A new polymorph of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole, C
12H
8N
4S, obtained under hydrothermal conditions, is described. In this structure, the two terminal pyridyl groups are inclined to the central thiadiazole ring with dihedral angles of 6.47 (2) and 29.95 (5)°, and the dihedral angle between the pyridyl ring planes is 23.65 (6)°. An intermolecular C—H
N weak interaction is observed. The structural differences of two polymorphs of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole are also discussed.
Supporting information
CCDC reference: 282698
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.101
- Data-to-parameter ratio = 12.0
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.770 1.000
Tmin(prime) and Tmax expected: 0.917 0.978
RR(prime) = 0.821
Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.82
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: APEX-II (Bruker, 2003); cell refinement: APEX-II; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
2,5-bis(4-pyridyl)-1,3,4-thiadiazole
top
Crystal data top
C12H8N4S | F(000) = 496 |
Mr = 240.28 | Dx = 1.504 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1940 reflections |
a = 13.395 (2) Å | θ = 3.2–27.3° |
b = 7.1833 (11) Å | µ = 0.28 mm−1 |
c = 11.4151 (18) Å | T = 293 K |
β = 104.948 (2)° | Lamellar, pale yellow |
V = 1061.2 (3) Å3 | 0.30 × 0.24 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker APEX-II CCD area-detector diffractometer | 1862 independent reflections |
Radiation source: fine-focus sealed tube | 1515 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→15 |
Tmin = 0.770, Tmax = 1.000 | k = −8→4 |
5414 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0679P)2 + 0.0172P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1862 reflections | Δρmax = 0.23 e Å−3 |
155 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.009 (2) |
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 | 0.70555 (3) | 0.13019 (6) | 0.87463 (4) | 0.0411 (2) | |
N1 | 1.11893 (11) | 0.1743 (2) | 0.93303 (14) | 0.0464 (4) | |
N2 | 0.75023 (11) | 0.1460 (2) | 0.67143 (14) | 0.0462 (4) | |
N3 | 0.64493 (12) | 0.1409 (2) | 0.64481 (14) | 0.0472 (4) | |
N4 | 0.28675 (12) | 0.1179 (2) | 0.71677 (16) | 0.0506 (4) | |
C1 | 0.97174 (13) | 0.0817 (2) | 0.77593 (15) | 0.0390 (4) | |
H1 | 0.9461 | 0.0253 | 0.7008 | 0.047* | |
C2 | 1.07654 (13) | 0.0957 (3) | 0.82551 (17) | 0.0432 (5) | |
H2 | 1.1204 | 0.0477 | 0.7818 | 0.052* | |
C3 | 1.05425 (13) | 0.2411 (2) | 0.99306 (16) | 0.0453 (5) | |
H3 | 1.0821 | 0.2961 | 1.0681 | 0.054* | |
C4 | 0.94792 (13) | 0.2340 (2) | 0.95096 (15) | 0.0404 (4) | |
H4 | 0.9060 | 0.2830 | 0.9968 | 0.048* | |
C5 | 0.90482 (13) | 0.1529 (2) | 0.83938 (15) | 0.0339 (4) | |
C6 | 0.79231 (13) | 0.1427 (2) | 0.78771 (16) | 0.0347 (4) | |
C7 | 0.61030 (13) | 0.1342 (2) | 0.74097 (15) | 0.0354 (4) | |
C8 | 0.49930 (12) | 0.1287 (2) | 0.73569 (16) | 0.0355 (4) | |
C9 | 0.46184 (15) | 0.1391 (2) | 0.83724 (18) | 0.0462 (5) | |
H9 | 0.5069 | 0.1503 | 0.9140 | 0.055* | |
C10 | 0.35611 (15) | 0.1328 (3) | 0.82321 (18) | 0.0510 (5) | |
H10 | 0.3321 | 0.1394 | 0.8926 | 0.061* | |
C11 | 0.32375 (14) | 0.1087 (3) | 0.61987 (18) | 0.0472 (5) | |
H11 | 0.2767 | 0.0991 | 0.5444 | 0.057* | |
C12 | 0.42750 (14) | 0.1123 (2) | 0.62359 (17) | 0.0420 (4) | |
H12 | 0.4491 | 0.1040 | 0.5526 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0303 (3) | 0.0582 (3) | 0.0354 (3) | 0.00014 (18) | 0.00981 (19) | 0.00226 (19) |
N1 | 0.0340 (8) | 0.0565 (9) | 0.0473 (9) | −0.0046 (7) | 0.0081 (7) | 0.0035 (7) |
N2 | 0.0293 (8) | 0.0719 (11) | 0.0374 (8) | −0.0008 (7) | 0.0085 (7) | −0.0038 (7) |
N3 | 0.0293 (8) | 0.0738 (11) | 0.0384 (8) | −0.0022 (7) | 0.0085 (7) | −0.0042 (7) |
N4 | 0.0335 (9) | 0.0587 (10) | 0.0617 (11) | −0.0001 (7) | 0.0162 (8) | 0.0020 (8) |
C1 | 0.0380 (10) | 0.0451 (9) | 0.0355 (9) | −0.0012 (8) | 0.0124 (7) | −0.0013 (7) |
C2 | 0.0329 (10) | 0.0542 (11) | 0.0455 (11) | 0.0020 (8) | 0.0155 (8) | 0.0032 (8) |
C3 | 0.0401 (10) | 0.0525 (11) | 0.0399 (10) | −0.0071 (8) | 0.0041 (8) | −0.0018 (8) |
C4 | 0.0382 (10) | 0.0443 (10) | 0.0403 (9) | −0.0003 (7) | 0.0131 (7) | −0.0036 (7) |
C5 | 0.0293 (9) | 0.0365 (9) | 0.0367 (9) | −0.0014 (6) | 0.0096 (7) | 0.0031 (7) |
C6 | 0.0304 (9) | 0.0378 (9) | 0.0370 (9) | −0.0002 (7) | 0.0107 (7) | −0.0017 (7) |
C7 | 0.0303 (9) | 0.0390 (9) | 0.0375 (9) | 0.0009 (7) | 0.0097 (7) | −0.0024 (7) |
C8 | 0.0293 (9) | 0.0344 (9) | 0.0433 (10) | 0.0005 (7) | 0.0100 (8) | −0.0016 (7) |
C9 | 0.0374 (10) | 0.0601 (12) | 0.0419 (10) | −0.0019 (8) | 0.0112 (8) | −0.0043 (8) |
C10 | 0.0427 (11) | 0.0654 (13) | 0.0513 (12) | −0.0027 (9) | 0.0239 (10) | −0.0040 (9) |
C11 | 0.0327 (10) | 0.0577 (12) | 0.0489 (11) | 0.0020 (8) | 0.0062 (8) | 0.0027 (9) |
C12 | 0.0342 (10) | 0.0527 (11) | 0.0397 (10) | 0.0032 (7) | 0.0106 (8) | 0.0026 (8) |
Geometric parameters (Å, º) top
S1—C6 | 1.7141 (17) | C3—H3 | 0.9300 |
S1—C7 | 1.7182 (18) | C4—C5 | 1.384 (2) |
N1—C3 | 1.325 (2) | C4—H4 | 0.9300 |
N1—C2 | 1.337 (2) | C5—C6 | 1.472 (2) |
N2—C6 | 1.302 (2) | C7—C8 | 1.473 (2) |
N2—N3 | 1.365 (2) | C8—C9 | 1.379 (3) |
N3—C7 | 1.298 (2) | C8—C12 | 1.393 (2) |
N4—C11 | 1.325 (3) | C9—C10 | 1.384 (3) |
N4—C10 | 1.330 (3) | C9—H9 | 0.9300 |
C1—C2 | 1.375 (2) | C10—H10 | 0.9300 |
C1—C5 | 1.387 (2) | C11—C12 | 1.379 (3) |
C1—H1 | 0.9300 | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.382 (2) | | |
| | | |
C6—S1—C7 | 86.79 (8) | N2—C6—S1 | 114.29 (14) |
C3—N1—C2 | 116.62 (16) | C5—C6—S1 | 123.21 (13) |
C6—N2—N3 | 112.18 (15) | N3—C7—C8 | 122.92 (16) |
C7—N3—N2 | 112.76 (15) | N3—C7—S1 | 113.96 (13) |
C11—N4—C10 | 116.29 (16) | C8—C7—S1 | 123.12 (13) |
C2—C1—C5 | 119.13 (16) | C9—C8—C12 | 117.51 (16) |
C2—C1—H1 | 120.4 | C9—C8—C7 | 123.13 (16) |
C5—C1—H1 | 120.4 | C12—C8—C7 | 119.36 (16) |
N1—C2—C1 | 123.72 (17) | C8—C9—C10 | 118.96 (18) |
N1—C2—H2 | 118.1 | C8—C9—H9 | 120.5 |
C1—C2—H2 | 118.1 | C10—C9—H9 | 120.5 |
N1—C3—C4 | 124.03 (17) | N4—C10—C9 | 124.13 (18) |
N1—C3—H3 | 118.0 | N4—C10—H10 | 117.9 |
C4—C3—H3 | 118.0 | C9—C10—H10 | 117.9 |
C3—C4—C5 | 118.91 (16) | N4—C11—C12 | 124.33 (17) |
C3—C4—H4 | 120.5 | N4—C11—H11 | 117.8 |
C5—C4—H4 | 120.5 | C12—C11—H11 | 117.8 |
C4—C5—C1 | 117.60 (16) | C11—C12—C8 | 118.76 (17) |
C4—C5—C6 | 122.05 (15) | C11—C12—H12 | 120.6 |
C1—C5—C6 | 120.35 (15) | C8—C12—H12 | 120.6 |
N2—C6—C5 | 122.49 (16) | | |
| | | |
C6—N2—N3—C7 | 0.1 (2) | N2—N3—C7—C8 | 179.64 (14) |
C3—N1—C2—C1 | 0.1 (3) | N2—N3—C7—S1 | −0.87 (19) |
C5—C1—C2—N1 | 0.2 (3) | C6—S1—C7—N3 | 1.04 (13) |
C2—N1—C3—C4 | −0.2 (3) | C6—S1—C7—C8 | −179.48 (13) |
N1—C3—C4—C5 | 0.0 (3) | N3—C7—C8—C9 | −173.72 (16) |
C3—C4—C5—C1 | 0.3 (2) | S1—C7—C8—C9 | 6.8 (2) |
C3—C4—C5—C6 | −179.06 (15) | N3—C7—C8—C12 | 6.3 (2) |
C2—C1—C5—C4 | −0.4 (2) | S1—C7—C8—C12 | −173.16 (13) |
C2—C1—C5—C6 | 179.00 (15) | C12—C8—C9—C10 | 0.0 (2) |
N3—N2—C6—C5 | −178.05 (14) | C7—C8—C9—C10 | −179.97 (15) |
N3—N2—C6—S1 | 0.71 (18) | C11—N4—C10—C9 | 0.1 (3) |
C4—C5—C6—N2 | 149.13 (17) | C8—C9—C10—N4 | −0.3 (3) |
C1—C5—C6—N2 | −30.2 (2) | C10—N4—C11—C12 | 0.5 (3) |
C4—C5—C6—S1 | −29.5 (2) | N4—C11—C12—C8 | −0.7 (3) |
C1—C5—C6—S1 | 151.11 (14) | C9—C8—C12—C11 | 0.4 (2) |
C7—S1—C6—N2 | −0.98 (13) | C7—C8—C12—C11 | −179.56 (15) |
C7—S1—C6—C5 | 177.77 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N4i | 0.93 | 2.57 | 3.361 (3) | 143 |
Symmetry code: (i) x+1, y, z. |