Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100010180/sk1408sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100010180/sk1408Isup2.hkl |
CCDC reference: 152615
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.
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.
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).
Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
C11H16N4OS | F(000) = 536 |
Mr = 252.34 | Dx = 1.323 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.7856 (3) Å | Cell parameters from 4020 reflections |
b = 7.7565 (1) Å | θ = 1.5–28.3° |
c = 11.9571 (2) Å | µ = 0.25 mm−1 |
β = 112.517 (1)° | T = 293 K |
V = 1266.75 (4) Å3 | Slab, yellow |
Z = 4 | 0.44 × 0.32 × 0.14 mm |
Siemens SMART CCD area detector diffractometer | 3071 independent reflections |
Radiation source: fine-focus sealed tube | 1860 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.2°, θmin = 1.5° |
ω scans | h = −19→19 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→10 |
Tmin = 0.899, Tmax = 0.966 | l = −15→14 |
8696 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-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 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
C11H16N4OS | V = 1266.75 (4) Å3 |
Mr = 252.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.7856 (3) Å | µ = 0.25 mm−1 |
b = 7.7565 (1) Å | T = 293 K |
c = 11.9571 (2) Å | 0.44 × 0.32 × 0.14 mm |
β = 112.517 (1)° |
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 = 0.966 | Rint = 0.065 |
8696 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.69 e Å−3 |
3071 reflections | Δρmin = −0.53 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.36457 (5) | 0.32764 (11) | 0.34616 (7) | 0.0541 (3) | |
O1 | −0.31787 (13) | −0.0445 (2) | 0.42355 (18) | 0.0482 (5) | |
H1A | −0.3296 | −0.0545 | 0.3511 | 0.072* | |
N1 | 0.19463 (16) | 0.4932 (3) | 0.2487 (2) | 0.0526 (6) | |
H1B | 0.1355 | 0.5131 | 0.2419 | 0.063* | |
H1C | 0.2191 | 0.5496 | 0.2050 | 0.063* | |
N2 | 0.20507 (14) | 0.2927 (3) | 0.39183 (19) | 0.0401 (5) | |
H2A | 0.2367 | 0.2166 | 0.4447 | 0.048* | |
N3 | 0.10843 (14) | 0.3311 (3) | 0.3731 (2) | 0.0393 (5) | |
N4 | −0.30888 (15) | 0.3375 (3) | 0.4342 (2) | 0.0446 (6) | |
C1 | 0.24870 (18) | 0.3743 (3) | 0.3275 (2) | 0.0391 (6) | |
C2 | 0.07703 (18) | 0.2630 (3) | 0.4485 (2) | 0.0390 (6) | |
H2B | 0.1195 | 0.1944 | 0.5100 | 0.047* | |
C3 | −0.02184 (17) | 0.2877 (3) | 0.4425 (2) | 0.0361 (6) | |
C4 | −0.05077 (18) | 0.2072 (3) | 0.5280 (2) | 0.0408 (6) | |
H4A | −0.0054 | 0.1411 | 0.5885 | 0.049* | |
C5 | −0.14423 (18) | 0.2225 (3) | 0.5257 (2) | 0.0397 (6) | |
H5A | −0.1605 | 0.1647 | 0.5835 | 0.048* | |
C6 | −0.21536 (17) | 0.3228 (3) | 0.4385 (2) | 0.0348 (5) | |
C7 | −0.18530 (18) | 0.4109 (3) | 0.3547 (2) | 0.0376 (6) | |
H7A | −0.2296 | 0.4820 | 0.2968 | 0.045* | |
C8 | −0.09159 (18) | 0.3932 (3) | 0.3573 (2) | 0.0371 (6) | |
H8A | −0.0743 | 0.4528 | 0.3010 | 0.045* | |
C9 | −0.3813 (2) | 0.4398 (4) | 0.3408 (3) | 0.0663 (10) | |
H9A | −0.4423 | 0.4361 | 0.3517 | 0.099* | |
H9B | −0.3904 | 0.3938 | 0.2627 | 0.099* | |
H9C | −0.3592 | 0.5570 | 0.3461 | 0.099* | |
C10 | −0.34758 (19) | 0.2260 (3) | 0.5034 (2) | 0.0443 (6) | |
H10A | −0.3974 | 0.2886 | 0.5210 | 0.053* | |
H10B | −0.2952 | 0.1984 | 0.5800 | 0.053* | |
C11 | −0.39135 (19) | 0.0603 (3) | 0.4398 (3) | 0.0492 (7) | |
H11A | −0.4212 | −0.0021 | 0.4871 | 0.059* | |
H11B | −0.4421 | 0.0862 | 0.3615 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0389 (4) | 0.0662 (5) | 0.0620 (5) | 0.0016 (3) | 0.0245 (4) | 0.0044 (4) |
O1 | 0.0441 (11) | 0.0440 (11) | 0.0596 (12) | 0.0044 (8) | 0.0232 (9) | −0.0008 (9) |
N1 | 0.0449 (13) | 0.0536 (15) | 0.0577 (16) | 0.0021 (11) | 0.0177 (12) | 0.0172 (12) |
N2 | 0.0318 (11) | 0.0401 (12) | 0.0472 (13) | 0.0021 (9) | 0.0137 (10) | 0.0062 (9) |
N3 | 0.0311 (11) | 0.0381 (12) | 0.0477 (13) | −0.0009 (9) | 0.0140 (10) | −0.0017 (9) |
N4 | 0.0315 (11) | 0.0407 (13) | 0.0603 (15) | 0.0058 (9) | 0.0161 (11) | 0.0100 (10) |
C1 | 0.0365 (14) | 0.0374 (13) | 0.0411 (15) | −0.0068 (10) | 0.0126 (12) | −0.0037 (11) |
C2 | 0.0347 (13) | 0.0304 (13) | 0.0477 (16) | −0.0019 (10) | 0.0111 (12) | 0.0002 (10) |
C3 | 0.0317 (13) | 0.0332 (13) | 0.0409 (14) | −0.0054 (10) | 0.0109 (11) | −0.0051 (10) |
C4 | 0.0335 (13) | 0.0394 (14) | 0.0436 (15) | 0.0031 (10) | 0.0080 (11) | 0.0082 (11) |
C5 | 0.0341 (13) | 0.0426 (14) | 0.0415 (15) | 0.0006 (11) | 0.0136 (11) | 0.0062 (11) |
C6 | 0.0327 (13) | 0.0294 (12) | 0.0397 (14) | −0.0009 (10) | 0.0111 (11) | −0.0037 (10) |
C7 | 0.0350 (13) | 0.0321 (13) | 0.0392 (15) | 0.0011 (10) | 0.0072 (11) | 0.0015 (10) |
C8 | 0.0356 (13) | 0.0368 (13) | 0.0361 (14) | −0.0047 (10) | 0.0104 (11) | −0.0010 (10) |
C9 | 0.0388 (16) | 0.068 (2) | 0.089 (3) | 0.0183 (15) | 0.0216 (17) | 0.0319 (18) |
C10 | 0.0384 (14) | 0.0486 (16) | 0.0502 (17) | 0.0045 (11) | 0.0219 (13) | 0.0010 (12) |
C11 | 0.0364 (14) | 0.0442 (16) | 0.071 (2) | 0.0011 (11) | 0.0246 (14) | 0.0028 (13) |
S1—C1 | 1.680 (3) | C4—C5 | 1.377 (3) |
O1—C11 | 1.428 (3) | C4—H4A | 0.9300 |
O1—H1A | 0.8200 | C5—C6 | 1.399 (3) |
N1—C1 | 1.342 (3) | C5—H5A | 0.9300 |
N1—H1B | 0.8600 | C6—C7 | 1.418 (3) |
N1—H1C | 0.8600 | C7—C8 | 1.381 (3) |
N2—C1 | 1.337 (3) | C7—H7A | 0.9300 |
N2—N3 | 1.391 (3) | C8—H8A | 0.9300 |
N2—H2A | 0.8600 | C9—H9A | 0.9600 |
N3—C2 | 1.275 (3) | C9—H9B | 0.9600 |
N4—C6 | 1.369 (3) | C9—H9C | 0.9600 |
N4—C9 | 1.452 (3) | C10—C11 | 1.507 (4) |
N4—C10 | 1.457 (3) | C10—H10A | 0.9700 |
C2—C3 | 1.449 (3) | C10—H10B | 0.9700 |
C2—H2B | 0.9300 | C11—H11A | 0.9700 |
C3—C4 | 1.397 (3) | C11—H11B | 0.9700 |
C3—C8 | 1.403 (3) | ||
C11—O1—H1A | 109.5 | N4—C6—C7 | 121.3 (2) |
C1—N1—H1B | 120.0 | C5—C6—C7 | 116.4 (2) |
C1—N1—H1C | 120.0 | C8—C7—C6 | 121.3 (2) |
H1B—N1—H1C | 120.0 | C8—C7—H7A | 119.4 |
C1—N2—N3 | 119.9 (2) | C6—C7—H7A | 119.4 |
C1—N2—H2A | 120.1 | C7—C8—C3 | 121.8 (2) |
N3—N2—H2A | 120.1 | C7—C8—H8A | 119.1 |
C2—N3—N2 | 115.3 (2) | C3—C8—H8A | 119.1 |
C6—N4—C9 | 120.7 (2) | N4—C9—H9A | 109.5 |
C6—N4—C10 | 122.7 (2) | N4—C9—H9B | 109.5 |
C9—N4—C10 | 115.3 (2) | H9A—C9—H9B | 109.5 |
N2—C1—N1 | 116.1 (2) | N4—C9—H9C | 109.5 |
N2—C1—S1 | 120.9 (2) | H9A—C9—H9C | 109.5 |
N1—C1—S1 | 122.9 (2) | H9B—C9—H9C | 109.5 |
N3—C2—C3 | 123.0 (2) | N4—C10—C11 | 113.9 (2) |
N3—C2—H2B | 118.5 | N4—C10—H10A | 108.8 |
C3—C2—H2B | 118.5 | C11—C10—H10A | 108.8 |
C4—C3—C8 | 116.5 (2) | N4—C10—H10B | 108.8 |
C4—C3—C2 | 119.4 (2) | C11—C10—H10B | 108.8 |
C8—C3—C2 | 124.1 (2) | H10A—C10—H10B | 107.7 |
C5—C4—C3 | 122.2 (2) | O1—C11—C10 | 110.6 (2) |
C5—C4—H4A | 118.9 | O1—C11—H11A | 109.5 |
C3—C4—H4A | 118.9 | C10—C11—H11A | 109.5 |
C4—C5—C6 | 121.7 (2) | O1—C11—H11B | 109.5 |
C4—C5—H5A | 119.2 | C10—C11—H11B | 109.5 |
C6—C5—H5A | 119.2 | H11A—C11—H11B | 108.1 |
N4—C6—C5 | 122.3 (2) | ||
C1—N2—N3—C2 | −171.7 (2) | C10—N4—C6—C7 | 168.4 (2) |
N3—N2—C1—N1 | 1.2 (3) | C4—C5—C6—N4 | 179.2 (2) |
N3—N2—C1—S1 | −178.74 (17) | C4—C5—C6—C7 | −1.4 (4) |
N2—N3—C2—C3 | −179.5 (2) | N4—C6—C7—C8 | −178.6 (2) |
N3—C2—C3—C4 | 179.4 (2) | C5—C6—C7—C8 | 2.1 (3) |
N3—C2—C3—C8 | −2.6 (4) | C6—C7—C8—C3 | 0.0 (4) |
C8—C3—C4—C5 | 3.3 (4) | C4—C3—C8—C7 | −2.7 (4) |
C2—C3—C4—C5 | −178.6 (2) | C2—C3—C8—C7 | 179.3 (2) |
C3—C4—C5—C6 | −1.3 (4) | C6—N4—C10—C11 | −87.1 (3) |
C9—N4—C6—C5 | −178.6 (3) | C9—N4—C10—C11 | 80.0 (3) |
C10—N4—C6—C5 | −12.2 (4) | N4—C10—C11—O1 | 64.6 (3) |
C9—N4—C6—C7 | 2.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N3 | 0.86 | 2.26 | 2.621 (3) | 105 |
O1—H1A···S1i | 0.82 | 2.39 | 3.187 (2) | 163 |
N1—H1C···O1ii | 0.86 | 2.60 | 3.244 (3) | 133 |
N2—H2A···O1iii | 0.86 | 2.06 | 2.923 (3) | 177 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H16N4OS |
Mr | 252.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.7856 (3), 7.7565 (1), 11.9571 (2) |
β (°) | 112.517 (1) |
V (Å3) | 1266.75 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.44 × 0.32 × 0.14 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.899, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8696, 3071, 1860 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.117, 0.93 |
No. of reflections | 3071 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.53 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
O1—C11 | 1.428 (3) | N3—C2 | 1.275 (3) |
N1—C1 | 1.342 (3) | N4—C6 | 1.369 (3) |
N2—C1 | 1.337 (3) | N4—C9 | 1.452 (3) |
N2—N3 | 1.391 (3) | N4—C10 | 1.457 (3) |
C1—N2—N3 | 119.9 (2) | C6—N4—C10 | 122.7 (2) |
C2—N3—N2 | 115.3 (2) | C9—N4—C10 | 115.3 (2) |
C6—N4—C9 | 120.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N3 | 0.86 | 2.26 | 2.621 (3) | 105 |
O1—H1A···S1i | 0.82 | 2.39 | 3.187 (2) | 163 |
N1—H1C···O1ii | 0.86 | 2.60 | 3.244 (3) | 133 |
N2—H2A···O1iii | 0.86 | 2.06 | 2.923 (3) | 177 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z+1. |
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 C═S 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 C═S 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].