Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039966/lh6546sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039966/lh6546Isup2.hkl |
CCDC reference: 296723
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.032
- wR factor = 0.077
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT301_ALERT_3_C Main Residue Disorder ......................... 23.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 17
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 30.00 From the CIF: _reflns_number_total 4232 Count of symmetry unique reflns 2442 Completeness (_total/calc) 173.30% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1790 Fraction of Friedel pairs measured 0.733 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion
A solution containing N-methyl-N-phenyl-3- thiosemicarbazone (1 g, 5.52 m mol) (Klayman et al., 1984), 2-phenyl ethyl amine (0.725 ml, 5.52 mmol) and pyridine-2-carbaldehyde (0.525 ml, 5.52 mmol) in CH3CN (5 ml) was heated under reflux for 1 h. The solution was chilled (overnight), and the crystals that separated were collected and washed well with CH3CN. After recrystallization from ethanol, the sample was dried in vacuo over P4O10. Single crystals of X-ray diffraction quality were prepared by the slow evaporation of an ethanol solution of the title compound (m.p. 436–438 K).
H atoms bonded to atom N2 were located in a difference map and refined isotropically. The remainning H atoms were placed in calculated positions, with C—H distances of 0.93 and 0.97 Å, and N—H distances of 0.90; the Uiso values were constrained to 1.2Ueq of the carrier atom for these H atoms. Please check changes·Please check values for N2 in Table 2; N—H is not quite the same as listed in CIF.
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
C15H16N4S | Dx = 1.305 Mg m−3 |
Mr = 284.39 | Melting point = 436–438 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4238 reflections |
a = 6.7341 (9) Å | θ = 1.7–30.0° |
b = 8.9533 (12) Å | µ = 0.22 mm−1 |
c = 24.003 (3) Å | T = 100 K |
V = 1447.2 (3) Å3 | Rod, colourless |
Z = 4 | 0.43 × 0.19 × 0.13 mm |
F(000) = 600 |
Bruker SMART APEX2 CCD area-detector diffractometer | 4232 independent reflections |
Radiation source: fine-focus sealed tube | 3928 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 8.33 pixels mm-1 | θmax = 30.0°, θmin = 1.7° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −12→12 |
Tmin = 0.951, Tmax = 0.972 | l = −33→33 |
22005 measured reflections |
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 atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0358P)2 + 0.2742P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4232 reflections | Δρmax = 0.29 e Å−3 |
244 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1790 Friedels |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (6) |
C15H16N4S | V = 1447.2 (3) Å3 |
Mr = 284.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7341 (9) Å | µ = 0.22 mm−1 |
b = 8.9533 (12) Å | T = 100 K |
c = 24.003 (3) Å | 0.43 × 0.19 × 0.13 mm |
Bruker SMART APEX2 CCD area-detector diffractometer | 4232 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3928 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.972 | Rint = 0.041 |
22005 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.077 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.19 e Å−3 |
4232 reflections | Absolute structure: Flack (1983), 1790 Friedels |
244 parameters | Absolute structure parameter: 0.02 (6) |
0 restraints |
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) | |
S1 | 0.93075 (5) | 0.37815 (4) | 0.096735 (14) | 0.02657 (8) | |
N3 | 0.46332 (15) | 0.12067 (11) | 0.08177 (4) | 0.01719 (19) | |
N2 | 0.59487 (16) | 0.23788 (11) | 0.07685 (4) | 0.0192 (2) | |
N1 | 0.78624 (16) | 0.12996 (13) | 0.14463 (4) | 0.0205 (2) | |
H1A | 0.7012 | 0.0524 | 0.1448 | 0.025* | 0.433 (11) |
H1B | 0.6837 | 0.0662 | 0.1482 | 0.025* | 0.567 (11) |
N4 | 0.01498 (16) | 0.03506 (11) | 0.00992 (4) | 0.0195 (2) | |
C1 | 0.7680 (2) | 0.20527 (15) | 0.26821 (5) | 0.0229 (3) | |
C2A | 0.5780 (11) | 0.2982 (8) | 0.2721 (4) | 0.0286 (15) | 0.433 (11) |
H2AA | 0.5619 | 0.3808 | 0.2491 | 0.034* | 0.433 (11) |
C3A | 0.4311 (8) | 0.2611 (8) | 0.3092 (4) | 0.0332 (19) | 0.433 (11) |
H3AA | 0.3173 | 0.3198 | 0.3109 | 0.040* | 0.433 (11) |
C4A | 0.4478 (10) | 0.1374 (9) | 0.3447 (3) | 0.0330 (14) | 0.433 (11) |
H4AA | 0.3459 | 0.1123 | 0.3691 | 0.040* | 0.433 (11) |
C5A | 0.6194 (12) | 0.0544 (8) | 0.3422 (3) | 0.0259 (12) | 0.433 (11) |
H5AA | 0.6372 | −0.0273 | 0.3657 | 0.031* | 0.433 (11) |
C7A | 0.9213 (12) | 0.2472 (8) | 0.2316 (3) | 0.0272 (13) | 0.433 (11) |
H7AA | 1.0455 | 0.2526 | 0.2520 | 0.033* | 0.433 (11) |
H7AB | 0.8934 | 0.3456 | 0.2166 | 0.033* | 0.433 (11) |
C8A | 0.942 (2) | 0.1353 (13) | 0.1835 (5) | 0.028 (2) | 0.433 (11) |
H8AA | 1.0639 | 0.1583 | 0.1636 | 0.034* | 0.433 (11) |
H8AB | 0.9578 | 0.0364 | 0.1994 | 0.034* | 0.433 (11) |
C2B | 0.6346 (9) | 0.3069 (6) | 0.2570 (2) | 0.0237 (8) | 0.567 (11) |
H2BA | 0.6592 | 0.3786 | 0.2299 | 0.028* | 0.567 (11) |
C3B | 0.4548 (8) | 0.3073 (7) | 0.2860 (2) | 0.0322 (10) | 0.567 (11) |
H3BA | 0.3587 | 0.3790 | 0.2784 | 0.039* | 0.567 (11) |
C4B | 0.4216 (7) | 0.1984 (8) | 0.3266 (2) | 0.0332 (13) | 0.567 (11) |
H4BA | 0.3026 | 0.1980 | 0.3463 | 0.040* | 0.567 (11) |
C5B | 0.5630 (9) | 0.0919 (7) | 0.3379 (2) | 0.0294 (12) | 0.567 (11) |
H5BA | 0.5386 | 0.0197 | 0.3649 | 0.035* | 0.567 (11) |
C7B | 0.9679 (7) | 0.1997 (6) | 0.2330 (2) | 0.0232 (8) | 0.567 (11) |
H7BA | 1.0011 | 0.3008 | 0.2218 | 0.028* | 0.567 (11) |
H7BB | 1.0735 | 0.1646 | 0.2572 | 0.028* | 0.567 (11) |
C8B | 0.9645 (14) | 0.1015 (9) | 0.1810 (4) | 0.0195 (11) | 0.567 (11) |
H8BA | 1.0842 | 0.1196 | 0.1595 | 0.023* | 0.567 (11) |
H8BB | 0.9650 | −0.0026 | 0.1922 | 0.023* | 0.567 (11) |
C6 | 0.7542 (2) | 0.09118 (14) | 0.30723 (5) | 0.0244 (3) | |
C9 | 0.16035 (18) | 0.01198 (13) | 0.04761 (5) | 0.0166 (2) | |
C10 | 0.16384 (19) | −0.11372 (14) | 0.08238 (5) | 0.0196 (2) | |
H10A | 0.2667 | −0.1278 | 0.1077 | 0.024* | |
C11 | 0.0109 (2) | −0.21646 (14) | 0.07821 (5) | 0.0211 (2) | |
H11A | 0.0101 | −0.3010 | 0.1007 | 0.025* | |
C12 | −0.1415 (2) | −0.19241 (15) | 0.04018 (5) | 0.0221 (3) | |
H12A | −0.2463 | −0.2595 | 0.0370 | 0.027* | |
C13 | −0.1328 (2) | −0.06508 (14) | 0.00691 (5) | 0.0217 (2) | |
H13A | −0.2344 | −0.0487 | −0.0186 | 0.026* | |
C14 | 0.31362 (17) | 0.12807 (14) | 0.04877 (5) | 0.0171 (2) | |
H14A | 0.3021 | 0.2095 | 0.0249 | 0.021* | |
C15 | 0.76441 (19) | 0.24057 (13) | 0.10752 (5) | 0.0190 (2) | |
H6 | 0.865 (3) | 0.023 (2) | 0.3113 (8) | 0.041 (5)* | |
H1N2 | 0.573 (3) | 0.3100 (19) | 0.0516 (6) | 0.029 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02573 (15) | 0.02491 (14) | 0.02908 (15) | −0.01218 (14) | 0.00132 (14) | −0.00302 (13) |
N3 | 0.0183 (5) | 0.0157 (4) | 0.0177 (4) | −0.0030 (4) | 0.0010 (4) | −0.0001 (4) |
N2 | 0.0186 (5) | 0.0175 (5) | 0.0216 (5) | −0.0041 (4) | −0.0005 (4) | 0.0031 (4) |
N1 | 0.0199 (5) | 0.0261 (5) | 0.0156 (4) | −0.0066 (5) | −0.0027 (4) | 0.0004 (4) |
N4 | 0.0195 (5) | 0.0190 (5) | 0.0199 (5) | −0.0005 (4) | −0.0026 (4) | 0.0023 (4) |
C1 | 0.0296 (7) | 0.0224 (6) | 0.0167 (5) | −0.0071 (5) | −0.0096 (5) | 0.0005 (4) |
C2A | 0.024 (4) | 0.0219 (19) | 0.040 (4) | 0.010 (2) | −0.017 (3) | −0.004 (2) |
C3A | 0.018 (3) | 0.032 (4) | 0.049 (5) | 0.011 (3) | −0.015 (4) | −0.020 (3) |
C4A | 0.027 (2) | 0.040 (3) | 0.032 (3) | −0.009 (3) | 0.002 (2) | −0.019 (2) |
C5A | 0.025 (3) | 0.029 (3) | 0.023 (2) | −0.001 (2) | 0.001 (2) | −0.0098 (19) |
C7A | 0.031 (3) | 0.031 (3) | 0.0191 (16) | −0.014 (2) | −0.011 (2) | −0.002 (2) |
C8A | 0.021 (4) | 0.039 (5) | 0.024 (3) | −0.004 (3) | 0.003 (2) | 0.009 (3) |
C2B | 0.023 (2) | 0.0240 (14) | 0.0241 (19) | 0.0021 (15) | −0.0043 (13) | −0.0029 (13) |
C3B | 0.028 (2) | 0.039 (2) | 0.030 (2) | 0.0126 (17) | −0.0092 (18) | −0.0085 (16) |
C4B | 0.0226 (17) | 0.054 (4) | 0.023 (2) | −0.005 (3) | 0.0061 (19) | −0.014 (2) |
C5B | 0.031 (3) | 0.038 (3) | 0.0194 (15) | −0.008 (2) | 0.0080 (19) | −0.0046 (17) |
C7B | 0.0164 (16) | 0.034 (2) | 0.0195 (12) | −0.0035 (14) | −0.0004 (11) | −0.0008 (15) |
C8B | 0.0115 (17) | 0.034 (3) | 0.0128 (14) | 0.0016 (18) | −0.0060 (12) | −0.0033 (18) |
C6 | 0.0368 (8) | 0.0195 (6) | 0.0170 (5) | −0.0005 (6) | −0.0039 (5) | −0.0014 (4) |
C9 | 0.0169 (5) | 0.0169 (5) | 0.0159 (5) | −0.0001 (5) | −0.0005 (4) | 0.0010 (4) |
C10 | 0.0197 (5) | 0.0192 (5) | 0.0198 (5) | −0.0005 (5) | −0.0022 (4) | 0.0041 (4) |
C11 | 0.0238 (6) | 0.0182 (5) | 0.0212 (5) | −0.0029 (5) | 0.0000 (5) | 0.0047 (4) |
C12 | 0.0215 (6) | 0.0210 (6) | 0.0238 (6) | −0.0063 (5) | −0.0012 (5) | 0.0010 (5) |
C13 | 0.0204 (6) | 0.0233 (6) | 0.0214 (5) | −0.0024 (5) | −0.0049 (5) | 0.0022 (5) |
C14 | 0.0183 (5) | 0.0163 (5) | 0.0168 (5) | −0.0009 (5) | 0.0004 (4) | 0.0024 (4) |
C15 | 0.0203 (6) | 0.0203 (5) | 0.0163 (5) | −0.0044 (5) | 0.0010 (4) | −0.0042 (4) |
S1—C15 | 1.6849 (13) | C7A—H7AB | 0.9700 |
N3—C14 | 1.2837 (15) | C8A—H8AA | 0.9700 |
N3—N2 | 1.3783 (14) | C8A—H8AB | 0.9700 |
N2—C15 | 1.3587 (16) | C2B—C3B | 1.396 (5) |
N2—H1N2 | 0.897 (17) | C2B—H2BA | 0.9300 |
N1—C15 | 1.3401 (16) | C3B—C4B | 1.396 (5) |
N1—C8A | 1.407 (13) | C3B—H3BA | 0.9300 |
N1—C8B | 1.506 (8) | C4B—C5B | 1.374 (6) |
N1—H1A | 0.9000 | C4B—H4BA | 0.9300 |
N1—H1B | 0.9000 | C5B—C6 | 1.483 (6) |
N4—C13 | 1.3416 (16) | C5B—H5BA | 0.9300 |
N4—C9 | 1.3488 (16) | C7B—C8B | 1.528 (9) |
C1—C2B | 1.306 (6) | C7B—H7BA | 0.9700 |
C1—C6 | 1.3890 (17) | C7B—H7BB | 0.9700 |
C1—C7A | 1.407 (7) | C8B—H8BA | 0.9700 |
C1—C2A | 1.529 (7) | C8B—H8BB | 0.9700 |
C1—C7B | 1.590 (5) | C6—H6 | 0.97 (2) |
C2A—C3A | 1.371 (8) | C9—C10 | 1.4013 (16) |
C2A—H2AA | 0.9300 | C9—C14 | 1.4651 (17) |
C3A—C4A | 1.401 (7) | C10—C11 | 1.3846 (17) |
C3A—H3AA | 0.9300 | C10—H10A | 0.9300 |
C4A—C5A | 1.376 (7) | C11—C12 | 1.3902 (18) |
C4A—H4AA | 0.9300 | C11—H11A | 0.9300 |
C5A—C6 | 1.280 (8) | C12—C13 | 1.3932 (17) |
C5A—H5AA | 0.9300 | C12—H12A | 0.9300 |
C7A—C8A | 1.535 (12) | C13—H13A | 0.9300 |
C7A—H7AA | 0.9700 | C14—H14A | 0.9300 |
C14—N3—N2 | 114.37 (10) | C2B—C3B—C4B | 119.0 (5) |
C15—N2—N3 | 120.47 (10) | C2B—C3B—H3BA | 120.5 |
C15—N2—H1N2 | 119.3 (11) | C4B—C3B—H3BA | 120.5 |
N3—N2—H1N2 | 120.1 (11) | C5B—C4B—C3B | 120.7 (5) |
C15—N1—C8A | 119.9 (5) | C5B—C4B—H4BA | 119.7 |
C15—N1—C8B | 126.7 (4) | C3B—C4B—H4BA | 119.7 |
C15—N1—H1A | 120.2 | C4B—C5B—C6 | 120.5 (4) |
C8A—N1—H1A | 120.0 | C4B—C5B—H5BA | 119.8 |
C8B—N1—H1A | 112.0 | C6—C5B—H5BA | 119.8 |
C15—N1—H1B | 116.6 | C8B—C7B—C1 | 116.1 (5) |
C8A—N1—H1B | 122.1 | C8B—C7B—H7BA | 108.3 |
C8B—N1—H1B | 116.7 | C1—C7B—H7BA | 108.3 |
C13—N4—C9 | 118.19 (10) | C8B—C7B—H7BB | 108.3 |
C2B—C1—C6 | 127.2 (3) | C1—C7B—H7BB | 108.3 |
C2B—C1—C7A | 101.0 (3) | H7BA—C7B—H7BB | 107.4 |
C6—C1—C7A | 131.8 (4) | N1—C8B—C7B | 112.8 (5) |
C6—C1—C2A | 107.6 (4) | N1—C8B—H8BA | 109.0 |
C7A—C1—C2A | 120.5 (3) | C7B—C8B—H8BA | 109.0 |
C2B—C1—C7B | 119.7 (2) | N1—C8B—H8BB | 109.0 |
C6—C1—C7B | 113.1 (2) | C7B—C8B—H8BB | 109.0 |
C2A—C1—C7B | 139.3 (3) | H8BA—C8B—H8BB | 107.8 |
C3A—C2A—C1 | 120.8 (5) | C5A—C6—C1 | 132.8 (4) |
C3A—C2A—H2AA | 119.6 | C1—C6—C5B | 112.9 (3) |
C1—C2A—H2AA | 119.6 | C5A—C6—H6 | 108.5 (11) |
C2A—C3A—C4A | 121.8 (6) | C1—C6—H6 | 118.7 (11) |
C2A—C3A—H3AA | 119.1 | C5B—C6—H6 | 128.4 (11) |
C4A—C3A—H3AA | 119.1 | N4—C9—C10 | 122.32 (11) |
C5A—C4A—C3A | 118.0 (6) | N4—C9—C14 | 114.55 (10) |
C5A—C4A—H4AA | 121.0 | C10—C9—C14 | 123.13 (11) |
C3A—C4A—H4AA | 121.0 | C11—C10—C9 | 118.56 (11) |
C6—C5A—C4A | 119.0 (6) | C11—C10—H10A | 120.7 |
C6—C5A—H5AA | 120.5 | C9—C10—H10A | 120.7 |
C4A—C5A—H5AA | 120.5 | C10—C11—C12 | 119.57 (11) |
C1—C7A—C8A | 111.3 (6) | C10—C11—H11A | 120.2 |
C1—C7A—H7AA | 109.4 | C12—C11—H11A | 120.2 |
C8A—C7A—H7AA | 109.4 | C11—C12—C13 | 118.19 (12) |
C1—C7A—H7AB | 109.4 | C11—C12—H12A | 120.9 |
C8A—C7A—H7AB | 109.4 | C13—C12—H12A | 120.9 |
H7AA—C7A—H7AB | 108.0 | N4—C13—C12 | 123.15 (12) |
N1—C8A—C7A | 116.9 (8) | N4—C13—H13A | 118.4 |
N1—C8A—H8AA | 108.1 | C12—C13—H13A | 118.4 |
C7A—C8A—H8AA | 108.1 | N3—C14—C9 | 121.90 (11) |
N1—C8A—H8AB | 108.1 | N3—C14—H14A | 119.0 |
C7A—C8A—H8AB | 108.1 | C9—C14—H14A | 119.0 |
H8AA—C8A—H8AB | 107.3 | N1—C15—N2 | 116.06 (11) |
C1—C2B—C3B | 119.7 (4) | N1—C15—S1 | 124.71 (10) |
C1—C2B—H2BA | 120.1 | N2—C15—S1 | 119.24 (9) |
C3B—C2B—H2BA | 120.1 | ||
C14—N3—N2—C15 | −177.02 (11) | C4A—C5A—C6—C1 | 0.3 (9) |
C2B—C1—C2A—C3A | 174.5 (18) | C4A—C5A—C6—C5B | −3.5 (10) |
C6—C1—C2A—C3A | −0.7 (6) | C2B—C1—C6—C5A | −1.3 (6) |
C7A—C1—C2A—C3A | −177.5 (5) | C7A—C1—C6—C5A | 177.1 (6) |
C7B—C1—C2A—C3A | 178.0 (4) | C2A—C1—C6—C5A | 0.7 (5) |
C1—C2A—C3A—C4A | −0.3 (8) | C7B—C1—C6—C5A | −178.3 (5) |
C2A—C3A—C4A—C5A | 1.4 (9) | C2B—C1—C6—C5B | 0.1 (4) |
C3A—C4A—C5A—C6 | −1.4 (9) | C7A—C1—C6—C5B | 178.5 (4) |
C2B—C1—C7A—C8A | −108.8 (6) | C2A—C1—C6—C5B | 2.1 (4) |
C6—C1—C7A—C8A | 72.5 (7) | C7B—C1—C6—C5B | −176.9 (3) |
C2A—C1—C7A—C8A | −111.5 (7) | C4B—C5B—C6—C5A | 176.7 (19) |
C7B—C1—C7A—C8A | 59.5 (11) | C4B—C5B—C6—C1 | −0.2 (5) |
C15—N1—C8A—C7A | 73.6 (10) | C13—N4—C9—C10 | 1.48 (18) |
C8B—N1—C8A—C7A | −161 (5) | C13—N4—C9—C14 | −178.92 (11) |
C1—C7A—C8A—N1 | 68.3 (10) | N4—C9—C10—C11 | −0.86 (18) |
C6—C1—C2B—C3B | 0.0 (6) | C14—C9—C10—C11 | 179.57 (11) |
C7A—C1—C2B—C3B | −178.8 (5) | C9—C10—C11—C12 | −0.28 (18) |
C2A—C1—C2B—C3B | −5.8 (10) | C10—C11—C12—C13 | 0.73 (19) |
C7B—C1—C2B—C3B | 176.8 (4) | C9—N4—C13—C12 | −1.00 (19) |
C1—C2B—C3B—C4B | 0.1 (8) | C11—C12—C13—N4 | −0.1 (2) |
C2B—C3B—C4B—C5B | −0.3 (8) | N2—N3—C14—C9 | 179.02 (10) |
C3B—C4B—C5B—C6 | 0.3 (7) | N4—C9—C14—N3 | −178.86 (11) |
C2B—C1—C7B—C8B | −90.4 (5) | C10—C9—C14—N3 | 0.73 (18) |
C6—C1—C7B—C8B | 86.9 (5) | C8A—N1—C15—N2 | −171.0 (6) |
C7A—C1—C7B—C8B | −103.6 (12) | C8B—N1—C15—N2 | 175.8 (4) |
C2A—C1—C7B—C8B | −91.7 (6) | C8A—N1—C15—S1 | 9.4 (6) |
C15—N1—C8B—C7B | 81.3 (7) | C8B—N1—C15—S1 | −3.8 (4) |
C8A—N1—C8B—C7B | 19 (4) | N3—N2—C15—N1 | −4.57 (16) |
C1—C7B—C8B—N1 | 49.0 (7) | N3—N2—C15—S1 | 175.08 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N3 | 0.90 | 2.23 | 2.6481 (15) | 108 |
N1—H1A···N3 | 0.90 | 2.29 | 2.6481 (15) | 104 |
N2—H1N2···N4i | 0.898 (16) | 2.063 (16) | 2.9597 (14) | 176 |
C10—H10A···Cg2ii | 0.93 | 2.85 | 3.625 (3) | 142 |
C12—H12A···Cg1iii | 0.93 | 2.87 | 3.6495 (15) | 142 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1/2, −y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H16N4S |
Mr | 284.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 6.7341 (9), 8.9533 (12), 24.003 (3) |
V (Å3) | 1447.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.43 × 0.19 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.951, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22005, 4232, 3928 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.04 |
No. of reflections | 4232 |
No. of parameters | 244 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.19 |
Absolute structure | Flack (1983), 1790 Friedels |
Absolute structure parameter | 0.02 (6) |
Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998), SHELXTL and PLATON (Spek, 2003).
S1—C15 | 1.6849 (13) | N1—C8A | 1.407 (13) |
N3—C14 | 1.2837 (15) | N1—C8B | 1.506 (8) |
N3—N2 | 1.3783 (14) | N4—C13 | 1.3416 (16) |
N2—C15 | 1.3587 (16) | N4—C9 | 1.3488 (16) |
N1—C15 | 1.3401 (16) | ||
C14—N3—N2 | 114.37 (10) | C15—N1—C8B | 126.7 (4) |
C15—N2—N3 | 120.47 (10) | N3—C14—C9 | 121.90 (11) |
C15—N1—C8A | 119.9 (5) | ||
C2A—C1—C7A—C8A | −111.5 (7) | C15—N1—C8B—C7B | 81.3 (7) |
C15—N1—C8A—C7A | 73.6 (10) | N3—N2—C15—S1 | 175.08 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N3 | 0.90 | 2.2322 | 2.6481 (15) | 108 |
N1—H1A···N3 | 0.90 | 2.2863 | 2.6481 (15) | 104 |
N2—H1N2···N4i | 0.898 (16) | 2.063 (16) | 2.9597 (14) | 176 |
C10—H10A···Cg2ii | 0.93 | 2.8467 | 3.625 (3) | 142 |
C12—H12A···Cg1iii | 0.93 | 2.8718 | 3.6495 (15) | 142 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1/2, −y−1/2, −z. |
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N-Heterocyclic thiosemicarbazones are widely explored for their antimicrobial activities. For example, N(4)-substituted thiosemicarbazones are shown to possess antitumour properties in mammalian cells with the inhibition of DNA synthesis through the coordination of iron (Borges et al., 1997). 4-Morpholino-2-formylpyridine thiosemicarbazone is reported to be an active antineoplastic agent in mice bearing Sarcoma 180 ascites cells (Agarwal or Agrawal et al., 1976). Similarly, the cytotoxicity of copper and iron complexes of 5-substituted 2-formylpyridine thiosemicarbazones against Ehrlich ascites tumour cells has been measured (Antholine et al., 1976). In light of these reports, we have synthesized the title compound, (I), with the aim of investigating its antimicrobial behaviour and the related metal complexes.
The title compound is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. The C15═S1 and C15—N2 bond distances are typical for these types of bonds, as are the remaining bond lengths and angles in (I) (Allen et al., 1987), and are similar to those in the structures of previously reported thiosemicarbazones (e.g. John et al., 2003; Joseph et al., 2004; Philip et al., 2004; Sreekanth et al., 2004; Usman et al., 2002). The thiosemicarbazone reveals an EE conformation since trans configurations are observed about both the C14═N3 and C15—N2 bonds.
The phenylethyl group (atoms C1–C8) is disordered over two sites with relative occupancies 0.433 (11) and 0.567 (11) for the A and B components. The pyridyl ring is coplanar with the thiosemicarbarzone group (S1/N2/N3/C14/C15), with an r.m.s. deviation of 0.025 Å and a maximum deviation of −0.173 (1) Å for atom S1. The C15—N1—C8A—C7A torsion angle of 73.6 (10)° [C15—N1—C8B—C7B = 81.3 (7)°], indicates a (+)-syn-clinal conformation in this part of the molecule. The dihedral angles between the thiosemicarbarzone group and the phenyl ring disorder components are 52.3 (2) and 50.78 (16) ° for the A and B disorder components, respectively.
In addition to an intramolecular N—H···N hydrogen-bonded S(5) ring (Bernstein et al., 1995), the molecules are linked by intramolecular N—H···N hydrogen bonds to form one-dimensional chains in the a-axis direction (Fig. 2 and Table 2). In the crystal structure, further stabilization is provided by weak C—H···π(arene) interactions (Table 2).