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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 2| February 2010| Page o421
https://doi.org/10.1107/S160053681000214X

(E)-1-(3-Cyano­benzyl­­idene)thio­semi­carbazide N,N-di­methyl­formamide solvate

Mei Shia*

aDepartment of Chemistry, Nanjing Xiaozhuang University, Nanjing 210017, People's Republic of China
*Correspondence e-mail: shimei2008@live.cn

(Received 5 January 2010; accepted 18 January 2010; online 23 January 2010)

The title compound, C9H8N4S·C3H7NO, adopts an E configuration about both the C=N and C—N bonds. Inter­molecular N—H⋯O hydrogen bonding links the compound to the DMF solvent molecule. The crystal packing is characterized by chains of mol­ecules linked by inter­molecular N—H⋯S hydrogen-bonding inter­actions.

Related literature

For the biological activity of thio­semicarbazones, see: Lovejoy & Richardson et al. (2002[Lovejoy, D. B. & Richardson, D. R. (2002). Blood, 100, 666-676.]). For a related structure, see: Wu et al. (2009[Wu, D.-H., Zhang, Y.-H., Li, Z.-F. & Li, Y.-H. (2009). Acta Cryst. E65, o107.]). For comparitive geometrical parameters, see: Sutton et al. (1965[Sutton, L. E. (1965). Tables of Interatomic Distances and Configurations in Molecules and Ions, Suppl. London: The Chemical Society.]).

[Scheme 1]

Experimental

Crystal data

  • C9H8N4S·C3H7NO

  • Mr = 277.35

  • Monoclinic, P 21 /n

  • a = 7.312 (7) Å

  • b = 8.945 (3) Å

  • c = 22.316 (19) Å

  • β = 92.12 (2)°

  • V = 1458.6 (19) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.22 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm
Data collection

  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.742, Tmax = 1.000

  • 9561 measured reflections

  • 3280 independent reflections

  • 2065 reflections with I > 2σ(I)

  • Rint = 0.052
Refinement

  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.109

  • S = 1.01

  • 3280 reflections

  • 172 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H3A⋯O1 0.86 1.96 2.795 (3) 162
N4—H4A⋯N1i 0.86 2.35 3.101 (3) 146
N4—H4B⋯S1ii 0.86 2.59 3.364 (2) 150
C8—H8A⋯O1 0.93 2.54 3.293 (3) 138
Symmetry codes: (i) -x+2, -y, -z+1; (ii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681000214X/pv2253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681000214X/pv2253Isup2.hkl

checkCIF report


Comment top

The antiproliferative activity of a series of thiosemicarbazones has been reported (Lovejoy & Richardson, 2002). As a research on thiosemicarbazones, the synthesis and crystal structure of a new Schiff base compound derived from thiosemicarbazide and 3-cyanobenzaldehyde has been presented in this article. The crystal structure of 4-cyanobenzaldehyde thiosemicarbazone which is closely related to the title compound has been reported recently (Wu et al. 2009).

The thiosemicarbazone moiety in the title compound (Fig. 1) is nearly planar and shows an E configuration about both the C9—N3 and C8═N2 bonds. The C—S bond distance of 1.680 (2) Å agrees well with similar bonds in related compounds, being intermediate between 1.82 Å for a C—S single bond and 1.56 Å for a C═S double bond (Sutton et al. 1965). All the bond distances except for the C6—C9 (bond length, 1.448 (3) Å) fall within the normal range. The intermolecular N—H···O hydrogen bond stabilizes the molecular conformation. In the crystal packing, adjacent molecules are linked by N—H···S hydrogen bonds (Table 1 and Fig. 2) to form chains running parallel to the a axis. Weak interactions of the type C—H···O are also present in the structure.

Related literature top

For the biological activity of thiosemicarbazones, see: Lovejoy & Richardson et al. (2002). For a related structure, see: Wu et al. (2009). For comparitive geometrical parameters, see: Sutton et al. (1965).

Experimental top

The title compound was synthesized by refluxing 3-cyanobenzaldehyde (2.1 g, 16 mmol) and thiosemicarbazide (1.46 g, 16 mmol) in absolute ethanol (50 ml) for 10 h. After cooling to room temperature, the white solid formed was isolated and dried under vacuum. The title compound was isolated using column chromatography (petroleum ether: ethyl acetate-2:1). Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of DMF solution.

Refinement top

H atoms were placed in calculated positions and refined using a riding model, with N—H = 0.86 Å, C—H = 0.93–0.96 Å and with Uiso(H) = 1.2 and 1.5 times Ueq of nonmethyl and methyl type H-atoms.

Structure description top

The antiproliferative activity of a series of thiosemicarbazones has been reported (Lovejoy & Richardson, 2002). As a research on thiosemicarbazones, the synthesis and crystal structure of a new Schiff base compound derived from thiosemicarbazide and 3-cyanobenzaldehyde has been presented in this article. The crystal structure of 4-cyanobenzaldehyde thiosemicarbazone which is closely related to the title compound has been reported recently (Wu et al. 2009).

The thiosemicarbazone moiety in the title compound (Fig. 1) is nearly planar and shows an E configuration about both the C9—N3 and C8═N2 bonds. The C—S bond distance of 1.680 (2) Å agrees well with similar bonds in related compounds, being intermediate between 1.82 Å for a C—S single bond and 1.56 Å for a C═S double bond (Sutton et al. 1965). All the bond distances except for the C6—C9 (bond length, 1.448 (3) Å) fall within the normal range. The intermolecular N—H···O hydrogen bond stabilizes the molecular conformation. In the crystal packing, adjacent molecules are linked by N—H···S hydrogen bonds (Table 1 and Fig. 2) to form chains running parallel to the a axis. Weak interactions of the type C—H···O are also present in the structure.

For the biological activity of thiosemicarbazones, see: Lovejoy & Richardson et al. (2002). For a related structure, see: Wu et al. (2009). For comparitive geometrical parameters, see: Sutton et al. (1965).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the a axis showing the two-dimensionnal hydrogen bondings network. H-atoms non involved in H-bonding interactions have been excluded for clarity.
(E)-1-(3-Cyanobenzylidene)thiosemicarbazide N,N-dimethylformamide solvate top
Crystal data top
C9H8N4S·C3H7NOF(000) = 584
Mr = 277.35Dx = 1.263 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2851 reflections
a = 7.312 (7) Åθ = 2.3–27.4°
b = 8.945 (3) ŵ = 0.22 mm−1
c = 22.316 (19) ÅT = 293 K
β = 92.12 (2)°Block, pale yellow
V = 1458.6 (19) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer		3280 independent reflections
Radiation source: fine-focus sealed tube2065 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
Detector resolution: 13.6612 pixels mm-1θmax = 27.4°, θmin = 2.5°
CCD_Profile_fitting scansh = −7→9
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −11→11
Tmin = 0.742, Tmax = 1.000l = −28→24
9561 measured reflections
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.020P)2 + 0.850P]
where P = (Fo2 + 2Fc2)/3
3280 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.18 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C9H8N4S·C3H7NOV = 1458.6 (19) Å3
Mr = 277.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.312 (7) ŵ = 0.22 mm−1
b = 8.945 (3) ÅT = 293 K
c = 22.316 (19) Å0.20 × 0.20 × 0.20 mm
β = 92.12 (2)°
Data collection top
Rigaku Mercury2
diffractometer		3280 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2065 reflections with I > 2σ(I)
Tmin = 0.742, Tmax = 1.000Rint = 0.052
9561 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.01Δρmax = 0.18 e Å−3
3280 reflectionsΔρmin = −0.20 e Å−3
172 parameters
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
S10.60691 (11)0.46135 (8)0.74146 (3)0.0636 (2)
N20.7389 (2)0.40996 (19)0.57477 (8)0.0425 (4)
N30.6727 (2)0.4707 (2)0.62652 (8)0.0451 (5)
H3A0.61980.55660.62580.054*
C60.8765 (3)0.2925 (2)0.46844 (10)0.0430 (5)
H6A0.88570.23270.50250.052*
N40.7782 (3)0.2634 (2)0.67556 (9)0.0585 (6)
H4A0.81810.23200.64200.070*
H4B0.79390.21020.70740.070*
C80.7256 (3)0.4903 (2)0.52748 (10)0.0428 (5)
H8A0.67240.58460.52880.051*
C90.6924 (3)0.3936 (2)0.67810 (10)0.0441 (5)
C71.0229 (3)0.0938 (3)0.41270 (10)0.0518 (6)
C10.7947 (3)0.4329 (2)0.47102 (9)0.0402 (5)
N11.0774 (3)−0.0249 (3)0.41178 (10)0.0714 (7)
C50.9444 (3)0.2423 (2)0.41459 (10)0.0444 (5)
C20.7832 (3)0.5198 (3)0.41938 (10)0.0501 (6)
H2B0.72950.61400.42070.060*
C30.8504 (3)0.4685 (3)0.36610 (10)0.0565 (6)
H3B0.84070.52810.33200.068*
C40.9316 (3)0.3298 (3)0.36311 (10)0.0535 (6)
H4C0.97700.29530.32730.064*
N50.4289 (3)0.9814 (2)0.63750 (9)0.0565 (5)
C100.4945 (4)0.8452 (3)0.64567 (13)0.0641 (7)
H10A0.49040.80550.68410.077*
O10.5606 (3)0.76602 (19)0.60695 (9)0.0718 (6)
C110.4348 (4)1.0502 (3)0.57878 (13)0.0756 (8)
H11A0.48690.98130.55120.113*
H11B0.50851.13890.58130.113*
H11C0.31291.07590.56500.113*
C120.3501 (4)1.0680 (4)0.68517 (15)0.0925 (11)
H12A0.35211.00990.72140.139*
H12B0.22611.09360.67400.139*
H12C0.42021.15770.69170.139*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0917 (5)0.0516 (4)0.0489 (4)−0.0029 (4)0.0207 (3)−0.0114 (3)
N20.0512 (12)0.0372 (9)0.0396 (10)0.0037 (8)0.0069 (9)−0.0025 (8)
N30.0550 (12)0.0366 (9)0.0444 (11)0.0082 (9)0.0102 (9)−0.0053 (8)
C60.0502 (14)0.0383 (12)0.0403 (12)0.0002 (10)0.0011 (10)0.0022 (9)
N40.0848 (16)0.0461 (11)0.0454 (12)0.0152 (11)0.0121 (11)0.0056 (9)
C80.0450 (13)0.0359 (12)0.0477 (14)0.0064 (10)0.0030 (10)−0.0018 (10)
C90.0508 (15)0.0351 (11)0.0465 (13)−0.0047 (10)0.0054 (11)−0.0038 (10)
C70.0604 (16)0.0490 (14)0.0468 (14)0.0050 (12)0.0114 (12)−0.0048 (11)
C10.0421 (13)0.0373 (12)0.0413 (12)0.0011 (9)0.0014 (10)−0.0015 (9)
N10.0898 (18)0.0539 (14)0.0718 (16)0.0190 (13)0.0214 (13)−0.0032 (12)
C50.0486 (14)0.0392 (12)0.0454 (13)0.0005 (10)0.0031 (11)−0.0050 (10)
C20.0603 (16)0.0407 (12)0.0492 (14)0.0063 (11)−0.0003 (12)0.0025 (11)
C30.0730 (18)0.0554 (15)0.0408 (14)0.0039 (13)0.0006 (12)0.0081 (12)
C40.0642 (17)0.0558 (15)0.0411 (14)−0.0010 (13)0.0075 (12)−0.0042 (11)
N50.0650 (14)0.0431 (11)0.0621 (14)0.0022 (10)0.0117 (11)−0.0079 (10)
C100.074 (2)0.0515 (16)0.0665 (18)−0.0059 (14)0.0011 (15)0.0052 (13)
O10.0870 (15)0.0432 (10)0.0860 (14)0.0116 (10)0.0131 (11)−0.0066 (10)
C110.088 (2)0.0541 (17)0.086 (2)0.0066 (15)0.0132 (17)0.0126 (15)
C120.095 (2)0.083 (2)0.102 (3)−0.0076 (19)0.034 (2)−0.0443 (19)
Geometric parameters (Å, º) top
S1—C91.680 (2)C2—C31.382 (3)
N2—C81.277 (3)C2—H2B0.9300
N2—N31.380 (2)C3—C41.378 (3)
N3—C91.345 (3)C3—H3B0.9300
N3—H3A0.8600C4—H4C0.9300
C6—C51.392 (3)N5—C101.320 (3)
C6—C11.393 (3)N5—C111.450 (3)
C6—H6A0.9300N5—C121.452 (3)
N4—C91.325 (3)C10—O11.230 (3)
N4—H4A0.8600C10—H10A0.9300
N4—H4B0.8600C11—H11A0.9600
C8—C11.467 (3)C11—H11B0.9600
C8—H8A0.9300C11—H11C0.9600
C7—N11.135 (3)C12—H12A0.9600
C7—C51.447 (3)C12—H12B0.9600
C1—C21.390 (3)C12—H12C0.9600
C5—C41.390 (3)
C8—N2—N3116.85 (18)C1—C2—H2B119.5
C9—N3—N2118.97 (18)C4—C3—C2120.5 (2)
C9—N3—H3A120.5C4—C3—H3B119.7
N2—N3—H3A120.5C2—C3—H3B119.7
C5—C6—C1119.6 (2)C3—C4—C5118.9 (2)
C5—C6—H6A120.2C3—C4—H4C120.6
C1—C6—H6A120.2C5—C4—H4C120.6
C9—N4—H4A120.0C10—N5—C11119.6 (2)
C9—N4—H4B120.0C10—N5—C12122.9 (3)
H4A—N4—H4B120.0C11—N5—C12117.5 (2)
N2—C8—C1119.7 (2)O1—C10—N5125.8 (3)
N2—C8—H8A120.2O1—C10—H10A117.1
C1—C8—H8A120.2N5—C10—H10A117.1
N4—C9—N3116.8 (2)N5—C11—H11A109.5
N4—C9—S1123.00 (18)N5—C11—H11B109.5
N3—C9—S1120.24 (17)H11A—C11—H11B109.5
N1—C7—C5177.1 (3)N5—C11—H11C109.5
C2—C1—C6118.9 (2)H11A—C11—H11C109.5
C2—C1—C8120.3 (2)H11B—C11—H11C109.5
C6—C1—C8120.8 (2)N5—C12—H12A109.5
C4—C5—C6121.1 (2)N5—C12—H12B109.5
C4—C5—C7120.5 (2)H12A—C12—H12B109.5
C6—C5—C7118.4 (2)N5—C12—H12C109.5
C3—C2—C1121.0 (2)H12A—C12—H12C109.5
C3—C2—H2B119.5H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.861.962.795 (3)162
N4—H4A···N20.862.252.610 (3)105
N4—H4A···N1i0.862.353.101 (3)146
N4—H4B···S1ii0.862.593.364 (2)150
C8—H8A···O10.932.543.293 (3)138
C11—H11A···O10.962.342.767 (3)106
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+3/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formulaC9H8N4S·C3H7NO
Mr277.35
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.312 (7), 8.945 (3), 22.316 (19)
β (°) 92.12 (2)
V (Å3)1458.6 (19)
Z4
Radiation typeMo Kα
µ (mm−1)0.22
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku Mercury2
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.742, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		9561, 3280, 2065
Rint0.052
(sin θ/λ)max (Å−1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.109, 1.01
No. of reflections3280
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.18, −0.20

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.861.962.795 (3)162.0
N4—H4A···N20.862.252.610 (3)105.2
N4—H4A···N1i0.862.353.101 (3)145.9
N4—H4B···S1ii0.862.593.364 (2)150.0
C8—H8A···O10.932.543.293 (3)138.4
C11—H11A···O10.962.342.767 (3)106.0
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+3/2, y−1/2, −z+3/2.
 

Acknowledgements

This work was supported by the Natural Science Foundation (2008NXY25) of Nanjing Xiaozhuang University.

References

First citationLovejoy, D. B. & Richardson, D. R. (2002). Blood, 100, 666–676.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSutton, L. E. (1965). Tables of Interatomic Distances and Configurations in Molecules and Ions, Suppl. London: The Chemical Society.  Google Scholar
 First citationWu, D.-H., Zhang, Y.-H., Li, Z.-F. & Li, Y.-H. (2009). Acta Cryst. E65, o107.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 2| February 2010| Page o421
https://doi.org/10.1107/S160053681000214X
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