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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1696.
Published online 2010 June 18. doi:  10.1107/S1600536810022622
PMCID: PMC3006822

1-[1-(4-Bromo­phen­yl)ethyl­idene]-4-(2,4-dimeth­oxy­phen­yl)thio­semicarbazide

Abstract

In the title compound, C17H18BrN3O2S, the dihedral angle between the aromatic rings is 9.15 (17)°. A bifurcated intra­molecular N—H(...)(N,O) hydrogen bond generates two S(5) rings and a weak intra­molecular C—H(...)S inter­action completes an S(6) ring motif. In the crystal, inversion dimers linked by pairs of N—H(...)S hydrogen bonds generate R 2 2(8) loops and weak C—H(...)S and C—H(...)π inter­actions are also present.

Related literature

For the pharmacological applications of thio­semicarbazones see: Beraldo & Gambino (2004 [triangle]); Pervez et al. (2008 [triangle], 2010a [triangle],b [triangle]). For related structures, see: Jian et al. (2005 [triangle]); Martínez et al. (2006 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1696-scheme1.jpg

Experimental

Crystal data

  • C17H18BrN3O2S
  • M r = 408.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1696-efi1.jpg
  • a = 5.8390 (2) Å
  • b = 30.3335 (11) Å
  • c = 9.9423 (4) Å
  • β = 94.910 (2)°
  • V = 1754.49 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.48 mm−1
  • T = 296 K
  • 0.25 × 0.22 × 0.20 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.642, T max = 0.652
  • 17115 measured reflections
  • 4346 independent reflections
  • 2654 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.100
  • S = 1.01
  • 4346 reflections
  • 220 parameters
  • H-atom parameters constrained
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022622/hb5499sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022622/hb5499Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

NA gratefully acknowledges the Higher Education Commission (HEC), Islamabad, Pakistan, for providing her with a Scholarship under the Indigenous PhD Program and also for partial funding of this research work.

supplementary crystallographic information

Comment

Thiosemicarbazones have wide pharmacological properties (Beraldo & Gambino, 2004). Prompted by this, we recently reported the synthesis and medicinal importance of some isatins-thiosemicarbazones (Pervez et al., 2008, 2010a,b). Now, we report the synthesis and crystal structure of the title compound (I), (Fig. I).

The crystal structure of (II) i.e. 4-fluoroacetophenone-N-propylthiosemicarbazone (Martinez et al., 2006) and (III) i.e. 4-phenyl-1-(1-phenylethylidene)thiosemicarbazide (Jian, et al., 2005) have been published. The title compound (I) is different from (II) and (III) due to attachment of substituants at the phenyl rings.

In (I), the phenyl ring A (C1–C6) of 2,4-dimethoxyanilino group, B (C11—C16) of 4-bromophenyl are planar with r. m. s. deviations of 0.0034 and 0.0036 Å, respectively. The thiosemicarbazone moiety C (N1—N3/C9/S1) is also planar with r. m. s. deviation of 0.0062 Å from its mean square plane. The dihedral angle between A/B, A/C and B/C is 9.15 (17), 2.07 (17) and 9.12 (16)°, respectively. Two S(5) ring motifs (Bernstein et al., 1995) (Table 1, Fig. 1) are formed due to strong intramolecular H-bonding of N—H···N and N—H···O types. The weak interaction of C—H···S type completes an S(6) ring motif. The molecules are dimerized due to intermolecular interactions of N—H···S type and complete R22(8) ring motif (Fig. 2). The dimers are interlinked through C—H···S interactions (Table 1). The C—H···π interaction (Table 1) also play role in stabilizing the molecules.

Experimental

A solution of 4-(2,4-dimethoxyphenyl)thiosemicarbazide (0.15 g, 0.66 mole) in warm ethanol (20 ml) was added drop wise to the stirred solution of 4-bromoacetophenone (0.13 g, 0.66 mol) in warm ethanol (10 ml) containing 2–3 drops of acetic acid. The resultant mixture was then heated under reflux for 30 min. After cooling the reaction mixture to room temperature, the yellow solid was collected by suction filtration, washing with ethanol furnished the title compound in pure form (0.21 g, 95%), m.p. 502 K. Colourless prisms of (I) were grown in chloroform-petroleum ether (1:5) system at room temperature by diffusion method.

Refinement

The H-atoms were positioned geometrically (N–H = 0.86 Å, C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C, N), where x = 1.5 for methyl and x = 1.2 for all other H-atoms.

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level. The dotted lines indicate the intra-molecular H-bonds.
Fig. 2.
The partial packing of (I), which shows that molecules form dimers.

Crystal data

C17H18BrN3O2SF(000) = 832
Mr = 408.31Dx = 1.546 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2654 reflections
a = 5.8390 (2) Åθ = 2.2–28.3°
b = 30.3335 (11) ŵ = 2.48 mm1
c = 9.9423 (4) ÅT = 296 K
β = 94.910 (2)°Prism, colorless
V = 1754.49 (11) Å30.25 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer4346 independent reflections
Radiation source: fine-focus sealed tube2654 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 7.5 pixels mm-1θmax = 28.3°, θmin = 2.2°
ω scansh = −4→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −40→40
Tmin = 0.642, Tmax = 0.652l = −13→13
17115 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0413P)2 + 0.4088P] where P = (Fo2 + 2Fc2)/3
4346 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/Ueq
Br11.68144 (7)0.28876 (1)0.66065 (3)0.0846 (1)
S10.69373 (12)0.00989 (2)0.87217 (7)0.0577 (2)
O10.7242 (3)0.14610 (6)0.55058 (18)0.0598 (7)
O20.0390 (3)0.09126 (7)0.3147 (2)0.0710 (8)
N10.7530 (3)0.08160 (7)0.7192 (2)0.0504 (7)
N21.0174 (3)0.06989 (7)0.8946 (2)0.0490 (7)
N31.1192 (3)0.10729 (7)0.8520 (2)0.0465 (7)
C10.5629 (4)0.08091 (8)0.6222 (2)0.0453 (8)
C20.3956 (5)0.04927 (10)0.6085 (3)0.0684 (11)
C30.2178 (5)0.05173 (10)0.5075 (3)0.0707 (11)
C40.2059 (4)0.08609 (9)0.4186 (3)0.0536 (9)
C50.3721 (4)0.11870 (9)0.4316 (3)0.0519 (9)
C60.5493 (4)0.11606 (8)0.5315 (2)0.0449 (8)
C70.7459 (5)0.17845 (10)0.4497 (3)0.0718 (11)
C8−0.1278 (5)0.05715 (11)0.2945 (3)0.0714 (11)
C90.8214 (4)0.05526 (8)0.8225 (2)0.0426 (8)
C101.2991 (4)0.12299 (8)0.9180 (2)0.0413 (8)
C111.3922 (4)0.16334 (8)0.8596 (2)0.0397 (7)
C121.2659 (4)0.18592 (9)0.7571 (3)0.0522 (9)
C131.3493 (5)0.22333 (9)0.7001 (3)0.0585 (10)
C141.5632 (4)0.23844 (9)0.7440 (3)0.0511 (9)
C151.6935 (5)0.21732 (9)0.8453 (3)0.0560 (10)
C161.6074 (4)0.17997 (9)0.9025 (3)0.0508 (9)
C171.4082 (5)0.10312 (9)1.0456 (3)0.0565 (9)
H10.843890.103500.710090.0605*
H20.401570.025640.668310.0820*
H2A1.074560.055880.964810.0587*
H30.105830.029850.500220.0849*
H50.363750.142510.372410.0623*
H7A0.613210.197270.443970.1075*
H7B0.757830.164260.364290.1075*
H7C0.881330.195760.472520.1075*
H8A−0.219190.056090.370270.1075*
H8B−0.051480.029380.286020.1075*
H8C−0.225140.062960.213730.1075*
H121.121060.175520.726130.0626*
H131.260850.238200.632260.0701*
H151.838200.227990.875360.0672*
H161.695790.165640.971450.0610*
H17A1.489710.076851.024620.0848*
H17B1.291340.095891.104180.0848*
H17C1.513610.123881.089730.0848*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.1088 (3)0.0700 (2)0.0736 (2)−0.0456 (2)0.0001 (2)0.0106 (2)
S10.0585 (4)0.0489 (4)0.0642 (4)−0.0114 (3)−0.0030 (3)0.0194 (3)
O10.0677 (12)0.0508 (11)0.0587 (12)−0.0148 (9)−0.0080 (9)0.0172 (9)
O20.0668 (12)0.0697 (14)0.0712 (13)0.0015 (11)−0.0242 (10)0.0076 (11)
N10.0543 (12)0.0453 (12)0.0496 (12)−0.0150 (10)−0.0074 (10)0.0128 (10)
N20.0522 (12)0.0458 (12)0.0470 (12)−0.0095 (10)−0.0066 (10)0.0129 (10)
N30.0493 (12)0.0431 (12)0.0464 (12)−0.0070 (9)−0.0005 (10)0.0087 (9)
C10.0483 (14)0.0439 (14)0.0429 (13)−0.0044 (11)−0.0008 (11)0.0061 (11)
C20.077 (2)0.0571 (18)0.0670 (19)−0.0215 (15)−0.0181 (16)0.0215 (15)
C30.0721 (19)0.063 (2)0.072 (2)−0.0253 (16)−0.0223 (16)0.0155 (16)
C40.0529 (16)0.0520 (16)0.0540 (16)0.0031 (12)−0.0056 (13)−0.0032 (13)
C50.0644 (17)0.0443 (14)0.0462 (15)0.0062 (12)−0.0006 (13)0.0072 (11)
C60.0517 (15)0.0390 (13)0.0442 (14)−0.0022 (11)0.0051 (12)0.0012 (10)
C70.090 (2)0.0543 (19)0.070 (2)−0.0172 (16)0.0010 (17)0.0197 (15)
C80.0591 (18)0.076 (2)0.075 (2)0.0018 (16)−0.0180 (15)−0.0104 (17)
C90.0461 (14)0.0407 (13)0.0412 (13)−0.0013 (10)0.0043 (11)0.0027 (10)
C100.0435 (14)0.0416 (13)0.0384 (13)0.0037 (10)0.0018 (11)−0.0006 (10)
C110.0417 (13)0.0388 (13)0.0384 (12)−0.0005 (10)0.0025 (10)−0.0044 (10)
C120.0475 (15)0.0506 (15)0.0572 (16)−0.0094 (12)−0.0030 (12)0.0095 (13)
C130.0617 (18)0.0552 (17)0.0567 (17)−0.0082 (13)−0.0053 (14)0.0109 (13)
C140.0603 (16)0.0469 (15)0.0465 (15)−0.0135 (12)0.0075 (13)−0.0047 (12)
C150.0539 (16)0.0591 (18)0.0544 (16)−0.0181 (13)0.0004 (13)−0.0090 (13)
C160.0507 (15)0.0525 (16)0.0480 (14)−0.0024 (12)−0.0029 (12)0.0005 (12)
C170.0650 (17)0.0505 (16)0.0515 (16)−0.0036 (13)−0.0099 (13)0.0063 (12)

Geometric parameters (Å, °)

Br1—C141.895 (3)C11—C121.387 (4)
S1—C91.660 (2)C12—C131.376 (4)
O1—C61.370 (3)C13—C141.366 (4)
O1—C71.417 (3)C14—C151.368 (4)
O2—C41.367 (3)C15—C161.382 (4)
O2—C81.423 (4)C2—H20.9300
N1—C11.407 (3)C3—H30.9300
N1—C91.335 (3)C5—H50.9300
N2—N31.365 (3)C7—H7A0.9600
N2—C91.371 (3)C7—H7B0.9600
N3—C101.282 (3)C7—H7C0.9600
N1—H10.8600C8—H8A0.9600
N2—H2A0.8600C8—H8B0.9600
C1—C21.368 (4)C8—H8C0.9600
C1—C61.394 (3)C12—H120.9300
C2—C31.383 (4)C13—H130.9300
C3—C41.365 (4)C15—H150.9300
C4—C51.384 (4)C16—H160.9300
C5—C61.374 (3)C17—H17A0.9600
C10—C111.478 (3)C17—H17B0.9600
C10—C171.497 (4)C17—H17C0.9600
C11—C161.387 (3)
C6—O1—C7118.27 (19)C14—C15—C16119.2 (3)
C4—O2—C8117.3 (2)C11—C16—C15121.6 (3)
C1—N1—C9133.2 (2)C1—C2—H2119.00
N3—N2—C9118.23 (19)C3—C2—H2119.00
N2—N3—C10120.6 (2)C2—C3—H3120.00
C9—N1—H1113.00C4—C3—H3120.00
C1—N1—H1113.00C4—C5—H5120.00
N3—N2—H2A121.00C6—C5—H5120.00
C9—N2—H2A121.00O1—C7—H7A109.00
C2—C1—C6118.1 (2)O1—C7—H7B109.00
N1—C1—C6115.5 (2)O1—C7—H7C109.00
N1—C1—C2126.4 (2)H7A—C7—H7B109.00
C1—C2—C3121.3 (3)H7A—C7—H7C109.00
C2—C3—C4120.3 (3)H7B—C7—H7C109.00
O2—C4—C3124.8 (2)O2—C8—H8A109.00
O2—C4—C5115.9 (2)O2—C8—H8B109.00
C3—C4—C5119.3 (3)O2—C8—H8C109.00
C4—C5—C6120.3 (3)H8A—C8—H8B109.00
O1—C6—C5124.6 (2)H8A—C8—H8C109.00
C1—C6—C5120.7 (2)H8B—C8—H8C109.00
O1—C6—C1114.75 (19)C11—C12—H12119.00
S1—C9—N1127.77 (18)C13—C12—H12119.00
S1—C9—N2119.25 (17)C12—C13—H13120.00
N1—C9—N2112.9 (2)C14—C13—H13120.00
C11—C10—C17121.5 (2)C14—C15—H15120.00
N3—C10—C11114.80 (19)C16—C15—H15120.00
N3—C10—C17123.7 (2)C11—C16—H16119.00
C10—C11—C16122.3 (2)C15—C16—H16119.00
C12—C11—C16117.2 (2)C10—C17—H17A109.00
C10—C11—C12120.5 (2)C10—C17—H17B109.00
C11—C12—C13121.7 (2)C10—C17—H17C109.00
C12—C13—C14119.4 (3)H17A—C17—H17B109.00
Br1—C14—C13119.2 (2)H17A—C17—H17C109.00
C13—C14—C15120.9 (3)H17B—C17—H17C110.00
Br1—C14—C15119.90 (19)
C7—O1—C6—C1169.2 (2)C2—C3—C4—O2179.3 (3)
C7—O1—C6—C5−10.1 (3)C2—C3—C4—C5−0.8 (4)
C8—O2—C4—C3−3.1 (4)O2—C4—C5—C6−178.9 (2)
C8—O2—C4—C5176.9 (2)C3—C4—C5—C61.1 (4)
C9—N1—C1—C2−2.8 (4)C4—C5—C6—O1178.5 (2)
C9—N1—C1—C6178.0 (2)C4—C5—C6—C1−0.8 (4)
C1—N1—C9—S10.2 (4)N3—C10—C11—C1211.5 (3)
C1—N1—C9—N2−177.7 (2)N3—C10—C11—C16−167.7 (2)
C9—N2—N3—C10178.1 (2)C17—C10—C11—C12−167.6 (2)
N3—N2—C9—S1−179.91 (16)C17—C10—C11—C1613.1 (4)
N3—N2—C9—N1−1.8 (3)C10—C11—C12—C13−179.4 (2)
N2—N3—C10—C11179.44 (19)C16—C11—C12—C13−0.1 (4)
N2—N3—C10—C17−1.4 (3)C10—C11—C16—C15178.9 (2)
N1—C1—C2—C3−179.0 (3)C12—C11—C16—C15−0.3 (4)
C6—C1—C2—C30.2 (4)C11—C12—C13—C140.9 (4)
N1—C1—C6—O10.1 (3)C12—C13—C14—Br1177.8 (2)
N1—C1—C6—C5179.5 (2)C12—C13—C14—C15−1.2 (4)
C2—C1—C6—O1−179.3 (2)Br1—C14—C15—C16−178.2 (2)
C2—C1—C6—C50.2 (4)C13—C14—C15—C160.7 (4)
C1—C2—C3—C40.1 (4)C14—C15—C16—C110.1 (4)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.122.573 (3)113
N1—H1···N30.862.052.538 (3)115
N2—H2A···S1i0.862.843.662 (2)161
C2—H2···S10.932.583.248 (3)129
C17—H17A···S1ii0.962.863.774 (3)161
C8—H8A···Cg1iii0.962.983.860 (3)153

Symmetry codes: (i) −x+2, −y, −z+2; (ii) x+1, y, z; (iii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5499).

References

  • Beraldo, H. & Gambino, D. (2004). Mini Rev. Med. Chem.4, 159–165.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Jian, F., Li, Y. & Xiao, H. (2005). Acta Cryst. E61, o2219–o2220.
  • Martínez, J., Adrio, L. A., Antelo, J. M., Ortigueira, J. M., Pereira, M. T., López-Torres, M. & Vila, M. J. (2006). J. Organomet. Chem. 691, 2891–2901.
  • Pervez, H., Iqbal, M. S., Tahir, M. Y., Nasim, F. H., Choudhary, M. I. Khan, K. M. & Yaqub, M. (2008). J. Enz. Inhib. Med. Chem.23, 848–854. [PubMed]
  • Pervez, H., Manzoor, N., Yaqub, M., Khan, A., Khan, K. M., Nasim, F. H. & Choudhary, M. I. (2010a). Lett. Drug Des. Discov.7, 102–108.
  • Pervez, H., Iqbal, M. S., Saira, N., Yaqub, M. & Tahir, M. N. (2010b). Acta Cryst. E66, o1169–o1170. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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