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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1078.
Published online 2010 April 14. doi:  10.1107/S1600536810012602
PMCID: PMC2979280

2-(4-Morpholine­carbothio­ylsulfan­yl)­acetic acid

Abstract

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 [triangle]). For the synthesis, see: Nachmias (1952 [triangle]).

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Object name is e-66-o1078-scheme1.jpg

Experimental

Crystal data

  • C7H11NO3S2
  • M r = 221.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1078-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.188
  • S = 1.11
  • 4495 reflections
  • 236 parameters
  • 5 restraints
  • H-atom parameters constrained
  • Δρmax = 1.52 e Å−3
  • Δρmin = −0.37 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2199 Friedel pairs
  • Flack parameter: 0.2 (1)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012602/xu2747Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

The carbon-carbon distances in the morpholine rings were retraied to 1.54±0.01 Å.

Hydrogen atoms were placed at calculated positions (C–H 0.97, O–H 0.82 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2–1.5 times Ueq(C,O). The final difference Fourier map had a peak 2.2 Å from S2.

The crystal is a racemic twin; the minor twin component refined to 17%.

Figures

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.

Crystal data

C7H11NO3S2F(000) = 928
Mr = 221.29Dx = 1.500 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 3880 reflections
a = 14.7311 (3) Åθ = 2.9–25.7°
b = 4.7474 (1) ŵ = 0.52 mm1
c = 28.0284 (5) ÅT = 293 K
V = 1960.15 (7) Å3Block, colorless
Z = 80.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer4495 independent reflections
Radiation source: fine-focus sealed tube3533 reflections with I > 2σ(I)
graphiteRint = 0.060
ω scansθmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −19→19
Tmin = 0.904, Tmax = 0.904k = −6→6
16961 measured reflectionsl = −36→36

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.188w = 1/[σ2(Fo2) + (0.1026P)2 + 0.7215P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
4495 reflectionsΔρmax = 1.52 e Å3
236 parametersΔρmin = −0.36 e Å3
5 restraintsAbsolute structure: Flack (1983), 2199 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.2 (1)

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

xyzUiso*/Ueq
S11.14478 (11)0.9468 (4)0.50019 (5)0.0443 (3)
S20.99909 (9)0.7699 (3)0.43159 (7)0.0498 (3)
S30.60753 (11)0.5544 (4)0.64749 (5)0.0461 (4)
S40.75227 (9)0.7362 (3)0.71543 (6)0.0482 (3)
O10.8902 (4)1.0465 (12)0.5349 (2)0.0628 (15)
H10.84690.96400.54680.094*
O20.9876 (3)0.7466 (9)0.56506 (17)0.0592 (12)
O31.3067 (4)0.5162 (10)0.3578 (2)0.0561 (15)
O40.8628 (3)0.4614 (10)0.6158 (2)0.0575 (14)
H40.90540.54310.60300.086*
O50.7633 (3)0.7541 (9)0.58260 (16)0.0596 (12)
O60.4379 (4)0.9934 (10)0.7892 (3)0.0605 (16)
N11.1727 (3)0.6195 (11)0.42631 (16)0.0446 (11)
N20.5791 (3)0.8762 (10)0.72174 (16)0.0439 (10)
C10.9717 (5)0.9533 (15)0.5416 (2)0.0475 (16)
C21.0451 (4)1.1257 (11)0.5176 (2)0.0510 (13)
H2A1.06241.27640.53920.061*
H2B1.01901.21260.48950.061*
C31.1053 (3)0.7611 (10)0.44898 (18)0.0363 (10)
C41.2672 (4)0.6143 (15)0.4401 (2)0.0527 (14)
H4A1.28350.42660.45070.063*
H4B1.27700.74390.46630.063*
C51.3265 (4)0.6978 (12)0.3981 (2)0.0533 (14)
H5A1.31490.89250.38950.064*
H5B1.39000.68050.40680.064*
C61.2189 (5)0.5326 (16)0.3440 (2)0.055 (2)
H6A1.20940.41050.31680.066*
H6B1.20550.72410.33430.066*
C71.1559 (5)0.4494 (18)0.3830 (3)0.061 (2)
H7A1.09370.47610.37260.073*
H7B1.16420.25140.39030.073*
C80.7808 (5)0.5473 (14)0.6087 (2)0.0425 (14)
C90.7074 (4)0.3719 (11)0.63020 (19)0.0452 (12)
H9A0.73200.27770.65810.054*
H9B0.69060.22720.60740.054*
C100.6437 (3)0.7404 (10)0.69901 (17)0.0348 (10)
C110.4816 (3)0.8793 (13)0.7084 (2)0.0486 (13)
H11A0.47040.74430.68310.058*
H11B0.46461.06490.69700.058*
C120.4262 (4)0.8035 (13)0.7521 (2)0.0528 (14)
H12A0.36250.79750.74340.063*
H12B0.44360.61700.76280.063*
C130.5344 (5)0.9823 (16)0.8041 (3)0.056 (2)
H13A0.54810.79610.81630.067*
H13B0.54451.11720.82950.067*
C140.5974 (4)1.0483 (14)0.7627 (2)0.0462 (15)
H14A0.59071.24490.75400.055*
H14B0.65971.01910.77270.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0386 (8)0.0618 (7)0.0325 (7)−0.0035 (7)−0.0021 (6)−0.0066 (9)
S20.0345 (6)0.0625 (9)0.0525 (7)−0.0025 (6)−0.0064 (5)−0.0034 (6)
S30.0434 (8)0.0601 (7)0.0348 (7)−0.0063 (7)−0.0038 (6)−0.0045 (9)
S40.0357 (6)0.0615 (8)0.0476 (6)−0.0024 (6)−0.0059 (6)0.0009 (6)
O10.061 (3)0.071 (3)0.056 (3)0.023 (3)0.011 (3)0.006 (2)
O20.055 (3)0.065 (3)0.058 (2)0.013 (2)0.009 (2)0.020 (2)
O30.047 (3)0.083 (4)0.039 (3)0.013 (2)0.013 (3)−0.0063 (18)
O40.044 (3)0.069 (3)0.059 (3)0.019 (2)0.013 (2)0.028 (2)
O50.061 (3)0.060 (3)0.058 (3)0.020 (2)0.012 (2)0.028 (2)
O60.034 (3)0.069 (4)0.078 (4)0.0018 (17)0.000 (3)−0.011 (2)
N10.032 (2)0.061 (3)0.041 (2)−0.003 (2)−0.0004 (18)−0.011 (2)
N20.032 (2)0.056 (3)0.043 (3)−0.002 (2)−0.0055 (18)−0.010 (2)
C10.054 (4)0.050 (3)0.039 (3)0.012 (3)0.003 (3)0.013 (3)
C20.073 (4)0.039 (3)0.041 (3)0.011 (3)0.004 (3)−0.006 (2)
C30.037 (3)0.040 (3)0.032 (2)−0.0069 (19)−0.0011 (17)0.003 (2)
C40.042 (3)0.069 (4)0.048 (3)0.002 (3)−0.003 (2)−0.004 (3)
C50.036 (3)0.051 (3)0.073 (4)0.004 (2)0.006 (3)0.008 (3)
C60.064 (5)0.069 (4)0.033 (4)0.011 (3)−0.002 (3)−0.012 (3)
C70.044 (4)0.073 (4)0.066 (5)0.004 (3)−0.005 (3)−0.036 (4)
C80.050 (4)0.049 (3)0.028 (3)0.005 (3)0.006 (2)−0.009 (2)
C90.056 (3)0.040 (3)0.039 (3)−0.005 (3)0.005 (2)0.001 (2)
C100.036 (2)0.040 (3)0.029 (2)−0.0089 (19)−0.0042 (18)0.007 (2)
C110.030 (2)0.062 (4)0.053 (3)0.006 (3)−0.011 (2)−0.006 (3)
C120.031 (3)0.053 (3)0.074 (4)−0.003 (2)−0.003 (2)0.003 (3)
C130.037 (4)0.080 (5)0.051 (5)0.003 (3)0.000 (3)−0.005 (3)
C140.044 (3)0.058 (3)0.037 (3)−0.015 (3)0.007 (3)−0.009 (3)

Geometric parameters (Å, °)

S1—C21.765 (6)C2—H2B0.9700
S1—C31.782 (5)C4—C51.518 (7)
S2—C31.640 (5)C4—H4A0.9700
S3—C101.774 (5)C4—H4B0.9700
S3—C91.775 (6)C5—H5A0.9700
S4—C101.664 (5)C5—H5B0.9700
O1—C11.294 (8)C6—C71.487 (8)
O1—H10.8200C6—H6A0.9700
O2—C11.204 (8)C6—H6B0.9700
O3—C61.352 (10)C7—H7A0.9700
O3—C51.450 (9)C7—H7B0.9700
O4—C81.291 (8)C8—C91.492 (9)
O4—H40.8200C9—H9A0.9700
O5—C81.251 (8)C9—H9B0.9700
O6—C121.387 (8)C11—C121.514 (7)
O6—C131.481 (10)C11—H11A0.9700
N1—C31.357 (7)C11—H11B0.9700
N1—C41.444 (7)C12—H12A0.9700
N1—C71.479 (8)C12—H12B0.9700
N2—C101.314 (7)C13—C141.519 (7)
N2—C141.434 (8)C13—H13A0.9700
N2—C111.484 (6)C13—H13B0.9700
C1—C21.514 (9)C14—H14A0.9700
C2—H2A0.9700C14—H14B0.9700
C2—S1—C3100.9 (3)N1—C7—C6110.7 (6)
C10—S3—C9102.5 (3)N1—C7—H7A109.5
C1—O1—H1120.0C6—C7—H7A109.5
C6—O3—C5112.3 (5)N1—C7—H7B109.5
C8—O4—H4120.0C6—C7—H7B109.5
C12—O6—C13107.9 (5)H7A—C7—H7B108.1
C3—N1—C4126.0 (4)O5—C8—O4122.1 (6)
C3—N1—C7122.2 (5)O5—C8—C9121.7 (6)
C4—N1—C7111.8 (5)O4—C8—C9116.1 (6)
C10—N2—C14122.1 (4)C8—C9—S3116.0 (4)
C10—N2—C11125.7 (4)C8—C9—H9A108.3
C14—N2—C11112.2 (5)S3—C9—H9A108.3
O2—C1—O1122.6 (7)C8—C9—H9B108.3
O2—C1—C2123.0 (6)S3—C9—H9B108.3
O1—C1—C2114.4 (6)H9A—C9—H9B107.4
C1—C2—S1117.2 (4)N2—C10—S4124.6 (4)
C1—C2—H2A108.0N2—C10—S3114.9 (4)
S1—C2—H2A108.0S4—C10—S3120.5 (3)
C1—C2—H2B108.0N2—C11—C12108.4 (4)
S1—C2—H2B108.0N2—C11—H11A110.0
H2A—C2—H2B107.2C12—C11—H11A110.0
N1—C3—S2124.9 (4)N2—C11—H11B110.0
N1—C3—S1112.6 (4)C12—C11—H11B110.0
S2—C3—S1122.6 (3)H11A—C11—H11B108.4
N1—C4—C5110.1 (5)O6—C12—C11112.6 (5)
N1—C4—H4A109.6O6—C12—H12A109.1
C5—C4—H4A109.6C11—C12—H12A109.1
N1—C4—H4B109.6O6—C12—H12B109.1
C5—C4—H4B109.6C11—C12—H12B109.1
H4A—C4—H4B108.2H12A—C12—H12B107.8
O3—C5—C4109.4 (5)O6—C13—C14111.3 (7)
O3—C5—H5A109.8O6—C13—H13A109.4
C4—C5—H5A109.8C14—C13—H13A109.4
O3—C5—H5B109.8O6—C13—H13B109.4
C4—C5—H5B109.8C14—C13—H13B109.4
H5A—C5—H5B108.2H13A—C13—H13B108.0
O3—C6—C7111.9 (6)N2—C14—C13112.3 (5)
O3—C6—H6A109.2N2—C14—H14A109.2
C7—C6—H6A109.2C13—C14—H14A109.2
O3—C6—H6B109.2N2—C14—H14B109.2
C7—C6—H6B109.2C13—C14—H14B109.1
H6A—C6—H6B107.9H14A—C14—H14B107.9
O2—C1—C2—S129.1 (9)O5—C8—C9—S3−35.2 (8)
O1—C1—C2—S1−150.9 (6)O4—C8—C9—S3149.5 (6)
C3—S1—C2—C174.8 (5)C10—S3—C9—C8−72.7 (5)
C4—N1—C3—S2178.2 (5)C14—N2—C10—S42.9 (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—S1179.8 (5)C11—N2—C10—S31.4 (7)
C2—S1—C3—N1175.4 (4)C9—S3—C10—N2−174.2 (4)
C2—S1—C3—S2−3.5 (4)C9—S3—C10—S46.0 (4)
C3—N1—C4—C5−126.6 (6)C10—N2—C11—C12128.6 (5)
C7—N1—C4—C553.0 (8)C14—N2—C11—C12−53.0 (7)
C6—O3—C5—C459.7 (7)C13—O6—C12—C11−63.0 (7)
N1—C4—C5—O3−55.2 (7)N2—C11—C12—O661.0 (7)
C5—O3—C6—C7−60.0 (8)C12—O6—C13—C1457.6 (7)
C3—N1—C7—C6127.4 (7)C10—N2—C14—C13−130.6 (6)
C4—N1—C7—C6−52.2 (9)C11—N2—C14—C1350.9 (8)
O3—C6—C7—N155.3 (8)O6—C13—C14—N2−52.6 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O50.821.882.685 (7)169
O4—H4···O20.821.882.689 (7)170

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2747).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Nachmias, G. (1952). Ann. Chim.12, 584–631.
  • Ng, S. W. & Hook, J. M. (1999). Acta Cryst. C55, 312–316.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). publCIF In preparation.

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