2-(4-Morpholine­carbothio­ylsulfan­yl)­acetic acid

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536810012602

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1078

https://doi.org/10.1107/S1600536810012602

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2-(4-Morpholinecarbothioylsulfanyl)acetic acid

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 April 2010; accepted 4 April 2010; online 14 April 2010)

The asymmetric unit of the title compound, C₇H₁₁NO₃S₂, contains two independent molecules with similar molecular structures. The morpholine ring adopts a chair conformation, and the C₂N—C(=S)—S fragment is planar in the two independent molecules (r.m.s. deviations = 0.01 and 0.02 Å). The two molecules are disposed about a false center of inversion and are held together by a pair of O—H⋯O hydrogen bonds. The crystal studied was a racemic twin; the minor twin component refined to 17%.

Related literature

For the hydrogen-bonded dicyclohexylammonium salt, see: Ng & Hook (1999 ). For the synthesis, see: Nachmias (1952 ).

Experimental

Crystal data

C₇H₁₁NO₃S₂
M_r = 221.29
Orthorhombic, P c a 2₁
a = 14.7311 (3) Å
b = 4.7474 (1) Å
c = 28.0284 (5) Å
V = 1960.15 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.904, T_max = 0.904
16961 measured reflections
4495 independent reflections
3533 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.188
S = 1.11
4495 reflections
236 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 1.52 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 2199 Friedel pairs
Flack parameter: 0.2 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5	0.82	1.88	2.685 (7)	169
O4—H4⋯O2	0.82	1.88	2.689 (7)	170

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: pubCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012602/xu2747sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012602/xu2747Isup2.hkl

checkCIF report

Comment top

The class of dithiocarbamyl-acetic acids, R₂NC(S)SCH₂CO₂H, are synthetic plant growth-hormones. In an earlier study, the R₂N = O(CH₂CH₂)₂N derivative was characterized as the dicyclohexylammonium salt (Ng & Hook, 1999). The acid itself (Scheme I), exists as a hydrogen-bonded dimer, the two independent molecules being connected across a false center-of-inversion (Fig. 1, Table 1). The carboxyl –CO₂ portions feature single as well as double carbon-oxygen bonds.

Related literature top

For the hydrogen-bonded dicyclohexylammonium salt, see: Ng & Hook (1999). For the synthesis, see: Nachmias (1952).

Experimental top

The carboxylic acid was synthesized from morpholine, carbon disulfide and chloroacetic acid (Nachmias, 1952), and was recrystallized from ethanol.

Structure description top

For the hydrogen-bonded dicyclohexylammonium salt, see: Ng & Hook (1999). For the synthesis, see: Nachmias (1952).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the pair of C₇H₁₁NO₃S₂ molecules disposed about a false center-of-inversion at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

2-(4-Morpholinecarbothioylsulfanyl)acetic acid top

Crystal data top

C₇H₁₁NO₃S₂	F(000) = 928
M_r = 221.29	D_x = 1.500 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3880 reflections
a = 14.7311 (3) Å	θ = 2.9–25.7°
b = 4.7474 (1) Å	µ = 0.52 mm⁻¹
c = 28.0284 (5) Å	T = 293 K
V = 1960.15 (7) Å³	Block, colorless
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	4495 independent reflections
Radiation source: fine-focus sealed tube	3533 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
T_min = 0.904, T_max = 0.904	k = −6→6
16961 measured reflections	l = −36→36

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)] = 0.066	H-atom parameters constrained
wR(F²) = 0.188	w = 1/[σ²(F_o²) + (0.1026P)² + 0.7215P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
4495 reflections	Δρ_max = 1.52 e Å⁻³
236 parameters	Δρ_min = −0.37 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 2199 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (1)

Crystal data top

C₇H₁₁NO₃S₂	V = 1960.15 (7) Å³
M_r = 221.29	Z = 8
Orthorhombic, Pca2₁	Mo Kα radiation
a = 14.7311 (3) Å	µ = 0.52 mm⁻¹
b = 4.7474 (1) Å	T = 293 K
c = 28.0284 (5) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	4495 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3533 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.904	R_int = 0.060
16961 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.188	Δρ_max = 1.52 e Å⁻³
S = 1.11	Δρ_min = −0.37 e Å⁻³
4495 reflections	Absolute structure: Flack (1983), 2199 Friedel pairs
236 parameters	Absolute structure parameter: 0.2 (1)
5 restraints

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

	x	y	z	U_iso*/U_eq
S1	1.14478 (11)	0.9468 (4)	0.50019 (5)	0.0443 (3)
S2	0.99909 (9)	0.7699 (3)	0.43159 (7)	0.0498 (3)
S3	0.60753 (11)	0.5544 (4)	0.64749 (5)	0.0461 (4)
S4	0.75227 (9)	0.7362 (3)	0.71543 (6)	0.0482 (3)
O1	0.8902 (4)	1.0465 (12)	0.5349 (2)	0.0628 (15)
H1	0.8469	0.9640	0.5468	0.094*
O2	0.9876 (3)	0.7466 (9)	0.56506 (17)	0.0592 (12)
O3	1.3067 (4)	0.5162 (10)	0.3578 (2)	0.0561 (15)
O4	0.8628 (3)	0.4614 (10)	0.6158 (2)	0.0575 (14)
H4	0.9054	0.5431	0.6030	0.086*
O5	0.7633 (3)	0.7541 (9)	0.58260 (16)	0.0596 (12)
O6	0.4379 (4)	0.9934 (10)	0.7892 (3)	0.0605 (16)
N1	1.1727 (3)	0.6195 (11)	0.42631 (16)	0.0446 (11)
N2	0.5791 (3)	0.8762 (10)	0.72174 (16)	0.0439 (10)
C1	0.9717 (5)	0.9533 (15)	0.5416 (2)	0.0475 (16)
C2	1.0451 (4)	1.1257 (11)	0.5176 (2)	0.0510 (13)
H2A	1.0624	1.2764	0.5392	0.061*
H2B	1.0190	1.2126	0.4895	0.061*
C3	1.1053 (3)	0.7611 (10)	0.44898 (18)	0.0363 (10)
C4	1.2672 (4)	0.6143 (15)	0.4401 (2)	0.0527 (14)
H4A	1.2835	0.4266	0.4507	0.063*
H4B	1.2770	0.7439	0.4663	0.063*
C5	1.3265 (4)	0.6978 (12)	0.3981 (2)	0.0533 (14)
H5A	1.3149	0.8925	0.3895	0.064*
H5B	1.3900	0.6805	0.4068	0.064*
C6	1.2189 (5)	0.5326 (16)	0.3440 (2)	0.055 (2)
H6A	1.2094	0.4105	0.3168	0.066*
H6B	1.2055	0.7241	0.3343	0.066*
C7	1.1559 (5)	0.4494 (18)	0.3830 (3)	0.061 (2)
H7A	1.0937	0.4761	0.3726	0.073*
H7B	1.1642	0.2514	0.3903	0.073*
C8	0.7808 (5)	0.5473 (14)	0.6087 (2)	0.0425 (14)
C9	0.7074 (4)	0.3719 (11)	0.63020 (19)	0.0452 (12)
H9A	0.7320	0.2777	0.6581	0.054*
H9B	0.6906	0.2272	0.6074	0.054*
C10	0.6437 (3)	0.7404 (10)	0.69901 (17)	0.0348 (10)
C11	0.4816 (3)	0.8793 (13)	0.7084 (2)	0.0486 (13)
H11A	0.4704	0.7443	0.6831	0.058*
H11B	0.4646	1.0649	0.6970	0.058*
C12	0.4262 (4)	0.8035 (13)	0.7521 (2)	0.0528 (14)
H12A	0.3625	0.7975	0.7434	0.063*
H12B	0.4436	0.6170	0.7628	0.063*
C13	0.5344 (5)	0.9823 (16)	0.8041 (3)	0.056 (2)
H13A	0.5481	0.7961	0.8163	0.067*
H13B	0.5445	1.1172	0.8295	0.067*
C14	0.5974 (4)	1.0483 (14)	0.7627 (2)	0.0462 (15)
H14A	0.5907	1.2449	0.7540	0.055*
H14B	0.6597	1.0191	0.7727	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0386 (8)	0.0618 (7)	0.0325 (7)	−0.0035 (7)	−0.0021 (6)	−0.0066 (9)
S2	0.0345 (6)	0.0625 (9)	0.0525 (7)	−0.0025 (6)	−0.0064 (5)	−0.0034 (6)
S3	0.0434 (8)	0.0601 (7)	0.0348 (7)	−0.0063 (7)	−0.0038 (6)	−0.0045 (9)
S4	0.0357 (6)	0.0615 (8)	0.0476 (6)	−0.0024 (6)	−0.0059 (6)	0.0009 (6)
O1	0.061 (3)	0.071 (3)	0.056 (3)	0.023 (3)	0.011 (3)	0.006 (2)
O2	0.055 (3)	0.065 (3)	0.058 (2)	0.013 (2)	0.009 (2)	0.020 (2)
O3	0.047 (3)	0.083 (4)	0.039 (3)	0.013 (2)	0.013 (3)	−0.0063 (18)
O4	0.044 (3)	0.069 (3)	0.059 (3)	0.019 (2)	0.013 (2)	0.028 (2)
O5	0.061 (3)	0.060 (3)	0.058 (3)	0.020 (2)	0.012 (2)	0.028 (2)
O6	0.034 (3)	0.069 (4)	0.078 (4)	0.0018 (17)	0.000 (3)	−0.011 (2)
N1	0.032 (2)	0.061 (3)	0.041 (2)	−0.003 (2)	−0.0004 (18)	−0.011 (2)
N2	0.032 (2)	0.056 (3)	0.043 (3)	−0.002 (2)	−0.0055 (18)	−0.010 (2)
C1	0.054 (4)	0.050 (3)	0.039 (3)	0.012 (3)	0.003 (3)	0.013 (3)
C2	0.073 (4)	0.039 (3)	0.041 (3)	0.011 (3)	0.004 (3)	−0.006 (2)
C3	0.037 (3)	0.040 (3)	0.032 (2)	−0.0069 (19)	−0.0011 (17)	0.003 (2)
C4	0.042 (3)	0.069 (4)	0.048 (3)	0.002 (3)	−0.003 (2)	−0.004 (3)
C5	0.036 (3)	0.051 (3)	0.073 (4)	0.004 (2)	0.006 (3)	0.008 (3)
C6	0.064 (5)	0.069 (4)	0.033 (4)	0.011 (3)	−0.002 (3)	−0.012 (3)
C7	0.044 (4)	0.073 (4)	0.066 (5)	0.004 (3)	−0.005 (3)	−0.036 (4)
C8	0.050 (4)	0.049 (3)	0.028 (3)	0.005 (3)	0.006 (2)	−0.009 (2)
C9	0.056 (3)	0.040 (3)	0.039 (3)	−0.005 (3)	0.005 (2)	0.001 (2)
C10	0.036 (2)	0.040 (3)	0.029 (2)	−0.0089 (19)	−0.0042 (18)	0.007 (2)
C11	0.030 (2)	0.062 (4)	0.053 (3)	0.006 (3)	−0.011 (2)	−0.006 (3)
C12	0.031 (3)	0.053 (3)	0.074 (4)	−0.003 (2)	−0.003 (2)	0.003 (3)
C13	0.037 (4)	0.080 (5)	0.051 (5)	0.003 (3)	0.000 (3)	−0.005 (3)
C14	0.044 (3)	0.058 (3)	0.037 (3)	−0.015 (3)	0.007 (3)	−0.009 (3)

Geometric parameters (Å, º) top

S1—C2	1.765 (6)	C2—H2B	0.9700
S1—C3	1.782 (5)	C4—C5	1.518 (7)
S2—C3	1.640 (5)	C4—H4A	0.9700
S3—C10	1.774 (5)	C4—H4B	0.9700
S3—C9	1.775 (6)	C5—H5A	0.9700
S4—C10	1.664 (5)	C5—H5B	0.9700
O1—C1	1.294 (8)	C6—C7	1.487 (8)
O1—H1	0.8200	C6—H6A	0.9700
O2—C1	1.204 (8)	C6—H6B	0.9700
O3—C6	1.352 (10)	C7—H7A	0.9700
O3—C5	1.450 (9)	C7—H7B	0.9700
O4—C8	1.291 (8)	C8—C9	1.492 (9)
O4—H4	0.8200	C9—H9A	0.9700
O5—C8	1.251 (8)	C9—H9B	0.9700
O6—C12	1.387 (8)	C11—C12	1.514 (7)
O6—C13	1.481 (10)	C11—H11A	0.9700
N1—C3	1.357 (7)	C11—H11B	0.9700
N1—C4	1.444 (7)	C12—H12A	0.9700
N1—C7	1.479 (8)	C12—H12B	0.9700
N2—C10	1.314 (7)	C13—C14	1.519 (7)
N2—C14	1.434 (8)	C13—H13A	0.9700
N2—C11	1.484 (6)	C13—H13B	0.9700
C1—C2	1.514 (9)	C14—H14A	0.9700
C2—H2A	0.9700	C14—H14B	0.9700

C2—S1—C3	100.9 (3)	N1—C7—C6	110.7 (6)
C10—S3—C9	102.5 (3)	N1—C7—H7A	109.5
C1—O1—H1	120.0	C6—C7—H7A	109.5
C6—O3—C5	112.3 (5)	N1—C7—H7B	109.5
C8—O4—H4	120.0	C6—C7—H7B	109.5
C12—O6—C13	107.9 (5)	H7A—C7—H7B	108.1
C3—N1—C4	126.0 (4)	O5—C8—O4	122.1 (6)
C3—N1—C7	122.2 (5)	O5—C8—C9	121.7 (6)
C4—N1—C7	111.8 (5)	O4—C8—C9	116.1 (6)
C10—N2—C14	122.1 (4)	C8—C9—S3	116.0 (4)
C10—N2—C11	125.7 (4)	C8—C9—H9A	108.3
C14—N2—C11	112.2 (5)	S3—C9—H9A	108.3
O2—C1—O1	122.6 (7)	C8—C9—H9B	108.3
O2—C1—C2	123.0 (6)	S3—C9—H9B	108.3
O1—C1—C2	114.4 (6)	H9A—C9—H9B	107.4
C1—C2—S1	117.2 (4)	N2—C10—S4	124.6 (4)
C1—C2—H2A	108.0	N2—C10—S3	114.9 (4)
S1—C2—H2A	108.0	S4—C10—S3	120.5 (3)
C1—C2—H2B	108.0	N2—C11—C12	108.4 (4)
S1—C2—H2B	108.0	N2—C11—H11A	110.0
H2A—C2—H2B	107.2	C12—C11—H11A	110.0
N1—C3—S2	124.9 (4)	N2—C11—H11B	110.0
N1—C3—S1	112.6 (4)	C12—C11—H11B	110.0
S2—C3—S1	122.6 (3)	H11A—C11—H11B	108.4
N1—C4—C5	110.1 (5)	O6—C12—C11	112.6 (5)
N1—C4—H4A	109.6	O6—C12—H12A	109.1
C5—C4—H4A	109.6	C11—C12—H12A	109.1
N1—C4—H4B	109.6	O6—C12—H12B	109.1
C5—C4—H4B	109.6	C11—C12—H12B	109.1
H4A—C4—H4B	108.2	H12A—C12—H12B	107.8
O3—C5—C4	109.4 (5)	O6—C13—C14	111.3 (7)
O3—C5—H5A	109.8	O6—C13—H13A	109.4
C4—C5—H5A	109.8	C14—C13—H13A	109.4
O3—C5—H5B	109.8	O6—C13—H13B	109.4
C4—C5—H5B	109.8	C14—C13—H13B	109.4
H5A—C5—H5B	108.2	H13A—C13—H13B	108.0
O3—C6—C7	111.9 (6)	N2—C14—C13	112.3 (5)
O3—C6—H6A	109.2	N2—C14—H14A	109.2
C7—C6—H6A	109.2	C13—C14—H14A	109.2
O3—C6—H6B	109.2	N2—C14—H14B	109.2
C7—C6—H6B	109.2	C13—C14—H14B	109.1
H6A—C6—H6B	107.9	H14A—C14—H14B	107.9

O2—C1—C2—S1	29.1 (9)	O5—C8—C9—S3	−35.2 (8)
O1—C1—C2—S1	−150.9 (6)	O4—C8—C9—S3	149.5 (6)
C3—S1—C2—C1	74.8 (5)	C10—S3—C9—C8	−72.7 (5)
C4—N1—C3—S2	178.2 (5)	C14—N2—C10—S4	2.9 (7)
C7—N1—C3—S2	−1.4 (8)	C11—N2—C10—S4	−178.8 (4)
C4—N1—C3—S1	−0.7 (7)	C14—N2—C10—S3	−176.9 (4)
C7—N1—C3—S1	179.8 (5)	C11—N2—C10—S3	1.4 (7)
C2—S1—C3—N1	175.4 (4)	C9—S3—C10—N2	−174.2 (4)
C2—S1—C3—S2	−3.5 (4)	C9—S3—C10—S4	6.0 (4)
C3—N1—C4—C5	−126.6 (6)	C10—N2—C11—C12	128.6 (5)
C7—N1—C4—C5	53.0 (8)	C14—N2—C11—C12	−53.0 (7)
C6—O3—C5—C4	59.7 (7)	C13—O6—C12—C11	−63.0 (7)
N1—C4—C5—O3	−55.2 (7)	N2—C11—C12—O6	61.0 (7)
C5—O3—C6—C7	−60.0 (8)	C12—O6—C13—C14	57.6 (7)
C3—N1—C7—C6	127.4 (7)	C10—N2—C14—C13	−130.6 (6)
C4—N1—C7—C6	−52.2 (9)	C11—N2—C14—C13	50.9 (8)
O3—C6—C7—N1	55.3 (8)	O6—C13—C14—N2	−52.6 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.82	1.88	2.685 (7)	169
O4—H4···O2	0.82	1.88	2.689 (7)	170

Experimental details

Crystal data
Chemical formula	C₇H₁₁NO₃S₂
M_r	221.29
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	14.7311 (3), 4.7474 (1), 28.0284 (5)
V (Å³)	1960.15 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.904, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	16961, 4495, 3533
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.188, 1.11
No. of reflections	4495
No. of parameters	236
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.52, −0.37
Absolute structure	Flack (1983), 2199 Friedel pairs
Absolute structure parameter	0.2 (1)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5	0.82	1.88	2.685 (7)	169
O4—H4···O2	0.82	1.88	2.689 (7)	170

Acknowledgements

We thank the University of Malaya (grant No. RG020/09AFR) for supporting this study.

References

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