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In the title compound, C16H25N3OS, the thio­semicarbazone group adopts an E configuration with respect to the C=N bond and is almost coplanar with the benzene ring, forming a dihedral angle of 9.3 (1)°. In the crystal packing, the mol­ecules lie along the a axis in an anti­parallel arrangement and are held in place by van der Waals inter­actions. As a consequence, there is relatively low anisotropic thermal motion in the terminal atoms of the n-octyl chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809054841/fj2264sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536809054841/fj2264Isup2.hkl
Contains datablock I

CCDC reference: 766884

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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)°.

Related literature top

For the related structures, see: Basuli et al. (2000); Narayana et al. (2007); Pal et al. (2002); Tian et al. (2002); Tarafder et al. (2008).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEP drawing (ellipsoids at the 40% probability level) of the compoud with atom-labelling scheme.
(E)-4-Octyloxybenzaldehyde thiosemicarbazone top
Crystal data top
C16H25N3OSZ = 2
Mr = 307.45F(000) = 332
Triclinic, P1Dx = 1.161 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.785 (2) ÅCell parameters from 146 reflections
b = 7.586 (2) Åθ = 3.0–18.1°
c = 20.789 (4) ŵ = 0.19 mm1
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
Data collection top
Enraf–Nonius dip1030 image-plate
diffractometer
2749 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
Graphite monochromatorθmax = 25.7°, θmin = 3.6°
ϕ–scans with narrow framesh = 77
9930 measured reflectionsk = 98
3226 independent reflectionsl = 2525
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-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 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H25N3OSγ = 104.42 (3)°
Mr = 307.45V = 879.2 (4) Å3
Triclinic, P1Z = 2
a = 5.785 (2) ÅMo Kα radiation
b = 7.586 (2) ŵ = 0.19 mm1
c = 20.789 (4) ÅT = 293 K
α = 94.74 (2)°0.42 × 0.40 × 0.14 mm
β = 91.85 (2)°
Data collection top
Enraf–Nonius dip1030 image-plate
diffractometer
2749 reflections with I > 2σ(I)
9930 measured reflectionsRint = 0.030
3226 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.04Δρmax = 0.19 e Å3
3226 reflectionsΔρmin = 0.18 e Å3
191 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S11.33919 (6)0.29398 (5)0.99374 (2)0.06930 (19)
N11.0386 (2)0.02579 (17)0.89975 (6)0.0648 (3)
N21.1983 (2)0.04336 (17)0.93483 (6)0.0690 (3)
H21.34350.02030.94210.083*
N30.9025 (2)0.29670 (17)0.94909 (6)0.0668 (3)
H3A0.80330.24890.92950.080*
H3B0.85340.40240.96310.080*
O10.6110 (2)0.55328 (16)0.73145 (6)0.0812 (3)
C11.1305 (2)0.20768 (19)0.95761 (7)0.0591 (3)
C21.1216 (3)0.1882 (2)0.88465 (7)0.0663 (4)
H2A1.27640.24980.89950.080*
C30.9864 (3)0.2818 (2)0.84546 (7)0.0630 (4)
C40.7501 (3)0.2031 (2)0.82202 (7)0.0681 (4)
H40.67250.08670.83210.082*
C50.6322 (3)0.2971 (2)0.78409 (8)0.0716 (4)
H50.47610.24310.76830.086*
C60.7444 (3)0.4721 (2)0.76919 (7)0.0677 (4)
C70.9777 (3)0.5528 (2)0.79263 (7)0.0726 (4)
H71.05360.67040.78330.087*
C81.0957 (3)0.4563 (2)0.82997 (7)0.0698 (4)
H81.25260.51000.84510.084*
C90.7089 (4)0.7404 (2)0.72041 (9)0.0880 (5)
H9A0.85640.75290.69830.106*
H9B0.74320.81610.76120.106*
C100.5257 (4)0.7986 (3)0.67937 (9)0.0890 (5)
H10A0.37170.76240.69820.107*
H10B0.56930.93090.68050.107*
C110.5012 (4)0.7192 (3)0.60985 (8)0.0811 (5)
H11A0.45230.58690.60850.097*
H11B0.65610.75220.59130.097*
C120.3221 (3)0.7838 (3)0.56889 (9)0.0817 (5)
H12A0.16600.74480.58630.098*
H12B0.36620.91640.57270.098*
C130.3025 (3)0.7155 (2)0.49799 (9)0.0826 (5)
H13A0.25730.58280.49400.099*
H13B0.45830.75430.48030.099*
C140.1228 (3)0.7824 (3)0.45814 (8)0.0810 (5)
H14A0.03310.74200.47560.097*
H14B0.16670.91500.46290.097*
C150.1029 (4)0.7182 (3)0.38689 (9)0.0891 (5)
H15A0.05620.58570.38190.107*
H15B0.25890.75730.36930.107*
C160.0752 (4)0.7893 (3)0.34816 (10)0.0987 (6)
H16A0.23290.74160.36240.148*
H16B0.07100.75090.30310.148*
H16C0.03470.92040.35440.148*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0526 (3)0.0696 (3)0.0871 (3)0.01517 (17)0.00582 (18)0.02038 (19)
N10.0600 (7)0.0703 (8)0.0671 (7)0.0211 (5)0.0045 (5)0.0120 (6)
N20.0551 (7)0.0706 (8)0.0817 (8)0.0141 (6)0.0097 (6)0.0204 (6)
N30.0527 (6)0.0681 (7)0.0810 (8)0.0158 (5)0.0032 (5)0.0155 (6)
O10.0863 (8)0.0834 (7)0.0823 (7)0.0315 (6)0.0029 (6)0.0277 (6)
C10.0534 (7)0.0639 (8)0.0604 (8)0.0158 (6)0.0003 (6)0.0060 (6)
C20.0666 (9)0.0705 (9)0.0627 (8)0.0181 (7)0.0032 (6)0.0120 (7)
C30.0680 (8)0.0687 (8)0.0555 (7)0.0224 (6)0.0007 (6)0.0090 (6)
C40.0709 (9)0.0664 (8)0.0691 (9)0.0191 (7)0.0004 (7)0.0152 (7)
C50.0677 (9)0.0792 (10)0.0713 (9)0.0228 (7)0.0027 (7)0.0159 (7)
C60.0774 (9)0.0744 (9)0.0587 (8)0.0309 (7)0.0027 (7)0.0132 (7)
C70.0831 (10)0.0666 (9)0.0687 (9)0.0177 (7)0.0007 (7)0.0153 (7)
C80.0712 (9)0.0711 (9)0.0662 (9)0.0159 (7)0.0042 (7)0.0102 (7)
C90.1125 (15)0.0781 (11)0.0813 (11)0.0368 (10)0.0047 (10)0.0185 (9)
C100.1121 (15)0.0853 (11)0.0837 (12)0.0468 (11)0.0025 (10)0.0239 (9)
C110.0900 (12)0.0816 (11)0.0815 (11)0.0349 (9)0.0066 (9)0.0225 (8)
C120.0882 (12)0.0861 (11)0.0802 (11)0.0350 (9)0.0053 (9)0.0224 (9)
C130.0886 (12)0.0810 (11)0.0843 (11)0.0299 (9)0.0039 (9)0.0174 (9)
C140.0875 (12)0.0802 (10)0.0797 (11)0.0276 (9)0.0040 (8)0.0146 (8)
C150.0945 (13)0.0900 (12)0.0859 (12)0.0307 (10)0.0021 (9)0.0068 (9)
C160.1001 (14)0.1156 (15)0.0842 (12)0.0372 (12)0.0079 (10)0.0060 (11)
Geometric parameters (Å, º) top
S1—C11.6930 (15)C9—H9A0.9700
N1—C21.275 (2)C9—H9B0.9700
N1—N21.3863 (16)C10—C111.507 (3)
N2—C11.341 (2)C10—H10A0.9700
N2—H20.8600C10—H10B0.9700
N3—C11.3227 (19)C11—C121.518 (2)
N3—H3A0.8600C11—H11A0.9700
N3—H3B0.8600C11—H11B0.9700
O1—C61.3665 (19)C12—C131.513 (3)
O1—C91.432 (2)C12—H12A0.9700
C2—C31.453 (2)C12—H12B0.9700
C2—H2A0.9300C13—C141.517 (2)
C3—C81.387 (2)C13—H13A0.9700
C3—C41.402 (2)C13—H13B0.9700
C4—C51.377 (2)C14—C151.512 (3)
C4—H40.9300C14—H14A0.9700
C5—C61.390 (2)C14—H14B0.9700
C5—H50.9300C15—C161.515 (3)
C6—C71.389 (2)C15—H15A0.9700
C7—C81.383 (2)C15—H15B0.9700
C7—H70.9300C16—H16A0.9600
C8—H80.9300C16—H16B0.9600
C9—C101.511 (3)C16—H16C0.9600
C2—N1—N2114.83 (13)C9—C10—H10A108.7
C1—N2—N1121.23 (12)C11—C10—H10B108.7
C1—N2—H2119.4C9—C10—H10B108.7
N1—N2—H2119.4H10A—C10—H10B107.6
C1—N3—H3A120.0C10—C11—C12113.38 (15)
C1—N3—H3B120.0C10—C11—H11A108.9
H3A—N3—H3B120.0C12—C11—H11A108.9
C6—O1—C9117.89 (14)C10—C11—H11B108.9
N3—C1—N2117.74 (13)C12—C11—H11B108.9
N3—C1—S1123.14 (12)H11A—C11—H11B107.7
N2—C1—S1119.09 (11)C13—C12—C11114.97 (15)
N1—C2—C3123.26 (14)C13—C12—H12A108.5
N1—C2—H2A118.4C11—C12—H12A108.5
C3—C2—H2A118.4C13—C12—H12B108.5
C8—C3—C4118.26 (14)C11—C12—H12B108.5
C8—C3—C2118.79 (14)H12A—C12—H12B107.5
C4—C3—C2122.94 (15)C12—C13—C14113.91 (15)
C5—C4—C3120.37 (15)C12—C13—H13A108.8
C5—C4—H4119.8C14—C13—H13A108.8
C3—C4—H4119.8C12—C13—H13B108.8
C4—C5—C6120.57 (15)C14—C13—H13B108.8
C4—C5—H5119.7H13A—C13—H13B107.7
C6—C5—H5119.7C15—C14—C13114.88 (16)
O1—C6—C7124.47 (15)C15—C14—H14A108.5
O1—C6—C5115.77 (15)C13—C14—H14A108.5
C7—C6—C5119.76 (15)C15—C14—H14B108.5
C8—C7—C6119.26 (15)C13—C14—H14B108.5
C8—C7—H7120.4H14A—C14—H14B107.5
C6—C7—H7120.4C14—C15—C16113.71 (16)
C7—C8—C3121.78 (15)C14—C15—H15A108.8
C7—C8—H8119.1C16—C15—H15A108.8
C3—C8—H8119.1C14—C15—H15B108.8
O1—C9—C10107.53 (17)C16—C15—H15B108.8
O1—C9—H9A110.2H15A—C15—H15B107.7
C10—C9—H9A110.2C15—C16—H16A109.5
O1—C9—H9B110.2C15—C16—H16B109.5
C10—C9—H9B110.2H16A—C16—H16B109.5
H9A—C9—H9B108.5C15—C16—H16C109.5
C11—C10—C9114.12 (15)H16A—C16—H16C109.5
C11—C10—H10A108.7H16B—C16—H16C109.5
C2—N1—N2—C1175.56 (13)O1—C6—C7—C8179.39 (14)
N1—N2—C1—N34.3 (2)C5—C6—C7—C80.7 (2)
N1—N2—C1—S1174.08 (10)C6—C7—C8—C30.9 (2)
N2—N1—C2—C3177.06 (12)C4—C3—C8—C70.2 (2)
N1—C2—C3—C8177.92 (14)C2—C3—C8—C7179.72 (13)
N1—C2—C3—C41.6 (2)C6—O1—C9—C10178.39 (13)
C8—C3—C4—C50.7 (2)O1—C9—C10—C1173.0 (2)
C2—C3—C4—C5178.83 (13)C9—C10—C11—C12178.21 (16)
C3—C4—C5—C60.8 (2)C10—C11—C12—C13176.73 (17)
C9—O1—C6—C76.4 (2)C11—C12—C13—C14179.85 (15)
C9—O1—C6—C5173.52 (14)C12—C13—C14—C15179.08 (16)
C4—C5—C6—O1179.76 (13)C13—C14—C15—C16179.20 (17)
C4—C5—C6—C70.1 (2)

Experimental details

Crystal data
Chemical formulaC16H25N3OS
Mr307.45
Crystal system, space groupTriclinic, 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)
V3)879.2 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.19
Crystal size (mm)0.42 × 0.40 × 0.14
Data collection
DiffractometerEnraf–Nonius dip1030 image-plate
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9930, 3226, 2749
Rint0.030
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.140, 1.04
No. of reflections3226
No. of parameters191
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

 

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