Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010704142X/sf3052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010704142X/sf3052Isup2.hkl |
CCDC reference: 665529
All reactions were carried out under an atmosphere of purified nitrogen. Solvents used were dried and distilled prior to use. The title compound was obtained as yellow block crystals using the method described by Tanaka & Ajiki (2004). Into a 20 ml three-necked flask equipped with an overhead stirrer was placed 5,5'-dithiobis(1-phenyl-1H-tetrazole) (177.2 mg, 4 mmol) and 4-nitrophenyldisulfide (38.54 mg, 1 mmol) in CH2Cl2 (5 ml). Once the components were mixed, bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, [Rh(cod)2]BF4 (6 mg, 0.03 mmol), was added and the resulting mixture stirred for 3 h at room temperature. The resulting solution was kept at 298 K for 1.5 h under air. The solution was concentrated and purified by silica-gel chromatography (hexane–EtOAc = 20:1 v/v). Yellow block crystals of (I) suitable for X-ray analysis were grown from a solution in hexane–EtOAc (1:1 v/v) at 298 K over a period of a few days in air. Analysis: m.p. 393–394 K; FT– IR (KBr pellet, cm−1): ν(s, C—H) 3066, ν(s, C—H monosubstitution) 766, ν(s, C═C) 1384, ν(s, C═C) 1593, ν(m, C═N) 1524, ν(w, C—S) 740, ν[s, N═O of NO2 (symmetric)] 1345, ν[s, N═O of NO2 (asymmetric)] 1566, ν(w, S—S) 555.
All H atoms were located in a difference map and their positional and isotropic displacement parameters were refined freely. [C—H = 0.86 (3)–0.99 (3) Å]. 67 reflections were not included in the data set as they were either partially obscured by the beam stop or were eliminated during data reduction.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
C12H8N6O2S2 | F(000) = 680 |
Mr = 332.36 | Dx = 1.601 Mg m−3 |
Monoclinic, P21/a | Melting point = 393–394 K |
Hall symbol: -P 2yab | Mo Kα radiation, λ = 0.71073 Å |
a = 7.4161 (2) Å | Cell parameters from 9419 reflections |
b = 21.6740 (6) Å | θ = 2.4–27.5° |
c = 9.0312 (3) Å | µ = 0.40 mm−1 |
β = 108.233 (6)° | T = 295 K |
V = 1378.76 (7) Å3 | Block, yellow |
Z = 4 | 0.22 × 0.20 × 0.15 mm |
Nonius KappaCCD area-detector diffractometer | 3104 independent reflections |
Radiation source: fine-focus sealed tube | 2656 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 2.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −9→9 |
Tmin = 0.910, Tmax = 0.943 | k = −25→28 |
9028 measured reflections | l = −11→8 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.8023P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.139 | (Δ/σ)max = 0.021 |
S = 1.16 | Δρmax = 0.34 e Å−3 |
3104 reflections | Δρmin = −0.26 e Å−3 |
231 parameters |
C12H8N6O2S2 | V = 1378.76 (7) Å3 |
Mr = 332.36 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 7.4161 (2) Å | µ = 0.40 mm−1 |
b = 21.6740 (6) Å | T = 295 K |
c = 9.0312 (3) Å | 0.22 × 0.20 × 0.15 mm |
β = 108.233 (6)° |
Nonius KappaCCD area-detector diffractometer | 3104 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2656 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.943 | Rint = 0.054 |
9028 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.139 | All H-atom parameters refined |
S = 1.16 | Δρmax = 0.34 e Å−3 |
3104 reflections | Δρmin = −0.26 e Å−3 |
231 parameters |
Experimental. IR spectroscopy performed with a Thermo Nicolet Avatar 330 spectrometer. Melting points were determined using an electro thermal melting point detection apparatus TG-DSC Mettler Toledo. |
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. |
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 > σ(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. There are no solvent molecules present and there is no disorder. All non-hydrogen atoms were refined anisotropically. The coordinates and U(iso) values for the hydrogen atoms were freely refined. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.41164 (9) | 0.66766 (3) | 0.27264 (8) | 0.0411 (2) | |
S2 | 0.42461 (9) | 0.57611 (3) | 0.22318 (7) | 0.0410 (2) | |
O1 | −0.2424 (4) | 0.54863 (15) | −0.4551 (3) | 0.0801 (8) | |
O2 | −0.1135 (4) | 0.45827 (12) | −0.4252 (3) | 0.0643 (7) | |
N1 | 0.1820 (3) | 0.67965 (9) | 0.4621 (2) | 0.0279 (4) | |
N2 | −0.0045 (3) | 0.68553 (11) | 0.4463 (2) | 0.0370 (5) | |
N3 | −0.0952 (3) | 0.68203 (12) | 0.2983 (3) | 0.0432 (6) | |
N4 | 0.0271 (3) | 0.67471 (11) | 0.2149 (2) | 0.0403 (5) | |
N5 | 0.2520 (3) | 0.50604 (10) | −0.0048 (3) | 0.0417 (5) | |
N6 | −0.1230 (4) | 0.51153 (13) | −0.3850 (3) | 0.0492 (6) | |
C1 | 0.3200 (3) | 0.67998 (11) | 0.6153 (2) | 0.0265 (5) | |
C2 | 0.4414 (4) | 0.63069 (13) | 0.6632 (3) | 0.0358 (6) | |
C3 | 0.5655 (4) | 0.63095 (15) | 0.8136 (3) | 0.0444 (7) | |
C4 | 0.5656 (4) | 0.67993 (16) | 0.9122 (3) | 0.0453 (7) | |
C5 | 0.4430 (4) | 0.72875 (14) | 0.8630 (3) | 0.0400 (6) | |
C6 | 0.3182 (3) | 0.72941 (13) | 0.7115 (3) | 0.0328 (5) | |
C7 | 0.1981 (3) | 0.67277 (11) | 0.3181 (3) | 0.0310 (5) | |
C8 | 0.2624 (3) | 0.56573 (12) | 0.0327 (3) | 0.0309 (5) | |
C9 | 0.1584 (4) | 0.61202 (12) | −0.0628 (3) | 0.0331 (5) | |
C10 | 0.0317 (4) | 0.59435 (13) | −0.2035 (3) | 0.0349 (6) | |
C11 | 0.0185 (3) | 0.53267 (13) | −0.2408 (3) | 0.0356 (6) | |
C12 | 0.1311 (4) | 0.49009 (14) | −0.1427 (4) | 0.0443 (7) | |
H2 | 0.442 (4) | 0.5990 (14) | 0.606 (3) | 0.033 (7)* | |
H3 | 0.647 (5) | 0.5982 (17) | 0.857 (4) | 0.058 (9)* | |
H4 | 0.644 (4) | 0.6795 (14) | 1.007 (4) | 0.046 (8)* | |
H5 | 0.445 (4) | 0.7619 (15) | 0.938 (4) | 0.048 (8)* | |
H6 | 0.237 (4) | 0.7605 (13) | 0.679 (3) | 0.032 (7)* | |
H9 | 0.168 (4) | 0.6540 (14) | −0.033 (3) | 0.042 (8)* | |
H10 | −0.046 (5) | 0.6227 (16) | −0.267 (4) | 0.052 (9)* | |
H12 | 0.126 (5) | 0.4497 (19) | −0.156 (4) | 0.067 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0413 (4) | 0.0501 (4) | 0.0355 (4) | −0.0108 (3) | 0.0173 (3) | −0.0122 (3) |
S2 | 0.0416 (4) | 0.0490 (5) | 0.0300 (3) | 0.0095 (3) | 0.0080 (3) | 0.0000 (3) |
O1 | 0.0594 (15) | 0.106 (2) | 0.0558 (15) | 0.0161 (15) | −0.0098 (12) | −0.0153 (15) |
O2 | 0.0794 (16) | 0.0598 (16) | 0.0556 (14) | −0.0283 (12) | 0.0240 (12) | −0.0243 (12) |
N1 | 0.0284 (9) | 0.0302 (11) | 0.0229 (10) | 0.0024 (8) | 0.0050 (7) | −0.0032 (8) |
N2 | 0.0296 (10) | 0.0452 (13) | 0.0338 (11) | 0.0055 (9) | 0.0064 (8) | −0.0055 (10) |
N3 | 0.0347 (11) | 0.0555 (15) | 0.0323 (12) | 0.0059 (10) | 0.0001 (9) | −0.0045 (10) |
N4 | 0.0379 (11) | 0.0510 (15) | 0.0264 (11) | 0.0035 (10) | 0.0019 (8) | −0.0024 (9) |
N5 | 0.0497 (13) | 0.0308 (12) | 0.0418 (13) | 0.0078 (10) | 0.0101 (10) | −0.0003 (10) |
N6 | 0.0462 (14) | 0.0622 (18) | 0.0400 (13) | −0.0127 (12) | 0.0147 (11) | −0.0133 (12) |
C1 | 0.0263 (11) | 0.0321 (13) | 0.0191 (10) | −0.0021 (9) | 0.0044 (8) | −0.0014 (9) |
C2 | 0.0379 (13) | 0.0335 (15) | 0.0351 (14) | 0.0050 (10) | 0.0100 (10) | 0.0002 (11) |
C3 | 0.0335 (13) | 0.0543 (19) | 0.0415 (15) | 0.0063 (12) | 0.0061 (11) | 0.0180 (13) |
C4 | 0.0334 (13) | 0.074 (2) | 0.0238 (13) | −0.0121 (13) | 0.0019 (10) | 0.0054 (13) |
C5 | 0.0398 (14) | 0.0541 (18) | 0.0264 (12) | −0.0147 (12) | 0.0107 (10) | −0.0123 (12) |
C6 | 0.0328 (12) | 0.0348 (14) | 0.0300 (12) | −0.0011 (10) | 0.0087 (9) | −0.0034 (10) |
C7 | 0.0372 (12) | 0.0295 (13) | 0.0251 (12) | −0.0003 (10) | 0.0079 (9) | −0.0035 (9) |
C8 | 0.0321 (12) | 0.0346 (13) | 0.0286 (12) | 0.0021 (10) | 0.0134 (9) | 0.0012 (10) |
C9 | 0.0420 (13) | 0.0268 (13) | 0.0321 (12) | 0.0000 (10) | 0.0140 (10) | 0.0003 (10) |
C10 | 0.0388 (13) | 0.0374 (15) | 0.0297 (12) | 0.0042 (11) | 0.0122 (10) | 0.0047 (11) |
C11 | 0.0360 (12) | 0.0408 (15) | 0.0328 (13) | −0.0059 (11) | 0.0150 (10) | −0.0071 (11) |
C12 | 0.0553 (17) | 0.0282 (15) | 0.0506 (17) | −0.0004 (12) | 0.0182 (13) | −0.0064 (12) |
S1—C7 | 1.760 (2) | C2—C3 | 1.382 (4) |
S1—S2 | 2.0427 (10) | C2—H2 | 0.86 (3) |
S2—C8 | 1.779 (2) | C3—C4 | 1.386 (5) |
O1—N6 | 1.217 (4) | C3—H3 | 0.94 (4) |
O2—N6 | 1.219 (3) | C4—C5 | 1.375 (4) |
N1—C7 | 1.351 (3) | C4—H4 | 0.87 (3) |
N1—N2 | 1.351 (3) | C5—C6 | 1.391 (3) |
N1—C1 | 1.441 (3) | C5—H5 | 0.99 (3) |
N2—N3 | 1.297 (3) | C6—H6 | 0.89 (3) |
N3—N4 | 1.357 (3) | C8—C9 | 1.389 (3) |
N4—C7 | 1.318 (3) | C9—C10 | 1.378 (4) |
N5—C12 | 1.332 (4) | C9—H9 | 0.94 (3) |
N5—C8 | 1.334 (3) | C10—C11 | 1.375 (4) |
N6—C11 | 1.467 (3) | C10—H10 | 0.91 (3) |
C1—C2 | 1.377 (3) | C11—C12 | 1.368 (4) |
C1—C6 | 1.382 (3) | C12—H12 | 0.88 (4) |
C7—S1—S2 | 102.68 (9) | C4—C5—C6 | 119.6 (3) |
C8—S2—S1 | 105.70 (9) | C4—C5—H5 | 118.2 (17) |
C7—N1—N2 | 107.75 (18) | C6—C5—H5 | 122.2 (18) |
C7—N1—C1 | 132.4 (2) | C1—C6—C5 | 118.4 (2) |
N2—N1—C1 | 119.77 (18) | C1—C6—H6 | 121.4 (17) |
N3—N2—N1 | 106.6 (2) | C5—C6—H6 | 120.1 (17) |
N2—N3—N4 | 111.0 (2) | N4—C7—N1 | 108.8 (2) |
C7—N4—N3 | 105.9 (2) | N4—C7—S1 | 125.03 (19) |
C12—N5—C8 | 117.2 (2) | N1—C7—S1 | 126.05 (18) |
O1—N6—O2 | 124.8 (3) | N5—C8—C9 | 124.5 (2) |
O1—N6—C11 | 117.2 (3) | N5—C8—S2 | 109.64 (18) |
O2—N6—C11 | 117.9 (3) | C9—C8—S2 | 125.8 (2) |
C2—C1—C6 | 122.5 (2) | C10—C9—C8 | 117.2 (2) |
C2—C1—N1 | 119.7 (2) | C10—C9—H9 | 119.9 (18) |
C6—C1—N1 | 117.6 (2) | C8—C9—H9 | 122.9 (18) |
C1—C2—C3 | 118.4 (3) | C11—C10—C9 | 118.2 (2) |
C1—C2—H2 | 123.7 (18) | C11—C10—H10 | 121 (2) |
C3—C2—H2 | 118.0 (18) | C9—C10—H10 | 121 (2) |
C2—C3—C4 | 120.1 (3) | C12—C11—C10 | 121.0 (2) |
C2—C3—H3 | 124 (2) | C12—C11—N6 | 119.1 (3) |
C4—C3—H3 | 116 (2) | C10—C11—N6 | 119.8 (2) |
C5—C4—C3 | 121.0 (2) | N5—C12—C11 | 121.8 (3) |
C5—C4—H4 | 120 (2) | N5—C12—H12 | 112 (2) |
C3—C4—H4 | 119 (2) | C11—C12—H12 | 126 (2) |
C7—S1—S2—C8 | 76.98 (12) | N2—N1—C7—S1 | 176.19 (19) |
C7—N1—N2—N3 | 0.2 (3) | C1—N1—C7—S1 | −5.6 (4) |
C1—N1—N2—N3 | −178.3 (2) | S2—S1—C7—N4 | −79.3 (2) |
N1—N2—N3—N4 | −0.8 (3) | S2—S1—C7—N1 | 105.7 (2) |
N2—N3—N4—C7 | 1.0 (3) | C12—N5—C8—C9 | −1.1 (4) |
C7—N1—C1—C2 | −55.4 (4) | C12—N5—C8—S2 | 177.8 (2) |
N2—N1—C1—C2 | 122.7 (3) | S1—S2—C8—N5 | −175.69 (16) |
C7—N1—C1—C6 | 127.6 (3) | S1—S2—C8—C9 | 3.1 (2) |
N2—N1—C1—C6 | −54.3 (3) | N5—C8—C9—C10 | 2.2 (4) |
C6—C1—C2—C3 | 0.1 (4) | S2—C8—C9—C10 | −176.44 (18) |
N1—C1—C2—C3 | −176.7 (2) | C8—C9—C10—C11 | −0.8 (4) |
C1—C2—C3—C4 | 0.1 (4) | C9—C10—C11—C12 | −1.5 (4) |
C2—C3—C4—C5 | 0.2 (4) | C9—C10—C11—N6 | 176.2 (2) |
C3—C4—C5—C6 | −0.7 (4) | O1—N6—C11—C12 | 167.2 (3) |
C2—C1—C6—C5 | −0.6 (4) | O2—N6—C11—C12 | −12.3 (4) |
N1—C1—C6—C5 | 176.3 (2) | O1—N6—C11—C10 | −10.5 (4) |
C4—C5—C6—C1 | 0.9 (4) | O2—N6—C11—C10 | 170.0 (2) |
N3—N4—C7—N1 | −0.9 (3) | C8—N5—C12—C11 | −1.4 (4) |
N3—N4—C7—S1 | −176.67 (19) | C10—C11—C12—N5 | 2.7 (4) |
N2—N1—C7—N4 | 0.5 (3) | N6—C11—C12—N5 | −174.9 (3) |
C1—N1—C7—N4 | 178.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N5i | 0.94 (4) | 2.61 (4) | 3.488 (4) | 156 (3) |
C9—H9···S1 | 0.95 (3) | 2.80 (3) | 3.256 (3) | 110.5 (19) |
C6—H6···Cg1ii | 0.89 (3) | 2.84 (3) | 3.558 (3) | 139 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C12H8N6O2S2 |
Mr | 332.36 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 295 |
a, b, c (Å) | 7.4161 (2), 21.6740 (6), 9.0312 (3) |
β (°) | 108.233 (6) |
V (Å3) | 1378.76 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.22 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.910, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9028, 3104, 2656 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.139, 1.16 |
No. of reflections | 3104 |
No. of parameters | 231 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.34, −0.26 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).
S1—C7 | 1.760 (2) | S2—C8 | 1.779 (2) |
S1—S2 | 2.0427 (10) | N1—C1 | 1.441 (3) |
C7—S1—S2 | 102.68 (9) | N1—C7—S1 | 126.05 (18) |
C8—S2—S1 | 105.70 (9) | N5—C8—S2 | 109.64 (18) |
O1—N6—O2 | 124.8 (3) | C9—C8—S2 | 125.8 (2) |
N4—C7—S1 | 125.03 (19) | ||
C7—S1—S2—C8 | 76.98 (12) | S1—S2—C8—N5 | −175.69 (16) |
S2—S1—C7—N4 | −79.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N5i | 0.94 (4) | 2.61 (4) | 3.488 (4) | 156 (3) |
C9—H9···S1 | 0.95 (3) | 2.80 (3) | 3.256 (3) | 110.5 (19) |
C6—H6···Cg1ii | 0.89 (3) | 2.84 (3) | 3.558 (3) | 139 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z. |
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This paper forms part of our continuing study of the synthesis and structural characterization of divalent sulfur compounds (Brito et al., 2006, and references therein). We are particularly interested in the synthesis of unsymmetrical disulfides as flexible ligands, and in their binding modes, for the fabrication of different coordination polymer topologies.
The molecular structure of the title compound, (I) is shown in Fig. 1, and selected geometric parameters are given in Table 1. Yellow crystals of (I) were obtained from the rhodium(I) complex-catalysed reaction of 5,5'-dinitro-2,2'-dithiodipyridine with 5,5-dithiobis(1-phenyl-1H-tetrazole). The molecule consists of a 5-nitropyridine ring and a 1-phenyl-1H-tetrazole ring linked by a bridging disulfide group.
A search of the Cambridge Structural Database (CSD, Version 5.28 of May 2007; Allen, 2002) did not find any disulfide compounds with the 1-pheny-1H-tetrazole fragment. The 5-nitropyridine fragment of (I) shows excellent agreement with the bonding geometries of previously reported structures (Brito, Mundaca et al., 2007). The nitro group is rotated by about −12.3 (4)° out the plane of the pyridine ring. In the strongly electronegative 1-phenyltetrazole system, the tetrazole ring is planar, with a mean deviation from the least-squares plane of 0.0036 (17) Å. The dihedral angle between the least-squares planes of the tetrazole and benzene rings is 55.17 (11)°. The tetrazole ring geometry found in (I), with the S substituent at C5, is normal for 1,5-disubstituted tetrazoles with alkyl or aryl substituents (Allen, 2002), as are all other geometric parameters, which fall within the expected ranges.
The gross structure adopted by compound (I) is essentially the same as those reported previously for precursor products, namely 5,5'-dinitro-2,2'-dithiodipyridine (Brito, Mundaca et al., 2007) and 5,5'-dithiobis(1-phenyl-1H-tetrazole) (Brito, Cárdenas et al., 2007). The larger observed differences between (I) and 5,5'-dinitro-2,2'-dithiodipyridine are only in the N—C—S and C—C—S bond angles, [109.64 (18) and 125.8 (2), and 120.02 (2) and 116.0 (2)°, respectively]. A database survey of C—S—S—C fragments (Allen et al., 1987) found that S—S bond distances are bimodally distributed: for torsion angles in the ranges 75–105° and 0–20°, the mean S—S bond distances are 2.031 (15) and 2.070 (22) Å, respectively. The corresponding value in the title compound is 2.0427 (10) Å, placing it in the lower quartile for Allen's first set. The N1—C1 bond length is 1.441 (3) Å, which is almost the same as a normal N—C(phenyl) single bond. These facts indicate that conjugation affects between the phenyl and tetrazole rings in (I) are negligible (Lyakhov et al., 2006). The C—S bond lengths differ by 0.019 Å and this, coupled with the apparent lack of S—S double-bond character, shows that there is probably no communication between the two ring systems via the disulfide bridge, despite having a π donor at one end and a π acceptor at the other. Using a bond length–bond order relationship (Pauling, 1960; Bürgi & Dunitz, 1987), it can be shown that the C—S bonds in compound (I) have partial double-bond character of 12% (1.78 Å) and 20% (1.76 Å), respectively. The latter value is different from that found in, say, 5,5'-dithiobis(1-phenyl-1H-tetrazole) (Brito, Mundaca et al., 2007), where the sulfide linkage has about 35% double-bond character. The relationship between bond order (n) and bond length (rn) for sulfur compounds (rn = rl − 0.27ln n) has been derived from the following standard (rl) bond lengths: C—S (single bond, n = 1) = 1.81 Å (dimethyl sulfide, ethyl methyl sulfide; Lide, 1993), C—S (double bond, n = 2) = 1.61 Å (thioformaldehyde; Lide, 1993) and C—S (triple bond, n = 3) = 1.54 Å (carbon monosulfide; Bell et al., 1972).
The molecular conformations are dominated by the near orthogonality of the lone pairs on the two adjacent S atoms (Glidewell et al., 2000). Furthermore, a short intramolecular C9—H9···S1 contact (Table 2), may stabilize the conformation adopted by the molecule in the solid state (Fig. 1). The molecules are linked into centrosymmetric R22(20) dimers centred at (1/2, 1/2, 1/2) by simple C—H···N interactions (Bernstein et al., 1995). Aromatic atom C3 at (x, y, z) acts as a hydrogen-bond donor to atom N5 at (−x + 1, −y + 1, −z + 1) (Fig. 2).
The crystal structure is further stabilized and reinforced by weak intermolecular C—H···π(arene) interactions, involving the benzene C—H groups and the benzene rings (Fig. 3 and Table 2), and by π–π interactions (Fig. 3). The π–π interactions occur between pyridine rings at (x, y, z) and (−x + 1, −y + 1/2, z), with a centroid-to- centroid distance of 3.894 (4) Å and a dihedral angle between the ring planes of 0.02 (1)°; these values are ideal for the development of this type of interaction.