The molecules of the title compound, C
14H
11ClN
2O
4S, are linked together into ribbons formed by weak C—H
O hydrogen bonds.
Supporting information
CCDC reference: 180546
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.005 Å
- R factor = 0.054
- wR factor = 0.116
- Data-to-parameter ratio = 13.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 27.42
From the CIF: _reflns_number_total 2714
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3229
Completeness (_total/calc) 84.05%
Alert A: < 85% complete (theta max?)
| Author response: ...As can be seen the crystal is a very thin
plate and this probably contributes to the difficulty.
Experience shows that crystals of materials of this
class of compound produce in many cases very small crystals
and that re-crystallisation does not help.
|
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
A solution of Meldrum's acid (3.45 mmol) and trimethyl orthoformate (17.3 mmol)
was heated to reflux for 2.5 h, then 2-amino-6-chlorobenzothiazole (3.45 mmol)
was added and the reaction mixture was heated for a further 30 min. The title
compound precipitated, was separated by filtration, and recrystallized form
ethanol, affording crystals suitable for X-ray diffraction (m.p.: 524 K,
yield: 65%).
H atoms were treated as riding atoms with C—H = 0.95–0.98 Å and N—H =
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, 2001); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
5-[(6-Chloro-[1,3]benzothiazol-2-ylamino)-methylene]-2,2-dimethyl-
[1,3]dioxane-4,6-dione
top
Crystal data top
C14H11ClN2O4S | Dx = 1.583 Mg m−3 |
Mr = 338.76 | Melting point: 524K K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3389 (4) Å | Cell parameters from 2714 reflections |
b = 28.583 (2) Å | θ = 3.1–27.4° |
c = 9.8618 (8) Å | µ = 0.44 mm−1 |
β = 109.178 (4)° | T = 120 K |
V = 1421.41 (19) Å3 | Plate, yellow |
Z = 4 | 0.20 × 0.15 × 0.01 mm |
F(000) = 696 | |
Data collection top
Nonius KappaCCD diffractometer | 2714 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1430 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ scans, and ω scans with κ offsets | θmax = 27.4°, θmin = 3.1° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −6→6 |
Tmin = 0.918, Tmax = 0.996 | k = −37→29 |
6289 measured reflections | l = −12→12 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0358P)2] where P = (Fo2 + 2Fc2)/3 |
2714 reflections | (Δ/σ)max < 0.001 |
201 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C14H11ClN2O4S | V = 1421.41 (19) Å3 |
Mr = 338.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.3389 (4) Å | µ = 0.44 mm−1 |
b = 28.583 (2) Å | T = 120 K |
c = 9.8618 (8) Å | 0.20 × 0.15 × 0.01 mm |
β = 109.178 (4)° | |
Data collection top
Nonius KappaCCD diffractometer | 2714 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1430 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.996 | Rint = 0.066 |
6289 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.33 e Å−3 |
2714 reflections | Δρmin = −0.36 e Å−3 |
201 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 | |
S1 | 0.50857 (17) | −0.02167 (3) | 0.82323 (11) | 0.0234 (3) | |
C2 | 0.7535 (7) | 0.01394 (13) | 0.7970 (4) | 0.0205 (9) | |
N21 | 0.8452 (5) | 0.05151 (10) | 0.8920 (3) | 0.0233 (8) | |
C22 | 1.0219 (6) | 0.08347 (12) | 0.8797 (4) | 0.0196 (9) | |
O11 | 1.3791 (4) | 0.18811 (9) | 1.0377 (3) | 0.0236 (6) | |
C12 | 1.1915 (7) | 0.20408 (13) | 1.1032 (4) | 0.0237 (10) | |
C121 | 1.3431 (7) | 0.23615 (14) | 1.2231 (4) | 0.0408 (12) | |
C122 | 0.9566 (7) | 0.22650 (13) | 0.9937 (4) | 0.0321 (11) | |
O13 | 1.1038 (5) | 0.16556 (9) | 1.1721 (3) | 0.0265 (7) | |
C14 | 1.0195 (7) | 0.12659 (13) | 1.0921 (4) | 0.0227 (10) | |
O14 | 0.8806 (5) | 0.09885 (9) | 1.1311 (3) | 0.0278 (7) | |
C15 | 1.1109 (6) | 0.12006 (12) | 0.9711 (4) | 0.0185 (9) | |
C16 | 1.3155 (7) | 0.14992 (13) | 0.9496 (4) | 0.0208 (9) | |
O16 | 1.4352 (5) | 0.14314 (8) | 0.8677 (3) | 0.0279 (7) | |
N3 | 0.8400 (5) | 0.00484 (10) | 0.6939 (3) | 0.0193 (8) | |
C3A | 0.7079 (6) | −0.03472 (13) | 0.6214 (4) | 0.0213 (9) | |
C4 | 0.7513 (7) | −0.05519 (13) | 0.5031 (4) | 0.0217 (9) | |
C5 | 0.6086 (7) | −0.09474 (13) | 0.4429 (4) | 0.0253 (10) | |
C6 | 0.4247 (7) | −0.11302 (13) | 0.5011 (4) | 0.0216 (9) | |
Cl6 | 0.24393 (19) | −0.16248 (3) | 0.41996 (11) | 0.0335 (3) | |
C7 | 0.3772 (6) | −0.09389 (13) | 0.6180 (4) | 0.0190 (9) | |
C7A | 0.5227 (7) | −0.05422 (12) | 0.6769 (4) | 0.0190 (9) | |
H21 | 0.7834 | 0.0544 | 0.9640 | 0.028* | |
H22 | 1.0887 | 0.0802 | 0.8020 | 0.024* | |
H12D | 1.4930 | 0.2192 | 1.2895 | 0.061* | |
H12E | 1.2258 | 0.2472 | 1.2748 | 0.061* | |
H12F | 1.4092 | 0.2630 | 1.1833 | 0.061* | |
H12A | 1.0152 | 0.2540 | 0.9528 | 0.048* | |
H12B | 0.8279 | 0.2361 | 1.0398 | 0.048* | |
H12C | 0.8735 | 0.2040 | 0.9171 | 0.048* | |
H4 | 0.8770 | −0.0422 | 0.4643 | 0.026* | |
H5 | 0.6360 | −0.1093 | 0.3623 | 0.030* | |
H7 | 0.2517 | −0.1071 | 0.6565 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0268 (6) | 0.0237 (6) | 0.0213 (6) | −0.0030 (4) | 0.0101 (4) | −0.0008 (5) |
C2 | 0.021 (2) | 0.021 (2) | 0.021 (2) | 0.0008 (17) | 0.0090 (18) | −0.0018 (19) |
N21 | 0.0256 (18) | 0.0274 (19) | 0.020 (2) | −0.0014 (15) | 0.0119 (15) | 0.0026 (16) |
C22 | 0.018 (2) | 0.022 (2) | 0.022 (2) | 0.0045 (17) | 0.0114 (17) | 0.0082 (19) |
O11 | 0.0258 (15) | 0.0235 (16) | 0.0243 (16) | −0.0049 (12) | 0.0120 (12) | −0.0067 (14) |
C12 | 0.031 (2) | 0.026 (2) | 0.020 (2) | −0.0049 (18) | 0.0161 (19) | −0.005 (2) |
C121 | 0.055 (3) | 0.036 (3) | 0.043 (3) | −0.016 (2) | 0.032 (2) | −0.015 (2) |
C122 | 0.034 (2) | 0.026 (2) | 0.041 (3) | 0.0015 (19) | 0.018 (2) | 0.001 (2) |
O13 | 0.0385 (16) | 0.0258 (16) | 0.0175 (15) | −0.0063 (13) | 0.0124 (12) | −0.0018 (14) |
C14 | 0.021 (2) | 0.021 (2) | 0.023 (3) | 0.0024 (18) | 0.0024 (18) | 0.002 (2) |
O14 | 0.0325 (16) | 0.0332 (18) | 0.0198 (16) | −0.0052 (13) | 0.0113 (12) | 0.0055 (14) |
C15 | 0.024 (2) | 0.015 (2) | 0.017 (2) | 0.0007 (17) | 0.0070 (17) | 0.0002 (19) |
C16 | 0.020 (2) | 0.021 (2) | 0.020 (2) | 0.0032 (18) | 0.0046 (18) | 0.003 (2) |
O16 | 0.0309 (16) | 0.0318 (17) | 0.0287 (18) | −0.0043 (13) | 0.0203 (14) | −0.0070 (14) |
N3 | 0.0190 (18) | 0.0162 (18) | 0.024 (2) | 0.0010 (13) | 0.0088 (15) | 0.0023 (16) |
C3A | 0.020 (2) | 0.021 (2) | 0.021 (2) | 0.0042 (17) | 0.0036 (18) | 0.0054 (19) |
C4 | 0.024 (2) | 0.024 (2) | 0.021 (2) | 0.0024 (17) | 0.0122 (17) | 0.007 (2) |
C5 | 0.034 (2) | 0.023 (2) | 0.019 (2) | 0.0082 (19) | 0.0085 (19) | 0.001 (2) |
C6 | 0.029 (2) | 0.017 (2) | 0.018 (2) | 0.0009 (17) | 0.0070 (18) | 0.0023 (19) |
Cl6 | 0.0460 (7) | 0.0263 (6) | 0.0299 (7) | −0.0094 (5) | 0.0147 (5) | −0.0065 (5) |
C7 | 0.023 (2) | 0.023 (2) | 0.018 (2) | −0.0007 (17) | 0.0147 (17) | 0.0065 (19) |
C7A | 0.021 (2) | 0.019 (2) | 0.018 (2) | 0.0009 (17) | 0.0086 (17) | 0.0006 (19) |
Geometric parameters (Å, º) top
S1—C7A | 1.740 (4) | C122—H12C | 0.9800 |
S1—C2 | 1.742 (4) | O13—C14 | 1.354 (4) |
C2—N3 | 1.274 (4) | C14—O14 | 1.230 (4) |
C2—N21 | 1.403 (4) | C14—C15 | 1.443 (5) |
N21—C22 | 1.347 (4) | C15—C16 | 1.456 (5) |
N21—H21 | 0.8800 | C16—O16 | 1.199 (4) |
C22—C15 | 1.360 (5) | N3—C3A | 1.399 (4) |
C22—H22 | 0.9500 | C3A—C4 | 1.391 (5) |
O11—C16 | 1.367 (4) | C3A—C7A | 1.394 (5) |
O11—C12 | 1.433 (4) | C4—C5 | 1.383 (5) |
C12—O13 | 1.450 (4) | C4—H4 | 0.9500 |
C12—C122 | 1.503 (5) | C5—C6 | 1.392 (5) |
C12—C121 | 1.505 (5) | C5—H5 | 0.9500 |
C121—H12D | 0.9800 | C6—C7 | 1.372 (5) |
C121—H12E | 0.9800 | C6—Cl6 | 1.750 (4) |
C121—H12F | 0.9800 | C7—C7A | 1.389 (5) |
C122—H12A | 0.9800 | C7—H7 | 0.9500 |
C122—H12B | 0.9800 | | |
| | | |
C7A—S1—C2 | 87.14 (18) | C14—O13—C12 | 116.6 (3) |
N3—C2—N21 | 123.4 (3) | O14—C14—O13 | 117.9 (4) |
N3—C2—S1 | 119.1 (3) | O14—C14—C15 | 125.3 (4) |
N21—C2—S1 | 117.5 (3) | O13—C14—C15 | 116.8 (3) |
C22—N21—C2 | 124.1 (3) | C22—C15—C14 | 120.5 (3) |
C22—N21—H21 | 118.0 | C22—C15—C16 | 118.0 (4) |
C2—N21—H21 | 118.0 | C14—C15—C16 | 121.3 (3) |
N21—C22—C15 | 124.4 (4) | O16—C16—O11 | 118.8 (3) |
N21—C22—H22 | 117.8 | O16—C16—C15 | 126.5 (4) |
C15—C22—H22 | 117.8 | O11—C16—C15 | 114.6 (3) |
C16—O11—C12 | 118.5 (3) | C2—N3—C3A | 108.6 (3) |
O11—C12—O13 | 110.5 (3) | C4—C3A—C7A | 119.8 (3) |
O11—C12—C122 | 110.7 (3) | C4—C3A—N3 | 125.0 (4) |
O13—C12—C122 | 109.8 (3) | C7A—C3A—N3 | 115.2 (4) |
O11—C12—C121 | 105.9 (3) | C5—C4—C3A | 118.9 (4) |
O13—C12—C121 | 105.5 (3) | C5—C4—H4 | 120.5 |
C122—C12—C121 | 114.3 (3) | C3A—C4—H4 | 120.5 |
C12—C121—H12D | 109.5 | C4—C5—C6 | 119.5 (4) |
C12—C121—H12E | 109.5 | C4—C5—H5 | 120.2 |
H12D—C121—H12E | 109.5 | C6—C5—H5 | 120.2 |
C12—C121—H12F | 109.5 | C7—C6—C5 | 123.2 (3) |
H12D—C121—H12F | 109.5 | C7—C6—Cl6 | 118.6 (3) |
H12E—C121—H12F | 109.5 | C5—C6—Cl6 | 118.2 (3) |
C12—C122—H12A | 109.5 | C6—C7—C7A | 116.4 (4) |
C12—C122—H12B | 109.5 | C6—C7—H7 | 121.8 |
H12A—C122—H12B | 109.5 | C7A—C7—H7 | 121.8 |
C12—C122—H12C | 109.5 | C7—C7A—C3A | 122.2 (4) |
H12A—C122—H12C | 109.5 | C7—C7A—S1 | 127.8 (3) |
H12B—C122—H12C | 109.5 | C3A—C7A—S1 | 110.0 (3) |
| | | |
C7A—S1—C2—N3 | 0.6 (3) | C14—C15—C16—O16 | 167.1 (4) |
C7A—S1—C2—N21 | −179.4 (3) | C22—C15—C16—O11 | 174.8 (3) |
N3—C2—N21—C22 | 4.1 (5) | C14—C15—C16—O11 | −10.0 (5) |
S1—C2—N21—C22 | −175.9 (3) | N21—C2—N3—C3A | 179.8 (3) |
C2—N21—C22—C15 | 179.8 (3) | S1—C2—N3—C3A | −0.2 (4) |
C16—O11—C12—O13 | 50.3 (4) | C2—N3—C3A—C4 | −179.7 (3) |
C16—O11—C12—C122 | −71.6 (4) | C2—N3—C3A—C7A | −0.4 (4) |
C16—O11—C12—C121 | 164.0 (3) | C7A—C3A—C4—C5 | 0.0 (5) |
O11—C12—O13—C14 | −50.3 (4) | N3—C3A—C4—C5 | 179.2 (3) |
C122—C12—O13—C14 | 72.1 (4) | C3A—C4—C5—C6 | 0.3 (5) |
C121—C12—O13—C14 | −164.3 (3) | C4—C5—C6—C7 | −0.5 (6) |
C12—O13—C14—O14 | −160.9 (3) | C4—C5—C6—Cl6 | 178.9 (3) |
C12—O13—C14—C15 | 21.8 (4) | C5—C6—C7—C7A | 0.5 (5) |
N21—C22—C15—C14 | 0.7 (5) | Cl6—C6—C7—C7A | −179.0 (3) |
N21—C22—C15—C16 | 175.9 (3) | C6—C7—C7A—C3A | −0.2 (5) |
O14—C14—C15—C22 | 7.3 (6) | C6—C7—C7A—S1 | 179.6 (3) |
O13—C14—C15—C22 | −175.7 (3) | C4—C3A—C7A—C7 | 0.0 (5) |
O14—C14—C15—C16 | −167.7 (3) | N3—C3A—C7A—C7 | −179.3 (3) |
O13—C14—C15—C16 | 9.3 (5) | C4—C3A—C7A—S1 | −179.9 (3) |
C12—O11—C16—O16 | 161.7 (3) | N3—C3A—C7A—S1 | 0.9 (4) |
C12—O11—C16—C15 | −20.9 (4) | C2—S1—C7A—C7 | 179.4 (3) |
C22—C15—C16—O16 | −8.0 (5) | C2—S1—C7A—C3A | −0.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···O14 | 0.88 | 2.01 | 2.671 (4) | 131 |
C5—H5···O16i | 0.95 | 2.38 | 3.299 (5) | 163 |
C7—H7···O14ii | 0.95 | 2.43 | 3.205 (5) | 138 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+2. |
Experimental details
Crystal data |
Chemical formula | C14H11ClN2O4S |
Mr | 338.76 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 5.3389 (4), 28.583 (2), 9.8618 (8) |
β (°) | 109.178 (4) |
V (Å3) | 1421.41 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.20 × 0.15 × 0.01 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.918, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6289, 2714, 1430 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.648 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.116, 0.94 |
No. of reflections | 2714 |
No. of parameters | 201 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.36 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21···O14 | 0.88 | 2.01 | 2.671 (4) | 131 |
C5—H5···O16i | 0.95 | 2.38 | 3.299 (5) | 163 |
C7—H7···O14ii | 0.95 | 2.43 | 3.205 (5) | 138 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+2. |
The title compound, (I), is a benzothiazole derivative prepared in our search for biologically active molecules by a similar procedure to that reported previously for GURGIP (Cannon et al., 2001; Cambridge Structural Database, Allen & Kennard, 1993)
GURGIP and compound (I) have similar molecular structures but have totally different supramolecular structures.
GURGIP 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.
Compound (I) has one intramolecular hydrogen bond, N21–H21···O14, which forms an R(6) ring, Bernstein et al. (1995). The molecules are linked together into ribbons formed by the weak hydrogen bonds, C5–H5···O16 and C7–H7···O14. These two bonds combine to form a C22(10) chain. These hydrogen bonds link the molecules head-to-tail as a result of the centres of symmetry at (1, 0, 1/2) for the former bond and (1/2, 0, 1) for the latter bond forming in each case R22(22) rings and hence forming ribbons (Fig. 2). The details of the hydrogen bonding are given in Table 1.
Examination of the structure with PLATON (Spek, 2001) showed that there were no solvent accessible voids in the crystal lattice.