2-Nitrophenyl 4-nitrophenyl disulfide

The structure of the title compound, C₁₂H₈N₂O₄S₂, contains no direction-specific intermolecular interactions, i.e. no C—H...O hydrogen bonds, no aromatic π–π-stacking interactions and no C—H...π(arene) interactions. This behaviour is compared with the three known symmetrical isomers of bis­(nitro­phenyl) di­sulfide, having the nitro groups on the two 2-, 3- or 4-positions, all of which exhibit direction-specific supramolecular aggregation.

S1. Comment

In bis(4-nitrophenyl) disulfide, (4-O₂NC₆H₄)₂S₂, (I), where the molecules lie across twofold rotation axes in space group C2/c, a single C—H···O hydrogen bond suffices to link the molecules into sheets, which are then linked by aromatic π···π stacking interactions to give a three-dimensional framework structure (Wardell et al., 2000). In the isomeric bis(2-nitrophenyl) disulfide, (II), the molecules are linked into chains by a single C—H···O hydrogen bond, and the chains are further linked into sheets by means of aromatic π···π stacking interactions (Glidewell et al., 2000). The structure of bis(3-nitrophenyl) disulfide, (III), on the other hand, contains no C—H···O hydrogen bonds, but the molecules are nonetheless linked into chains by aromatic π···π stacking interactions (Cannon et al., 2000). \sch

Intrigued by the different supramolecular structures adopted by the isomers (I)-(III), we have now investigated the `intermediate' isomer (IV), 2-nitrophenyl 4-nitrophenyl disulfide. The intramolecular dimensions and overall molecular conformation of (IV) are comparable with those in (I)-(III), with both nitro groups in (IV) nearly coplanar with the adjacent aryl rings. Also noteworthy are the C—C—C, C—C—S and C—C—N angles at the ipso positions (Table 1), where the C—C—C angles, in particular, are consistent with the electron-donating and electron-withdrawing properties of thiolate and nitro substituents, respectively (Domenicano & Murray-Rust, 1979). We also note that the S2—S1—C11—C12 torsion angle is close to 180°, consistent (Low et al., 2000) with the near co-planarity of the 2-nitro group and the C11—C16 ring.

However, the striking feature of the structure of (IV) is the complete absence of C—H···O hydrogen bonds and of both aromatic π···π stacking interactions and C—H···π(arene) interactions, so that there are no direction-specific intermolecular interactions. By not forming C—H···O hydrogen bonds, (IV) resembles (III), rather than (I) and (II). The supramolecular structures of (I)-(IV), as defined by the direction-specific intermolecular interactions, are thus three-, two-, one- and zero-dimensional, respectively, with very modest changes in molecular constitution leading to significant changes in the supramolecular aggregation.

The absence of any C—H···O hydrogen bonds in (III) and (IV) is highly unusual, as such interactions are generally the dominant feature of the crystal structures of compounds containing nitroarenethiolate, O₂NC₆H₄SX, fragments (Kucsman et al., 1984; Aupers et al., 1999; Low et al., 2000; Glidewell et al., 2000), as well as those of simple nitrobenzenes (Boonstra, 1963; Trotter & Williston, 1966; Choi & Abel, 1972; Herbstein & Kapon, 1990; Boese et al., 1992; Sekine et al., 1994).

Much effort continues to be expended in attempts to compute, using a variety of ab initio, semi-empirical and heuristic methods, the structures of simple molecular compounds (Lommerse et al., 2000; Motherwell, 2001). However, the unexpected differences between the crystal structures of members of simple series of isomeric compounds, such as compounds (I)-(IV) and other series where hard (Braga et al., 1995) hydrogen bonds are absent, as reported elsewhere (Farrell et al., 2002; Glidewell et al., 2002), together with the entire phenomenon of polymorphism, in particular the rather frequent observation of concomitant polymorphism (Bernstein et al., 1999), raise at least the suspicion that, for systems characterized by weak and/or long-range intermolecular forces, the crystal structures may, in general, be intrinsically non-computable.

S2. Experimental

A sample of the title compound was obtained by reaction of equimolar quantities of 2-nitrobenzenesulfenyl chloride and (4-nitrobenzenethiolato)triphenylstannane in chloroform solution. Crystals of (IV) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol [m.p. 429–431 K; literature m.p. 429 K (Lukashevich & Sergeeva, 1949)].

S3. Refinement

Compound (IV) crystallized in the monoclinic system; space group P2₁/c was uniquely assigned from the systematic absences. H atoms were treated as riding atoms, with C—H = 0.93 Å.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

Fig. 1. A view of the molecule of (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

2-Nitrophenyl 4-nitrophenyl disulfide

Crystal data

C12H8N2O4S2	F(000) = 632
Mr = 308.34	Dx = 1.579 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4661 reflections
a = 11.4923 (6) Å	θ = 2.9–32.5°
b = 7.9061 (4) Å	µ = 0.43 mm^−1
c = 14.3117 (7) Å	T = 298 K
β = 94.335 (1)°	Block, colourless
V = 1296.63 (11) Å^3	0.33 × 0.20 × 0.12 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	4661 independent reflections
Radiation source: fine-focus sealed X-ray tube	2924 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ scans and ω scans	θmax = 32.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→15
Tmin = 0.873, Tmax = 0.951	k = −11→11
13378 measured reflections	l = −21→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.056P)^2] where P = (Fo^2 + 2Fc^2)/3
4661 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

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

	x	y	z	Uiso*/Ueq
S1	0.16358 (3)	0.52555 (5)	0.10632 (3)	0.04601 (11)
C11	0.07525 (11)	0.34112 (16)	0.11723 (9)	0.0371 (3)
C12	−0.04477 (12)	0.35258 (17)	0.13031 (9)	0.0383 (3)
N12	−0.10064 (11)	0.51619 (16)	0.13679 (8)	0.0461 (3)
O121	−0.04083 (11)	0.64271 (15)	0.13112 (10)	0.0694 (4)
O122	−0.20539 (10)	0.52300 (17)	0.14711 (10)	0.0718 (4)
C13	−0.11428 (13)	0.2109 (2)	0.13591 (10)	0.0484 (3)
C14	−0.06638 (15)	0.0523 (2)	0.12949 (11)	0.0541 (4)
C15	0.05116 (14)	0.03787 (19)	0.11789 (11)	0.0512 (4)
C16	0.12087 (13)	0.17865 (18)	0.11173 (11)	0.0455 (3)
S2	0.32356 (3)	0.43292 (5)	0.07788 (3)	0.04890 (12)
C21	0.39917 (11)	0.40630 (17)	0.19007 (10)	0.0398 (3)
C22	0.52018 (12)	0.4233 (2)	0.19514 (10)	0.0460 (3)
C23	0.58406 (12)	0.4059 (2)	0.27933 (10)	0.0472 (3)
C24	0.52634 (12)	0.37059 (17)	0.35856 (10)	0.0402 (3)
N24	0.59401 (11)	0.35597 (15)	0.44898 (9)	0.0479 (3)
O241	0.69786 (10)	0.39064 (19)	0.45323 (9)	0.0709 (4)
O242	0.54394 (11)	0.31008 (15)	0.51711 (8)	0.0616 (3)
C25	0.40704 (13)	0.35009 (18)	0.35498 (10)	0.0461 (3)
C26	0.34329 (12)	0.36788 (18)	0.27030 (10)	0.0455 (3)
H13	−0.1934	0.2227	0.1440	0.058*
H14	−0.1126	−0.0437	0.1329	0.065*
H15	0.0841	−0.0691	0.1141	0.061*
H16	0.1999	0.1648	0.1038	0.055*
H22	0.5576	0.4466	0.1412	0.055*
H23	0.6648	0.4176	0.2832	0.057*
H25	0.3702	0.3246	0.4089	0.055*
H26	0.2627	0.3542	0.2667	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.03872 (19)	0.03994 (18)	0.0594 (2)	−0.00225 (14)	0.00402 (15)	0.00509 (15)
C11	0.0342 (6)	0.0395 (7)	0.0373 (7)	−0.0005 (5)	0.0010 (5)	0.0015 (5)
C12	0.0349 (6)	0.0428 (7)	0.0369 (7)	0.0044 (5)	0.0017 (5)	−0.0002 (5)
N12	0.0393 (6)	0.0478 (7)	0.0515 (7)	0.0076 (5)	0.0058 (5)	0.0003 (5)
O121	0.0566 (7)	0.0403 (6)	0.1118 (11)	0.0067 (5)	0.0091 (7)	0.0041 (6)
O122	0.0433 (7)	0.0695 (8)	0.1047 (10)	0.0139 (6)	0.0192 (7)	−0.0065 (7)
C13	0.0368 (7)	0.0531 (8)	0.0557 (9)	−0.0044 (6)	0.0072 (6)	−0.0027 (7)
C14	0.0500 (9)	0.0442 (8)	0.0691 (10)	−0.0099 (7)	0.0105 (7)	−0.0028 (7)
C15	0.0528 (9)	0.0376 (7)	0.0634 (9)	0.0029 (6)	0.0051 (7)	−0.0028 (6)
C16	0.0361 (7)	0.0442 (8)	0.0561 (9)	0.0046 (6)	0.0032 (6)	−0.0019 (6)
S2	0.03749 (19)	0.0644 (3)	0.0455 (2)	−0.00415 (16)	0.00749 (14)	0.00276 (16)
C21	0.0337 (6)	0.0397 (7)	0.0467 (7)	−0.0028 (5)	0.0074 (5)	−0.0015 (6)
C22	0.0353 (7)	0.0559 (8)	0.0481 (8)	−0.0071 (6)	0.0123 (6)	−0.0029 (6)
C23	0.0314 (7)	0.0550 (8)	0.0561 (9)	−0.0048 (6)	0.0093 (6)	−0.0036 (7)
C24	0.0373 (7)	0.0375 (7)	0.0460 (8)	−0.0026 (5)	0.0046 (5)	−0.0015 (5)
N24	0.0441 (7)	0.0448 (7)	0.0543 (7)	−0.0002 (5)	−0.0001 (6)	0.0008 (5)
O241	0.0437 (7)	0.0948 (9)	0.0721 (8)	−0.0136 (6)	−0.0089 (6)	0.0093 (7)
O242	0.0618 (7)	0.0710 (8)	0.0524 (6)	−0.0011 (6)	0.0063 (5)	0.0112 (5)
C25	0.0380 (7)	0.0545 (8)	0.0472 (8)	−0.0057 (6)	0.0115 (6)	0.0031 (6)
C26	0.0288 (6)	0.0580 (9)	0.0506 (8)	−0.0056 (6)	0.0085 (6)	0.0019 (6)

Geometric parameters (Å, º)

S1—C11	1.7902 (13)	S2—C21	1.7794 (15)
S1—S2	2.0483 (5)	C21—C26	1.3910 (18)
C11—C16	1.3919 (19)	C21—C22	1.3936 (18)
C11—C12	1.4087 (18)	C22—C23	1.370 (2)
C12—C13	1.382 (2)	C22—H22	0.9300
C12—N12	1.4503 (18)	C23—C24	1.3848 (19)
N12—O121	1.2199 (17)	C23—H23	0.9300
N12—O122	1.2250 (16)	C24—C25	1.3776 (19)
C13—C14	1.375 (2)	C24—N24	1.4631 (19)
C13—H13	0.9300	N24—O241	1.2215 (16)
C14—C15	1.378 (2)	N24—O242	1.2241 (16)
C14—H14	0.9300	C25—C26	1.375 (2)
C15—C16	1.378 (2)	C25—H25	0.9300
C15—H15	0.9300	C26—H26	0.9300
C16—H16	0.9300
C11—S1—S2	104.45 (5)	C21—S2—S1	104.32 (5)
C12—C11—C16	116.33 (12)	C22—C21—C26	119.95 (13)
C12—C11—S1	121.77 (10)	C22—C21—S2	116.93 (10)
C16—C11—S1	121.88 (10)	C26—C21—S2	123.12 (11)
C11—C12—C13	122.12 (12)	C23—C22—C21	120.16 (12)
C11—C12—N12	120.57 (12)	C23—C22—H22	119.9
C13—C12—N12	117.31 (12)	C21—C22—H22	119.9
O121—N12—O122	122.40 (13)	C22—C23—C24	118.85 (13)
O121—N12—C12	118.21 (12)	C22—C23—H23	120.6
O122—N12—C12	119.39 (13)	C24—C23—H23	120.6
C14—C13—C12	119.95 (13)	C23—C24—C25	122.02 (13)
C14—C13—H13	120.0	C23—C24—N24	118.99 (13)
C12—C13—H13	120.0	C25—C24—N24	118.99 (12)
C13—C14—C15	118.99 (14)	O241—N24—O242	122.90 (14)
C13—C14—H14	120.5	O241—N24—C24	118.58 (12)
C15—C14—H14	120.5	O242—N24—C24	118.52 (13)
C16—C15—C14	121.38 (14)	C26—C25—C24	118.90 (12)
C16—C15—H15	119.3	C26—C25—H25	120.6
C14—C15—H15	119.3	C24—C25—H25	120.6
C15—C16—C11	121.23 (13)	C25—C26—C21	120.09 (13)
C15—C16—H16	119.4	C25—C26—H26	120.0
C11—C16—H16	119.4	C21—C26—H26	120.0
S1—S2—C21—C22	−150.29 (11)	C13—C12—N12—O122	0.2 (2)
S2—S1—C11—C12	−175.34 (10)	C23—C24—N24—O241	6.6 (2)
C11—S1—S2—C21	−90.27 (7)	C23—C24—N24—O242	−173.6 (2)
C11—C12—N12—O121	−0.4 (2)	C25—C24—N24—O241	−172.9 (2)
C11—C12—N12—O122	179.2 (2)	C25—C24—N24—O242	6.9 (2)
C13—C12—N12—O121	−179.3 (2)