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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o292–o293.
Published online 2010 January 9. doi:  10.1107/S1600536810000024
PMCID: PMC2979978

2,2′-Dithio­dianiline: a redetermination at 100 K

Abstract

Structural studies of the title compound [systematic name: 2,2′-(disulfanedi­yl)dianiline], C12H12N2S2, were previously performed at room temperature [Gomes de Mesquita (1967 [triangle]). Acta Cryst. 23, 671; Lee & Bryant (1970 [triangle]). Acta Cryst. B26, 1729; Ribar et al. (1975 [triangle]). Bull. Yugoslav. Crystallogr. Centre, A10, 68]. The results of the current redetermination allow a clarification of the nature of the intra- and inter­molecular N—H(...)S hydrogen bonding described in the literature for this compound. On cooling to 100 K, the unit cell contracts most in the c axis, and it changes rather less in the directions involving the strongly hydrogen-bonded chains, which are the a and b axes. In the crystal structure, N—H(...)N hydrogen bonds link neighbouring mol­ecules into two-dimensional frameworks parallel to the ab plane. An additional inter­molecular N—H(...)S hydrogen bond has also been established, based on freely refined H-atom positions. Inter­molecular C—H(...)π inter­actions further stabilize the crystal structure.

Related literature

For previously reported structure determinations of the title compound, see: Gomes de Mesquita (1967 [triangle]); Lee & Bryant (1970 [triangle]); Ribar et al. (1975 [triangle]). For general background to and applications of the title compound, see: Garbarczyk et al. (1999 [triangle]); Kalluraya et al. (2000 [triangle]); Kalluraya & Chimbalkar (2001 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

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Object name is e-66-0o292-scheme1.jpg

Experimental

Crystal data

  • C12H12N2S2
  • M r = 248.36
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o292-efi1.jpg
  • a = 8.2531 (1) Å
  • b = 13.0278 (2) Å
  • c = 22.3655 (4) Å
  • V = 2404.73 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.42 mm−1
  • T = 100 K
  • 0.23 × 0.18 × 0.17 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.912, T max = 0.934
  • 47724 measured reflections
  • 2750 independent reflections
  • 2417 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.124
  • S = 1.19
  • 2750 reflections
  • 193 parameters
  • All H-atom parameters refined
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810000024/tk2598sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000024/tk2598Isup2.hkl

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

Acknowledgments

HKF and JHG thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Nitrogen- and sulphur- containing compounds are important intermediates in the synthesis of various heterocyclic compounds. Ortho amino thiophenols are important precursors in the preparation of a variety of heterocycles such as benzothiadiazepines, thiadiazoles, thiadiazines etc. (Kalluraya et al., 2000; Kalluraya & Chimbalkar, 2001). The title compound was obtained during an attempt to study the aerial oxidation of aminothiophenols. Molecular and crystal structures of thioamide derivatives have been analyzed (Garbarczyk et al., 1999).

A search of the November 2008 release of the Cambridge Structural Database (Allen, 2002) reveals that the room temperature crystal structures of the title compound (Fig. 1) were first reported with R = 0.057 for 369 reflections (Gomes de Mesquita, 1967), then followed with R = 0.086 for 1313 reflections (Lee & Bryant, 1970) and R = 0.042 (Ribar et al., 1975). The current redetermination at 100 K increases significantly the precision of the structural and geometrical parameters and provides a lower R value (R = 0.048 based on 2750 independent observed reflections).

Comparison with the previously reported unit cell parameters (Ribar et al., 1975) reveals that on cooling to 100 K, a expands by 0.41 %, whereas b and c contract by 1.15 and 1.74 %, respectively. This can be explained by the fact that along the c axis, the molecules are interconnected by weak C—H···π interactions only whereas along the a and b axes, the molecules are interconnected by the stronger hydrogen bonds (Figs 2 & 3, Table 1). The previously reported structure (Lee & Bryant, 1970) suggests two intramolecular N—H···S hydrogen bonds, but the current work observes no such intramolecular hydrogen bonds with bond angle larger than 120°. The bond lengths are comparable to but more precise than the previously reported structures (Lee & Bryant, 1970; Ribar et al., 1975).

In the crystal structure, molecules are linked into two-dimensional frameworks parallel to the ab plane (Fig. 3) rather than one-dimensional infinite chains as reported previously (Lee & Bryant, 1970). Based on freely refined hydrogen atom positions, an additional intermolecular N2—H2N2···S1 hydrogen bond (Table 1) has also been established. Intermolecular C4—H4A···Cg1 and C9—H9A···Cg2 interactions (Table 1) further stabilize the crystal structure.

Experimental

The title compound is obtained by exposing 2-aminobenzenethiol to sunlight in an open beaker for two days. The reagent 2-aminobenzenethiol undergoes self aerial oxidation to furnish the crystals. The crude product obtained through the photochemical condition was washed with ethanol and dried. Single crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.

Refinement

All the H atoms were located from difference Fourier map [range of C—H = 0.93 (3) - 1.00 (3) Å, and see Table 1 for N–H distances] and allowed to refine freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.
Fig. 2.
Part of the crystal structure, viewed along the a axis, showing two interlayers being joined along the c axis by weak intermolecular C—H···π interactions. Hydrogen atoms not involved in intermolecular interactions ...
Fig. 3.
The crystal structure of the title compound, viewed along the c axis, showing a two-dimensional framework parallel to the ab plane. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C12H12N2S2F(000) = 1040
Mr = 248.36Dx = 1.372 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 9179 reflections
a = 8.2531 (1) Åθ = 3.1–29.9°
b = 13.0278 (2) ŵ = 0.42 mm1
c = 22.3655 (4) ÅT = 100 K
V = 2404.73 (6) Å3Block, yellow
Z = 80.23 × 0.18 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2750 independent reflections
Radiation source: fine-focus sealed tube2417 reflections with I > 2σ(I)
graphiteRint = 0.040
[var phi] and ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −10→10
Tmin = 0.912, Tmax = 0.934k = −16→16
47724 measured reflectionsl = −29→29

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124All H-atom parameters refined
S = 1.19w = 1/[σ2(Fo2) + (0.0383P)2 + 5.2113P] where P = (Fo2 + 2Fc2)/3
2750 reflections(Δ/σ)max < 0.001
193 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = −0.43 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
S10.02244 (8)0.44246 (5)0.29158 (3)0.02175 (17)
S2−0.18075 (7)0.49532 (5)0.33614 (3)0.01897 (17)
N10.1434 (3)0.65943 (19)0.27327 (11)0.0261 (5)
N2−0.3466 (3)0.28926 (19)0.32376 (10)0.0226 (5)
C10.2321 (3)0.6022 (2)0.31445 (12)0.0208 (5)
C20.3664 (3)0.6450 (2)0.34391 (13)0.0267 (6)
C30.4491 (3)0.5893 (2)0.38682 (14)0.0308 (7)
C40.4032 (3)0.4902 (2)0.40210 (13)0.0287 (6)
C50.2712 (3)0.4467 (2)0.37320 (12)0.0233 (5)
C60.1857 (3)0.5017 (2)0.32969 (11)0.0193 (5)
C7−0.2077 (3)0.40351 (19)0.39331 (11)0.0171 (5)
C8−0.1543 (3)0.4247 (2)0.45123 (12)0.0220 (5)
C9−0.1837 (3)0.3567 (2)0.49755 (12)0.0275 (6)
C10−0.2661 (4)0.2664 (2)0.48554 (13)0.0295 (6)
C11−0.3206 (3)0.2437 (2)0.42842 (13)0.0251 (6)
C12−0.2934 (3)0.31171 (19)0.38114 (11)0.0190 (5)
H2A0.402 (4)0.715 (3)0.3335 (14)0.034 (9)*
H3A0.536 (4)0.621 (3)0.4078 (15)0.038 (9)*
H4A0.457 (4)0.451 (3)0.4337 (15)0.033 (9)*
H5A0.240 (4)0.379 (2)0.3819 (13)0.025 (8)*
H8A−0.100 (4)0.492 (2)0.4590 (14)0.027 (8)*
H9A−0.153 (4)0.373 (2)0.5377 (14)0.022 (8)*
H10A−0.285 (4)0.219 (3)0.5158 (14)0.030 (9)*
H11A−0.374 (4)0.179 (3)0.4193 (14)0.029 (8)*
H1N10.199 (5)0.706 (3)0.2542 (18)0.048 (11)*
H2N10.083 (5)0.620 (3)0.2483 (16)0.040 (10)*
H1N2−0.422 (5)0.244 (3)0.3209 (15)0.037 (9)*
H2N2−0.362 (4)0.343 (3)0.3004 (14)0.025 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0167 (3)0.0245 (3)0.0240 (3)−0.0045 (2)0.0039 (2)−0.0044 (3)
S20.0123 (3)0.0188 (3)0.0258 (3)−0.0004 (2)0.0000 (2)0.0029 (2)
N10.0241 (12)0.0220 (12)0.0321 (13)0.0011 (10)0.0068 (10)0.0039 (10)
N20.0204 (11)0.0205 (11)0.0268 (12)−0.0038 (9)−0.0012 (9)−0.0006 (9)
C10.0160 (12)0.0212 (12)0.0253 (12)0.0025 (10)0.0079 (10)−0.0026 (10)
C20.0163 (12)0.0258 (14)0.0381 (15)−0.0049 (11)0.0101 (11)−0.0089 (12)
C30.0112 (12)0.0430 (17)0.0382 (16)−0.0015 (12)0.0018 (11)−0.0154 (13)
C40.0152 (12)0.0395 (17)0.0313 (15)0.0069 (11)0.0002 (11)−0.0045 (13)
C50.0185 (12)0.0235 (13)0.0278 (13)0.0035 (10)0.0050 (10)−0.0007 (11)
C60.0140 (11)0.0219 (12)0.0220 (12)−0.0008 (9)0.0057 (9)−0.0013 (10)
C70.0100 (11)0.0188 (12)0.0225 (12)0.0029 (9)0.0026 (9)0.0022 (9)
C80.0144 (12)0.0275 (14)0.0242 (13)0.0028 (10)−0.0004 (10)−0.0030 (10)
C90.0211 (13)0.0400 (17)0.0214 (13)0.0066 (12)0.0004 (10)0.0007 (12)
C100.0278 (14)0.0325 (16)0.0282 (14)0.0090 (12)0.0086 (12)0.0095 (12)
C110.0214 (13)0.0206 (13)0.0333 (14)0.0022 (11)0.0068 (11)0.0029 (11)
C120.0114 (11)0.0212 (12)0.0244 (12)0.0028 (9)0.0038 (9)−0.0009 (10)

Geometric parameters (Å, °)

S1—C61.771 (3)C4—C51.388 (4)
S1—S22.0687 (9)C4—H4A0.97 (3)
S2—C71.765 (3)C5—C61.400 (4)
N1—C11.392 (4)C5—H5A0.94 (3)
N1—H1N10.87 (4)C7—C81.396 (4)
N1—H2N10.91 (4)C7—C121.416 (3)
N2—C121.388 (3)C8—C91.384 (4)
N2—H1N20.86 (4)C8—H8A1.00 (3)
N2—H2N20.88 (3)C9—C101.386 (4)
C1—C21.405 (4)C9—H9A0.96 (3)
C1—C61.407 (4)C10—C111.386 (4)
C2—C31.383 (4)C10—H10A0.93 (3)
C2—H2A0.98 (3)C11—C121.397 (4)
C3—C41.388 (4)C11—H11A0.97 (3)
C3—H3A0.95 (4)
C6—S1—S2103.87 (9)C6—C5—H5A119 (2)
C7—S2—S1103.05 (8)C5—C6—C1120.5 (2)
C1—N1—H1N1115 (3)C5—C6—S1119.7 (2)
C1—N1—H2N1113 (2)C1—C6—S1119.8 (2)
H1N1—N1—H2N1112 (3)C8—C7—C12120.2 (2)
C12—N2—H1N2116 (2)C8—C7—S2119.9 (2)
C12—N2—H2N2115 (2)C12—C7—S2119.74 (19)
H1N2—N2—H2N2113 (3)C9—C8—C7120.9 (3)
N1—C1—C2120.8 (3)C9—C8—H8A120.6 (18)
N1—C1—C6121.0 (2)C7—C8—H8A118.4 (18)
C2—C1—C6118.1 (3)C8—C9—C10119.0 (3)
C3—C2—C1120.4 (3)C8—C9—H9A121.3 (18)
C3—C2—H2A120 (2)C10—C9—H9A119.7 (18)
C1—C2—H2A119 (2)C9—C10—C11121.2 (3)
C2—C3—C4121.6 (3)C9—C10—H10A121 (2)
C2—C3—H3A119 (2)C11—C10—H10A118 (2)
C4—C3—H3A119 (2)C10—C11—C12120.7 (3)
C5—C4—C3118.7 (3)C10—C11—H11A121.7 (19)
C5—C4—H4A119 (2)C12—C11—H11A117.6 (19)
C3—C4—H4A122 (2)N2—C12—C11121.0 (2)
C4—C5—C6120.7 (3)N2—C12—C7120.9 (2)
C4—C5—H5A120 (2)C11—C12—C7118.0 (2)
C6—S1—S2—C7−89.29 (13)S1—S2—C7—C899.8 (2)
N1—C1—C2—C3176.9 (2)S1—S2—C7—C12−84.50 (19)
C6—C1—C2—C3−0.4 (4)C12—C7—C8—C90.1 (4)
C1—C2—C3—C40.1 (4)S2—C7—C8—C9175.7 (2)
C2—C3—C4—C50.2 (4)C7—C8—C9—C100.6 (4)
C3—C4—C5—C6−0.3 (4)C8—C9—C10—C11−0.7 (4)
C4—C5—C6—C10.0 (4)C9—C10—C11—C120.1 (4)
C4—C5—C6—S1177.7 (2)C10—C11—C12—N2179.6 (3)
N1—C1—C6—C5−177.0 (2)C10—C11—C12—C70.5 (4)
C2—C1—C6—C50.3 (4)C8—C7—C12—N2−179.7 (2)
N1—C1—C6—S15.4 (3)S2—C7—C12—N24.7 (3)
C2—C1—C6—S1−177.36 (19)C8—C7—C12—C11−0.6 (3)
S2—S1—C6—C598.6 (2)S2—C7—C12—C11−176.27 (19)
S2—S1—C6—C1−83.8 (2)

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids for C7–C12 and C1–C16 phenyl rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1N1···N2i0.87 (4)2.39 (4)3.222 (3)160 (4)
N2—H1N2···N1ii0.86 (4)2.39 (4)3.184 (3)155 (3)
N2—H2N2···S1iii0.88 (4)2.61 (3)3.436 (2)156 (3)
C4—H4A···Cg1iv0.97 (3)2.95 (3)3.689 (3)134 (2)
C9—H9A···Cg2v0.96 (3)2.89 (3)3.637 (3)135 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2598).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bruker (2009). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • Garbarczyk, J., Kamyszek, G. & Boese, R. (1999). J. Mol. Struct.479, 21–30.
  • Gomes de Mesquita, A. H. (1967). Acta Cryst.23, 671–672.
  • Kalluraya, B. & Chimbalkar, R. M. (2001). Indian J. Heterocycl. Chem.11, 171–172.
  • Kalluraya, B., Vishwanatha, P., Isloor, A. M., Rai, G. & Kotian, M. (2000). Boll. Chim. Farm. Anno.139, 263–266. [PubMed]
  • Lee, J. D. & Bryant, M. W. R. (1970). Acta Cryst. B26, 1729–1735.
  • Ribar, B., Lazar, D., Argay, G. & Kalman, A. (1975). Bull. Yugoslav. Crystallogr. Centre, A10, 68.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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