

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809054841/fj2264sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536809054841/fj2264Isup2.hkl |
CCDC reference: 766884
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.140
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 -- C1 .. 6.11 su PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 8 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 87 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 3 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 3
Alert level G PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large.. 0.10 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
4-n-octyloxybenzaldehyde (6.09 g, 26 mmol) was added to a hot solution of thiosemicarbazide (2.38 g, 26 mmol) in methanol (200 ml). The mixture was refluxed for 30 min and cooled down to room temperature. The product was recrystallized from dichloromethane to give colorless microcrystals. M.P. 381 K. Brilliant colorless flat rectangular shaped crystals suitable for X-ray difraction were obtained from a mixture of dichloromethane and toluene (10:5; v/v) after 5 days.
Data collection was performed on a image plate with a phi scan over 180° that allows to get a completion (for the triclinic space group) of 97%. All H atoms were located geometrically and treated as riding atoms, with C—H = 0.93–0.96 Å, N—H = 0.86 and with Uĩso~(H) = 1.2U~eq~(C or N) or 1.5U~eq~(C) for methyl H atoms.
Data collection: XPRESS (MacScience, 2002); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELX97 (Sheldrick, 2008); program(s) used to refine structure: SHELX97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![]() | Fig. 1. ORTEP drawing (ellipsoids at the 40% probability level) of the compoud with atom-labelling scheme. |
C16H25N3OS | Z = 2 |
Mr = 307.45 | F(000) = 332 |
Triclinic, P1 | Dx = 1.161 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.785 (2) Å | Cell parameters from 146 reflections |
b = 7.586 (2) Å | θ = 3.0–18.1° |
c = 20.789 (4) Å | µ = 0.19 mm−1 |
α = 94.74 (2)° | T = 293 K |
β = 91.85 (2)° | Plate, colorless |
γ = 104.42 (3)° | 0.42 × 0.40 × 0.14 mm |
V = 879.2 (4) Å3 |
Enraf–Nonius dip1030 image-plate diffractometer | 2749 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 25.7°, θmin = 3.6° |
ϕ–scans with narrow frames | h = −7→7 |
9930 measured reflections | k = −9→8 |
3226 independent reflections | l = −25→25 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1026P)2 + 0.0242P] where P = (Fo2 + 2Fc2)/3 |
3226 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C16H25N3OS | γ = 104.42 (3)° |
Mr = 307.45 | V = 879.2 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.785 (2) Å | Mo Kα radiation |
b = 7.586 (2) Å | µ = 0.19 mm−1 |
c = 20.789 (4) Å | T = 293 K |
α = 94.74 (2)° | 0.42 × 0.40 × 0.14 mm |
β = 91.85 (2)° |
Enraf–Nonius dip1030 image-plate diffractometer | 2749 reflections with I > 2σ(I) |
9930 measured reflections | Rint = 0.030 |
3226 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
3226 reflections | Δρmin = −0.18 e Å−3 |
191 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
S1 | 1.33919 (6) | −0.29398 (5) | 0.99374 (2) | 0.06930 (19) | |
N1 | 1.0386 (2) | 0.02579 (17) | 0.89975 (6) | 0.0648 (3) | |
N2 | 1.1983 (2) | −0.04336 (17) | 0.93483 (6) | 0.0690 (3) | |
H2 | 1.3435 | 0.0203 | 0.9421 | 0.083* | |
N3 | 0.9025 (2) | −0.29670 (17) | 0.94909 (6) | 0.0668 (3) | |
H3A | 0.8033 | −0.2489 | 0.9295 | 0.080* | |
H3B | 0.8534 | −0.4024 | 0.9631 | 0.080* | |
O1 | 0.6110 (2) | 0.55328 (16) | 0.73145 (6) | 0.0812 (3) | |
C1 | 1.1305 (2) | −0.20768 (19) | 0.95761 (7) | 0.0591 (3) | |
C2 | 1.1216 (3) | 0.1882 (2) | 0.88465 (7) | 0.0663 (4) | |
H2A | 1.2764 | 0.2498 | 0.8995 | 0.080* | |
C3 | 0.9864 (3) | 0.2818 (2) | 0.84546 (7) | 0.0630 (4) | |
C4 | 0.7501 (3) | 0.2031 (2) | 0.82202 (7) | 0.0681 (4) | |
H4 | 0.6725 | 0.0867 | 0.8321 | 0.082* | |
C5 | 0.6322 (3) | 0.2971 (2) | 0.78409 (8) | 0.0716 (4) | |
H5 | 0.4761 | 0.2431 | 0.7683 | 0.086* | |
C6 | 0.7444 (3) | 0.4721 (2) | 0.76919 (7) | 0.0677 (4) | |
C7 | 0.9777 (3) | 0.5528 (2) | 0.79263 (7) | 0.0726 (4) | |
H7 | 1.0536 | 0.6704 | 0.7833 | 0.087* | |
C8 | 1.0957 (3) | 0.4563 (2) | 0.82997 (7) | 0.0698 (4) | |
H8 | 1.2526 | 0.5100 | 0.8451 | 0.084* | |
C9 | 0.7089 (4) | 0.7404 (2) | 0.72041 (9) | 0.0880 (5) | |
H9A | 0.8564 | 0.7529 | 0.6983 | 0.106* | |
H9B | 0.7432 | 0.8161 | 0.7612 | 0.106* | |
C10 | 0.5257 (4) | 0.7986 (3) | 0.67937 (9) | 0.0890 (5) | |
H10A | 0.3717 | 0.7624 | 0.6982 | 0.107* | |
H10B | 0.5693 | 0.9309 | 0.6805 | 0.107* | |
C11 | 0.5012 (4) | 0.7192 (3) | 0.60985 (8) | 0.0811 (5) | |
H11A | 0.4523 | 0.5869 | 0.6085 | 0.097* | |
H11B | 0.6561 | 0.7522 | 0.5913 | 0.097* | |
C12 | 0.3221 (3) | 0.7838 (3) | 0.56889 (9) | 0.0817 (5) | |
H12A | 0.1660 | 0.7448 | 0.5863 | 0.098* | |
H12B | 0.3662 | 0.9164 | 0.5727 | 0.098* | |
C13 | 0.3025 (3) | 0.7155 (2) | 0.49799 (9) | 0.0826 (5) | |
H13A | 0.2573 | 0.5828 | 0.4940 | 0.099* | |
H13B | 0.4583 | 0.7543 | 0.4803 | 0.099* | |
C14 | 0.1228 (3) | 0.7824 (3) | 0.45814 (8) | 0.0810 (5) | |
H14A | −0.0331 | 0.7420 | 0.4756 | 0.097* | |
H14B | 0.1667 | 0.9150 | 0.4629 | 0.097* | |
C15 | 0.1029 (4) | 0.7182 (3) | 0.38689 (9) | 0.0891 (5) | |
H15A | 0.0562 | 0.5857 | 0.3819 | 0.107* | |
H15B | 0.2589 | 0.7573 | 0.3693 | 0.107* | |
C16 | −0.0752 (4) | 0.7893 (3) | 0.34816 (10) | 0.0987 (6) | |
H16A | −0.2329 | 0.7416 | 0.3624 | 0.148* | |
H16B | −0.0710 | 0.7509 | 0.3031 | 0.148* | |
H16C | −0.0347 | 0.9204 | 0.3544 | 0.148* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0526 (3) | 0.0696 (3) | 0.0871 (3) | 0.01517 (17) | −0.00582 (18) | 0.02038 (19) |
N1 | 0.0600 (7) | 0.0703 (8) | 0.0671 (7) | 0.0211 (5) | −0.0045 (5) | 0.0120 (6) |
N2 | 0.0551 (7) | 0.0706 (8) | 0.0817 (8) | 0.0141 (6) | −0.0097 (6) | 0.0204 (6) |
N3 | 0.0527 (6) | 0.0681 (7) | 0.0810 (8) | 0.0158 (5) | −0.0032 (5) | 0.0155 (6) |
O1 | 0.0863 (8) | 0.0834 (7) | 0.0823 (7) | 0.0315 (6) | −0.0029 (6) | 0.0277 (6) |
C1 | 0.0534 (7) | 0.0639 (8) | 0.0604 (8) | 0.0158 (6) | 0.0003 (6) | 0.0060 (6) |
C2 | 0.0666 (9) | 0.0705 (9) | 0.0627 (8) | 0.0181 (7) | −0.0032 (6) | 0.0120 (7) |
C3 | 0.0680 (8) | 0.0687 (8) | 0.0555 (7) | 0.0224 (6) | 0.0007 (6) | 0.0090 (6) |
C4 | 0.0709 (9) | 0.0664 (8) | 0.0691 (9) | 0.0191 (7) | 0.0004 (7) | 0.0152 (7) |
C5 | 0.0677 (9) | 0.0792 (10) | 0.0713 (9) | 0.0228 (7) | −0.0027 (7) | 0.0159 (7) |
C6 | 0.0774 (9) | 0.0744 (9) | 0.0587 (8) | 0.0309 (7) | 0.0027 (7) | 0.0132 (7) |
C7 | 0.0831 (10) | 0.0666 (9) | 0.0687 (9) | 0.0177 (7) | 0.0007 (7) | 0.0153 (7) |
C8 | 0.0712 (9) | 0.0711 (9) | 0.0662 (9) | 0.0159 (7) | −0.0042 (7) | 0.0102 (7) |
C9 | 0.1125 (15) | 0.0781 (11) | 0.0813 (11) | 0.0368 (10) | −0.0047 (10) | 0.0185 (9) |
C10 | 0.1121 (15) | 0.0853 (11) | 0.0837 (12) | 0.0468 (11) | 0.0025 (10) | 0.0239 (9) |
C11 | 0.0900 (12) | 0.0816 (11) | 0.0815 (11) | 0.0349 (9) | 0.0066 (9) | 0.0225 (8) |
C12 | 0.0882 (12) | 0.0861 (11) | 0.0802 (11) | 0.0350 (9) | 0.0053 (9) | 0.0224 (9) |
C13 | 0.0886 (12) | 0.0810 (11) | 0.0843 (11) | 0.0299 (9) | 0.0039 (9) | 0.0174 (9) |
C14 | 0.0875 (12) | 0.0802 (10) | 0.0797 (11) | 0.0276 (9) | 0.0040 (8) | 0.0146 (8) |
C15 | 0.0945 (13) | 0.0900 (12) | 0.0859 (12) | 0.0307 (10) | −0.0021 (9) | 0.0068 (9) |
C16 | 0.1001 (14) | 0.1156 (15) | 0.0842 (12) | 0.0372 (12) | −0.0079 (10) | 0.0060 (11) |
S1—C1 | 1.6930 (15) | C9—H9A | 0.9700 |
N1—C2 | 1.275 (2) | C9—H9B | 0.9700 |
N1—N2 | 1.3863 (16) | C10—C11 | 1.507 (3) |
N2—C1 | 1.341 (2) | C10—H10A | 0.9700 |
N2—H2 | 0.8600 | C10—H10B | 0.9700 |
N3—C1 | 1.3227 (19) | C11—C12 | 1.518 (2) |
N3—H3A | 0.8600 | C11—H11A | 0.9700 |
N3—H3B | 0.8600 | C11—H11B | 0.9700 |
O1—C6 | 1.3665 (19) | C12—C13 | 1.513 (3) |
O1—C9 | 1.432 (2) | C12—H12A | 0.9700 |
C2—C3 | 1.453 (2) | C12—H12B | 0.9700 |
C2—H2A | 0.9300 | C13—C14 | 1.517 (2) |
C3—C8 | 1.387 (2) | C13—H13A | 0.9700 |
C3—C4 | 1.402 (2) | C13—H13B | 0.9700 |
C4—C5 | 1.377 (2) | C14—C15 | 1.512 (3) |
C4—H4 | 0.9300 | C14—H14A | 0.9700 |
C5—C6 | 1.390 (2) | C14—H14B | 0.9700 |
C5—H5 | 0.9300 | C15—C16 | 1.515 (3) |
C6—C7 | 1.389 (2) | C15—H15A | 0.9700 |
C7—C8 | 1.383 (2) | C15—H15B | 0.9700 |
C7—H7 | 0.9300 | C16—H16A | 0.9600 |
C8—H8 | 0.9300 | C16—H16B | 0.9600 |
C9—C10 | 1.511 (3) | C16—H16C | 0.9600 |
C2—N1—N2 | 114.83 (13) | C9—C10—H10A | 108.7 |
C1—N2—N1 | 121.23 (12) | C11—C10—H10B | 108.7 |
C1—N2—H2 | 119.4 | C9—C10—H10B | 108.7 |
N1—N2—H2 | 119.4 | H10A—C10—H10B | 107.6 |
C1—N3—H3A | 120.0 | C10—C11—C12 | 113.38 (15) |
C1—N3—H3B | 120.0 | C10—C11—H11A | 108.9 |
H3A—N3—H3B | 120.0 | C12—C11—H11A | 108.9 |
C6—O1—C9 | 117.89 (14) | C10—C11—H11B | 108.9 |
N3—C1—N2 | 117.74 (13) | C12—C11—H11B | 108.9 |
N3—C1—S1 | 123.14 (12) | H11A—C11—H11B | 107.7 |
N2—C1—S1 | 119.09 (11) | C13—C12—C11 | 114.97 (15) |
N1—C2—C3 | 123.26 (14) | C13—C12—H12A | 108.5 |
N1—C2—H2A | 118.4 | C11—C12—H12A | 108.5 |
C3—C2—H2A | 118.4 | C13—C12—H12B | 108.5 |
C8—C3—C4 | 118.26 (14) | C11—C12—H12B | 108.5 |
C8—C3—C2 | 118.79 (14) | H12A—C12—H12B | 107.5 |
C4—C3—C2 | 122.94 (15) | C12—C13—C14 | 113.91 (15) |
C5—C4—C3 | 120.37 (15) | C12—C13—H13A | 108.8 |
C5—C4—H4 | 119.8 | C14—C13—H13A | 108.8 |
C3—C4—H4 | 119.8 | C12—C13—H13B | 108.8 |
C4—C5—C6 | 120.57 (15) | C14—C13—H13B | 108.8 |
C4—C5—H5 | 119.7 | H13A—C13—H13B | 107.7 |
C6—C5—H5 | 119.7 | C15—C14—C13 | 114.88 (16) |
O1—C6—C7 | 124.47 (15) | C15—C14—H14A | 108.5 |
O1—C6—C5 | 115.77 (15) | C13—C14—H14A | 108.5 |
C7—C6—C5 | 119.76 (15) | C15—C14—H14B | 108.5 |
C8—C7—C6 | 119.26 (15) | C13—C14—H14B | 108.5 |
C8—C7—H7 | 120.4 | H14A—C14—H14B | 107.5 |
C6—C7—H7 | 120.4 | C14—C15—C16 | 113.71 (16) |
C7—C8—C3 | 121.78 (15) | C14—C15—H15A | 108.8 |
C7—C8—H8 | 119.1 | C16—C15—H15A | 108.8 |
C3—C8—H8 | 119.1 | C14—C15—H15B | 108.8 |
O1—C9—C10 | 107.53 (17) | C16—C15—H15B | 108.8 |
O1—C9—H9A | 110.2 | H15A—C15—H15B | 107.7 |
C10—C9—H9A | 110.2 | C15—C16—H16A | 109.5 |
O1—C9—H9B | 110.2 | C15—C16—H16B | 109.5 |
C10—C9—H9B | 110.2 | H16A—C16—H16B | 109.5 |
H9A—C9—H9B | 108.5 | C15—C16—H16C | 109.5 |
C11—C10—C9 | 114.12 (15) | H16A—C16—H16C | 109.5 |
C11—C10—H10A | 108.7 | H16B—C16—H16C | 109.5 |
C2—N1—N2—C1 | 175.56 (13) | O1—C6—C7—C8 | −179.39 (14) |
N1—N2—C1—N3 | −4.3 (2) | C5—C6—C7—C8 | 0.7 (2) |
N1—N2—C1—S1 | 174.08 (10) | C6—C7—C8—C3 | −0.9 (2) |
N2—N1—C2—C3 | 177.06 (12) | C4—C3—C8—C7 | 0.2 (2) |
N1—C2—C3—C8 | −177.92 (14) | C2—C3—C8—C7 | 179.72 (13) |
N1—C2—C3—C4 | 1.6 (2) | C6—O1—C9—C10 | −178.39 (13) |
C8—C3—C4—C5 | 0.7 (2) | O1—C9—C10—C11 | −73.0 (2) |
C2—C3—C4—C5 | −178.83 (13) | C9—C10—C11—C12 | −178.21 (16) |
C3—C4—C5—C6 | −0.8 (2) | C10—C11—C12—C13 | 176.73 (17) |
C9—O1—C6—C7 | −6.4 (2) | C11—C12—C13—C14 | −179.85 (15) |
C9—O1—C6—C5 | 173.52 (14) | C12—C13—C14—C15 | 179.08 (16) |
C4—C5—C6—O1 | −179.76 (13) | C13—C14—C15—C16 | −179.20 (17) |
C4—C5—C6—C7 | 0.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C16H25N3OS |
Mr | 307.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.785 (2), 7.586 (2), 20.789 (4) |
α, β, γ (°) | 94.74 (2), 91.85 (2), 104.42 (3) |
V (Å3) | 879.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.42 × 0.40 × 0.14 |
Data collection | |
Diffractometer | Enraf–Nonius dip1030 image-plate diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9930, 3226, 2749 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.140, 1.04 |
No. of reflections | 3226 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: XPRESS (MacScience, 2002), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELX97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
When used in coordination chemistry this molecule is potentially a bidentate ligand acting through the α- or β-nitrogen and thiolate sulfur anion forming a four- and five-membered chelate ring, respectively (Pal et al., 2002), although a behavior as monocoordinated ligand through sulfur has also been reported (Tian et al., 2002). In the crystal structure the molecules are interconnected by N—H···N and N–H···S hydrogen bonds as found in other thiosemicarbazone species (Narayana et al., 2007; Tarafder et al., 2008). The crystal structure is also stabilized by C–H···π interactions. The octyl chain presents an anti conformation with the exception of the O1—C9—C10—C11 part that has a torsion angle of -72.7 (3)°.