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Acta Cryst. (2009). E65, o2188    [ doi:10.1107/S1600536809031857 ]

2-Amino-6-methyl-1,3-benzothiazole-decanedioic acid (2/1)

X.-J. Shi, Z.-C. Wang, Q. Chen and X.-J. Zhao

Abstract top

Co-crystallization of 2-amino-6-methyl-1,3-benzothiazole with decanedioic acid under hydrothermal conditions afforded the title 2:1 co-crystal, 2C8H8N2S·C10H18O4. The decanedioic acid molecule is located on an inversion centre. In the crystal, intermolecular N-H...O and O-H...O hydrogen bonds connect the components into a two-dimensional wave-like layer structure extending parallel to (100).

Comment top

During the past decades, molecular self-/assembly by classical coordination bonds and/or intermolecular non-covalent interactions such as hydrogen-bonding, π···π stacking, electrostatic interactions and so on, has been becoming more and more attractive in biology, biochemistry and new material fields (Sun et al., 2008; Hunter, 1993; Yang et al., 2005).

Acting as one of the excellent building blocks with multiple hydrogen-bonding sites and metal ion binding donors, aminobenzothiazole and its derivatives have been extensively utilized in the new materials, biochemistry and agriculture chemistry, due to the lower toxicity, high biological activity as well as excellent chemical reactivity (Lynch et al., 1998; Lynch et al., 1999; Sun et al., 2008; Popović et al., 2002; Antiñolo et al., 2007; Dong et al., 2002; Chen et al., 2008). On the other hand, the long decanedioic acid with adjustable deprotonated form and flexible aliphatic chain has also exhibited novel functions such as dianion templating (Xian et al., 2009) and heterosynthons with nitrogen-containing compounds (Braga et al., 2006; Aakeröy et al., 2007) in the fields of metal complexes and molecular co-crystals.

Thus, as a continuation of molecular assembly behavior in the solid state, in the present paper, the rigid 2-amino-6-methyl-1,3-benzothiazole (Ambt) and flexible decanedioic acid were selected as building blocks to cocrystallize. As a result, an intermolecular hydrogen bonded adduct, (I), was obtained under the hydrothermal conditions.

As shown in Fig. 1, the asymmetric unit of (I) comprises one neutral Ambt molecule with no crystallographically imposed symmetry and half a decanedioic acid located on a centre of inversion. Obviously, no proton transfer was observed for the neutral cocrystal, which is much different from the 2-aminobenzothiazolium 2,4-dicarboxybenzoate monohydrate (Zhang et al., 2009). The exocyclic amino group of Ambt is roughly coplanar with the benzothiazole ring. Similarily, the carboxylic residues of decanedioic acid are also co-planar with their long aliphatic chain. In the packing structure of I, two pairs of the intermolecuar O1—H1 ···N1 and N2—H2A ···O2 hydrogen-bonding interactions (Table 1) connect the two Ambt molecules and one decanedioic acid.

Related literature top

For molecular self-assembly and crystal engineering, see: Sun et al. (2008); Hunter (1993); Yang et al. (2005). For the solid structures and properties of metal complexes of aminobenzothiazole and its derivatives, see: Lynch et al. (1998, 1999); Sun et al. (2008); Popović et al. (2002); Antiñolo et al. (2007); Dong et al. (2002); Chen et al. (2008); Zhang et al. (2009). For the structures of decanedioic acid-based metal complexes and co-crystals, see: Xian et al. (2009); Braga et al. (2006); Aakeröy et al. (2007).

Experimental top

To an aqueous solution of Ambt (40.4 mg, 0.2 mmol) was slowly added an aqueous solution of decanedioic acid (20.2 mg, 0.1 mmol) with constant stirring. After further stirring for about ten minutes, the resulting mixture was sealed in a stainless steel vessel and heated at 140 oC for 3 days. After the mixture was cooled to room temperature at a rate of 5 oC / h, pale-yellow block-shaped crystals suitable for X-ray diffraction were obtained directly, washed with ethanol and dried in air.Yield: 34% based on Ambt. Anal. calcd for C13H17N2O2S: C, 58.84; H, 6.46; N, 10.56%. Found: C, 58.78; H, 6.56; N,10.70%.

Refinement top

H-atoms were located in difference maps, but were subsequently placed in calculated positions and treated as riding, with C—H = 0.93 Å, O—H = 0.82 Å, and N—H = 0.86 Å. all H atoms were allocated displacement parameters related to those of their parent atoms [Uiso(H)] = 1.2 Ueq (C, N, O)

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawnat the 30% probability level. The dashed lines indicate intermolecular hydrogen bonds.[Symmetry code: (A) 4 – x, 1 – y, – z]
[Figure 2] Fig. 2. The two-dimensional layer of (I) formed by N–H···O and O–H ···O hydrogen bonding interactions.
2-Amino-6-methyl-1,3-benzothiazole–decanedioic acid (2/1) top
Crystal data top
2C8H8N2S·C10H18O4F(000) = 564
Mr = 530.71Dx = 1.258 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 5.3791 (5) ÅCell parameters from 1765 reflections
b = 21.822 (2) Åθ = 2.5–22.8°
c = 11.9431 (11) ŵ = 0.23 mm−1
β = 91.666 (1)°T = 293 K
V = 1401.3 (2) Å3Block, pale-yellow
Z = 20.32 × 0.24 × 0.22 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2470 independent reflections
Radiation source: fine-focus sealed tube1822 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.931, Tmax = 0.952k = −25→21
7545 measured reflectionsl = −14→14
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0483P)2 + 0.3107P]
where P = (Fo2 + 2Fc2)/3
2470 reflections(Δ/σ)max < 0.001
164 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
2C8H8N2S·C10H18O4V = 1401.3 (2) Å3
Mr = 530.71Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.3791 (5) ŵ = 0.23 mm−1
b = 21.822 (2) ÅT = 293 K
c = 11.9431 (11) Å0.32 × 0.24 × 0.22 mm
β = 91.666 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2470 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1822 reflections with I > 2σ(I)
Tmin = 0.931, Tmax = 0.952Rint = 0.024
7545 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.23 e Å−3
S = 1.05Δρmin = −0.26 e Å−3
2470 reflectionsAbsolute structure: ?
164 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
S10.47667 (11)0.17050 (3)0.20230 (5)0.0647 (2)
O11.1513 (3)0.27012 (7)−0.03449 (11)0.0595 (4)
H11.04560.25310.00260.089*
O21.2105 (3)0.32343 (7)0.12223 (12)0.0662 (4)
N10.8009 (3)0.21067 (7)0.06387 (13)0.0502 (4)
N20.8217 (3)0.25824 (8)0.23838 (14)0.0628 (5)
H2A0.94200.28150.21890.075*
H2B0.76430.26100.30460.075*
C10.7248 (4)0.21790 (9)0.16608 (16)0.0495 (5)
C20.4781 (4)0.13827 (9)0.06865 (17)0.0536 (5)
C30.3269 (4)0.09285 (10)0.02272 (19)0.0658 (6)
H3A0.20240.07540.06480.079*
C40.3619 (4)0.07353 (10)−0.0861 (2)0.0647 (6)
C50.5474 (4)0.10135 (11)−0.14663 (18)0.0650 (6)
H5A0.57030.0889−0.22010.078*
C60.6984 (4)0.14661 (10)−0.10228 (17)0.0599 (6)
H6A0.82140.1643−0.14490.072*
C70.6645 (4)0.16541 (9)0.00673 (16)0.0488 (5)
C80.1999 (6)0.02374 (13)−0.1383 (2)0.0920 (9)
H8A0.08190.0101−0.08500.138*
H8B0.3023−0.0101−0.15970.138*
H8C0.11300.0397−0.20330.138*
C91.2624 (4)0.31276 (9)0.02632 (16)0.0469 (5)
C101.4559 (4)0.34752 (9)−0.03539 (16)0.0511 (5)
H10A1.37580.3681−0.09870.061*
H10B1.57400.3185−0.06480.061*
C111.5968 (4)0.39443 (9)0.03408 (16)0.0509 (5)
H11A1.69310.37350.09240.061*
H11B1.47880.42100.07010.061*
C121.7698 (4)0.43316 (9)−0.03430 (17)0.0517 (5)
H12A1.88550.4064−0.07130.062*
H12B1.67260.4544−0.09200.062*
C131.9159 (4)0.47985 (9)0.03387 (16)0.0511 (5)
H13A2.01640.45850.09010.061*
H13B1.80000.50580.07270.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0678 (4)0.0744 (4)0.0529 (3)−0.0197 (3)0.0191 (3)0.0042 (3)
O10.0673 (10)0.0637 (9)0.0484 (8)−0.0271 (7)0.0198 (7)−0.0071 (7)
O20.0763 (11)0.0750 (10)0.0484 (8)−0.0275 (8)0.0207 (7)−0.0107 (7)
N10.0517 (10)0.0565 (10)0.0428 (9)−0.0120 (8)0.0086 (7)0.0036 (7)
N20.0740 (13)0.0691 (12)0.0460 (9)−0.0193 (10)0.0129 (9)−0.0042 (9)
C10.0512 (12)0.0513 (11)0.0464 (11)−0.0036 (9)0.0074 (9)0.0084 (9)
C20.0538 (12)0.0549 (12)0.0524 (11)−0.0087 (10)0.0061 (9)0.0091 (10)
C30.0606 (14)0.0675 (14)0.0695 (14)−0.0214 (12)0.0070 (11)0.0113 (12)
C40.0671 (15)0.0618 (13)0.0646 (14)−0.0132 (12)−0.0080 (11)0.0024 (11)
C50.0712 (15)0.0740 (15)0.0497 (12)−0.0096 (12)−0.0002 (11)−0.0010 (11)
C60.0615 (14)0.0691 (14)0.0495 (12)−0.0136 (11)0.0063 (10)0.0034 (10)
C70.0482 (12)0.0515 (11)0.0465 (11)−0.0050 (9)0.0012 (9)0.0087 (9)
C80.097 (2)0.0889 (19)0.0893 (18)−0.0331 (17)−0.0044 (16)−0.0102 (16)
C90.0476 (12)0.0457 (11)0.0477 (11)−0.0043 (9)0.0069 (9)0.0008 (9)
C100.0518 (12)0.0497 (11)0.0525 (12)−0.0099 (9)0.0122 (9)−0.0013 (9)
C110.0491 (12)0.0511 (12)0.0527 (11)−0.0076 (9)0.0057 (9)0.0029 (9)
C120.0474 (12)0.0519 (12)0.0561 (12)−0.0085 (9)0.0078 (9)−0.0001 (9)
C130.0482 (12)0.0515 (12)0.0538 (11)−0.0069 (9)0.0053 (9)0.0040 (9)
Geometric parameters (Å, °) top
S1—C21.744 (2)C6—C71.382 (3)
S1—C11.753 (2)C6—H6A0.9300
O1—C91.313 (2)C8—H8A0.9600
O1—H10.8200C8—H8B0.9600
O2—C91.209 (2)C8—H8C0.9600
N1—C11.308 (2)C9—C101.499 (3)
N1—C71.397 (2)C10—C111.508 (3)
N2—C11.329 (2)C10—H10A0.9700
N2—H2A0.8600C10—H10B0.9700
N2—H2B0.8600C11—C121.514 (3)
C2—C31.385 (3)C11—H11A0.9700
C2—C71.395 (3)C11—H11B0.9700
C3—C41.385 (3)C12—C131.510 (3)
C3—H3A0.9300C12—H12A0.9700
C4—C51.388 (3)C12—H12B0.9700
C4—C81.516 (3)C13—C13i1.513 (4)
C5—C61.375 (3)C13—H13A0.9700
C5—H5A0.9300C13—H13B0.9700
C2—S1—C189.34 (9)C4—C8—H8C109.5
C9—O1—H1109.5H8A—C8—H8C109.5
C1—N1—C7111.53 (16)H8B—C8—H8C109.5
C1—N2—H2A120.0O2—C9—O1123.13 (17)
C1—N2—H2B120.0O2—C9—C10123.42 (18)
H2A—N2—H2B120.0O1—C9—C10113.44 (16)
N1—C1—N2123.95 (18)C9—C10—C11114.71 (16)
N1—C1—S1114.85 (15)C9—C10—H10A108.6
N2—C1—S1121.18 (15)C11—C10—H10A108.6
C3—C2—C7121.1 (2)C9—C10—H10B108.6
C3—C2—S1129.25 (16)C11—C10—H10B108.6
C7—C2—S1109.65 (15)H10A—C10—H10B107.6
C4—C3—C2119.7 (2)C10—C11—C12112.90 (16)
C4—C3—H3A120.2C10—C11—H11A109.0
C2—C3—H3A120.2C12—C11—H11A109.0
C3—C4—C5118.4 (2)C10—C11—H11B109.0
C3—C4—C8120.8 (2)C12—C11—H11B109.0
C5—C4—C8120.8 (2)H11A—C11—H11B107.8
C6—C5—C4122.6 (2)C13—C12—C11113.84 (16)
C6—C5—H5A118.7C13—C12—H12A108.8
C4—C5—H5A118.7C11—C12—H12A108.8
C5—C6—C7118.9 (2)C13—C12—H12B108.8
C5—C6—H6A120.6C11—C12—H12B108.8
C7—C6—H6A120.6H12A—C12—H12B107.7
C6—C7—C2119.34 (19)C12—C13—C13i114.4 (2)
C6—C7—N1126.03 (18)C12—C13—H13A108.7
C2—C7—N1114.63 (17)C13i—C13—H13A108.7
C4—C8—H8A109.5C12—C13—H13B108.7
C4—C8—H8B109.5C13i—C13—H13B108.7
H8A—C8—H8B109.5H13A—C13—H13B107.6
C7—N1—C1—N2−179.62 (19)C5—C6—C7—C2−0.2 (3)
C7—N1—C1—S1−0.5 (2)C5—C6—C7—N1−179.8 (2)
C2—S1—C1—N10.29 (17)C3—C2—C7—C60.0 (3)
C2—S1—C1—N2179.42 (18)S1—C2—C7—C6−179.96 (17)
C1—S1—C2—C3−180.0 (2)C3—C2—C7—N1179.69 (19)
C1—S1—C2—C70.02 (16)S1—C2—C7—N1−0.3 (2)
C7—C2—C3—C40.5 (3)C1—N1—C7—C6−179.8 (2)
S1—C2—C3—C4−179.45 (19)C1—N1—C7—C20.5 (3)
C2—C3—C4—C5−0.9 (4)O2—C9—C10—C114.3 (3)
C2—C3—C4—C8179.8 (2)O1—C9—C10—C11−176.76 (17)
C3—C4—C5—C60.8 (4)C9—C10—C11—C12−173.70 (17)
C8—C4—C5—C6−179.9 (2)C10—C11—C12—C13−179.12 (17)
C4—C5—C6—C7−0.2 (4)C11—C12—C13—C13i−178.3 (2)
Symmetry codes: (i) −x+4, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.782.597 (2)171
N2—H2A···O20.862.092.914 (2)161
N2—H2B···O1ii0.862.142.954 (2)157
Symmetry codes: (ii) x−1/2, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.782.597 (2)171
N2—H2A···O20.862.092.914 (2)161
N2—H2B···O1i0.862.142.954 (2)157
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2.
Acknowledgements top

The authors gratefully acknowledge financial support from Tianjin Normal University.

references
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