The structure of the first stable monosubstituted sulfur diimide

The title compound, 4-(4-methylphenyl)-1,3-diaza-2,4-dithiabuta-1,2-diene, C₇H₈N₂S₂, was the first example of a stable monosubstituted sulfur diimide to be documented [Jones (1988). PhD thesis, Imperial College, University of London, England]. Although a partial description of this structure was published previously, the full details are presented here. This allows a detailed comparison against the only other example of this system published to date, highlighting differences in bonding, conformation and packing.

Computing details

Data collection: Nicolet software; cell refinement: Nicolet software; data reduction: Nicolet software; program(s) used to solve structure: SHELXTL83 (Sheldrick, 1983) and SHELXLE (Hübschle et al., 2011); program(s) used to refine structure: SHELXTL83 (Sheldrick, 1983) and SHELXL2013 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).

4-(4-Methylphenyl)-1,3-diaza-2,4-dithiabuta-1,2-diene

Crystal data

C7H8N2S2	Z = 4
Mr = 184.27	F(000) = 384
Orthorhombic, P212121	Dx = 1.389 Mg m^−3
a = 6.223 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.178 (2) Å	µ = 4.96 mm^−1
c = 19.732 (5) Å	T = 293 K
V = 881.4 (4) Å^3	0.35 × 0.10 × 0.05 mm

Data collection

Scintillation diffractometer	θmax = 57.0°, θmin = 4.5°
Absorption correction: empirical (using intensity measurements) psi scans	h = 0→6
Tmin = 0.55, Tmax = 0.78	k = 0→7
647 independent reflections	l = 0→21
603 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.011P)^2 + 1.0000sinθ] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.065	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.13 e Å^−3
647 reflections	Δρmin = −0.15 e Å^−3
105 parameters	Absolute structure: No quotients, so Flack parameter determined by classical intensity fit.
1 restraint	Absolute structure parameter: 0.20 (8)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	1.0675 (9)	0.7290 (10)	0.4722 (2)	0.0875 (18)
H1N	1.168 (6)	0.714 (11)	0.502 (2)	0.11 (2)*
S2	1.1895 (3)	0.8023 (3)	0.41043 (8)	0.0845 (5)
N3	1.0517 (7)	0.7902 (7)	0.3456 (2)	0.0755 (14)
S4	0.8085 (2)	0.7014 (2)	0.34886 (7)	0.0650 (4)
C1	0.7322 (8)	0.7226 (8)	0.2630 (2)	0.0511 (13)
C2	0.8628 (8)	0.7917 (8)	0.2129 (2)	0.0584 (14)
H2	1.0023	0.8288	0.2231	0.070*
C3	0.7868 (9)	0.8060 (8)	0.1478 (3)	0.0621 (14)
H3	0.8760	0.8539	0.1143	0.075*
C4	0.5811 (9)	0.7510 (9)	0.1310 (3)	0.0634 (17)
C5	0.4541 (9)	0.6771 (9)	0.1813 (3)	0.0682 (17)
H5	0.3161	0.6366	0.1708	0.082*
C6	0.5276 (9)	0.6617 (8)	0.2472 (3)	0.0602 (15)
H6	0.4401	0.6108	0.2806	0.072*
C7	0.4947 (10)	0.7683 (10)	0.0588 (2)	0.091 (2)
H7A	0.4758	0.6463	0.0398	0.136*
H7B	0.5950	0.8374	0.0317	0.136*
H7C	0.3592	0.8321	0.0596	0.136*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.083 (3)	0.116 (5)	0.064 (3)	−0.003 (5)	0.000 (3)	−0.007 (4)
S2	0.0819 (10)	0.0866 (11)	0.0851 (10)	−0.0211 (13)	−0.0108 (10)	0.0003 (11)
N3	0.073 (3)	0.073 (3)	0.080 (3)	−0.025 (3)	−0.010 (3)	0.017 (3)
S4	0.0606 (8)	0.0736 (9)	0.0608 (8)	0.0030 (10)	0.0103 (8)	0.0105 (9)
C1	0.055 (3)	0.043 (3)	0.056 (3)	0.003 (3)	0.011 (3)	0.002 (3)
C2	0.054 (3)	0.054 (3)	0.067 (3)	0.001 (3)	0.007 (3)	0.006 (3)
C3	0.064 (3)	0.057 (3)	0.066 (3)	0.007 (4)	0.011 (3)	0.001 (4)
C4	0.069 (4)	0.056 (5)	0.065 (3)	0.009 (4)	0.003 (3)	−0.009 (3)
C5	0.053 (3)	0.064 (4)	0.087 (4)	−0.007 (4)	0.004 (3)	−0.019 (4)
C6	0.056 (3)	0.055 (4)	0.070 (3)	−0.009 (3)	0.014 (3)	−0.008 (3)
C7	0.097 (5)	0.104 (6)	0.071 (4)	0.005 (5)	−0.012 (4)	−0.009 (4)

Geometric parameters (Å, º)

N1—S2	1.530 (5)	C3—H3	0.9300
N1—H1N	0.860 (2)	C4—C5	1.376 (7)
S2—N3	1.543 (5)	C4—C7	1.527 (6)
N3—S4	1.643 (4)	C5—C6	1.383 (7)
S4—C1	1.767 (5)	C5—H5	0.9300
C1—C2	1.372 (6)	C6—H6	0.9300
C1—C6	1.381 (7)	C7—H7A	0.9600
C2—C3	1.373 (6)	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
C3—C4	1.380 (7)
S2—N1—H1N	103 (4)	C5—C4—C7	120.2 (6)
N1—S2—N3	111.5 (3)	C3—C4—C7	121.8 (6)
S2—N3—S4	120.1 (3)	C4—C5—C6	121.3 (5)
N3—S4—C1	100.2 (3)	C4—C5—H5	119.4
C2—C1—C6	119.9 (5)	C6—C5—H5	119.4
C2—C1—S4	124.2 (4)	C1—C6—C5	119.4 (5)
C6—C1—S4	115.9 (4)	C1—C6—H6	120.3
C1—C2—C3	119.8 (5)	C5—C6—H6	120.3
C1—C2—H2	120.1	C4—C7—H7A	109.5
C3—C2—H2	120.1	C4—C7—H7B	109.5
C2—C3—C4	121.6 (5)	H7A—C7—H7B	109.5
C2—C3—H3	119.2	C4—C7—H7C	109.5
C4—C3—H3	119.2	H7A—C7—H7C	109.5
C5—C4—C3	118.0 (5)	H7B—C7—H7C	109.5
N1—S2—N3—S4	−1.5 (5)	C2—C3—C4—C5	−1.3 (9)
S2—N3—S4—C1	−179.8 (4)	C2—C3—C4—C7	179.4 (6)
N3—S4—C1—C2	1.9 (5)	C3—C4—C5—C6	1.4 (9)
N3—S4—C1—C6	−179.0 (5)	C7—C4—C5—C6	−179.3 (6)
C6—C1—C2—C3	2.3 (9)	C2—C1—C6—C5	−2.2 (8)
S4—C1—C2—C3	−178.7 (5)	S4—C1—C6—C5	178.7 (4)
C1—C2—C3—C4	−0.5 (9)	C4—C5—C6—C1	0.3 (9)