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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2762.
Published online 2009 October 17. doi:  10.1107/S1600536809041452
PMCID: PMC2971184

2-{[4-(1,3-Benzothia­zol-2-yl)phen­yl](meth­yl)amino}acetic acid

Abstract

In the title compound, C16H14N2O2S, the dihedral angle between the benzothia­zole ring system and benzene ring is 3.11 (2)°. In the crystal structure, inter­molecular O—H(...)N hydrogen bonds link mol­ecules into chains along [100] and these chains are, in turn, linked into a three-dimensional network via weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

In an effort to develop in vivo β-sheet imaging probes, many derivatives of thio­flavin T, a water-soluble fluorescent dye, have been synthesized and evaluated, see: Kung et al. (2001 [triangle]); Qu et al. (2007 [triangle]). For the synthetic procedure, see: Stephenson et al., 2007 [triangle].

An external file that holds a picture, illustration, etc.
Object name is e-65-o2762-scheme1.jpg

Experimental

Crystal data

  • C16H14N2O2S
  • M r = 298.35
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2762-efi1.jpg
  • a = 11.9516 (10) Å
  • b = 9.4390 (8) Å
  • c = 25.418 (2) Å
  • V = 2867.5 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 298 K
  • 0.16 × 0.15 × 0.12 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.964, T max = 0.973
  • 12100 measured reflections
  • 3234 independent reflections
  • 2156 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.134
  • S = 1.06
  • 3234 reflections
  • 194 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809041452/lh2913sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041452/lh2913Isup2.hkl

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

supplementary crystallographic information

Comment

Thioflavin T (ThT) as a water-soluble fluorescence dye has been drawing great attention due to its ability to label amyloid fibrils. In an effort to develop in vivo beta-sheet imaging probes, many derivatives of thioflavin T compounds have been synthesized and evaluated (e.g. Kung et al., 2001; Qu et al., 2007). In this context, we have synthesized the title compound and report its crystal structure herein.

In the molecular structure (Fig. 1), the dihedral angle between the benzothiazole unit and benzene ring is 3.11 (2), and the conformation of the substituted methylamino group is defined by the C16—N2—C14—C15 torsion angle of 86.8 (3)°. All bond lengths and bond angles are as expected. In the crystal structure, intermolecular O-H···N hydrogen bonds link molecules into one-dimensional chains and these chains, are in turn linked into a three-dimensional network via weak intermolecular C—H···O hydrogen bonds (Fig. 2).

Experimental

Compound (I) was synthesized according to the method described by Stephenson et al. (2007). Yellow single crystals suitable for an X-ray diffraction study were obtained by slow evaporation of an methanol solution of the title compound.

Refinement

All H atoms were placed in idealized positions [C–H=0.96 Å (methyl), 0.97Å (methylene) and 0.93 Å (aromatic)] and included in the refinement in the riding-model approximation, with Uiso(H)= 1.5Ueq(methyl C) and 1.2Ueq(methylene and aromatic C). The H atom bonded to the carboxyl group O atom was found from the difference map. The O—H distance was refined freely with Uiso(H)= 1.5Ueq(O)

Figures

Fig. 1.
The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
Part of the crystal structure of (I) showing hydrogen bonds as dashed lines. Only H atoms involved in hydrogen bonds are shown.

Crystal data

C16H14N2O2SF(000) = 1248
Mr = 298.35Dx = 1.382 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1634 reflections
a = 11.9516 (10) Åθ = 2.3–22.4°
b = 9.4390 (8) ŵ = 0.23 mm1
c = 25.418 (2) ÅT = 298 K
V = 2867.5 (4) Å3Block, colorless
Z = 80.16 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer3234 independent reflections
Radiation source: fine-focus sealed tube2156 reflections with I > 2σ(I)
graphiteRint = 0.057
[var phi] and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→6
Tmin = 0.964, Tmax = 0.973k = −11→12
12100 measured reflectionsl = −31→31

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)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0495P)2] where P = (Fo2 + 2Fc2)/3
3234 reflections(Δ/σ)max < 0.001
194 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

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)

xyzUiso*/Ueq
C10.36303 (18)0.1030 (2)0.62901 (9)0.0352 (6)
C20.3131 (2)−0.0017 (3)0.71444 (10)0.0448 (6)
C30.2757 (3)−0.0521 (3)0.76272 (11)0.0604 (8)
H30.2112−0.01600.77830.072*
C40.3367 (3)−0.1562 (3)0.78658 (11)0.0654 (9)
H40.3122−0.19320.81850.079*
C50.4342 (3)−0.2081 (3)0.76424 (11)0.0599 (8)
H50.4747−0.27780.78170.072*
C60.4720 (2)−0.1582 (3)0.71657 (10)0.0483 (7)
H60.5374−0.19370.70170.058*
C70.4106 (2)−0.0537 (3)0.69110 (10)0.0386 (6)
C80.36685 (18)0.1881 (2)0.58153 (9)0.0347 (6)
C90.28533 (19)0.2883 (3)0.56974 (10)0.0408 (6)
H90.22510.29930.59260.049*
C100.2907 (2)0.3716 (3)0.52558 (10)0.0422 (6)
H100.23340.43570.51880.051*
C110.38126 (18)0.3618 (2)0.49032 (9)0.0344 (6)
C120.46109 (19)0.2571 (3)0.50147 (9)0.0409 (6)
H120.52060.24380.47840.049*
C130.45351 (19)0.1741 (3)0.54534 (10)0.0419 (6)
H130.50820.10590.55120.050*
C140.3081 (2)0.5541 (2)0.43544 (10)0.0432 (6)
H14A0.34190.62910.41470.052*
H14B0.28040.59590.46780.052*
C150.21108 (19)0.4931 (3)0.40533 (9)0.0368 (6)
C160.4788 (2)0.4267 (3)0.40869 (11)0.0550 (8)
H16A0.55100.42520.42520.082*
H16B0.47650.50130.38310.082*
H16C0.46550.33740.39170.082*
N10.43700 (15)0.0080 (2)0.64281 (8)0.0372 (5)
N20.39284 (16)0.4510 (2)0.44825 (8)0.0421 (5)
O10.13080 (15)0.58713 (18)0.39831 (8)0.0520 (5)
H10.065 (2)0.540 (3)0.3813 (11)0.078*
O20.20655 (15)0.37398 (19)0.38956 (8)0.0583 (5)
S10.25427 (6)0.12637 (8)0.67437 (3)0.0549 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0333 (12)0.0360 (14)0.0363 (14)−0.0010 (10)−0.0001 (11)−0.0032 (11)
C20.0506 (15)0.0454 (15)0.0384 (15)0.0003 (13)0.0038 (12)0.0027 (13)
C30.075 (2)0.063 (2)0.0438 (18)−0.0004 (16)0.0151 (15)0.0044 (16)
C40.096 (3)0.064 (2)0.0361 (17)−0.0114 (18)0.0031 (17)0.0104 (15)
C50.075 (2)0.0537 (19)0.0507 (19)−0.0072 (16)−0.0165 (17)0.0119 (15)
C60.0468 (15)0.0481 (17)0.0500 (18)−0.0014 (12)−0.0079 (13)0.0083 (14)
C70.0409 (13)0.0366 (14)0.0382 (15)−0.0057 (11)−0.0041 (12)0.0019 (12)
C80.0352 (12)0.0349 (13)0.0339 (14)−0.0012 (11)−0.0016 (11)0.0002 (11)
C90.0354 (13)0.0442 (15)0.0429 (16)0.0037 (11)0.0052 (11)−0.0003 (13)
C100.0396 (13)0.0380 (14)0.0490 (17)0.0071 (11)−0.0049 (12)0.0035 (13)
C110.0333 (12)0.0351 (13)0.0348 (14)−0.0058 (10)−0.0085 (10)−0.0013 (11)
C120.0358 (13)0.0518 (16)0.0351 (15)0.0058 (11)0.0029 (11)0.0043 (12)
C130.0371 (13)0.0488 (16)0.0399 (15)0.0107 (11)−0.0021 (12)0.0042 (13)
C140.0538 (15)0.0338 (14)0.0419 (15)−0.0024 (12)−0.0093 (13)0.0073 (12)
C150.0433 (13)0.0327 (14)0.0345 (14)−0.0036 (11)−0.0002 (11)0.0057 (11)
C160.0535 (16)0.0594 (19)0.0520 (18)−0.0068 (14)0.0062 (14)0.0155 (15)
N10.0332 (10)0.0386 (12)0.0398 (12)−0.0026 (9)−0.0011 (9)0.0040 (10)
N20.0408 (11)0.0411 (12)0.0444 (13)0.0004 (10)−0.0046 (10)0.0112 (10)
O10.0432 (10)0.0364 (10)0.0762 (14)0.0012 (8)−0.0150 (10)−0.0006 (9)
O20.0598 (12)0.0422 (12)0.0727 (14)0.0036 (9)−0.0132 (11)−0.0167 (10)
S10.0550 (4)0.0613 (5)0.0484 (5)0.0181 (3)0.0152 (3)0.0110 (4)

Geometric parameters (Å, °)

C1—N11.307 (3)C10—C111.408 (3)
C1—C81.450 (3)C10—H100.9300
C1—S11.752 (2)C11—N21.368 (3)
C2—C31.390 (3)C11—C121.403 (3)
C2—C71.397 (3)C12—C131.366 (3)
C2—S11.730 (3)C12—H120.9300
C3—C41.366 (4)C13—H130.9300
C3—H30.9300C14—N21.441 (3)
C4—C51.386 (4)C14—C151.504 (3)
C4—H40.9300C14—H14A0.9700
C5—C61.377 (4)C14—H14B0.9700
C5—H50.9300C15—O21.195 (3)
C6—C71.390 (3)C15—O11.319 (3)
C6—H60.9300C16—N21.456 (3)
C7—N11.395 (3)C16—H16A0.9600
C8—C91.391 (3)C16—H16B0.9600
C8—C131.392 (3)C16—H16C0.9600
C9—C101.372 (3)O1—H11.00 (3)
C9—H90.9300
N1—C1—C8125.6 (2)N2—C11—C12121.5 (2)
N1—C1—S1114.31 (18)N2—C11—C10122.4 (2)
C8—C1—S1120.10 (17)C12—C11—C10116.1 (2)
C3—C2—C7121.5 (3)C13—C12—C11121.6 (2)
C3—C2—S1128.9 (2)C13—C12—H12119.2
C7—C2—S1109.53 (18)C11—C12—H12119.2
C4—C3—C2117.8 (3)C12—C13—C8122.3 (2)
C4—C3—H3121.1C12—C13—H13118.8
C2—C3—H3121.1C8—C13—H13118.8
C3—C4—C5121.4 (3)N2—C14—C15113.5 (2)
C3—C4—H4119.3N2—C14—H14A108.9
C5—C4—H4119.3C15—C14—H14A108.9
C6—C5—C4121.1 (3)N2—C14—H14B108.9
C6—C5—H5119.5C15—C14—H14B108.9
C4—C5—H5119.5H14A—C14—H14B107.7
C5—C6—C7118.6 (3)O2—C15—O1123.7 (2)
C5—C6—H6120.7O2—C15—C14124.4 (2)
C7—C6—H6120.7O1—C15—C14111.9 (2)
C6—C7—N1125.9 (2)N2—C16—H16A109.5
C6—C7—C2119.5 (2)N2—C16—H16B109.5
N1—C7—C2114.6 (2)H16A—C16—H16B109.5
C9—C8—C13116.3 (2)N2—C16—H16C109.5
C9—C8—C1122.3 (2)H16A—C16—H16C109.5
C13—C8—C1121.4 (2)H16B—C16—H16C109.5
C10—C9—C8122.2 (2)C1—N1—C7111.7 (2)
C10—C9—H9118.9C11—N2—C14121.4 (2)
C8—C9—H9118.9C11—N2—C16121.0 (2)
C9—C10—C11121.3 (2)C14—N2—C16116.5 (2)
C9—C10—H10119.3C15—O1—H1109.4 (16)
C11—C10—H10119.3C2—S1—C189.89 (12)
C7—C2—C3—C4−0.9 (4)C10—C11—C12—C13−2.9 (3)
S1—C2—C3—C4179.1 (2)C11—C12—C13—C8−0.1 (4)
C2—C3—C4—C51.6 (5)C9—C8—C13—C122.2 (4)
C3—C4—C5—C6−1.3 (5)C1—C8—C13—C12−177.3 (2)
C4—C5—C6—C70.3 (4)N2—C14—C15—O2−5.5 (4)
C5—C6—C7—N1−179.9 (2)N2—C14—C15—O1174.4 (2)
C5—C6—C7—C20.3 (4)C8—C1—N1—C7178.9 (2)
C3—C2—C7—C60.0 (4)S1—C1—N1—C70.4 (3)
S1—C2—C7—C6180.00 (19)C6—C7—N1—C1179.8 (2)
C3—C2—C7—N1−179.8 (2)C2—C7—N1—C1−0.4 (3)
S1—C2—C7—N10.2 (3)C12—C11—N2—C14177.0 (2)
N1—C1—C8—C9−179.4 (2)C10—C11—N2—C14−4.5 (3)
S1—C1—C8—C9−1.0 (3)C12—C11—N2—C169.8 (3)
N1—C1—C8—C130.1 (4)C10—C11—N2—C16−171.8 (2)
S1—C1—C8—C13178.57 (18)C15—C14—N2—C11−81.0 (3)
C13—C8—C9—C10−1.4 (4)C15—C14—N2—C1686.8 (3)
C1—C8—C9—C10178.1 (2)C3—C2—S1—C1180.0 (3)
C8—C9—C10—C11−1.5 (4)C7—C2—S1—C10.00 (19)
C9—C10—C11—N2−174.9 (2)N1—C1—S1—C2−0.23 (19)
C9—C10—C11—C123.6 (3)C8—C1—S1—C2−178.8 (2)
N2—C11—C12—C13175.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N1i1.00 (3)1.71 (3)2.695 (3)167 (2)
C4—H4···O2ii0.932.503.368 (3)156
C14—H14A···O2iii0.972.473.242 (3)137

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2913).

References

  • Bruker (2007). SAINT-Plus and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kung, H. F., Lee, C.-W., Zhuang, Z.-P., Kung, M.-P., Hou, C. & Plssl, K. (2001). J. Am. Chem. Soc.123, 12740–12741. [PubMed]
  • Qu, W., Kung, M.-P., Hou, C., Oya, S. & Kung, H. F. (2007). J. Med. Chem.50, 3380–3387. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stephenson, K. A., Chandra, R., Zhuang, Z.-P., Hou, C., Oya, S., Kung, M.-P. & Kung, H. F. (2007). Bioconjugate Chem.18, 238–246. [PMC free article] [PubMed]

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