.98 (17)	C12—C13—H13B	109.8
N2—C8—H8A	109.4	H13A—C13—H13B	108.2
C9—C8—H8A	109.4	C1—N1—C3	111.49 (17)
N2—C8—H8B	109.4	C8—N2—C10	112.46 (15)
C9—C8—H8B	109.4	C8—N2—C12	112.13 (15)
H8A—C8—H8B	108.0	C10—N2—C12	111.54 (16)
O1—C9—C8	110.92 (17)	C8—N2—H2A	106.8
O1—C9—H9A	109.5	C10—N2—H2A	106.8
C8—C9—H9A	109.5	C12—N2—H2A	106.8
O1—C9—H9B	109.5	C9—O1—H1	109.5
C8—C9—H9B	109.5	C11—O2—H2	109.5
H9A—C9—H9B	108.0	C13—O3—H3	109.5
N2—C10—C11	111.68 (18)	C2—S1—C1	90.44 (9)

C7—C2—C3—N1	178.88 (18)	S2—C1—N1—C3	−178.71 (15)
S1—C2—C3—N1	−1.0 (2)	S1—C1—N1—C3	−1.5 (2)
C7—C2—C3—C4	0.1 (3)	C4—C3—N1—C1	−179.62 (19)
S1—C2—C3—C4	−179.79 (15)	C2—C3—N1—C1	1.7 (2)
N1—C3—C4—C5	−179.2 (2)	C9—C8—N2—C10	−153.34 (17)
C2—C3—C4—C5	−0.5 (3)	C9—C8—N2—C12	80.0 (2)
C3—C4—C5—C6	0.7 (3)	C11—C10—N2—C8	72.5 (2)
C4—C5—C6—C7	−0.4 (3)	C11—C10—N2—C12	−160.57 (18)
C5—C6—C7—C2	−0.1 (3)	C13—C12—N2—C8	−153.34 (18)
C3—C2—C7—C6	0.2 (3)	C13—C12—N2—C10	79.5 (2)
S1—C2—C7—C6	−179.94 (16)	C7—C2—S1—C1	−179.76 (19)
N2—C8—C9—O1	55.1 (2)	C3—C2—S1—C1	0.09 (14)
N2—C10—C11—O2	49.9 (2)	N1—C1—S1—C2	0.85 (15)
N2—C12—C13—O3	48.2 (2)	S2—C1—S1—C2	178.27 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.96	2.770 (2)	168
O2—H2···S2ⁱ	0.82	2.43	3.2258 (17)	165
O3—H3···S2	0.82	2.35	3.1621 (16)	169
C8—H8A···O1ⁱⁱ	0.97	2.50	3.385 (3)	151
C10—H10B···O3ⁱⁱⁱ	0.97	2.47	3.425 (3)	167

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₆NO₃⁺·C₇H₄NS₂⁻
M_r	316.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	16.496 (2), 5.7184 (8), 17.462 (3)
β (°)	111.524 (2)
V (Å³)	1532.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.56 × 0.38 × 0.23

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.803, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	7572, 2827, 2185
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.04
No. of reflections	2827
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.96	2.770 (2)	168.3
O2—H2···S2ⁱ	0.82	2.43	3.2258 (17)	165.4
O3—H3···S2	0.82	2.35	3.1621 (16)	168.7
C8—H8A···O1ⁱⁱ	0.97	2.50	3.385 (3)	151
C10—H10B···O3ⁱⁱⁱ	0.97	2.47	3.425 (3)	167

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2.

Acknowledgements

The work was supported by the National Natural Science Foundation of China (No. 20772037) and the NSF of Guangdong Province, China (No. 06025033).

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