The title compound, C
14H
12N
2O
4S, has a supramolecular structure consisting of base-paired dimers with an
R22(12) motif formed by a centrosymmetrically related pair of N—H
O hydrogen bonds.
Supporting information
CCDC reference: 159761
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.045
- wR factor = 0.123
- Data-to-parameter ratio = 17.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.50
From the CIF: _reflns_number_total 3392
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 4026
Completeness (_total/calc) 84.25%
Alert A: < 85% complete (theta max?)
Alert Level C:
PLAT_320 Alert C Check Hybridisation of S(51) in main residue ?
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
A mixture of the Meldrum's acid (6.94 mmol) and trimethyl orthoformate (34.7 mmol) was heated to reflux for 2.5 h, then 2-aminobenzothiazole (6.94 mmol)
was added and the mixture was heated for a further 5 min. The title compound
precipitated and was separated by filtration and was recrystallized from a
dimethylformamide–ethanol mixture, affording crystals suitable for X-ray
diffraction (m.p. 480–481 K, yield: 60%).
H atoms were treated as riding with C—H distances in the range 0.95–0.98 Å
and an N—H distance of 0.88 Å.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
5-(1,3-Benzothiazol-2-yliminomethyl)-2,2-dimethyl-1,3-dioxane-4,6-dione
top
Crystal data top
C14H12N2O4S | Dx = 1.526 Mg m−3 |
Mr = 304.32 | Melting point: 480 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.3459 (13) Å | Cell parameters from 6132 reflections |
b = 19.235 (4) Å | θ = 1.0–30.5° |
c = 11.144 (2) Å | µ = 0.26 mm−1 |
β = 103.07 (3)° | T = 150 K |
V = 1325.0 (5) Å3 | Needle, orange |
Z = 4 | 0.38 × 0.05 × 0.05 mm |
F(000) = 632 | |
Data collection top
KappaCCD diffractometer | 3392 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2645 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
ϕ and ω scans with κ offsets | θmax = 30.5°, θmin = 2.1° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −9→8 |
Tmin = 0.908, Tmax = 0.987 | k = −22→27 |
12128 measured reflections | l = −13→15 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0684P)2 + 0.1432P] where P = (Fo2 + 2Fc2)/3 |
3392 reflections | (Δ/σ)max = 0.001 |
192 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
Crystal data top
C14H12N2O4S | V = 1325.0 (5) Å3 |
Mr = 304.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.3459 (13) Å | µ = 0.26 mm−1 |
b = 19.235 (4) Å | T = 150 K |
c = 11.144 (2) Å | 0.38 × 0.05 × 0.05 mm |
β = 103.07 (3)° | |
Data collection top
KappaCCD diffractometer | 3392 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2645 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.987 | Rint = 0.081 |
12128 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.42 e Å−3 |
3392 reflections | Δρmin = −0.52 e Å−3 |
192 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
(Fox & Holmes, 1966) which effectively corrects for absorption effects. High
redundancy data were used in the scaling program hence the 'multi-scan' code
word was used. no transmission coefficients are available from the program
(only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input
file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.30516 (18) | 0.33588 (5) | 1.01481 (10) | 0.0176 (3) | |
C2 | 1.2845 (3) | 0.26447 (8) | 1.05018 (14) | 0.0160 (3) | |
C21 | 1.4987 (3) | 0.22996 (9) | 1.05657 (16) | 0.0214 (4) | |
C22 | 1.2121 (3) | 0.26217 (9) | 1.17025 (14) | 0.0211 (4) | |
O3 | 1.13153 (17) | 0.22842 (6) | 0.95487 (10) | 0.0175 (3) | |
C4 | 0.9419 (3) | 0.25966 (8) | 0.90183 (14) | 0.0164 (3) | |
O41 | 0.80048 (19) | 0.22442 (6) | 0.83965 (11) | 0.0232 (3) | |
C5 | 0.9286 (2) | 0.33450 (8) | 0.92197 (14) | 0.0155 (3) | |
C6 | 1.1201 (2) | 0.37333 (8) | 0.97893 (13) | 0.0149 (3) | |
O61 | 1.12713 (19) | 0.43617 (6) | 0.99149 (10) | 0.0200 (3) | |
C51 | 0.7346 (3) | 0.36591 (8) | 0.87199 (14) | 0.0164 (3) | |
N51 | 0.6866 (2) | 0.43317 (7) | 0.87370 (12) | 0.0166 (3) | |
S51 | 0.41125 (6) | 0.54339 (2) | 0.82927 (4) | 0.01825 (14) | |
C52 | 0.4810 (3) | 0.45697 (8) | 0.81356 (14) | 0.0159 (3) | |
N53 | 0.3390 (2) | 0.41683 (7) | 0.74643 (12) | 0.0178 (3) | |
C54 | 0.1509 (3) | 0.45444 (8) | 0.70129 (15) | 0.0166 (3) | |
C55 | −0.0374 (3) | 0.42851 (9) | 0.62415 (15) | 0.0226 (4) | |
C56 | −0.2110 (3) | 0.47256 (10) | 0.58642 (17) | 0.0259 (4) | |
C57 | −0.2004 (3) | 0.54215 (9) | 0.62270 (17) | 0.0254 (4) | |
C58 | −0.0151 (3) | 0.56924 (9) | 0.69764 (15) | 0.0206 (4) | |
C59 | 0.1594 (3) | 0.52439 (8) | 0.73635 (14) | 0.0164 (3) | |
H21A | 1.4915 | 0.1815 | 1.0824 | 0.032* | |
H21B | 1.6113 | 0.2545 | 1.1163 | 0.032* | |
H21C | 1.5332 | 0.2314 | 0.9752 | 0.032* | |
H22A | 1.0651 | 0.2809 | 1.1577 | 0.032* | |
H22B | 1.3105 | 0.2902 | 1.2321 | 0.032* | |
H22C | 1.2136 | 0.2140 | 1.1989 | 0.032* | |
H51A | 0.6212 | 0.3362 | 0.8314 | 0.020* | |
H51 | 0.7842 | 0.4628 | 0.9126 | 0.020* | |
H55 | −0.0456 | 0.3814 | 0.5982 | 0.027* | |
H56 | −0.3404 | 0.4552 | 0.5347 | 0.031* | |
H57 | −0.3226 | 0.5714 | 0.5954 | 0.030* | |
H58 | −0.0069 | 0.6167 | 0.7219 | 0.025* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0176 (5) | 0.0113 (6) | 0.0220 (6) | −0.0004 (4) | 0.0004 (5) | 0.0039 (4) |
C2 | 0.0187 (8) | 0.0103 (7) | 0.0171 (8) | 0.0001 (6) | 0.0000 (6) | 0.0000 (6) |
C21 | 0.0202 (8) | 0.0186 (8) | 0.0240 (9) | 0.0030 (7) | 0.0017 (7) | 0.0011 (7) |
C22 | 0.0298 (9) | 0.0161 (8) | 0.0171 (8) | 0.0022 (7) | 0.0047 (7) | 0.0017 (6) |
O3 | 0.0193 (6) | 0.0114 (6) | 0.0196 (6) | 0.0014 (4) | −0.0002 (5) | −0.0022 (4) |
C4 | 0.0180 (8) | 0.0146 (8) | 0.0163 (8) | 0.0018 (6) | 0.0035 (6) | 0.0004 (6) |
O41 | 0.0215 (6) | 0.0173 (6) | 0.0278 (6) | −0.0006 (5) | −0.0010 (5) | −0.0078 (5) |
C5 | 0.0183 (8) | 0.0126 (8) | 0.0147 (7) | 0.0005 (6) | 0.0015 (6) | −0.0006 (6) |
C6 | 0.0190 (8) | 0.0135 (8) | 0.0124 (7) | 0.0008 (6) | 0.0038 (6) | 0.0017 (6) |
O61 | 0.0237 (6) | 0.0104 (6) | 0.0242 (6) | −0.0010 (4) | 0.0021 (5) | −0.0006 (4) |
C51 | 0.0184 (7) | 0.0147 (8) | 0.0154 (7) | −0.0001 (6) | 0.0019 (6) | −0.0010 (6) |
N51 | 0.0172 (7) | 0.0129 (7) | 0.0177 (7) | 0.0006 (5) | −0.0001 (5) | −0.0008 (5) |
S51 | 0.0188 (2) | 0.0114 (2) | 0.0221 (2) | 0.00052 (14) | −0.00051 (16) | −0.00246 (14) |
C52 | 0.0202 (8) | 0.0120 (8) | 0.0151 (8) | 0.0004 (6) | 0.0030 (6) | 0.0005 (6) |
N53 | 0.0198 (7) | 0.0138 (7) | 0.0181 (7) | 0.0014 (5) | 0.0004 (5) | −0.0009 (5) |
C54 | 0.0195 (8) | 0.0142 (8) | 0.0156 (8) | 0.0010 (6) | 0.0029 (6) | 0.0019 (6) |
C55 | 0.0254 (9) | 0.0165 (8) | 0.0232 (9) | −0.0009 (7) | −0.0004 (7) | −0.0013 (7) |
C56 | 0.0194 (8) | 0.0270 (9) | 0.0265 (9) | −0.0021 (7) | −0.0046 (7) | 0.0022 (7) |
C57 | 0.0195 (8) | 0.0264 (10) | 0.0276 (9) | 0.0060 (7) | 0.0000 (7) | 0.0060 (7) |
C58 | 0.0236 (8) | 0.0147 (8) | 0.0233 (8) | 0.0037 (7) | 0.0047 (7) | 0.0009 (7) |
C59 | 0.0181 (8) | 0.0154 (8) | 0.0150 (8) | 0.0001 (6) | 0.0026 (6) | −0.0002 (6) |
Geometric parameters (Å, º) top
O1—C6 | 1.3583 (18) | C51—H51A | 0.9500 |
O1—C2 | 1.4430 (18) | N51—C52 | 1.402 (2) |
C2—O3 | 1.4439 (18) | N51—H51 | 0.8800 |
C2—C21 | 1.500 (2) | S51—C59 | 1.7355 (16) |
C2—C22 | 1.511 (2) | S51—C52 | 1.7391 (15) |
C21—H21A | 0.9800 | C52—N53 | 1.290 (2) |
C21—H21B | 0.9800 | N53—C54 | 1.389 (2) |
C21—H21C | 0.9800 | C54—C55 | 1.397 (2) |
C22—H22A | 0.9800 | C54—C59 | 1.399 (2) |
C22—H22B | 0.9800 | C55—C56 | 1.378 (2) |
C22—H22C | 0.9800 | C55—H55 | 0.9500 |
O3—C4 | 1.3555 (18) | C56—C57 | 1.395 (3) |
C4—O41 | 1.2097 (18) | C56—H56 | 0.9500 |
C4—C5 | 1.462 (2) | C57—C58 | 1.381 (2) |
C5—C51 | 1.371 (2) | C57—H57 | 0.9500 |
C5—C6 | 1.445 (2) | C58—C59 | 1.393 (2) |
C6—O61 | 1.2164 (19) | C58—H58 | 0.9500 |
C51—N51 | 1.330 (2) | | |
| | | |
C6—O1—C2 | 117.34 (12) | N51—C51—C5 | 127.59 (15) |
O1—C2—O3 | 110.10 (11) | N51—C51—H51A | 116.2 |
O1—C2—C21 | 107.27 (13) | C5—C51—H51A | 116.2 |
O3—C2—C21 | 105.88 (12) | C51—N51—C52 | 120.14 (14) |
O1—C2—C22 | 109.54 (12) | C51—N51—H51 | 119.9 |
O3—C2—C22 | 110.41 (13) | C52—N51—H51 | 119.9 |
C21—C2—C22 | 113.52 (14) | C59—S51—C52 | 87.69 (8) |
C2—C21—H21A | 109.5 | N53—C52—N51 | 122.31 (14) |
C2—C21—H21B | 109.5 | N53—C52—S51 | 118.05 (12) |
H21A—C21—H21B | 109.5 | N51—C52—S51 | 119.64 (11) |
C2—C21—H21C | 109.5 | C52—N53—C54 | 109.19 (13) |
H21A—C21—H21C | 109.5 | N53—C54—C55 | 125.62 (14) |
H21B—C21—H21C | 109.5 | N53—C54—C59 | 115.11 (14) |
C2—C22—H22A | 109.5 | C55—C54—C59 | 119.26 (15) |
C2—C22—H22B | 109.5 | C56—C55—C54 | 118.82 (16) |
H22A—C22—H22B | 109.5 | C56—C55—H55 | 120.6 |
C2—C22—H22C | 109.5 | C54—C55—H55 | 120.6 |
H22A—C22—H22C | 109.5 | C55—C56—C57 | 121.22 (16) |
H22B—C22—H22C | 109.5 | C55—C56—H56 | 119.4 |
C4—O3—C2 | 119.39 (12) | C57—C56—H56 | 119.4 |
O41—C4—O3 | 118.15 (14) | C58—C57—C56 | 121.05 (16) |
O41—C4—C5 | 125.35 (14) | C58—C57—H57 | 119.5 |
O3—C4—C5 | 116.47 (13) | C56—C57—H57 | 119.5 |
C51—C5—C6 | 122.64 (14) | C57—C58—C59 | 117.52 (15) |
C51—C5—C4 | 116.67 (14) | C57—C58—H58 | 121.2 |
C6—C5—C4 | 120.27 (14) | C59—C58—H58 | 121.2 |
O61—C6—O1 | 119.10 (14) | C58—C59—C54 | 122.13 (15) |
O61—C6—C5 | 124.69 (14) | C58—C59—S51 | 127.93 (13) |
O1—C6—C5 | 116.13 (13) | C54—C59—S51 | 109.94 (12) |
| | | |
C6—O1—C2—O3 | 52.11 (17) | C51—N51—C52—N53 | −6.1 (2) |
C6—O1—C2—C21 | 166.88 (13) | C51—N51—C52—S51 | 173.61 (12) |
C6—O1—C2—C22 | −69.48 (16) | C59—S51—C52—N53 | 0.74 (14) |
O1—C2—O3—C4 | −44.54 (17) | C59—S51—C52—N51 | −179.02 (13) |
C21—C2—O3—C4 | −160.19 (13) | N51—C52—N53—C54 | 178.81 (14) |
C22—C2—O3—C4 | 76.54 (16) | S51—C52—N53—C54 | −0.94 (18) |
C2—O3—C4—O41 | −166.52 (13) | C52—N53—C54—C55 | 179.34 (16) |
C2—O3—C4—C5 | 15.38 (19) | C52—N53—C54—C59 | 0.7 (2) |
O41—C4—C5—C51 | 4.2 (2) | N53—C54—C55—C56 | −179.64 (15) |
O3—C4—C5—C51 | −177.86 (13) | C59—C54—C55—C56 | −1.0 (3) |
O41—C4—C5—C6 | −168.60 (15) | C54—C55—C56—C57 | 0.8 (3) |
O3—C4—C5—C6 | 9.3 (2) | C55—C56—C57—C58 | 0.1 (3) |
C2—O1—C6—O61 | 153.43 (13) | C56—C57—C58—C59 | −0.6 (3) |
C2—O1—C6—C5 | −29.61 (18) | C57—C58—C59—C54 | 0.3 (3) |
C51—C5—C6—O61 | 2.3 (2) | C57—C58—C59—S51 | 179.63 (13) |
C4—C5—C6—O61 | 174.68 (15) | N53—C54—C59—C58 | 179.29 (14) |
C51—C5—C6—O1 | −174.44 (13) | C55—C54—C59—C58 | 0.5 (3) |
C4—C5—C6—O1 | −2.1 (2) | N53—C54—C59—S51 | −0.18 (18) |
C6—C5—C51—N51 | −4.4 (3) | C55—C54—C59—S51 | −178.92 (13) |
C4—C5—C51—N51 | −177.04 (15) | C52—S51—C59—C58 | −179.69 (16) |
C5—C51—N51—C52 | 177.55 (15) | C52—S51—C59—C54 | −0.27 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N51—H51···O61i | 0.88 | 2.23 | 3.028 (2) | 151 |
N51—H51···O61 | 0.88 | 2.22 | 2.807 (2) | 124 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | C14H12N2O4S |
Mr | 304.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 6.3459 (13), 19.235 (4), 11.144 (2) |
β (°) | 103.07 (3) |
V (Å3) | 1325.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.38 × 0.05 × 0.05 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.908, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12128, 3392, 2645 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.714 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.123, 1.08 |
No. of reflections | 3392 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.52 |
Selected geometric parameters (Å, º) topC51—N51 | 1.330 (2) | S51—C52 | 1.7391 (15) |
N51—C52 | 1.402 (2) | C52—N53 | 1.290 (2) |
S51—C59 | 1.7355 (16) | N53—C54 | 1.389 (2) |
| | | |
C51—N51—C52 | 120.14 (14) | C52—N53—C54 | 109.19 (13) |
C59—S51—C52 | 87.69 (8) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N51—H51···O61i | 0.88 | 2.23 | 3.028 (2) | 151 |
N51—H51···O61 | 0.88 | 2.22 | 2.807 (2) | 124 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
We have focused on benzothiazole derivatives, which have shown diverse applications, as analgesics (Mehra et al., 1980), anti-inflammatory agents, antineoplasics (Cheng et al., 1993) and antimicrobial agents (Mehra et al., 1980; El-Shaaer et al., 1998), in our search for biological active molecules. Benzothiazole derivatives have been prepared by a known reaction (Quiroga et al., 1998). The title compound, (I), was prepared by condensation of Meldrum's acid, 2,2-dimethyl-1,3-dioxane-4,6-dione), 2-aminobenzothiazole and trimethyl orthoformate.
The supramolecular structure consists of base-paired dimers with an R22(12) motif (Bernstein et al., 1995), formed by the N51—H51···O61i hydrogen bond which is repeated across the centre at (1,1/2,1).
Geometric parameters are given in Table 1 and details of hydrogen bonds are given in Table 2. Fig. 1 shows a view of the molecule.
Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.