Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017699/ob1085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017699/ob1085Isup2.hkl |
CCDC reference: 199429
Compound (I) was prepared by refluxing a methanolic solution of di-2-pyridyl ketone (0.184 g, 1 mmol) with pyrrolidine-1-thiocarboxylic acid hydrazide (0.145 g, 1 mmol) and glacial acetic acid (3 drops) for 3 h. The needle-shaped yellow crystals which separated on cooling were filtered and washed with ethanol. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a methanolic solution. Elemental anaylsis, found (calculated): C 62.10 (62.71), H 5.56 (5.50), N 22.43 (22.49)%.
H atoms were geometrically fixed and treated as riding atoms on the parent C and N atoms, with C—H distances in the range 0.93–0.97 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C, N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C16H17N5S | Z = 4 |
Mr = 311.41 | F(000) = 656 |
Triclinic, P1 | Dx = 1.329 Mg m−3 |
a = 9.0068 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.2034 (8) Å | Cell parameters from 2342 reflections |
c = 15.8750 (12) Å | θ = 2.6–28.3° |
α = 103.753 (2)° | µ = 0.21 mm−1 |
β = 90.361 (2)° | T = 293 K |
γ = 90.392 (1)° | Block, orange |
V = 1555.9 (2) Å3 | 0.5 × 0.4 × 0.3 mm |
Siemens SMART CCD area-detector diffractometer | 7299 independent reflections |
Radiation source: fine-focus sealed tube | 4123 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.6° |
ω scans | h = −12→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −14→12 |
Tmin = 0.901, Tmax = 0.939 | l = −21→17 |
9895 measured reflections |
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)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0522P)2 + 1.3792P] where P = (Fo2 + 2Fc2)/3 |
7299 reflections | (Δ/σ)max < 0.001 |
407 parameters | Δρmax = 0.29 e Å−3 |
2 restraints | Δρmin = −0.26 e Å−3 |
C16H17N5S | γ = 90.392 (1)° |
Mr = 311.41 | V = 1555.9 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.0068 (7) Å | Mo Kα radiation |
b = 11.2034 (8) Å | µ = 0.21 mm−1 |
c = 15.8750 (12) Å | T = 293 K |
α = 103.753 (2)° | 0.5 × 0.4 × 0.3 mm |
β = 90.361 (2)° |
Siemens SMART CCD area-detector diffractometer | 7299 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4123 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.939 | Rint = 0.027 |
9895 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 2 restraints |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.29 e Å−3 |
7299 reflections | Δρmin = −0.26 e Å−3 |
407 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1A | 0.24904 (11) | 0.13556 (8) | 0.49540 (7) | 0.0486 (3) | |
C4A | −0.0523 (4) | 0.3447 (3) | 0.3265 (2) | 0.0446 (9) | |
H4AA | −0.0639 | 0.3004 | 0.3687 | 0.053* | |
N2A | 0.3176 (3) | 0.6097 (2) | 0.50737 (18) | 0.0385 (7) | |
N3A | 0.1811 (3) | 0.3692 (2) | 0.44349 (17) | 0.0341 (6) | |
N4A | 0.2692 (3) | 0.3802 (2) | 0.51489 (17) | 0.0375 (7) | |
H4AB | 0.3031 | 0.4512 | 0.5416 | 0.045* | |
N5A | 0.3875 (3) | 0.3041 (3) | 0.61600 (18) | 0.0434 (7) | |
C3A | −0.1393 (4) | 0.3179 (4) | 0.2524 (2) | 0.0543 (10) | |
H3AB | −0.2106 | 0.2557 | 0.2442 | 0.065* | |
C2A | −0.1192 (5) | 0.3842 (4) | 0.1915 (3) | 0.0596 (12) | |
H2AB | −0.1773 | 0.3690 | 0.1414 | 0.071* | |
C1A | −0.0112 (6) | 0.4739 (4) | 0.2061 (2) | 0.0618 (12) | |
H1AA | 0.0039 | 0.5173 | 0.1636 | 0.074* | |
N1A | 0.0742 (4) | 0.5029 (3) | 0.27790 (19) | 0.0505 (8) | |
C5A | 0.0518 (4) | 0.4376 (3) | 0.3372 (2) | 0.0352 (8) | |
C6A | 0.1492 (3) | 0.4663 (3) | 0.41616 (19) | 0.0294 (7) | |
C7A | 0.1956 (4) | 0.5944 (3) | 0.4556 (2) | 0.0315 (7) | |
C8A | 0.1147 (4) | 0.6943 (3) | 0.4439 (2) | 0.0384 (8) | |
H8AA | 0.0306 | 0.6825 | 0.4085 | 0.046* | |
C9A | 0.1607 (4) | 0.8114 (3) | 0.4853 (2) | 0.0454 (9) | |
H9AA | 0.1069 | 0.8793 | 0.4789 | 0.054* | |
C10A | 0.2864 (4) | 0.8266 (3) | 0.5359 (3) | 0.0499 (10) | |
H10A | 0.3208 | 0.9048 | 0.5632 | 0.060* | |
C11A | 0.3599 (4) | 0.7244 (3) | 0.5453 (2) | 0.0476 (9) | |
H11A | 0.4446 | 0.7353 | 0.5802 | 0.057* | |
C12A | 0.3042 (4) | 0.2780 (3) | 0.5444 (2) | 0.0360 (8) | |
C13A | 0.4499 (5) | 0.2082 (4) | 0.6547 (3) | 0.0559 (11) | |
H13A | 0.5022 | 0.1471 | 0.6118 | 0.067* | |
H13B | 0.3726 | 0.1676 | 0.6802 | 0.067* | |
C14A | 0.5544 (6) | 0.2780 (5) | 0.7228 (3) | 0.0854 (16) | |
H14A | 0.5562 | 0.2419 | 0.7727 | 0.103* | |
H14B | 0.6542 | 0.2771 | 0.7001 | 0.103* | |
C15A | 0.4983 (7) | 0.4042 (5) | 0.7474 (3) | 0.0895 (17) | |
H15A | 0.5787 | 0.4620 | 0.7682 | 0.107* | |
H15B | 0.4246 | 0.4122 | 0.7926 | 0.107* | |
C16A | 0.4300 (5) | 0.4276 (4) | 0.6658 (2) | 0.0532 (10) | |
H16A | 0.3439 | 0.4801 | 0.6790 | 0.064* | |
H16B | 0.5012 | 0.4654 | 0.6344 | 0.064* | |
S1B | 0.77432 (12) | 0.32572 (9) | 0.94732 (7) | 0.0497 (3) | |
C4B | 0.4791 (4) | 0.1999 (3) | 1.1507 (2) | 0.0413 (8) | |
H4BA | 0.4942 | 0.2435 | 1.1084 | 0.050* | |
N2B | 0.8171 (3) | −0.1209 (3) | 1.00160 (18) | 0.0400 (7) | |
N3B | 0.7010 (3) | 0.1248 (2) | 1.03527 (18) | 0.0367 (7) | |
N4B | 0.7913 (3) | 0.0941 (2) | 0.96568 (17) | 0.0380 (7) | |
H4BB | 0.8257 | 0.0207 | 0.9502 | 0.046* | |
N5B | 0.9116 (3) | 0.1327 (3) | 0.85051 (18) | 0.0405 (7) | |
C3B | 0.3826 (4) | 0.2426 (3) | 1.2177 (2) | 0.0467 (9) | |
H3BB | 0.3317 | 0.3155 | 1.2212 | 0.056* | |
C2B | 0.3621 (4) | 0.1763 (3) | 1.2796 (2) | 0.0463 (9) | |
H2BB | 0.2958 | 0.2021 | 1.3248 | 0.056* | |
C1B | 0.4427 (4) | 0.0712 (4) | 1.2722 (2) | 0.0499 (10) | |
H1BA | 0.4307 | 0.0275 | 1.3147 | 0.060* | |
N1B | 0.5370 (3) | 0.0273 (3) | 1.20830 (18) | 0.0446 (7) | |
C5B | 0.5534 (3) | 0.0910 (3) | 1.1472 (2) | 0.0319 (7) | |
C6B | 0.6564 (3) | 0.0404 (3) | 1.0736 (2) | 0.0322 (7) | |
C7B | 0.6931 (4) | −0.0921 (3) | 1.0489 (2) | 0.0333 (7) | |
C8B | 0.6039 (4) | −0.1824 (3) | 1.0684 (2) | 0.0424 (9) | |
H8BA | 0.5169 | −0.1614 | 1.0996 | 0.051* | |
C9B | 0.6442 (5) | −0.3035 (3) | 1.0415 (3) | 0.0542 (10) | |
H9BA | 0.5851 | −0.3652 | 1.0543 | 0.065* | |
C10B | 0.7730 (5) | −0.3323 (4) | 0.9955 (3) | 0.0581 (11) | |
H10B | 0.8040 | −0.4134 | 0.9779 | 0.070* | |
C11B | 0.8545 (4) | −0.2387 (4) | 0.9763 (3) | 0.0511 (10) | |
H11B | 0.9404 | −0.2585 | 0.9439 | 0.061* | |
C12B | 0.8283 (4) | 0.1793 (3) | 0.9196 (2) | 0.0370 (8) | |
C13B | 0.9658 (5) | 0.2058 (4) | 0.7913 (3) | 0.0556 (11) | |
H13E | 1.0576 | 0.2469 | 0.8118 | 0.067* | 0.684 (19) |
H13F | 0.8939 | 0.2652 | 0.7836 | 0.067* | 0.684 (19) |
H13C | 1.0161 | 0.2786 | 0.8231 | 0.067* | 0.316 (19) |
H13D | 0.8857 | 0.2290 | 0.7585 | 0.067* | 0.316 (19) |
C14B | 1.082 (2) | 0.1260 (16) | 0.7404 (14) | 0.060 (6) | 0.316 (19) |
H14C | 1.0848 | 0.1375 | 0.6818 | 0.072* | 0.316 (19) |
H14D | 1.1784 | 0.1464 | 0.7673 | 0.072* | 0.316 (19) |
C14C | 0.9950 (15) | 0.1081 (7) | 0.7086 (5) | 0.068 (3) | 0.684 (19) |
H14E | 0.9056 | 0.0897 | 0.6734 | 0.082* | 0.684 (19) |
H14F | 1.0722 | 0.1348 | 0.6747 | 0.082* | 0.684 (19) |
C15B | 1.0426 (6) | 0.0006 (5) | 0.7391 (3) | 0.0831 (16) | |
H15E | 1.0259 | −0.0758 | 0.6975 | 0.100* | 0.684 (19) |
H15F | 1.1471 | 0.0101 | 0.7514 | 0.100* | 0.684 (19) |
H15C | 1.1353 | −0.0409 | 0.7400 | 0.100* | 0.316 (19) |
H15D | 0.9862 | −0.0421 | 0.6894 | 0.100* | 0.316 (19) |
C16B | 0.9585 (4) | 0.0040 (3) | 0.8218 (2) | 0.0444 (9) | |
H16C | 0.8732 | −0.0511 | 0.8108 | 0.053* | |
H16D | 1.0220 | −0.0188 | 0.8649 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0605 (6) | 0.0325 (5) | 0.0564 (6) | −0.0019 (4) | −0.0033 (5) | 0.0180 (4) |
C4A | 0.046 (2) | 0.048 (2) | 0.039 (2) | −0.0014 (18) | −0.0016 (17) | 0.0105 (17) |
N2A | 0.0368 (16) | 0.0331 (16) | 0.0455 (17) | −0.0001 (13) | −0.0029 (14) | 0.0092 (13) |
N3A | 0.0367 (15) | 0.0336 (15) | 0.0325 (15) | 0.0021 (12) | 0.0003 (13) | 0.0088 (12) |
N4A | 0.0453 (17) | 0.0283 (15) | 0.0385 (17) | −0.0008 (13) | −0.0077 (14) | 0.0076 (12) |
N5A | 0.0503 (18) | 0.0438 (18) | 0.0402 (17) | 0.0058 (15) | −0.0058 (15) | 0.0181 (14) |
C3A | 0.053 (2) | 0.057 (3) | 0.046 (2) | −0.004 (2) | −0.007 (2) | −0.002 (2) |
C2A | 0.073 (3) | 0.058 (3) | 0.039 (2) | 0.022 (2) | −0.015 (2) | −0.005 (2) |
C1A | 0.109 (4) | 0.048 (2) | 0.031 (2) | 0.014 (3) | −0.006 (2) | 0.0131 (18) |
N1A | 0.082 (2) | 0.0373 (17) | 0.0339 (17) | −0.0005 (16) | −0.0012 (16) | 0.0121 (14) |
C5A | 0.045 (2) | 0.0279 (17) | 0.0310 (18) | 0.0071 (15) | 0.0022 (15) | 0.0034 (14) |
C6A | 0.0325 (17) | 0.0266 (16) | 0.0291 (17) | 0.0032 (13) | 0.0047 (14) | 0.0065 (13) |
C7A | 0.0352 (18) | 0.0316 (17) | 0.0293 (17) | −0.0005 (14) | 0.0081 (15) | 0.0101 (14) |
C8A | 0.0401 (19) | 0.0342 (19) | 0.041 (2) | 0.0019 (16) | −0.0010 (16) | 0.0098 (16) |
C9A | 0.056 (2) | 0.0306 (19) | 0.052 (2) | 0.0052 (17) | 0.0042 (19) | 0.0148 (17) |
C10A | 0.058 (2) | 0.033 (2) | 0.058 (2) | −0.0122 (18) | −0.001 (2) | 0.0073 (18) |
C11A | 0.044 (2) | 0.045 (2) | 0.052 (2) | −0.0104 (18) | −0.0087 (18) | 0.0069 (18) |
C12A | 0.0358 (19) | 0.0343 (19) | 0.041 (2) | 0.0047 (15) | 0.0067 (16) | 0.0159 (15) |
C13A | 0.058 (3) | 0.060 (3) | 0.060 (3) | 0.007 (2) | −0.007 (2) | 0.035 (2) |
C14A | 0.096 (4) | 0.096 (4) | 0.078 (4) | −0.006 (3) | −0.030 (3) | 0.049 (3) |
C15A | 0.125 (5) | 0.085 (4) | 0.058 (3) | 0.002 (3) | −0.032 (3) | 0.017 (3) |
C16A | 0.062 (3) | 0.054 (2) | 0.042 (2) | 0.001 (2) | −0.0055 (19) | 0.0096 (19) |
S1B | 0.0603 (6) | 0.0350 (5) | 0.0567 (6) | 0.0043 (5) | 0.0055 (5) | 0.0165 (4) |
C4B | 0.052 (2) | 0.037 (2) | 0.0355 (19) | 0.0021 (17) | −0.0028 (17) | 0.0084 (16) |
N2B | 0.0353 (16) | 0.0376 (17) | 0.0463 (18) | 0.0050 (13) | 0.0001 (14) | 0.0085 (14) |
N3B | 0.0386 (16) | 0.0330 (15) | 0.0382 (16) | 0.0012 (13) | 0.0022 (13) | 0.0082 (13) |
N4B | 0.0437 (17) | 0.0304 (15) | 0.0405 (17) | 0.0050 (13) | 0.0088 (14) | 0.0094 (13) |
N5B | 0.0457 (18) | 0.0381 (17) | 0.0398 (17) | −0.0005 (14) | 0.0072 (14) | 0.0132 (13) |
C3B | 0.050 (2) | 0.043 (2) | 0.042 (2) | 0.0112 (18) | −0.0012 (18) | −0.0003 (17) |
C2B | 0.043 (2) | 0.051 (2) | 0.039 (2) | 0.0023 (18) | 0.0043 (17) | −0.0013 (18) |
C1B | 0.060 (3) | 0.055 (2) | 0.035 (2) | 0.007 (2) | 0.0118 (19) | 0.0104 (18) |
N1B | 0.0533 (19) | 0.0472 (18) | 0.0350 (16) | 0.0094 (15) | 0.0054 (15) | 0.0125 (14) |
C5B | 0.0325 (17) | 0.0349 (18) | 0.0272 (17) | −0.0026 (14) | −0.0038 (14) | 0.0056 (14) |
C6B | 0.0328 (18) | 0.0357 (18) | 0.0291 (17) | −0.0009 (14) | −0.0038 (14) | 0.0098 (14) |
C7B | 0.0392 (19) | 0.0343 (18) | 0.0266 (17) | −0.0006 (15) | −0.0078 (15) | 0.0077 (14) |
C8B | 0.049 (2) | 0.040 (2) | 0.039 (2) | −0.0006 (17) | −0.0004 (17) | 0.0105 (16) |
C9B | 0.072 (3) | 0.038 (2) | 0.056 (3) | −0.010 (2) | −0.002 (2) | 0.0176 (19) |
C10B | 0.074 (3) | 0.032 (2) | 0.067 (3) | 0.010 (2) | −0.001 (2) | 0.0083 (19) |
C11B | 0.048 (2) | 0.045 (2) | 0.059 (3) | 0.0108 (19) | 0.0033 (19) | 0.0101 (19) |
C12B | 0.0351 (19) | 0.0364 (19) | 0.041 (2) | −0.0031 (15) | −0.0024 (16) | 0.0124 (16) |
C13B | 0.057 (3) | 0.064 (3) | 0.056 (3) | 0.002 (2) | 0.013 (2) | 0.035 (2) |
C14B | 0.044 (10) | 0.093 (12) | 0.053 (11) | 0.024 (8) | 0.019 (8) | 0.039 (9) |
C14C | 0.068 (7) | 0.095 (6) | 0.053 (5) | 0.018 (5) | 0.014 (4) | 0.038 (4) |
C15B | 0.111 (4) | 0.078 (4) | 0.059 (3) | 0.016 (3) | 0.037 (3) | 0.011 (3) |
C16B | 0.049 (2) | 0.041 (2) | 0.041 (2) | −0.0039 (17) | 0.0036 (17) | 0.0056 (17) |
S1A—C12A | 1.671 (4) | N2B—C7B | 1.348 (4) |
C4A—C5A | 1.376 (5) | N3B—C6B | 1.303 (4) |
C4A—C3A | 1.379 (5) | N3B—N4B | 1.354 (4) |
C4A—H4AA | 0.9300 | N4B—C12B | 1.375 (4) |
N2A—C11A | 1.335 (4) | N4B—H4BB | 0.8600 |
N2A—C7A | 1.353 (4) | N5B—C12B | 1.335 (4) |
N3A—C6A | 1.297 (4) | N5B—C13B | 1.469 (4) |
N3A—N4A | 1.361 (3) | N5B—C16B | 1.471 (4) |
N4A—C12A | 1.374 (4) | C3B—C2B | 1.377 (5) |
N4A—H4AB | 0.8600 | C3B—H3BB | 0.9300 |
N5A—C12A | 1.330 (4) | C2B—C1B | 1.370 (5) |
N5A—C16A | 1.468 (5) | C2B—H2BB | 0.9300 |
N5A—C13A | 1.471 (4) | C1B—N1B | 1.331 (4) |
C3A—C2A | 1.364 (6) | C1B—H1BA | 0.9300 |
C3A—H3AB | 0.9300 | N1B—C5B | 1.343 (4) |
C2A—C1A | 1.372 (6) | C5B—C6B | 1.501 (4) |
C2A—H2AB | 0.9300 | C6B—C7B | 1.482 (4) |
C1A—N1A | 1.344 (5) | C7B—C8B | 1.381 (5) |
C1A—H1AA | 0.9300 | C8B—C9B | 1.374 (5) |
N1A—C5A | 1.338 (4) | C8B—H8BA | 0.9300 |
C5A—C6A | 1.496 (4) | C9B—C10B | 1.373 (6) |
C6A—C7A | 1.479 (4) | C9B—H9BA | 0.9300 |
C7A—C8A | 1.388 (4) | C10B—C11B | 1.370 (5) |
C8A—C9A | 1.380 (5) | C10B—H10B | 0.9300 |
C8A—H8AA | 0.9300 | C11B—H11B | 0.9300 |
C9A—C10A | 1.370 (5) | C13B—C14B | 1.489 (14) |
C9A—H9AA | 0.9300 | C13B—C14C | 1.522 (7) |
C10A—C11A | 1.365 (5) | C13B—H13E | 0.9599 |
C10A—H10A | 0.9300 | C13B—H13F | 0.9599 |
C11A—H11A | 0.9300 | C13B—H13C | 0.9598 |
C13A—C14A | 1.498 (6) | C13B—H13D | 0.9601 |
C13A—H13A | 0.9700 | C14B—C15B | 1.440 (18) |
C13A—H13B | 0.9700 | C14B—H13E | 1.5635 |
C14A—C15A | 1.468 (7) | C14B—H14C | 0.9700 |
C14A—H14A | 0.9700 | C14B—H14D | 0.9700 |
C14A—H14B | 0.9700 | C14B—H15F | 1.4767 |
C15A—C16A | 1.509 (5) | C14C—C15B | 1.466 (7) |
C15A—H15A | 0.9700 | C14C—H14E | 0.9700 |
C15A—H15B | 0.9700 | C14C—H14F | 0.9700 |
C16A—H16A | 0.9700 | C15B—C16B | 1.512 (5) |
C16A—H16B | 0.9700 | C15B—H15E | 0.9598 |
S1B—C12B | 1.670 (3) | C15B—H15F | 0.9600 |
C4B—C3B | 1.375 (5) | C15B—H15C | 0.9601 |
C4B—C5B | 1.385 (4) | C15B—H15D | 0.9599 |
C4B—H4BA | 0.9300 | C16B—H16C | 0.9700 |
N2B—C11B | 1.331 (4) | C16B—H16D | 0.9700 |
C5A—C4A—C3A | 119.3 (3) | C4B—C5B—C6B | 120.3 (3) |
C5A—C4A—H4AA | 120.4 | N3B—C6B—C7B | 126.7 (3) |
C3A—C4A—H4AA | 120.4 | N3B—C6B—C5B | 111.9 (3) |
C11A—N2A—C7A | 117.8 (3) | C7B—C6B—C5B | 121.3 (3) |
C6A—N3A—N4A | 119.4 (3) | N2B—C7B—C8B | 121.1 (3) |
N3A—N4A—C12A | 120.0 (3) | N2B—C7B—C6B | 115.6 (3) |
N3A—N4A—H4AB | 120.0 | C8B—C7B—C6B | 123.2 (3) |
C12A—N4A—H4AB | 120.0 | C9B—C8B—C7B | 119.6 (4) |
C12A—N5A—C16A | 126.0 (3) | C9B—C8B—H8BA | 120.2 |
C12A—N5A—C13A | 122.5 (3) | C7B—C8B—H8BA | 120.2 |
C16A—N5A—C13A | 111.5 (3) | C10B—C9B—C8B | 119.2 (4) |
C2A—C3A—C4A | 119.0 (4) | C10B—C9B—H9BA | 120.4 |
C2A—C3A—H3AB | 120.5 | C8B—C9B—H9BA | 120.4 |
C4A—C3A—H3AB | 120.5 | C11B—C10B—C9B | 118.3 (4) |
C3A—C2A—C1A | 118.3 (4) | C11B—C10B—H10B | 120.8 |
C3A—C2A—H2AB | 120.8 | C9B—C10B—H10B | 120.8 |
C1A—C2A—H2AB | 120.8 | N2B—C11B—C10B | 123.4 (4) |
N1A—C1A—C2A | 124.1 (4) | N2B—C11B—H11B | 118.3 |
N1A—C1A—H1AA | 118.0 | C10B—C11B—H11B | 118.3 |
C2A—C1A—H1AA | 118.0 | N5B—C12B—N4B | 112.9 (3) |
C5A—N1A—C1A | 116.6 (3) | N5B—C12B—S1B | 123.7 (2) |
N1A—C5A—C4A | 122.7 (3) | N4B—C12B—S1B | 123.4 (3) |
N1A—C5A—C6A | 117.2 (3) | N5B—C13B—C14B | 103.2 (6) |
C4A—C5A—C6A | 120.1 (3) | N5B—C13B—C14C | 102.5 (4) |
N3A—C6A—C7A | 127.1 (3) | C14B—C13B—C14C | 35.6 (7) |
N3A—C6A—C5A | 112.4 (3) | N5B—C13B—H13E | 111.3 |
C7A—C6A—C5A | 120.5 (3) | C14B—C13B—H13E | 75.9 |
N2A—C7A—C8A | 121.3 (3) | C14C—C13B—H13E | 109.0 |
N2A—C7A—C6A | 116.6 (3) | N5B—C13B—H13F | 111.3 |
C8A—C7A—C6A | 122.0 (3) | C14B—C13B—H13F | 139.2 |
C9A—C8A—C7A | 119.2 (3) | C14C—C13B—H13F | 113.2 |
C9A—C8A—H8AA | 120.4 | H13E—C13B—H13F | 109.4 |
C7A—C8A—H8AA | 120.4 | N5B—C13B—H13C | 110.5 |
C10A—C9A—C8A | 119.3 (3) | C14B—C13B—H13C | 106.4 |
C10A—C9A—H9AA | 120.3 | C14C—C13B—H13C | 135.7 |
C8A—C9A—H9AA | 120.3 | H13E—C13B—H13C | 31.4 |
C11A—C10A—C9A | 118.5 (3) | H13F—C13B—H13C | 81.5 |
C11A—C10A—H10A | 120.8 | N5B—C13B—H13D | 111.2 |
C9A—C10A—H10A | 120.8 | C14B—C13B—H13D | 116.2 |
N2A—C11A—C10A | 123.9 (3) | C14C—C13B—H13D | 84.3 |
N2A—C11A—H11A | 118.0 | H13E—C13B—H13D | 131.0 |
C10A—C11A—H11A | 118.0 | H13F—C13B—H13D | 30.3 |
N5A—C12A—N4A | 112.9 (3) | H13C—C13B—H13D | 109.1 |
N5A—C12A—S1A | 123.3 (2) | C15B—C14B—C13B | 107.3 (10) |
N4A—C12A—S1A | 123.7 (3) | C15B—C14B—H13E | 130.5 |
N5A—C13A—C14A | 103.4 (3) | C13B—C14B—H13E | 36.6 |
N5A—C13A—H13A | 111.1 | C15B—C14B—H14C | 110.2 |
C14A—C13A—H13A | 111.1 | C13B—C14B—H14C | 110.2 |
N5A—C13A—H13B | 111.1 | H13E—C14B—H14C | 114.3 |
C14A—C13A—H13B | 111.1 | C15B—C14B—H14D | 110.2 |
H13A—C13A—H13B | 109.0 | C13B—C14B—H14D | 110.2 |
C15A—C14A—C13A | 106.1 (4) | H13E—C14B—H14D | 75.0 |
C15A—C14A—H14A | 110.5 | H14C—C14B—H14D | 108.5 |
C13A—C14A—H14A | 110.5 | C15B—C14B—H15F | 38.4 |
C15A—C14A—H14B | 110.5 | C13B—C14B—H15F | 130.9 |
C13A—C14A—H14B | 110.5 | H13E—C14B—H15F | 127.6 |
H14A—C14A—H14B | 108.7 | H14C—C14B—H15F | 114.8 |
C14A—C15A—C16A | 105.5 (4) | H14D—C14B—H15F | 73.0 |
C14A—C15A—H15A | 110.6 | C15B—C14C—C13B | 104.3 (5) |
C16A—C15A—H15A | 110.6 | C15B—C14C—H14E | 110.9 |
C14A—C15A—H15B | 110.6 | C13B—C14C—H14E | 110.9 |
C16A—C15A—H15B | 110.6 | C15B—C14C—H14F | 110.9 |
H15A—C15A—H15B | 108.8 | C13B—C14C—H14F | 110.9 |
N5A—C16A—C15A | 103.3 (3) | H14E—C14C—H14F | 108.9 |
N5A—C16A—H16A | 111.1 | C14B—C15B—C14C | 36.9 (7) |
C15A—C16A—H16A | 111.1 | C14B—C15B—C16B | 106.5 (7) |
N5A—C16A—H16B | 111.1 | C14C—C15B—C16B | 106.5 (4) |
C15A—C16A—H16B | 111.1 | C14B—C15B—H15E | 138.7 |
H16A—C16A—H16B | 109.1 | C14C—C15B—H15E | 113.4 |
C3B—C4B—C5B | 119.1 (3) | C16B—C15B—H15E | 111.0 |
C3B—C4B—H4BA | 120.5 | C14B—C15B—H15F | 72.9 |
C5B—C4B—H4BA | 120.5 | C14C—C15B—H15F | 107.3 |
C11B—N2B—C7B | 118.3 (3) | C16B—C15B—H15F | 110.0 |
C6B—N3B—N4B | 119.7 (3) | H15E—C15B—H15F | 108.6 |
N3B—N4B—C12B | 120.4 (3) | C14B—C15B—H15C | 105.5 |
N3B—N4B—H4BB | 119.8 | C14C—C15B—H15C | 134.6 |
C12B—N4B—H4BB | 119.8 | C16B—C15B—H15C | 110.0 |
C12B—N5B—C13B | 123.2 (3) | H15E—C15B—H15C | 77.3 |
C12B—N5B—C16B | 125.9 (3) | H15F—C15B—H15C | 34.3 |
C13B—N5B—C16B | 111.0 (3) | C14B—C15B—H15D | 115.4 |
C4B—C3B—C2B | 119.4 (3) | C14C—C15B—H15D | 82.1 |
C4B—C3B—H3BB | 120.3 | C16B—C15B—H15D | 110.7 |
C2B—C3B—H3BB | 120.3 | H15E—C15B—H15D | 33.8 |
C1B—C2B—C3B | 117.7 (3) | H15F—C15B—H15D | 133.2 |
C1B—C2B—H2BB | 121.2 | H15C—C15B—H15D | 108.5 |
C3B—C2B—H2BB | 121.2 | N5B—C16B—C15B | 103.8 (3) |
N1B—C1B—C2B | 124.5 (3) | N5B—C16B—H16C | 111.0 |
N1B—C1B—H1BA | 117.7 | C15B—C16B—H16C | 111.0 |
C2B—C1B—H1BA | 117.7 | N5B—C16B—H16D | 111.0 |
C1B—N1B—C5B | 117.3 (3) | C15B—C16B—H16D | 111.0 |
N1B—C5B—C4B | 122.0 (3) | H16C—C16B—H16D | 109.0 |
N1B—C5B—C6B | 117.7 (3) | ||
C6A—N3A—N4A—C12A | −179.8 (3) | C1B—N1B—C5B—C4B | 1.7 (5) |
C5A—C4A—C3A—C2A | 0.3 (6) | C1B—N1B—C5B—C6B | −178.4 (3) |
C4A—C3A—C2A—C1A | 1.0 (6) | C3B—C4B—C5B—N1B | −1.7 (5) |
C3A—C2A—C1A—N1A | −1.7 (6) | C3B—C4B—C5B—C6B | 178.4 (3) |
C2A—C1A—N1A—C5A | 1.1 (6) | N4B—N3B—C6B—C7B | −0.5 (5) |
C1A—N1A—C5A—C4A | 0.3 (5) | N4B—N3B—C6B—C5B | −178.0 (3) |
C1A—N1A—C5A—C6A | 178.1 (3) | N1B—C5B—C6B—N3B | −159.1 (3) |
C3A—C4A—C5A—N1A | −0.9 (5) | C4B—C5B—C6B—N3B | 20.8 (4) |
C3A—C4A—C5A—C6A | −178.8 (3) | N1B—C5B—C6B—C7B | 23.2 (4) |
N4A—N3A—C6A—C7A | −1.7 (5) | C4B—C5B—C6B—C7B | −156.9 (3) |
N4A—N3A—C6A—C5A | 179.9 (3) | C11B—N2B—C7B—C8B | −2.2 (5) |
N1A—C5A—C6A—N3A | −144.6 (3) | C11B—N2B—C7B—C6B | −178.9 (3) |
C4A—C5A—C6A—N3A | 33.4 (4) | N3B—C6B—C7B—N2B | 22.0 (5) |
N1A—C5A—C6A—C7A | 36.9 (4) | C5B—C6B—C7B—N2B | −160.7 (3) |
C4A—C5A—C6A—C7A | −145.2 (3) | N3B—C6B—C7B—C8B | −154.7 (3) |
C11A—N2A—C7A—C8A | −1.5 (5) | C5B—C6B—C7B—C8B | 22.6 (5) |
C11A—N2A—C7A—C6A | −178.6 (3) | N2B—C7B—C8B—C9B | 2.0 (5) |
N3A—C6A—C7A—N2A | 22.3 (5) | C6B—C7B—C8B—C9B | 178.5 (3) |
C5A—C6A—C7A—N2A | −159.4 (3) | C7B—C8B—C9B—C10B | −0.1 (6) |
N3A—C6A—C7A—C8A | −154.7 (3) | C8B—C9B—C10B—C11B | −1.6 (6) |
C5A—C6A—C7A—C8A | 23.6 (4) | C7B—N2B—C11B—C10B | 0.4 (6) |
N2A—C7A—C8A—C9A | 0.5 (5) | C9B—C10B—C11B—N2B | 1.6 (6) |
C6A—C7A—C8A—C9A | 177.4 (3) | C13B—N5B—C12B—N4B | −179.7 (3) |
C7A—C8A—C9A—C10A | 1.1 (5) | C16B—N5B—C12B—N4B | 1.8 (5) |
C8A—C9A—C10A—C11A | −1.7 (6) | C13B—N5B—C12B—S1B | 0.4 (5) |
C7A—N2A—C11A—C10A | 1.0 (5) | C16B—N5B—C12B—S1B | −178.1 (3) |
C9A—C10A—C11A—N2A | 0.7 (6) | N3B—N4B—C12B—N5B | −176.7 (3) |
C16A—N5A—C12A—N4A | 5.4 (5) | N3B—N4B—C12B—S1B | 3.1 (4) |
C13A—N5A—C12A—N4A | −174.2 (3) | C12B—N5B—C13B—C14B | 165.9 (11) |
C16A—N5A—C12A—S1A | −175.0 (3) | C16B—N5B—C13B—C14B | −15.4 (12) |
C13A—N5A—C12A—S1A | 5.4 (5) | C12B—N5B—C13B—C14C | −157.5 (6) |
N3A—N4A—C12A—N5A | −178.2 (3) | C16B—N5B—C13B—C14C | 21.2 (7) |
N3A—N4A—C12A—S1A | 2.2 (4) | N5B—C13B—C14B—C15B | 27.1 (17) |
C12A—N5A—C13A—C14A | 170.5 (4) | C14C—C13B—C14B—C15B | −66.0 (15) |
C16A—N5A—C13A—C14A | −9.2 (4) | N5B—C13B—C14C—C15B | −33.0 (9) |
N5A—C13A—C14A—C15A | 25.8 (5) | C14B—C13B—C14C—C15B | 62.2 (11) |
C13A—C14A—C15A—C16A | −32.9 (6) | C13B—C14B—C15B—C14C | 66.8 (12) |
C12A—N5A—C16A—C15A | 170.0 (4) | C13B—C14B—C15B—C16B | −28.9 (17) |
C13A—N5A—C16A—C15A | −10.4 (5) | C13B—C14C—C15B—C14B | −62.4 (10) |
C14A—C15A—C16A—N5A | 26.3 (5) | C13B—C14C—C15B—C16B | 33.3 (9) |
C6B—N3B—N4B—C12B | 174.0 (3) | C12B—N5B—C16B—C15B | 177.2 (4) |
C5B—C4B—C3B—C2B | 0.0 (5) | C13B—N5B—C16B—C15B | −1.4 (4) |
C4B—C3B—C2B—C1B | 1.5 (5) | C14B—C15B—C16B—N5B | 18.5 (12) |
C3B—C2B—C1B—N1B | −1.5 (6) | C14C—C15B—C16B—N5B | −20.1 (7) |
C2B—C1B—N1B—C5B | −0.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AB···N2A | 0.86 | 1.98 | 2.636 (3) | 132 |
N4B—H4BB···N2B | 0.86 | 1.95 | 2.616 (3) | 133 |
C2B—H2BB···N3Ai | 0.93 | 2.55 | 3.395 (4) | 152 |
Symmetry code: (i) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H17N5S |
Mr | 311.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.0068 (7), 11.2034 (8), 15.8750 (12) |
α, β, γ (°) | 103.753 (2), 90.361 (2), 90.392 (1) |
V (Å3) | 1555.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.901, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9895, 7299, 4123 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.170, 1.02 |
No. of reflections | 7299 |
No. of parameters | 407 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.26 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
S1A—C12A | 1.671 (4) | S1B—C12B | 1.670 (3) |
N3A—C6A | 1.297 (4) | N3B—C6B | 1.303 (4) |
N3A—N4A | 1.361 (3) | N3B—N4B | 1.354 (4) |
N4A—C12A | 1.374 (4) | N4B—C12B | 1.375 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4A—H4AB···N2A | 0.86 | 1.98 | 2.636 (3) | 132 |
N4B—H4BB···N2B | 0.86 | 1.95 | 2.616 (3) | 133 |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
A great number of studies have been devoted to the search for derivatives of thiosemicarbazides, which have been used as drugs and have the ability to form complexes (Petering & van Giessen, 1965). Thiosemicarbazones of α-N-heterocyclic carbaldehydes act as tridentate ligands. The biological activity of the thiosemicarbazone depends on the parent aldehyde or ketone (Padhye & Kauffman, 1985; Liberta & West, 1992; Lukevics et al., 1995). Among thousands of screened compounds (Klayman et al., 1979), 2-acetylpyridine thiosemicarbazones were the first compounds reported as potent antimalarial agents. Among these, the 2-acetylpyridine thiosemicarbazones of the highest activity are those having the N4 atom disubstituted or as part of the ring system.
As part of our studies of thiosemicarbazones and their metal complexes (Usman et al., 2002), we have now prepared the title quadridentate N3S compound, (I), and analysed its crystal structure. Compound (I) was prepared (Ali & Livingstone, 1974; Campbell, 1975; Livingstone, 1965) by adopting the procedures reported by Scovill (1991). Thiosemicarbazones are reported to exhibit thione-thiol tautomerism in solution. However, the absence of a peak at ca δ 4.0 p.p.m. in the 1H NMR spectrum of (I) indicates that the compound exists as a thione in solution. This fact is supported by the crystallographic data. \sch
There are two crystallographically independent molecules, A and B, in the asymmetric unit of (I), with bond lengths and angles which agree with each other. The values are within normal ranges (Allen et al., 1987). Molecules A and B are related by a local pseudo-twofold rotation axis (Fig. 1). Both molecules show an E configuration about the C6—N3 and C12—N4 bonds relative to the N3—N4 bond. The S and the hydrazine N3 atoms in both molecules are in the Z configuration with respect to the C12—N4 bond. A similar conformation was observed in di-2-pyridylketone thiosemicarbazone (Duan et al., 1996), where the N4 position is unsubstituted.
The C12—S1 and C12—N4 bond distances in both molecules are typical of the C═S double bond and the C—N single bond, respectively (Table 1). The comparison of the N3—N4 bond distance [1.361 (3) Å in molecule A and 1.354 (4) Å in molecule B] with the corresponding distance in di-2-pyridylketone thiosemicarbazone (1.371 Å) is indicative of a single bond and suggests the thione form of (I).
In both molecules of (I), the pentamethyleneimine five-membered ring (N5/C13—C16) is out of planarity and tends towards an envelope conformation. In molecule A, atom C14 deviates by 0.410 (5) Å from the N5/C13/C15/C16 plane. In molecule B, this ring shows disorder, so that in the major and minor configurations, atoms C14B and C14C deviate in opposite directions by 0.382 (2) and 0.543 (2) Å, respectively, from the N5/C13/C15/C16 plane.
In both molecules A and B, the relative configurations of the two pyridyl rings with respect to the planar thiosemicarbazone [S1/N3/N4/C6/C12] are conditioned by the sp2-hybridized C6 atom [average bond angle subtended at C6 is 120.0° in molecule A and 119.8° in molecule B]. The dihedral angles between the thiosemicarbazone and the two pyridyl rings are relatively small [35.8 (1) and 22.7 (2)° in molecule A, and 21.7 (2) and 22.7 (2)° in molecule B], due to a resonance effect between the π systems.
An intramolecular N4—H4···N2 hydrogen bond forms a six-membered N2—C7—C6—N3—N4—H4 ring in both molecules of (I) (Fig. 1 and Table 2). In the packing, the molecules are stacked into molecular columns parallel to the b direction.