2,2'-Dithio-dianiline: a redetermination at 100 K.

STRUCTURAL STUDIES OF THE TITLE COMPOUND [SYSTEMATIC NAME: 2,2'-(disulfanedi-yl)dianiline], C(12)H(12)N(2)S(2), were previously performed at room temperature [Gomes de Mesquita (1967 ▶). Acta Cryst.23, 671; Lee & Bryant (1970 ▶). Acta Cryst. B26, 1729; Ribar et al. (1975 ▶). Bull. Yugoslav. Crystallogr. Centre, A10, 68]. The results of the current redetermination allow a clarification of the nature of the intra- and inter-molecular 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 mol-ecules into two-dimensional frameworks parallel to the ab plane. An additional inter-molecular N-H⋯S hydrogen bond has also been established, based on freely refined H-atom positions. Inter-molecular C-H⋯π inter-actions further stabilize the crystal structure.

Related literature

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

Experimental

Crystal data

C12H12N2S2

M = 248.36

Orthorhombic,

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 ▶) 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 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

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

C12H12N2S2	F(000) = 1040
Mr = 248.36	Dx = 1.372 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9179 reflections
a = 8.2531 (1) Å	θ = 3.1–29.9°
b = 13.0278 (2) Å	µ = 0.42 mm−1
c = 22.3655 (4) Å	T = 100 K
V = 2404.73 (6) Å3	Block, yellow
Z = 8	0.23 × 0.18 × 0.17 mm

Bruker SMART APEXII CCD area-detector diffractometer	2750 independent reflections
Radiation source: fine-focus sealed tube	2417 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.912, Tmax = 0.934	k = −16→16
47724 measured reflections	l = −29→29

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	All H-atom parameters refined
S = 1.19	w = 1/[σ2(Fo2) + (0.0383P)2 + 5.2113P] where P = (Fo2 + 2Fc2)/3
2750 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.02244 (8)	0.44246 (5)	0.29158 (3)	0.02175 (17)
S2	−0.18075 (7)	0.49532 (5)	0.33614 (3)	0.01897 (17)
N1	0.1434 (3)	0.65943 (19)	0.27327 (11)	0.0261 (5)
N2	−0.3466 (3)	0.28926 (19)	0.32376 (10)	0.0226 (5)
C1	0.2321 (3)	0.6022 (2)	0.31445 (12)	0.0208 (5)
C2	0.3664 (3)	0.6450 (2)	0.34391 (13)	0.0267 (6)
C3	0.4491 (3)	0.5893 (2)	0.38682 (14)	0.0308 (7)
C4	0.4032 (3)	0.4902 (2)	0.40210 (13)	0.0287 (6)
C5	0.2712 (3)	0.4467 (2)	0.37320 (12)	0.0233 (5)
C6	0.1857 (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)
H2A	0.402 (4)	0.715 (3)	0.3335 (14)	0.034 (9)*
H3A	0.536 (4)	0.621 (3)	0.4078 (15)	0.038 (9)*
H4A	0.457 (4)	0.451 (3)	0.4337 (15)	0.033 (9)*
H5A	0.240 (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)*
H1N1	0.199 (5)	0.706 (3)	0.2542 (18)	0.048 (11)*
H2N1	0.083 (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)*

	U11	U22	U33	U12	U13	U23
S1	0.0167 (3)	0.0245 (3)	0.0240 (3)	−0.0045 (2)	0.0039 (2)	−0.0044 (3)
S2	0.0123 (3)	0.0188 (3)	0.0258 (3)	−0.0004 (2)	0.0000 (2)	0.0029 (2)
N1	0.0241 (12)	0.0220 (12)	0.0321 (13)	0.0011 (10)	0.0068 (10)	0.0039 (10)
N2	0.0204 (11)	0.0205 (11)	0.0268 (12)	−0.0038 (9)	−0.0012 (9)	−0.0006 (9)
C1	0.0160 (12)	0.0212 (12)	0.0253 (12)	0.0025 (10)	0.0079 (10)	−0.0026 (10)
C2	0.0163 (12)	0.0258 (14)	0.0381 (15)	−0.0049 (11)	0.0101 (11)	−0.0089 (12)
C3	0.0112 (12)	0.0430 (17)	0.0382 (16)	−0.0015 (12)	0.0018 (11)	−0.0154 (13)
C4	0.0152 (12)	0.0395 (17)	0.0313 (15)	0.0069 (11)	0.0002 (11)	−0.0045 (13)
C5	0.0185 (12)	0.0235 (13)	0.0278 (13)	0.0035 (10)	0.0050 (10)	−0.0007 (11)
C6	0.0140 (11)	0.0219 (12)	0.0220 (12)	−0.0008 (9)	0.0057 (9)	−0.0013 (10)
C7	0.0100 (11)	0.0188 (12)	0.0225 (12)	0.0029 (9)	0.0026 (9)	0.0022 (9)
C8	0.0144 (12)	0.0275 (14)	0.0242 (13)	0.0028 (10)	−0.0004 (10)	−0.0030 (10)
C9	0.0211 (13)	0.0400 (17)	0.0214 (13)	0.0066 (12)	0.0004 (10)	0.0007 (12)
C10	0.0278 (14)	0.0325 (16)	0.0282 (14)	0.0090 (12)	0.0086 (12)	0.0095 (12)
C11	0.0214 (13)	0.0206 (13)	0.0333 (14)	0.0022 (11)	0.0068 (11)	0.0029 (11)
C12	0.0114 (11)	0.0212 (12)	0.0244 (12)	0.0028 (9)	0.0038 (9)	−0.0009 (10)

S1—C6	1.771 (3)	C4—C5	1.388 (4)
S1—S2	2.0687 (9)	C4—H4A	0.97 (3)
S2—C7	1.765 (3)	C5—C6	1.400 (4)
N1—C1	1.392 (4)	C5—H5A	0.94 (3)
N1—H1N1	0.87 (4)	C7—C8	1.396 (4)
N1—H2N1	0.91 (4)	C7—C12	1.416 (3)
N2—C12	1.388 (3)	C8—C9	1.384 (4)
N2—H1N2	0.86 (4)	C8—H8A	1.00 (3)
N2—H2N2	0.88 (3)	C9—C10	1.386 (4)
C1—C2	1.405 (4)	C9—H9A	0.96 (3)
C1—C6	1.407 (4)	C10—C11	1.386 (4)
C2—C3	1.383 (4)	C10—H10A	0.93 (3)
C2—H2A	0.98 (3)	C11—C12	1.397 (4)
C3—C4	1.388 (4)	C11—H11A	0.97 (3)
C3—H3A	0.95 (4)
C6—S1—S2	103.87 (9)	C6—C5—H5A	119 (2)
C7—S2—S1	103.05 (8)	C5—C6—C1	120.5 (2)
C1—N1—H1N1	115 (3)	C5—C6—S1	119.7 (2)
C1—N1—H2N1	113 (2)	C1—C6—S1	119.8 (2)
H1N1—N1—H2N1	112 (3)	C8—C7—C12	120.2 (2)
C12—N2—H1N2	116 (2)	C8—C7—S2	119.9 (2)
C12—N2—H2N2	115 (2)	C12—C7—S2	119.74 (19)
H1N2—N2—H2N2	113 (3)	C9—C8—C7	120.9 (3)
N1—C1—C2	120.8 (3)	C9—C8—H8A	120.6 (18)
N1—C1—C6	121.0 (2)	C7—C8—H8A	118.4 (18)
C2—C1—C6	118.1 (3)	C8—C9—C10	119.0 (3)
C3—C2—C1	120.4 (3)	C8—C9—H9A	121.3 (18)
C3—C2—H2A	120 (2)	C10—C9—H9A	119.7 (18)
C1—C2—H2A	119 (2)	C9—C10—C11	121.2 (3)
C2—C3—C4	121.6 (3)	C9—C10—H10A	121 (2)
C2—C3—H3A	119 (2)	C11—C10—H10A	118 (2)
C4—C3—H3A	119 (2)	C10—C11—C12	120.7 (3)
C5—C4—C3	118.7 (3)	C10—C11—H11A	121.7 (19)
C5—C4—H4A	119 (2)	C12—C11—H11A	117.6 (19)
C3—C4—H4A	122 (2)	N2—C12—C11	121.0 (2)
C4—C5—C6	120.7 (3)	N2—C12—C7	120.9 (2)
C4—C5—H5A	120 (2)	C11—C12—C7	118.0 (2)
C6—S1—S2—C7	−89.29 (13)	S1—S2—C7—C8	99.8 (2)
N1—C1—C2—C3	176.9 (2)	S1—S2—C7—C12	−84.50 (19)
C6—C1—C2—C3	−0.4 (4)	C12—C7—C8—C9	0.1 (4)
C1—C2—C3—C4	0.1 (4)	S2—C7—C8—C9	175.7 (2)
C2—C3—C4—C5	0.2 (4)	C7—C8—C9—C10	0.6 (4)
C3—C4—C5—C6	−0.3 (4)	C8—C9—C10—C11	−0.7 (4)
C4—C5—C6—C1	0.0 (4)	C9—C10—C11—C12	0.1 (4)
C4—C5—C6—S1	177.7 (2)	C10—C11—C12—N2	179.6 (3)
N1—C1—C6—C5	−177.0 (2)	C10—C11—C12—C7	0.5 (4)
C2—C1—C6—C5	0.3 (4)	C8—C7—C12—N2	−179.7 (2)
N1—C1—C6—S1	5.4 (3)	S2—C7—C12—N2	4.7 (3)
C2—C1—C6—S1	−177.36 (19)	C8—C7—C12—C11	−0.6 (3)
S2—S1—C6—C5	98.6 (2)	S2—C7—C12—C11	−176.27 (19)
S2—S1—C6—C1	−83.8 (2)

Cg1 and Cg2 are the centroids for C7–C12 and C1–C16 phenyl rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2i	0.87 (4)	2.39 (4)	3.222 (3)	160 (4)
N2—H1N2···N1ii	0.86 (4)	2.39 (4)	3.184 (3)	155 (3)
N2—H2N2···S1iii	0.88 (4)	2.61 (3)	3.436 (2)	156 (3)
C4—H4A···Cg1iv	0.97 (3)	2.95 (3)	3.689 (3)	134 (2)
C9—H9A···Cg2v	0.96 (3)	2.89 (3)	3.637 (3)	135 (2)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C7–C12 and C1–C16 phenyl rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2i	0.87 (4)	2.39 (4)	3.222 (3)	160 (4)
N2—H1N2⋯N1ii	0.86 (4)	2.39 (4)	3.184 (3)	155 (3)
N2—H2N2⋯S1iii	0.88 (4)	2.61 (3)	3.436 (2)	156 (3)
C4—H4A⋯Cg1iv	0.97 (3)	2.95 (3)	3.689 (3)	134 (2)
C9—H9A⋯Cg2v	0.96 (3)	2.89 (3)	3.637 (3)	135 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .