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In the crystal structure of the title compound, C11H16N4OS, the phenyl ring and the thio­semicarbazone moiety from a dihedral angle of 7.7 (1)°. The crystal structure is governed by N-H...O and O-H...S hydrogen bonds leading to the formation of a two-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100010180/sk1408sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100010180/sk1408Isup2.hkl
Contains datablock I

CCDC reference: 152615

Comment top

There is considerable interest in the chemistry of Schiff-base compounds containing N and S donors and their metal complexes. This is due to their non-linear optical properties (Tian et al., 1996) and chelating ability with transition metal ions (Ali & Tarafdar, 1977; Ali & Bose, 1984; Davies et al., 1990; Tian et al., 1996). Thiosemicarbazones are derivatives of carbonyl compounds which exhibit a wide range of biological activities. The title compound, (I), is a Schiff-base derivative, more soluble in polar solvent, having potential second-order optical non-linearities. This work is a continuation of our studies on ligands with sulfur and nitrogen as donor atoms and their metal complexes (Fun et al., 1995; 1996; Tian, Wu et al., 1999; Tian, Yu et al., 1999). \sch

The thiosemicarbazone moiety shows an E configuration about both the C2—N3 and C1—N2 bonds as found in dithiocarbazates (Fun et al., 1995, 1996; Shanmuga Sundara Raj et al., 2000) and thiosemicarbazones (Mathew & Palenik, 1971; Tian, Wu et al., 1999; Tian, Yu et al., 1999). The bond lengths, C1—S1 [1.680 (3) Å] and C1—N2 [1.337 (3) Å], respectively, confirm that the crystal contains the thione and thiol tautomers. The CS distance agrees well with the similar structures which lies intermediate between 1.82 Å for C—S single bond and 1.56 Å for a CS double bond (Sutton, 1965). The C—N distance is indicative of double-bond character. The phenyl and the thiosemicarbazone moiety makes a dihedral angle of 7.7 (1)° indicating the slight deviation from planarity of the molecule.

In the crystal lattice, the molecules of the title compound are arranged in two individual parallel layers connected through N—H···O (N1···O1) and O—H···S hydrogen bonds; these two layers are aligned nearly perpendicular to each other. It is extended to form a two-dimensional network through another N—H···O hydrogen bond (N2···O1) (Table 2). The molecular chain runs along the c axis. The molecules are stacked with a repeating distance of 4.400 (1) Å between the centroids of the phenyl ring. The packing of the molecules are also stabilized by the N—H···π interaction [N1···Cg(-x, 1/2 + y, 1/2 − z) = 3.225 (2); H1C···Cg = 2.698 (1) Å; N1—H1C···Cg = 120.9, Cg-centroid of the phenyl ring].

Experimental top

The title compound was prepared by the reaction of 4-[(2-hydroxyethyl)methylamino]benzaldehyde and thiosemicarbazone under reflux in ethanol solution for 3 h. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of an acetone solution at room temperature.

Refinement top

All the hydrogen atoms were located from a difference Fourier map, fixed at calculated distances and allowed to ride on the parent atoms to which they are attached during refinement. The highest peak and deepest hole are located around the S atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.
4-[N-methyl-N-hydroxyethyl)amino]benzaldehyde thiosemicarbazone top
Crystal data top
C11H16N4OSF(000) = 536
Mr = 252.34Dx = 1.323 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 14.7856 (3) ÅCell parameters from 4020 reflections
b = 7.7565 (1) Åθ = 1.5–28.3°
c = 11.9571 (2) ŵ = 0.25 mm1
β = 112.517 (1)°T = 293 K
V = 1266.75 (4) Å3Slab, yellow
Z = 40.44 × 0.32 × 0.14 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3071 independent reflections
Radiation source: fine-focus sealed tube1860 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Detector resolution: 8.33 pixels mm-1θmax = 28.2°, θmin = 1.5°
ω scansh = 1919
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 910
Tmin = 0.899, Tmax = 0.966l = 1514
8696 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)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.1109P)2]
where P = (Fo2 + 2Fc2)/3
3071 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.69 e Å3
0 restraintsΔρmin = 0.53 e Å3
Crystal data top
C11H16N4OSV = 1266.75 (4) Å3
Mr = 252.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.7856 (3) ŵ = 0.25 mm1
b = 7.7565 (1) ÅT = 293 K
c = 11.9571 (2) Å0.44 × 0.32 × 0.14 mm
β = 112.517 (1)°
Data collection top
Siemens SMART CCD area detector
diffractometer
3071 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1860 reflections with I > 2σ(I)
Tmin = 0.899, Tmax = 0.966Rint = 0.065
8696 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 0.93Δρmax = 0.69 e Å3
3071 reflectionsΔρmin = 0.53 e Å3
154 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. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.36457 (5)0.32764 (11)0.34616 (7)0.0541 (3)
O10.31787 (13)0.0445 (2)0.42355 (18)0.0482 (5)
H1A0.32960.05450.35110.072*
N10.19463 (16)0.4932 (3)0.2487 (2)0.0526 (6)
H1B0.13550.51310.24190.063*
H1C0.21910.54960.20500.063*
N20.20507 (14)0.2927 (3)0.39183 (19)0.0401 (5)
H2A0.23670.21660.44470.048*
N30.10843 (14)0.3311 (3)0.3731 (2)0.0393 (5)
N40.30888 (15)0.3375 (3)0.4342 (2)0.0446 (6)
C10.24870 (18)0.3743 (3)0.3275 (2)0.0391 (6)
C20.07703 (18)0.2630 (3)0.4485 (2)0.0390 (6)
H2B0.11950.19440.51000.047*
C30.02184 (17)0.2877 (3)0.4425 (2)0.0361 (6)
C40.05077 (18)0.2072 (3)0.5280 (2)0.0408 (6)
H4A0.00540.14110.58850.049*
C50.14423 (18)0.2225 (3)0.5257 (2)0.0397 (6)
H5A0.16050.16470.58350.048*
C60.21536 (17)0.3228 (3)0.4385 (2)0.0348 (5)
C70.18530 (18)0.4109 (3)0.3547 (2)0.0376 (6)
H7A0.22960.48200.29680.045*
C80.09159 (18)0.3932 (3)0.3573 (2)0.0371 (6)
H8A0.07430.45280.30100.045*
C90.3813 (2)0.4398 (4)0.3408 (3)0.0663 (10)
H9A0.44230.43610.35170.099*
H9B0.39040.39380.26270.099*
H9C0.35920.55700.34610.099*
C100.34758 (19)0.2260 (3)0.5034 (2)0.0443 (6)
H10A0.39740.28860.52100.053*
H10B0.29520.19840.58000.053*
C110.39135 (19)0.0603 (3)0.4398 (3)0.0492 (7)
H11A0.42120.00210.48710.059*
H11B0.44210.08620.36150.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0389 (4)0.0662 (5)0.0620 (5)0.0016 (3)0.0245 (4)0.0044 (4)
O10.0441 (11)0.0440 (11)0.0596 (12)0.0044 (8)0.0232 (9)0.0008 (9)
N10.0449 (13)0.0536 (15)0.0577 (16)0.0021 (11)0.0177 (12)0.0172 (12)
N20.0318 (11)0.0401 (12)0.0472 (13)0.0021 (9)0.0137 (10)0.0062 (9)
N30.0311 (11)0.0381 (12)0.0477 (13)0.0009 (9)0.0140 (10)0.0017 (9)
N40.0315 (11)0.0407 (13)0.0603 (15)0.0058 (9)0.0161 (11)0.0100 (10)
C10.0365 (14)0.0374 (13)0.0411 (15)0.0068 (10)0.0126 (12)0.0037 (11)
C20.0347 (13)0.0304 (13)0.0477 (16)0.0019 (10)0.0111 (12)0.0002 (10)
C30.0317 (13)0.0332 (13)0.0409 (14)0.0054 (10)0.0109 (11)0.0051 (10)
C40.0335 (13)0.0394 (14)0.0436 (15)0.0031 (10)0.0080 (11)0.0082 (11)
C50.0341 (13)0.0426 (14)0.0415 (15)0.0006 (11)0.0136 (11)0.0062 (11)
C60.0327 (13)0.0294 (12)0.0397 (14)0.0009 (10)0.0111 (11)0.0037 (10)
C70.0350 (13)0.0321 (13)0.0392 (15)0.0011 (10)0.0072 (11)0.0015 (10)
C80.0356 (13)0.0368 (13)0.0361 (14)0.0047 (10)0.0104 (11)0.0010 (10)
C90.0388 (16)0.068 (2)0.089 (3)0.0183 (15)0.0216 (17)0.0319 (18)
C100.0384 (14)0.0486 (16)0.0502 (17)0.0045 (11)0.0219 (13)0.0010 (12)
C110.0364 (14)0.0442 (16)0.071 (2)0.0011 (11)0.0246 (14)0.0028 (13)
Geometric parameters (Å, º) top
S1—C11.680 (3)C4—C51.377 (3)
O1—C111.428 (3)C4—H4A0.9300
O1—H1A0.8200C5—C61.399 (3)
N1—C11.342 (3)C5—H5A0.9300
N1—H1B0.8600C6—C71.418 (3)
N1—H1C0.8600C7—C81.381 (3)
N2—C11.337 (3)C7—H7A0.9300
N2—N31.391 (3)C8—H8A0.9300
N2—H2A0.8600C9—H9A0.9600
N3—C21.275 (3)C9—H9B0.9600
N4—C61.369 (3)C9—H9C0.9600
N4—C91.452 (3)C10—C111.507 (4)
N4—C101.457 (3)C10—H10A0.9700
C2—C31.449 (3)C10—H10B0.9700
C2—H2B0.9300C11—H11A0.9700
C3—C41.397 (3)C11—H11B0.9700
C3—C81.403 (3)
C11—O1—H1A109.5N4—C6—C7121.3 (2)
C1—N1—H1B120.0C5—C6—C7116.4 (2)
C1—N1—H1C120.0C8—C7—C6121.3 (2)
H1B—N1—H1C120.0C8—C7—H7A119.4
C1—N2—N3119.9 (2)C6—C7—H7A119.4
C1—N2—H2A120.1C7—C8—C3121.8 (2)
N3—N2—H2A120.1C7—C8—H8A119.1
C2—N3—N2115.3 (2)C3—C8—H8A119.1
C6—N4—C9120.7 (2)N4—C9—H9A109.5
C6—N4—C10122.7 (2)N4—C9—H9B109.5
C9—N4—C10115.3 (2)H9A—C9—H9B109.5
N2—C1—N1116.1 (2)N4—C9—H9C109.5
N2—C1—S1120.9 (2)H9A—C9—H9C109.5
N1—C1—S1122.9 (2)H9B—C9—H9C109.5
N3—C2—C3123.0 (2)N4—C10—C11113.9 (2)
N3—C2—H2B118.5N4—C10—H10A108.8
C3—C2—H2B118.5C11—C10—H10A108.8
C4—C3—C8116.5 (2)N4—C10—H10B108.8
C4—C3—C2119.4 (2)C11—C10—H10B108.8
C8—C3—C2124.1 (2)H10A—C10—H10B107.7
C5—C4—C3122.2 (2)O1—C11—C10110.6 (2)
C5—C4—H4A118.9O1—C11—H11A109.5
C3—C4—H4A118.9C10—C11—H11A109.5
C4—C5—C6121.7 (2)O1—C11—H11B109.5
C4—C5—H5A119.2C10—C11—H11B109.5
C6—C5—H5A119.2H11A—C11—H11B108.1
N4—C6—C5122.3 (2)
C1—N2—N3—C2171.7 (2)C10—N4—C6—C7168.4 (2)
N3—N2—C1—N11.2 (3)C4—C5—C6—N4179.2 (2)
N3—N2—C1—S1178.74 (17)C4—C5—C6—C71.4 (4)
N2—N3—C2—C3179.5 (2)N4—C6—C7—C8178.6 (2)
N3—C2—C3—C4179.4 (2)C5—C6—C7—C82.1 (3)
N3—C2—C3—C82.6 (4)C6—C7—C8—C30.0 (4)
C8—C3—C4—C53.3 (4)C4—C3—C8—C72.7 (4)
C2—C3—C4—C5178.6 (2)C2—C3—C8—C7179.3 (2)
C3—C4—C5—C61.3 (4)C6—N4—C10—C1187.1 (3)
C9—N4—C6—C5178.6 (3)C9—N4—C10—C1180.0 (3)
C10—N4—C6—C512.2 (4)N4—C10—C11—O164.6 (3)
C9—N4—C6—C72.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N30.862.262.621 (3)105
O1—H1A···S1i0.822.393.187 (2)163
N1—H1C···O1ii0.862.603.244 (3)133
N2—H2A···O1iii0.862.062.923 (3)177
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC11H16N4OS
Mr252.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)14.7856 (3), 7.7565 (1), 11.9571 (2)
β (°) 112.517 (1)
V3)1266.75 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.44 × 0.32 × 0.14
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.899, 0.966
No. of measured, independent and
observed [I > 2σ(I)] reflections
8696, 3071, 1860
Rint0.065
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.117, 0.93
No. of reflections3071
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.53

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
O1—C111.428 (3)N3—C21.275 (3)
N1—C11.342 (3)N4—C61.369 (3)
N2—C11.337 (3)N4—C91.452 (3)
N2—N31.391 (3)N4—C101.457 (3)
C1—N2—N3119.9 (2)C6—N4—C10122.7 (2)
C2—N3—N2115.3 (2)C9—N4—C10115.3 (2)
C6—N4—C9120.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N30.862.262.621 (3)105
O1—H1A···S1i0.822.393.187 (2)163
N1—H1C···O1ii0.862.603.244 (3)133
N2—H2A···O1iii0.862.062.923 (3)177
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y, z+1.
 

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