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The title compound [systematic name: 2-(p-tolyldiazenyl)phenyl isothiocyanate], C14H11N3S, is non-ionic in nature. Highly electronegative atoms like Br or Cl in sulfenyl halides make the S atom sufficiently electron deficient for strong ortho azo-sulfur interaction in sulfenyl bromides or chlorides of ortho mercaptoazo compounds; this leads to a planar thiadiazolium structure, in which the S atom interacts with the ortho azo group. However, in case of the 4'-Me title compound, the S atom is not sufficiently electron deficient, and no intramolecular ortho azo-sulfur interaction exists. The molecule is almost planar. There are no hydrogen bonds and the crystal structure is stabilized by van der Waals interactions.
Supporting information
CCDC reference: 234858
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.074
- wR factor = 0.231
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.94
PLAT230_ALERT_2_B Hirshfeld Test Diff for N1 - C1 = 11.27 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for N2 - C8 = 10.25 su
Alert level C
REFLT03_ALERT_3_C Reflection count < 95% complete
From the CIF: _diffrn_reflns_theta_max 70.10
From the CIF: _diffrn_reflns_theta_full 0.00
From the CIF: _reflns_number_total 2266
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 2410
Completeness (_total/calc) 94.02%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.94
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C7
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 6
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 EXPRESS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
4'-methylazobenzene-2-sulphenylcyanide
top
Crystal data top
C14H11N3S | F(000) = 528 |
Mr = 253.33 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/c | Melting point: 372 K K |
Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54180 Å |
a = 14.516 (2) Å | Cell parameters from 25 reflections |
b = 4.784 (2) Å | θ = 55–65° |
c = 19.194 (4) Å | µ = 2.13 mm−1 |
β = 107.62 (1)° | T = 293 K |
V = 1270.4 (6) Å3 | Needle, yellow |
Z = 4 | 0.53 × 0.40 × 0.20 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1509 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 70.1°, θmin = 3.2° |
2ω scans | h = 0→17 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→5 |
Tmin = 0.414, Tmax = 0.654 | l = −23→22 |
2342 measured reflections | 4 standard reflections every 600 reflections |
2266 independent reflections | intensity decay: none |
Refinement top
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.231 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1132P)2 + 1.0209P] where P = (Fo2 + 2Fc2)/3 |
2266 reflections | (Δ/σ)max = 0.048 |
166 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.43550 (9) | 0.3735 (3) | 0.32812 (8) | 0.0831 (5) | |
N1 | 0.2541 (2) | 0.1802 (8) | 0.30513 (19) | 0.0594 (10) | |
N2 | 0.1734 (2) | 0.0833 (8) | 0.28805 (18) | 0.0574 (9) | |
N3 | 0.6026 (4) | 0.7010 (13) | 0.3830 (3) | 0.115 (2) | |
C1 | 0.2688 (3) | 0.3892 (9) | 0.3623 (2) | 0.0514 (10) | |
C2 | 0.3610 (3) | 0.5036 (10) | 0.3797 (2) | 0.0580 (11) | |
C3 | 0.3888 (3) | 0.7039 (11) | 0.4342 (2) | 0.0653 (12) | |
C4 | 0.3254 (3) | 0.7863 (11) | 0.4699 (2) | 0.0684 (13) | |
C5 | 0.2334 (3) | 0.6764 (11) | 0.4527 (2) | 0.0661 (12) | |
C6 | 0.2055 (3) | 0.4743 (10) | 0.3987 (2) | 0.0576 (11) | |
C7 | 0.5342 (4) | 0.5769 (13) | 0.3616 (3) | 0.0797 (15) | |
C8 | 0.1600 (3) | −0.1271 (9) | 0.2296 (2) | 0.0505 (10) | |
C9 | 0.2312 (3) | −0.2110 (10) | 0.1995 (2) | 0.0578 (11) | |
C10 | 0.2086 (3) | −0.4127 (10) | 0.1446 (2) | 0.0608 (12) | |
C11 | 0.1167 (3) | −0.5285 (8) | 0.1198 (2) | 0.0500 (10) | |
C12 | 0.0492 (3) | −0.4404 (9) | 0.1519 (2) | 0.0525 (10) | |
C13 | 0.0699 (3) | −0.2439 (9) | 0.2065 (2) | 0.0508 (10) | |
C14 | 0.0937 (4) | −0.7442 (10) | 0.0602 (2) | 0.0738 (14) | |
H3 | 0.4503 | 0.7816 | 0.4463 | 0.073 (5)* | |
H4 | 0.3445 | 0.9196 | 0.5067 | 0.073 (5)* | |
H5 | 0.1907 | 0.7372 | 0.4770 | 0.073 (5)* | |
H6 | 0.1439 | 0.3965 | 0.3870 | 0.073 (5)* | |
H9 | 0.2928 | −0.1340 | 0.2157 | 0.073 (5)* | |
H10 | 0.2559 | −0.4706 | 0.1241 | 0.073 (5)* | |
H12 | −0.0127 | −0.5165 | 0.1362 | 0.073 (5)* | |
H13 | 0.0228 | −0.1902 | 0.2276 | 0.073 (5)* | |
H14A | 0.0455 | −0.8702 | 0.0668 | 0.139 (15)* | |
H14B | 0.1512 | −0.8470 | 0.0620 | 0.139 (15)* | |
H14C | 0.0696 | −0.6533 | 0.0136 | 0.139 (15)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0722 (8) | 0.0961 (11) | 0.0887 (10) | −0.0054 (7) | 0.0360 (7) | −0.0237 (8) |
N1 | 0.0493 (18) | 0.069 (3) | 0.060 (2) | −0.0035 (17) | 0.0166 (15) | 0.0112 (19) |
N2 | 0.0558 (19) | 0.063 (2) | 0.058 (2) | 0.0059 (17) | 0.0250 (16) | 0.0111 (18) |
N3 | 0.090 (3) | 0.134 (5) | 0.135 (5) | −0.034 (3) | 0.056 (3) | −0.008 (4) |
C1 | 0.067 (2) | 0.046 (2) | 0.0397 (18) | −0.0006 (19) | 0.0131 (17) | −0.0003 (17) |
C2 | 0.061 (2) | 0.062 (3) | 0.052 (2) | 0.000 (2) | 0.0177 (18) | 0.002 (2) |
C3 | 0.062 (3) | 0.072 (3) | 0.060 (2) | −0.016 (2) | 0.016 (2) | −0.005 (2) |
C4 | 0.083 (3) | 0.066 (3) | 0.053 (2) | −0.011 (3) | 0.017 (2) | −0.011 (2) |
C5 | 0.077 (3) | 0.068 (3) | 0.062 (2) | −0.003 (2) | 0.033 (2) | −0.008 (2) |
C6 | 0.064 (2) | 0.057 (3) | 0.051 (2) | −0.011 (2) | 0.0166 (19) | −0.001 (2) |
C7 | 0.067 (3) | 0.098 (4) | 0.081 (3) | −0.004 (3) | 0.034 (3) | 0.000 (3) |
C8 | 0.070 (2) | 0.043 (2) | 0.0395 (18) | 0.0030 (19) | 0.0178 (17) | 0.0009 (17) |
C9 | 0.053 (2) | 0.066 (3) | 0.052 (2) | −0.006 (2) | 0.0109 (17) | 0.004 (2) |
C10 | 0.064 (2) | 0.069 (3) | 0.057 (2) | 0.016 (2) | 0.031 (2) | 0.006 (2) |
C11 | 0.072 (2) | 0.037 (2) | 0.0418 (19) | 0.0100 (19) | 0.0188 (18) | 0.0013 (17) |
C12 | 0.059 (2) | 0.050 (3) | 0.050 (2) | −0.0033 (19) | 0.0187 (17) | −0.0012 (18) |
C13 | 0.056 (2) | 0.051 (3) | 0.051 (2) | 0.0013 (19) | 0.0239 (17) | −0.0018 (19) |
C14 | 0.119 (4) | 0.051 (3) | 0.049 (2) | 0.012 (3) | 0.022 (2) | −0.006 (2) |
Geometric parameters (Å, º) top
S1—C7 | 1.690 (6) | C6—H6 | 0.93 |
S1—C2 | 1.785 (4) | C10—C9 | 1.393 (6) |
N1—N2 | 1.208 (4) | C10—H10 | 0.93 |
N1—C1 | 1.452 (5) | C9—H9 | 0.93 |
N2—C8 | 1.475 (5) | C3—C4 | 1.362 (6) |
C8—C13 | 1.367 (5) | C3—C2 | 1.385 (6) |
C8—C9 | 1.387 (6) | C3—H3 | 0.93 |
C1—C6 | 1.374 (6) | C12—H12 | 0.93 |
C1—C2 | 1.389 (6) | C5—C4 | 1.378 (6) |
C11—C12 | 1.373 (5) | C5—H5 | 0.93 |
C11—C10 | 1.390 (6) | C4—H4 | 0.93 |
C11—C14 | 1.502 (6) | C14—H14A | 0.96 |
C13—C12 | 1.370 (6) | C14—H14B | 0.96 |
C13—H13 | 0.93 | C14—H14C | 0.96 |
C6—C5 | 1.385 (6) | C7—N3 | 1.123 (6) |
| | | |
C7—S1—C2 | 100.0 (2) | C10—C9—H9 | 120.6 |
N2—N1—C1 | 112.2 (3) | C4—C3—C2 | 119.6 (4) |
N1—N2—C8 | 111.2 (3) | C4—C3—H3 | 120.2 |
C13—C8—C9 | 120.4 (4) | C2—C3—H3 | 120.2 |
C13—C8—N2 | 114.8 (3) | C3—C2—C1 | 119.6 (4) |
C9—C8—N2 | 124.8 (4) | C3—C2—S1 | 125.0 (3) |
C6—C1—C2 | 120.4 (4) | C1—C2—S1 | 115.5 (3) |
C6—C1—N1 | 128.3 (4) | C13—C12—C11 | 122.1 (4) |
C2—C1—N1 | 111.4 (4) | C13—C12—H12 | 118.9 |
C12—C11—C10 | 117.8 (4) | C11—C12—H12 | 118.9 |
C12—C11—C14 | 122.0 (4) | C4—C5—C6 | 119.3 (4) |
C10—C11—C14 | 120.2 (4) | C4—C5—H5 | 120.4 |
C8—C13—C12 | 119.7 (4) | C6—C5—H5 | 120.4 |
C8—C13—H13 | 120.1 | C3—C4—C5 | 121.5 (4) |
C12—C13—H13 | 120.1 | C3—C4—H4 | 119.3 |
C1—C6—C5 | 119.8 (4) | C5—C4—H4 | 119.3 |
C1—C6—H6 | 120.1 | C11—C14—H14A | 109.5 |
C5—C6—H6 | 120.1 | C11—C14—H14B | 109.5 |
C11—C10—C9 | 121.1 (4) | H14A—C14—H14B | 109.5 |
C11—C10—H10 | 119.5 | C11—C14—H14C | 109.5 |
C9—C10—H10 | 119.5 | H14A—C14—H14C | 109.5 |
C8—C9—C10 | 118.8 (4) | H14B—C14—H14C | 109.5 |
C8—C9—H9 | 120.6 | N3—C7—S1 | 176.3 (6) |
| | | |
C1—N1—N2—C8 | 179.7 (3) | C4—C3—C2—C1 | −0.1 (7) |
N1—N2—C8—C13 | −179.1 (4) | C4—C3—C2—S1 | −179.9 (4) |
N1—N2—C8—C9 | 2.0 (6) | C6—C1—C2—C3 | 0.2 (7) |
N2—N1—C1—C6 | 2.7 (6) | N1—C1—C2—C3 | −178.9 (4) |
N2—N1—C1—C2 | −178.3 (4) | C6—C1—C2—S1 | −180.0 (3) |
C9—C8—C13—C12 | −1.5 (6) | N1—C1—C2—S1 | 0.9 (5) |
N2—C8—C13—C12 | 179.5 (3) | C7—S1—C2—C3 | −3.8 (5) |
C2—C1—C6—C5 | 0.3 (7) | C7—S1—C2—C1 | 176.4 (4) |
N1—C1—C6—C5 | 179.3 (4) | C8—C13—C12—C11 | 0.8 (6) |
C12—C11—C10—C9 | −0.8 (6) | C10—C11—C12—C13 | 0.3 (6) |
C14—C11—C10—C9 | 179.6 (4) | C14—C11—C12—C13 | 179.9 (4) |
C13—C8—C9—C10 | 1.0 (6) | C1—C6—C5—C4 | −1.0 (7) |
N2—C8—C9—C10 | 179.9 (4) | C2—C3—C4—C5 | −0.5 (8) |
C11—C10—C9—C8 | 0.2 (6) | C6—C5—C4—C3 | 1.1 (8) |
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