supplementary materials


cv5398 scheme

Acta Cryst. (2013). E69, o723    [ doi:10.1107/S1600536813009720 ]

1,5-Bis[1-(4-bromophenyl)ethylidene]thiocarbonohydrazide

Z. Gao

Abstract top

The asymmetric unit of the title compound, C17H16Br2N4S, contains two independent molecules in which the benzene rings form dihedral angles of 20.0 (1) and 55.3 (1)°. In the crystal, a pair of N-H...S hydrogen bonds link the two different independent molecules into a dimer.

Comment top

In a continuation of our structural study of thiocarbonohydrazides (Feng et al., 2011), we present here the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related thiocarbonohydrazides (Feng et al., 2011; Zhao, 2011; Schmitt et al., 2011). The benzene rings C4—C9 and C12—C17 form a dihedral angle of 20.0 (1)°, while benzene rings C21—C26 and C29—C34 form a dihedral angle of 55.3 (1)°.

In the crystal, intermolecular N—H···S hydrogen bonds link two independent molecules into dimer (Fig. 1).

Related literature top

For the crystal structures of related compounds, see: Feng et al. (2011); Zhao (2011); Schmitt et al. (2011).

Experimental top

p-Br-Acetophenone (1.0 mmol) and thiocarbohydrazide (0.5 mmol) were mixed in 25 ml flash in the methanol. After 6 h stirring at 354 K, the resulting mixture was cooled to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid.

Refinement top

All H atoms were placed in geometrically idealized positions (N—H 0.86 and C—H 0.93–0.96 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2–1.5 Ueq(C) (C, N).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A hydrogen-bonded (dashed lines) dimer in the asymmetric unit of (I) showing the atomic numbering and 50% probability displacement ellipsoids
1,5-Bis[1-(4-bromophenyl)ethylidene]thiocarbonohydrazide top
Crystal data top
C17H16Br2N4SZ = 4
Mr = 468.22F(000) = 928
Triclinic, P1Dx = 1.679 Mg m3
a = 11.5800 (11) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.6950 (12) ÅCell parameters from 2095 reflections
c = 14.2860 (13) Åθ = 2.8–21.2°
α = 118.401 (2)°µ = 4.49 mm1
β = 90.977 (1)°T = 298 K
γ = 108.404 (1)°Yellow, block
V = 1852.6 (3) Å30.43 × 0.37 × 0.33 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
6456 independent reflections
Radiation source: fine-focus sealed tube2949 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
phi and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 713
Tmin = 0.248, Tmax = 0.319k = 1614
9457 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.214 w = 1/[σ2(Fo2) + (0.1033P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
6456 reflectionsΔρmax = 0.90 e Å3
438 parametersΔρmin = 1.33 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0038 (8)
Crystal data top
C17H16Br2N4Sγ = 108.404 (1)°
Mr = 468.22V = 1852.6 (3) Å3
Triclinic, P1Z = 4
a = 11.5800 (11) ÅMo Kα radiation
b = 13.6950 (12) ŵ = 4.49 mm1
c = 14.2860 (13) ÅT = 298 K
α = 118.401 (2)°0.43 × 0.37 × 0.33 mm
β = 90.977 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
6456 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2949 reflections with I > 2σ(I)
Tmin = 0.248, Tmax = 0.319Rint = 0.081
9457 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.214Δρmax = 0.90 e Å3
S = 0.96Δρmin = 1.33 e Å3
6456 reflectionsAbsolute structure: ?
438 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Br10.86326 (12)1.60584 (12)1.59389 (9)0.0846 (5)
Br21.15040 (11)0.55332 (10)0.95650 (10)0.0669 (4)
Br30.32652 (11)0.37660 (11)0.03711 (8)0.0723 (4)
Br40.09677 (12)1.33393 (11)0.64953 (10)0.0787 (5)
N50.4538 (7)0.8654 (6)0.6079 (6)0.045 (2)
H5B0.49430.85590.65190.055*
N60.4306 (7)0.7886 (6)0.4978 (6)0.046 (2)
N70.3534 (7)0.9606 (6)0.5655 (6)0.049 (2)
H70.35500.91570.49870.058*
N80.2919 (7)1.0377 (6)0.5921 (6)0.047 (2)
S20.4295 (3)1.0494 (3)0.7779 (2)0.0688 (9)
C180.4121 (9)0.9556 (8)0.6457 (7)0.045 (2)
C190.4609 (8)0.6957 (8)0.4612 (7)0.041 (2)
C200.5183 (9)0.6633 (9)0.5305 (7)0.056 (3)
H20A0.60050.72140.56700.084*
H20B0.52260.58600.48610.084*
H20C0.46880.66150.58340.084*
C210.4303 (8)0.6187 (8)0.3412 (7)0.042 (2)
C220.4345 (9)0.6678 (8)0.2735 (8)0.052 (3)
H220.45880.75010.30530.062*
C230.4042 (9)0.5988 (9)0.1630 (8)0.057 (3)
H230.40860.63280.11960.069*
C240.3668 (8)0.4769 (9)0.1180 (7)0.047 (3)
C250.3645 (9)0.4233 (9)0.1799 (8)0.051 (3)
H250.34070.34090.14700.061*
C260.3982 (9)0.4952 (8)0.2910 (8)0.050 (3)
H260.39980.46100.33350.060*
C270.2443 (9)1.0463 (7)0.5156 (8)0.044 (2)
C280.2551 (10)0.9804 (9)0.3973 (8)0.061 (3)
H28A0.33160.96650.39330.091*
H28B0.25401.02770.36510.091*
H28C0.18650.90530.35880.091*
C290.1686 (8)1.1214 (8)0.5468 (7)0.041 (2)
C300.1683 (9)1.1928 (8)0.6561 (8)0.051 (3)
H300.22091.19710.70910.061*
C310.0914 (10)1.2570 (9)0.6868 (9)0.058 (3)
H310.09281.30500.76000.069*
C320.0137 (9)1.2497 (8)0.6096 (8)0.048 (3)
C330.0121 (10)1.1817 (9)0.5017 (9)0.061 (3)
H330.04131.17800.44970.073*
C340.0898 (10)1.1187 (9)0.4703 (8)0.053 (3)
H340.08961.07360.39680.064*
C10.6961 (9)0.9711 (8)0.9249 (7)0.044 (2)
C20.6406 (8)1.2301 (8)1.1112 (7)0.042 (2)
C30.5534 (10)1.2427 (9)1.0443 (8)0.061 (3)
H3A0.59381.25850.99220.091*
H3B0.52831.30771.09040.091*
H3C0.48161.17021.00710.091*
C40.6932 (8)1.3211 (8)1.2269 (7)0.043 (2)
C50.6906 (8)1.4327 (8)1.2704 (7)0.044 (2)
H5A0.65401.45261.22690.053*
C60.7420 (9)1.5178 (9)1.3795 (8)0.056 (3)
H60.73991.59391.40820.068*
C70.7958 (9)1.4894 (9)1.4448 (7)0.051 (3)
C80.7975 (10)1.3767 (10)1.4055 (8)0.066 (3)
H80.83051.35621.45040.079*
C90.7471 (10)1.2936 (10)1.2942 (8)0.059 (3)
H90.75001.21771.26490.071*
C100.9075 (9)0.9240 (8)1.0604 (7)0.042 (2)
C110.9352 (11)1.0257 (10)1.1749 (8)0.076 (4)
H11A0.91161.08711.17560.114*
H11B1.02251.05731.20430.114*
H11C0.88930.99761.21820.114*
C120.9696 (8)0.8369 (8)1.0347 (7)0.042 (2)
C130.9539 (9)0.7456 (8)0.9292 (7)0.050 (3)
H130.90450.74030.87360.060*
C141.0085 (10)0.6628 (9)0.9037 (8)0.056 (3)
H140.99790.60370.83200.067*
C151.0793 (9)0.6687 (9)0.9861 (9)0.050 (3)
C161.0998 (10)0.7599 (10)1.0913 (8)0.062 (3)
H161.15090.76641.14650.074*
C171.0443 (10)0.8407 (10)1.1137 (8)0.061 (3)
H171.05730.90101.18540.073*
S10.6625 (3)0.8667 (2)0.79389 (19)0.0573 (8)
N10.6438 (7)1.0560 (6)0.9636 (6)0.046 (2)
H10.58791.05460.92200.055*
N20.6838 (7)1.1437 (7)1.0710 (6)0.045 (2)
N30.7716 (7)0.9799 (7)1.0024 (6)0.051 (2)
H30.78331.03661.06810.061*
N40.8306 (7)0.9031 (7)0.9815 (6)0.046 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0993 (10)0.0729 (10)0.0402 (7)0.0114 (7)0.0123 (6)0.0105 (6)
Br20.0741 (8)0.0582 (8)0.0797 (9)0.0427 (6)0.0312 (6)0.0316 (6)
Br30.0858 (9)0.0716 (9)0.0357 (6)0.0361 (7)0.0156 (5)0.0051 (6)
Br40.0866 (9)0.0617 (9)0.0857 (9)0.0481 (7)0.0081 (7)0.0234 (7)
N50.060 (5)0.032 (5)0.037 (5)0.026 (4)0.007 (4)0.007 (4)
N60.059 (5)0.031 (5)0.038 (5)0.022 (4)0.011 (4)0.008 (4)
N70.064 (6)0.038 (5)0.036 (5)0.030 (4)0.004 (4)0.006 (4)
N80.067 (6)0.035 (5)0.034 (5)0.032 (4)0.003 (4)0.006 (4)
S20.112 (3)0.0566 (19)0.0339 (15)0.0562 (17)0.0061 (14)0.0046 (13)
C180.056 (6)0.031 (6)0.042 (6)0.023 (5)0.006 (5)0.009 (5)
C190.049 (6)0.035 (6)0.041 (6)0.023 (5)0.012 (4)0.015 (5)
C200.074 (7)0.052 (7)0.039 (6)0.037 (6)0.013 (5)0.011 (5)
C210.040 (6)0.038 (6)0.043 (6)0.018 (5)0.012 (4)0.014 (5)
C220.070 (7)0.031 (6)0.043 (6)0.020 (5)0.007 (5)0.009 (5)
C230.074 (8)0.056 (8)0.048 (7)0.029 (6)0.023 (5)0.028 (6)
C240.037 (6)0.044 (7)0.043 (6)0.023 (5)0.013 (4)0.006 (5)
C250.062 (7)0.034 (6)0.050 (7)0.024 (5)0.015 (5)0.014 (5)
C260.057 (7)0.025 (6)0.062 (7)0.014 (5)0.010 (5)0.019 (5)
C270.053 (6)0.017 (5)0.045 (6)0.010 (4)0.002 (5)0.006 (4)
C280.067 (7)0.065 (8)0.051 (7)0.033 (6)0.013 (5)0.025 (6)
C290.044 (6)0.030 (6)0.049 (6)0.011 (4)0.011 (4)0.021 (5)
C300.067 (7)0.043 (6)0.041 (6)0.030 (5)0.009 (5)0.013 (5)
C310.071 (8)0.039 (7)0.056 (7)0.029 (6)0.015 (6)0.014 (5)
C320.059 (7)0.030 (6)0.053 (7)0.024 (5)0.000 (5)0.016 (5)
C330.072 (8)0.042 (7)0.066 (8)0.021 (6)0.004 (6)0.026 (6)
C340.071 (7)0.037 (6)0.045 (6)0.018 (5)0.008 (5)0.017 (5)
C10.051 (6)0.032 (6)0.041 (6)0.013 (5)0.007 (5)0.015 (5)
C20.041 (6)0.046 (6)0.042 (6)0.022 (5)0.010 (4)0.020 (5)
C30.076 (8)0.068 (8)0.039 (6)0.046 (6)0.017 (5)0.016 (5)
C40.050 (6)0.032 (6)0.042 (6)0.020 (5)0.008 (4)0.013 (5)
C50.056 (7)0.033 (6)0.041 (6)0.020 (5)0.015 (4)0.015 (5)
C60.066 (7)0.031 (6)0.060 (7)0.015 (5)0.020 (6)0.015 (5)
C70.063 (7)0.040 (7)0.034 (6)0.014 (5)0.012 (5)0.009 (5)
C80.085 (9)0.068 (9)0.048 (7)0.036 (7)0.015 (6)0.026 (6)
C90.075 (8)0.057 (7)0.049 (7)0.034 (6)0.019 (5)0.021 (6)
C100.061 (7)0.031 (6)0.036 (6)0.024 (5)0.016 (5)0.013 (5)
C110.105 (9)0.067 (8)0.043 (6)0.050 (7)0.008 (6)0.007 (6)
C120.044 (6)0.027 (5)0.045 (6)0.016 (4)0.015 (4)0.009 (5)
C130.065 (7)0.041 (6)0.027 (5)0.019 (5)0.008 (4)0.006 (5)
C140.073 (8)0.049 (7)0.041 (6)0.034 (6)0.016 (5)0.011 (5)
C150.046 (6)0.047 (7)0.066 (7)0.026 (5)0.019 (5)0.030 (6)
C160.073 (8)0.064 (8)0.043 (7)0.037 (6)0.007 (5)0.016 (6)
C170.085 (8)0.063 (8)0.035 (6)0.049 (6)0.009 (5)0.011 (5)
S10.081 (2)0.0479 (17)0.0348 (14)0.0368 (15)0.0041 (12)0.0074 (12)
N10.055 (5)0.038 (5)0.041 (5)0.026 (4)0.005 (4)0.013 (4)
N20.050 (5)0.047 (5)0.032 (4)0.028 (4)0.017 (4)0.009 (4)
N30.074 (6)0.037 (5)0.035 (5)0.030 (4)0.002 (4)0.006 (4)
N40.052 (5)0.046 (5)0.038 (5)0.030 (4)0.009 (4)0.012 (4)
Geometric parameters (Å, º) top
Br1—C71.902 (9)C33—H330.9300
Br2—C151.885 (10)C34—H340.9300
Br3—C241.918 (9)C1—N31.333 (11)
Br4—C321.903 (10)C1—N11.367 (11)
N5—C181.342 (11)C1—S11.667 (9)
N5—N61.374 (10)C2—N21.310 (11)
N5—H5B0.8600C2—C41.478 (12)
N6—C191.292 (11)C2—C31.482 (12)
N7—C181.363 (11)C3—H3A0.9600
N7—N81.366 (10)C3—H3B0.9600
N7—H70.8600C3—H3C0.9600
N8—C271.285 (11)C4—C51.360 (12)
S2—C181.666 (9)C4—C91.388 (13)
C19—C211.484 (12)C5—C61.394 (13)
C19—C201.484 (12)C5—H5A0.9300
C20—H20A0.9600C6—C71.373 (14)
C20—H20B0.9600C6—H60.9300
C20—H20C0.9600C7—C81.376 (14)
C21—C261.397 (12)C8—C91.412 (13)
C21—C221.410 (13)C8—H80.9300
C22—C231.364 (13)C9—H90.9300
C22—H220.9300C10—N41.282 (11)
C23—C241.378 (13)C10—C121.486 (12)
C23—H230.9300C10—C111.501 (13)
C24—C251.388 (13)C11—H11A0.9600
C25—C261.375 (13)C11—H11B0.9600
C25—H250.9300C11—H11C0.9600
C26—H260.9300C12—C171.382 (13)
C27—C291.474 (13)C12—C131.386 (12)
C27—C281.522 (13)C13—C141.374 (13)
C28—H28A0.9600C13—H130.9300
C28—H28B0.9600C14—C151.378 (13)
C28—H28C0.9600C14—H140.9300
C29—C341.391 (12)C15—C161.374 (13)
C29—C301.395 (13)C16—C171.363 (14)
C30—C311.378 (13)C16—H160.9300
C30—H300.9300C17—H170.9300
C31—C321.357 (13)N1—N21.372 (10)
C31—H310.9300N1—H10.8600
C32—C331.366 (14)N3—N41.350 (10)
C33—C341.374 (14)N3—H30.8600
C18—N5—N6118.9 (8)N3—C1—N1113.2 (8)
C18—N5—H5B120.5N3—C1—S1125.1 (8)
N6—N5—H5B120.5N1—C1—S1121.7 (7)
C19—N6—N5119.3 (8)N2—C2—C4115.2 (8)
C18—N7—N8119.5 (8)N2—C2—C3123.0 (8)
C18—N7—H7120.3C4—C2—C3121.5 (8)
N8—N7—H7120.3C2—C3—H3A109.5
C27—N8—N7118.1 (8)C2—C3—H3B109.5
N5—C18—N7113.3 (8)H3A—C3—H3B109.5
N5—C18—S2122.5 (7)C2—C3—H3C109.5
N7—C18—S2124.2 (7)H3A—C3—H3C109.5
N6—C19—C21114.5 (8)H3B—C3—H3C109.5
N6—C19—C20124.5 (8)C5—C4—C9118.4 (9)
C21—C19—C20121.0 (8)C5—C4—C2121.7 (9)
C19—C20—H20A109.5C9—C4—C2120.0 (9)
C19—C20—H20B109.5C4—C5—C6120.8 (9)
H20A—C20—H20B109.5C4—C5—H5A119.6
C19—C20—H20C109.5C6—C5—H5A119.6
H20A—C20—H20C109.5C7—C6—C5120.1 (9)
H20B—C20—H20C109.5C7—C6—H6119.9
C26—C21—C22117.5 (9)C5—C6—H6119.9
C26—C21—C19121.3 (9)C6—C7—C8121.3 (9)
C22—C21—C19121.1 (8)C6—C7—Br1119.5 (8)
C23—C22—C21122.3 (9)C8—C7—Br1119.1 (8)
C23—C22—H22118.8C7—C8—C9117.0 (10)
C21—C22—H22118.8C7—C8—H8121.5
C22—C23—C24117.7 (10)C9—C8—H8121.5
C22—C23—H23121.2C4—C9—C8122.3 (10)
C24—C23—H23121.2C4—C9—H9118.9
C23—C24—C25122.8 (9)C8—C9—H9118.9
C23—C24—Br3119.1 (8)N4—C10—C12116.0 (8)
C25—C24—Br3117.9 (7)N4—C10—C11125.2 (9)
C26—C25—C24118.3 (9)C12—C10—C11118.7 (8)
C26—C25—H25120.9C10—C11—H11A109.5
C24—C25—H25120.9C10—C11—H11B109.5
C25—C26—C21121.3 (9)H11A—C11—H11B109.5
C25—C26—H26119.4C10—C11—H11C109.5
C21—C26—H26119.4H11A—C11—H11C109.5
N8—C27—C29115.9 (9)H11B—C11—H11C109.5
N8—C27—C28125.0 (9)C17—C12—C13116.2 (9)
C29—C27—C28119.0 (8)C17—C12—C10122.4 (8)
C27—C28—H28A109.5C13—C12—C10121.4 (9)
C27—C28—H28B109.5C14—C13—C12122.5 (9)
H28A—C28—H28B109.5C14—C13—H13118.8
C27—C28—H28C109.5C12—C13—H13118.8
H28A—C28—H28C109.5C13—C14—C15119.0 (10)
H28B—C28—H28C109.5C13—C14—H14120.5
C34—C29—C30117.6 (9)C15—C14—H14120.5
C34—C29—C27122.3 (9)C16—C15—C14120.2 (9)
C30—C29—C27119.9 (8)C16—C15—Br2119.1 (8)
C31—C30—C29121.0 (9)C14—C15—Br2120.8 (8)
C31—C30—H30119.5C17—C16—C15119.3 (10)
C29—C30—H30119.5C17—C16—H16120.4
C32—C31—C30119.6 (10)C15—C16—H16120.4
C32—C31—H31120.2C16—C17—C12122.9 (10)
C30—C31—H31120.2C16—C17—H17118.6
C31—C32—C33121.1 (10)C12—C17—H17118.6
C31—C32—Br4120.5 (8)C1—N1—N2117.6 (7)
C33—C32—Br4118.4 (7)C1—N1—H1121.2
C32—C33—C34119.7 (9)N2—N1—H1121.2
C32—C33—H33120.1C2—N2—N1120.2 (8)
C34—C33—H33120.1C1—N3—N4122.5 (8)
C33—C34—C29120.9 (10)C1—N3—H3118.8
C33—C34—H34119.5N4—N3—H3118.8
C29—C34—H34119.5C10—N4—N3117.5 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5B···S10.862.713.551 (8)168
N1—H1···S20.862.693.551 (8)174
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5B···S10.862.713.551 (8)168
N1—H1···S20.862.693.551 (8)174
Acknowledgements top

The author acknowledges financial support by Dongchang College, Liaocheng University.

references
References top

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