Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034149/cf2118sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034149/cf2118Isup2.hkl |
CCDC reference: 657783
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.009 Å
- R factor = 0.066
- wR factor = 0.155
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.97 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Eriksson et al. (2007); Gundersen et al. (2007); Sabb & Vogel (2007); Seethalakshmi et al. (2006); Smith et al. (2007).
A solution of 3-formyl-2-phenylindozinethiosemicarbazone (0.12 g, 0.40 mmol) and ω-bromoacetophenone (0.085 g, 0.40 mmol) in anhydrous ethanol (10 ml) was stirred at room temperature, until all the thiosemicarbazone had disappeared (monitored by thin-layer chromatography). The resulting mixture was allowed to settle, and the title compound was collected by filtration and dried in vacuo. Dark green single crystals of (I) suitable for X-ray crystallographic analysis were obtained by recrystallization from 95% ethanol.
All of the hydrogen atoms were placed in calculated positions, with C—H = 0.93, N—H = 0.86 and O—H = 0.85 Å, and with Uiso(H) = 1.5Ueq(parent).
It is well known that both 1,3-thiazole and indolizine rings have a wide range of bioactivities. Some compounds with these rings have been used as sphingosine kinase inhibitors (Smith et al., 2007), antitumor agents (Eriksson et al., 2007), antituberculins (Gundersen et al., 2007) and CNS agents (Sabb & Vogel, 2007). Hydrazones have also shown extensive bioactivities. The title compound was prepared to investigate additive properties of the groups.
The molecular structure of (I) is shown in Fig.1. The 1,3-thiazole ring has normal geometric parameters (Seethalakshmi et al., 2006); the C1—S1[1.715 (5) Å] and C3—S1 [1.723 (6) Å] bond lengths are intermediate between typical C—S single- and double-bond distances, indicating significant electron delocalization. The C1—S1—C3 [89.3 (3)°] bond angle in (I) is almost the same as the corresponding value 89.81 (8)° in a related structure (Seethalakshmi et al., 2006). The values of the C1—N2—N3—C10 [-178.4 (5)°] and N2—N3—C10—C11 [179.3 (5)°] torsion angles indicate that the C1—N2—N3—C10—C11 chain is nearly planar. The thiazole ring makes a dihedral angle of 9.5 (1)° with the N4/C11—C18 ring. Thus, a fully extended conjugated system is formed.
The molecular packing (Fig. 2) shows the occurrence of short intermolecular C—H···π interactions between C21—H21 and the pyridine ring (C14—C18/N4; centroid Cg), with a C21···Cg distance of 3.614 (6)Å (Table 1). Thus the two molecules form a centrosymmetric dimeric arrangement. As seen in Fig. 3, the water molecule acts as donor for intermolecular O—H···Br hydrogen bonds, and also acts as acceptor for an intermolecular N—H···O hydrogen bond. The Br- anion acts as acceptor for an intermolecular N—H···Br hydrogen bond. Therefore, a chain is formed along the a axis via a combination of intermolecular N—H···O, N—H···Br and O—H···Br interactions.
For related literature, see: Eriksson et al. (2007); Gundersen et al. (2007); Sabb & Vogel (2007); Seethalakshmi et al. (2006); Smith et al. (2007).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C24H19N4S+·Br−·H2O | F(000) = 1008 |
Mr = 493.42 | Dx = 1.459 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1679 (12) Å | Cell parameters from 2831 reflections |
b = 11.1657 (18) Å | θ = 2.2–22.5° |
c = 32.640 (4) Å | µ = 1.95 mm−1 |
β = 91.708 (2)° | T = 298 K |
V = 2246.9 (6) Å3 | Prism, dark green |
Z = 4 | 0.42 × 0.36 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 3904 independent reflections |
Radiation source: fine-focus sealed tube | 2795 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
φ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→7 |
Tmin = 0.495, Tmax = 0.697 | k = −13→13 |
10856 measured reflections | l = −28→38 |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.048P)2 + 4.8524P] where P = (Fo2 + 2Fc2)/3 |
3904 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
C24H19N4S+·Br−·H2O | V = 2246.9 (6) Å3 |
Mr = 493.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.1679 (12) Å | µ = 1.95 mm−1 |
b = 11.1657 (18) Å | T = 298 K |
c = 32.640 (4) Å | 0.42 × 0.36 × 0.20 mm |
β = 91.708 (2)° |
Bruker SMART CCD area-detector diffractometer | 3904 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2795 reflections with I > 2σ(I) |
Tmin = 0.495, Tmax = 0.697 | Rint = 0.058 |
10856 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.52 e Å−3 |
3904 reflections | Δρmin = −0.61 e Å−3 |
280 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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.75959 (10) | 0.38600 (5) | 0.11839 (2) | 0.0566 (2) | |
N1 | 0.3347 (7) | 0.1191 (4) | 0.18113 (13) | 0.0385 (10) | |
H1 | 0.2916 | 0.1879 | 0.1723 | 0.046* | |
N2 | 0.6267 (7) | 0.0997 (4) | 0.13683 (13) | 0.0412 (11) | |
H2 | 0.6065 | 0.1681 | 0.1252 | 0.049* | |
N3 | 0.7942 (7) | 0.0233 (4) | 0.12601 (14) | 0.0402 (11) | |
N4 | 1.1713 (7) | −0.1100 (4) | 0.09626 (13) | 0.0404 (10) | |
O1 | 0.2693 (7) | 0.3484 (4) | 0.15315 (16) | 0.0754 (14) | |
H1A | 0.3790 | 0.3640 | 0.1389 | 0.091* | |
H1B | 0.1548 | 0.3639 | 0.1390 | 0.091* | |
S1 | 0.5445 (3) | −0.07581 (13) | 0.18834 (6) | 0.0568 (5) | |
C1 | 0.5020 (8) | 0.0612 (4) | 0.16573 (16) | 0.0349 (12) | |
C2 | 0.2345 (8) | 0.0580 (5) | 0.21305 (16) | 0.0381 (12) | |
C3 | 0.3310 (10) | −0.0484 (6) | 0.2199 (2) | 0.0588 (17) | |
H3 | 0.2867 | −0.1021 | 0.2397 | 0.071* | |
C4 | 0.0481 (9) | 0.1089 (5) | 0.23317 (16) | 0.0410 (13) | |
C5 | −0.0156 (10) | 0.0657 (6) | 0.27091 (18) | 0.0538 (15) | |
H5 | 0.0686 | 0.0078 | 0.2843 | 0.065* | |
C6 | −0.1995 (11) | 0.1064 (6) | 0.2888 (2) | 0.0657 (19) | |
H6 | −0.2419 | 0.0742 | 0.3136 | 0.079* | |
C7 | −0.3215 (10) | 0.1950 (6) | 0.27000 (19) | 0.0557 (16) | |
H7 | −0.4467 | 0.2227 | 0.2821 | 0.067* | |
C8 | −0.2584 (9) | 0.2428 (5) | 0.23340 (18) | 0.0493 (14) | |
H8 | −0.3393 | 0.3039 | 0.2211 | 0.059* | |
C9 | −0.0750 (8) | 0.2002 (5) | 0.21481 (17) | 0.0408 (13) | |
H9 | −0.0335 | 0.2326 | 0.1900 | 0.049* | |
C10 | 0.9165 (8) | 0.0641 (5) | 0.09851 (16) | 0.0379 (12) | |
H10 | 0.8847 | 0.1394 | 0.0878 | 0.046* | |
C11 | 1.0987 (8) | 0.0020 (4) | 0.08310 (16) | 0.0368 (12) | |
C12 | 1.2477 (8) | 0.0448 (5) | 0.05520 (15) | 0.0367 (12) | |
C13 | 1.4131 (9) | −0.0377 (5) | 0.05280 (17) | 0.0447 (14) | |
H13 | 1.5358 | −0.0298 | 0.0371 | 0.054* | |
C14 | 1.3657 (9) | −0.1348 (5) | 0.07770 (16) | 0.0443 (14) | |
C15 | 1.4690 (10) | −0.2445 (6) | 0.08584 (19) | 0.0545 (16) | |
H15 | 1.6006 | −0.2618 | 0.0740 | 0.065* | |
C16 | 1.3770 (12) | −0.3254 (6) | 0.1111 (2) | 0.0679 (19) | |
H16 | 1.4452 | −0.3982 | 0.1166 | 0.081* | |
C17 | 1.1786 (12) | −0.2986 (6) | 0.1288 (2) | 0.0659 (19) | |
H17 | 1.1153 | −0.3547 | 0.1458 | 0.079* | |
C18 | 1.0774 (10) | −0.1927 (5) | 0.12170 (19) | 0.0543 (16) | |
H18 | 0.9463 | −0.1759 | 0.1338 | 0.065* | |
C19 | 1.2270 (9) | 0.1601 (5) | 0.03296 (15) | 0.0376 (12) | |
C20 | 1.0416 (10) | 0.1895 (5) | 0.00987 (17) | 0.0474 (14) | |
H20 | 0.9269 | 0.1355 | 0.0082 | 0.057* | |
C21 | 1.0248 (10) | 0.2966 (6) | −0.01045 (19) | 0.0555 (16) | |
H21 | 0.9003 | 0.3146 | −0.0260 | 0.067* | |
C22 | 1.1929 (12) | 0.3774 (6) | −0.0077 (2) | 0.0663 (18) | |
H22 | 1.1811 | 0.4509 | −0.0210 | 0.080* | |
C23 | 1.3781 (11) | 0.3494 (6) | 0.0146 (2) | 0.071 (2) | |
H23 | 1.4925 | 0.4037 | 0.0161 | 0.085* | |
C24 | 1.3951 (10) | 0.2421 (6) | 0.0346 (2) | 0.0576 (16) | |
H24 | 1.5217 | 0.2240 | 0.0495 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0546 (4) | 0.0407 (3) | 0.0742 (5) | 0.0031 (3) | −0.0020 (3) | 0.0023 (3) |
N1 | 0.036 (2) | 0.030 (2) | 0.050 (3) | 0.004 (2) | −0.002 (2) | 0.002 (2) |
N2 | 0.043 (3) | 0.034 (2) | 0.046 (3) | 0.013 (2) | −0.001 (2) | 0.003 (2) |
N3 | 0.035 (3) | 0.033 (2) | 0.053 (3) | 0.0100 (19) | −0.002 (2) | −0.004 (2) |
N4 | 0.035 (2) | 0.039 (2) | 0.047 (3) | 0.008 (2) | 0.001 (2) | 0.002 (2) |
O1 | 0.052 (3) | 0.059 (3) | 0.116 (4) | 0.006 (2) | 0.007 (3) | 0.034 (3) |
S1 | 0.0525 (9) | 0.0320 (8) | 0.0862 (12) | 0.0110 (6) | 0.0066 (8) | 0.0112 (7) |
C1 | 0.027 (3) | 0.032 (3) | 0.045 (3) | 0.004 (2) | −0.007 (2) | −0.001 (2) |
C2 | 0.035 (3) | 0.037 (3) | 0.042 (3) | −0.007 (2) | −0.004 (2) | 0.003 (2) |
C3 | 0.053 (4) | 0.050 (4) | 0.074 (4) | 0.005 (3) | 0.010 (3) | 0.022 (3) |
C4 | 0.040 (3) | 0.041 (3) | 0.042 (3) | −0.009 (3) | −0.002 (2) | 0.000 (3) |
C5 | 0.060 (4) | 0.052 (4) | 0.050 (4) | 0.000 (3) | 0.001 (3) | 0.014 (3) |
C6 | 0.072 (5) | 0.074 (5) | 0.052 (4) | −0.009 (4) | 0.022 (4) | 0.001 (4) |
C7 | 0.046 (4) | 0.067 (4) | 0.054 (4) | −0.006 (3) | 0.011 (3) | −0.013 (3) |
C8 | 0.043 (3) | 0.050 (3) | 0.055 (4) | 0.004 (3) | 0.003 (3) | −0.011 (3) |
C9 | 0.039 (3) | 0.043 (3) | 0.041 (3) | −0.003 (2) | 0.003 (2) | −0.003 (2) |
C10 | 0.037 (3) | 0.032 (3) | 0.045 (3) | 0.003 (2) | 0.000 (3) | −0.004 (2) |
C11 | 0.032 (3) | 0.034 (3) | 0.044 (3) | 0.008 (2) | −0.004 (2) | −0.002 (2) |
C12 | 0.038 (3) | 0.039 (3) | 0.033 (3) | 0.001 (2) | −0.004 (2) | −0.003 (2) |
C13 | 0.029 (3) | 0.057 (4) | 0.048 (3) | 0.008 (3) | 0.001 (2) | −0.005 (3) |
C14 | 0.041 (3) | 0.048 (3) | 0.043 (3) | 0.014 (3) | −0.003 (3) | −0.008 (3) |
C15 | 0.046 (4) | 0.059 (4) | 0.058 (4) | 0.026 (3) | −0.001 (3) | −0.010 (3) |
C16 | 0.071 (5) | 0.049 (4) | 0.083 (5) | 0.033 (3) | −0.002 (4) | 0.009 (4) |
C17 | 0.076 (5) | 0.043 (4) | 0.080 (5) | 0.008 (3) | 0.013 (4) | 0.016 (3) |
C18 | 0.049 (4) | 0.047 (4) | 0.068 (4) | 0.006 (3) | 0.013 (3) | 0.006 (3) |
C19 | 0.041 (3) | 0.035 (3) | 0.036 (3) | 0.000 (2) | 0.001 (2) | −0.008 (2) |
C20 | 0.048 (4) | 0.036 (3) | 0.058 (4) | 0.000 (3) | −0.002 (3) | −0.005 (3) |
C21 | 0.046 (4) | 0.055 (4) | 0.065 (4) | 0.014 (3) | −0.007 (3) | 0.003 (3) |
C22 | 0.079 (5) | 0.039 (3) | 0.082 (5) | 0.008 (3) | 0.003 (4) | 0.008 (3) |
C23 | 0.057 (4) | 0.046 (4) | 0.109 (6) | −0.018 (3) | −0.011 (4) | 0.010 (4) |
C24 | 0.050 (4) | 0.056 (4) | 0.066 (4) | −0.008 (3) | −0.008 (3) | 0.011 (3) |
N1—C1 | 1.329 (6) | C9—H9 | 0.930 |
N1—C2 | 1.404 (6) | C10—C11 | 1.424 (7) |
N1—H1 | 0.860 | C10—H10 | 0.930 |
N2—C1 | 1.308 (6) | C11—C12 | 1.397 (7) |
N2—N3 | 1.394 (6) | C12—C13 | 1.379 (7) |
N2—H2 | 0.860 | C12—C19 | 1.481 (7) |
N3—C10 | 1.274 (6) | C13—C14 | 1.391 (8) |
N4—C18 | 1.381 (7) | C13—H13 | 0.930 |
N4—C14 | 1.388 (7) | C14—C15 | 1.403 (8) |
N4—C11 | 1.392 (6) | C15—C16 | 1.358 (9) |
O1—H1A | 0.850 | C15—H15 | 0.930 |
O1—H1B | 0.850 | C16—C17 | 1.401 (9) |
S1—C1 | 1.715 (5) | C16—H16 | 0.930 |
S1—C3 | 1.723 (6) | C17—C18 | 1.354 (8) |
C2—C3 | 1.344 (8) | C17—H17 | 0.930 |
C2—C4 | 1.456 (7) | C18—H18 | 0.930 |
C3—H3 | 0.930 | C19—C24 | 1.384 (8) |
C4—C5 | 1.391 (8) | C19—C20 | 1.390 (8) |
C4—C9 | 1.396 (7) | C20—C21 | 1.369 (8) |
C5—C6 | 1.369 (9) | C20—H20 | 0.930 |
C5—H5 | 0.930 | C21—C22 | 1.375 (9) |
C6—C7 | 1.377 (9) | C21—H21 | 0.930 |
C6—H6 | 0.930 | C22—C23 | 1.372 (10) |
C7—C8 | 1.375 (8) | C22—H22 | 0.930 |
C7—H7 | 0.930 | C23—C24 | 1.367 (9) |
C8—C9 | 1.384 (7) | C23—H23 | 0.930 |
C8—H8 | 0.930 | C24—H24 | 0.930 |
C1—N1—C2 | 114.1 (4) | N4—C11—C12 | 107.3 (4) |
C1—N1—H1 | 123.0 | N4—C11—C10 | 125.3 (5) |
C2—N1—H1 | 123.0 | C12—C11—C10 | 127.2 (5) |
C1—N2—N3 | 115.9 (4) | C13—C12—C11 | 108.1 (5) |
C1—N2—H2 | 122.0 | C13—C12—C19 | 127.3 (5) |
N3—N2—H2 | 122.0 | C11—C12—C19 | 124.6 (5) |
C10—N3—N2 | 114.8 (4) | C12—C13—C14 | 108.6 (5) |
C18—N4—C14 | 120.8 (5) | C12—C13—H13 | 125.7 |
C18—N4—C11 | 130.5 (4) | C14—C13—H13 | 125.7 |
C14—N4—C11 | 108.6 (4) | N4—C14—C13 | 107.4 (5) |
H1A—O1—H1B | 108.8 | N4—C14—C15 | 119.0 (5) |
C1—S1—C3 | 89.3 (3) | C13—C14—C15 | 133.6 (5) |
N2—C1—N1 | 126.3 (5) | C16—C15—C14 | 120.0 (5) |
N2—C1—S1 | 121.2 (4) | C16—C15—H15 | 120.0 |
N1—C1—S1 | 112.4 (4) | C14—C15—H15 | 120.0 |
C3—C2—N1 | 110.5 (5) | C15—C16—C17 | 119.6 (6) |
C3—C2—C4 | 128.5 (5) | C15—C16—H16 | 120.2 |
N1—C2—C4 | 121.1 (5) | C17—C16—H16 | 120.2 |
C2—C3—S1 | 113.6 (4) | C18—C17—C16 | 121.3 (6) |
C2—C3—H3 | 123.2 | C18—C17—H17 | 119.3 |
S1—C3—H3 | 123.2 | C16—C17—H17 | 119.3 |
C5—C4—C9 | 118.0 (5) | C17—C18—N4 | 119.2 (5) |
C5—C4—C2 | 120.8 (5) | C17—C18—H18 | 120.4 |
C9—C4—C2 | 121.2 (5) | N4—C18—H18 | 120.4 |
C6—C5—C4 | 121.5 (6) | C24—C19—C20 | 117.9 (5) |
C6—C5—H5 | 119.2 | C24—C19—C12 | 120.2 (5) |
C4—C5—H5 | 119.2 | C20—C19—C12 | 122.0 (5) |
C5—C6—C7 | 119.8 (6) | C21—C20—C19 | 121.2 (6) |
C5—C6—H6 | 120.1 | C21—C20—H20 | 119.4 |
C7—C6—H6 | 120.1 | C19—C20—H20 | 119.4 |
C8—C7—C6 | 120.1 (6) | C20—C21—C22 | 119.7 (6) |
C8—C7—H7 | 120.0 | C20—C21—H21 | 120.2 |
C6—C7—H7 | 120.0 | C22—C21—H21 | 120.2 |
C7—C8—C9 | 120.3 (6) | C23—C22—C21 | 119.9 (6) |
C7—C8—H8 | 119.9 | C23—C22—H22 | 120.0 |
C9—C8—H8 | 119.9 | C21—C22—H22 | 120.0 |
C8—C9—C4 | 120.2 (5) | C24—C23—C22 | 120.3 (6) |
C8—C9—H9 | 119.9 | C24—C23—H23 | 119.9 |
C4—C9—H9 | 119.9 | C22—C23—H23 | 119.9 |
N3—C10—C11 | 124.4 (5) | C23—C24—C19 | 121.0 (6) |
N3—C10—H10 | 117.8 | C23—C24—H24 | 119.5 |
C11—C10—H10 | 117.8 | C19—C24—H24 | 119.5 |
C1—N2—N3—C10 | −178.4 (5) | N4—C11—C12—C13 | −2.5 (6) |
N3—N2—C1—N1 | 179.3 (5) | C10—C11—C12—C13 | 172.3 (5) |
N3—N2—C1—S1 | −0.3 (6) | N4—C11—C12—C19 | 178.1 (5) |
C2—N1—C1—N2 | −177.8 (5) | C10—C11—C12—C19 | −7.2 (8) |
C2—N1—C1—S1 | 1.9 (5) | C11—C12—C13—C14 | 2.4 (6) |
C3—S1—C1—N2 | 178.4 (5) | C19—C12—C13—C14 | −178.2 (5) |
C3—S1—C1—N1 | −1.3 (4) | C18—N4—C14—C13 | 177.3 (5) |
C1—N1—C2—C3 | −1.5 (7) | C11—N4—C14—C13 | −0.3 (6) |
C1—N1—C2—C4 | −179.7 (5) | C18—N4—C14—C15 | −1.4 (8) |
N1—C2—C3—S1 | 0.5 (7) | C11—N4—C14—C15 | −179.0 (5) |
C4—C2—C3—S1 | 178.5 (4) | C12—C13—C14—N4 | −1.3 (6) |
C1—S1—C3—C2 | 0.4 (5) | C12—C13—C14—C15 | 177.2 (6) |
C3—C2—C4—C5 | 19.0 (9) | N4—C14—C15—C16 | 1.0 (9) |
N1—C2—C4—C5 | −163.1 (5) | C13—C14—C15—C16 | −177.4 (7) |
C3—C2—C4—C9 | −159.4 (6) | C14—C15—C16—C17 | 0.1 (10) |
N1—C2—C4—C9 | 18.4 (8) | C15—C16—C17—C18 | −0.8 (11) |
C9—C4—C5—C6 | 3.4 (9) | C16—C17—C18—N4 | 0.4 (11) |
C2—C4—C5—C6 | −175.1 (6) | C14—N4—C18—C17 | 0.7 (9) |
C4—C5—C6—C7 | −2.3 (10) | C11—N4—C18—C17 | 177.7 (6) |
C5—C6—C7—C8 | −0.2 (10) | C13—C12—C19—C24 | −52.9 (8) |
C6—C7—C8—C9 | 1.5 (9) | C11—C12—C19—C24 | 126.5 (6) |
C7—C8—C9—C4 | −0.3 (8) | C13—C12—C19—C20 | 126.8 (6) |
C5—C4—C9—C8 | −2.1 (8) | C11—C12—C19—C20 | −53.8 (7) |
C2—C4—C9—C8 | 176.4 (5) | C24—C19—C20—C21 | −0.4 (8) |
N2—N3—C10—C11 | 179.3 (5) | C12—C19—C20—C21 | 179.9 (5) |
C18—N4—C11—C12 | −175.6 (5) | C19—C20—C21—C22 | −0.7 (9) |
C14—N4—C11—C12 | 1.7 (6) | C20—C21—C22—C23 | 1.3 (10) |
C18—N4—C11—C10 | 9.5 (9) | C21—C22—C23—C24 | −0.9 (11) |
C14—N4—C11—C10 | −173.2 (5) | C22—C23—C24—C19 | −0.3 (11) |
N3—C10—C11—N4 | −1.3 (8) | C20—C19—C24—C23 | 0.9 (9) |
N3—C10—C11—C12 | −175.1 (5) | C12—C19—C24—C23 | −179.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.90 | 2.744 (6) | 166 |
O1—H1A···Br1 | 0.85 | 2.47 | 3.288 (5) | 161 |
O1—H1B···Br1i | 0.85 | 2.52 | 3.337 (5) | 161 |
N2—H2···Br1 | 0.86 | 2.62 | 3.359 (5) | 144 |
C9—H9···O1 | 0.93 | 2.60 | 3.399 (7) | 145 |
C18—H18···N3 | 0.93 | 2.42 | 2.984 (7) | 119 |
C21—H21···Cgii | 0.93 | 2.93 | 3.614 | 132 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C24H19N4S+·Br−·H2O |
Mr | 493.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 6.1679 (12), 11.1657 (18), 32.640 (4) |
β (°) | 91.708 (2) |
V (Å3) | 2246.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.95 |
Crystal size (mm) | 0.42 × 0.36 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.495, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10856, 3904, 2795 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.155, 1.10 |
No. of reflections | 3904 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.61 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.90 | 2.744 (6) | 166 |
O1—H1A···Br1 | 0.85 | 2.47 | 3.288 (5) | 161 |
O1—H1B···Br1i | 0.85 | 2.52 | 3.337 (5) | 161 |
N2—H2···Br1 | 0.86 | 2.62 | 3.359 (5) | 144 |
C9—H9···O1 | 0.93 | 2.60 | 3.399 (7) | 145 |
C18—H18···N3 | 0.93 | 2.42 | 2.984 (7) | 119 |
C21—H21···Cgii | 0.93 | 2.93 | 3.614 | 132 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y, −z. |
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It is well known that both 1,3-thiazole and indolizine rings have a wide range of bioactivities. Some compounds with these rings have been used as sphingosine kinase inhibitors (Smith et al., 2007), antitumor agents (Eriksson et al., 2007), antituberculins (Gundersen et al., 2007) and CNS agents (Sabb & Vogel, 2007). Hydrazones have also shown extensive bioactivities. The title compound was prepared to investigate additive properties of the groups.
The molecular structure of (I) is shown in Fig.1. The 1,3-thiazole ring has normal geometric parameters (Seethalakshmi et al., 2006); the C1—S1[1.715 (5) Å] and C3—S1 [1.723 (6) Å] bond lengths are intermediate between typical C—S single- and double-bond distances, indicating significant electron delocalization. The C1—S1—C3 [89.3 (3)°] bond angle in (I) is almost the same as the corresponding value 89.81 (8)° in a related structure (Seethalakshmi et al., 2006). The values of the C1—N2—N3—C10 [-178.4 (5)°] and N2—N3—C10—C11 [179.3 (5)°] torsion angles indicate that the C1—N2—N3—C10—C11 chain is nearly planar. The thiazole ring makes a dihedral angle of 9.5 (1)° with the N4/C11—C18 ring. Thus, a fully extended conjugated system is formed.
The molecular packing (Fig. 2) shows the occurrence of short intermolecular C—H···π interactions between C21—H21 and the pyridine ring (C14—C18/N4; centroid Cg), with a C21···Cg distance of 3.614 (6)Å (Table 1). Thus the two molecules form a centrosymmetric dimeric arrangement. As seen in Fig. 3, the water molecule acts as donor for intermolecular O—H···Br hydrogen bonds, and also acts as acceptor for an intermolecular N—H···O hydrogen bond. The Br- anion acts as acceptor for an intermolecular N—H···Br hydrogen bond. Therefore, a chain is formed along the a axis via a combination of intermolecular N—H···O, N—H···Br and O—H···Br interactions.