Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017207/fg1703sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017207/fg1703Isup2.hkl |
CCDC reference: 199528
Ethyl coumarin-3-carboxylate was synthesized according to the procedure reported by Bonsignore et al. (1995); the 1H and 13C NMR data for this compound are reported elsewhere (Martínez-Martínez et al., 2001). 2-Aminobenzothiazole (of reagent grade) was purchased from Aldrich and used as received. Equimolar quantities of 2-aminobenzothiazole (2 mmol) and ethyl coumarin-3-carboxylate (2 mmol) were suspended in toluene (15 ml; Aldrich). The resulting suspension was heated to boiling point on a hot plate until the reagents dissolved completely?. The homogeneous solution was allowed to cool to room temperature, and after several days, yellow crystals suitable for X-ray diffraction separated in almost quantitative yield (m.p. 279–380 K) IR (KBr, cm−1): ν 1763 (C═O), 751 (C—S); 1H NMR (p.p.m.): δ 8.74 (s, 1H, H4), 7.90 (d, 1H, H5), 7.72 (dd, 1H, H7), 7.62 (d, 1H, H24), 7.44 (s, 2H, NH2), 7.42 (d, 1H, H8), 7.39 (dd, 1H, H6), 7.30 (d, 1H, H27), 7.17 (dd, 1H, H26), 6.97 (dd, 1H, H25), 4.27 (q, 2H, CH2), 1.29 (t, 3H, CH3); 13C NMR (p.p.m.): δ 166.4 (C22), 162.6 (C11), 156.0 (C2), 154.5 (C9), 152.8 (C29), 148.7 (C4), 134.5 (C7), 130.9 (C28), 130.3 (C5), 125.4 (C25), 124.8 (C6), 120.8 (C24), 120.7 (C26), 117.7 (C27), 117.8 (C10), 117.6 (C3), 116.1 (C8), 61.2 (CH2), 14.0 (CH3). The melting point was measured on an electrothermal IA 9100 apparatus and is uncorrected. IR spectrum was recorded using a Perkin-Elmer 16 F PC IR spectrophotometer. UV-vis diffuse reflectance spectra were recorded on a CARY SE UV-VIS-NIR spectrophotometer with 0.1 molal samples in KBr discs (IR spectroscopic grade). NMR spectra were recorded in a Varian Mercury-300 MHz instrument.
The complex crystallized in the monoclinic system and space groups Pc and P2/c were allowed from the systematic absences; however, structure solution was only possible in space group Pc. H atoms were all clearly revealed in difference maps and were treated as riding atoms, with C—H distances of 0.93 and 0.96 Å, and N—H distances of 0.86 Å.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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: SHELXL97 and WinGX2003 (Farrugia, 1999).
C12H10O4·C7H6N2S | F(000) = 768 |
Mr = 368.40 | Dx = 1.367 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 600 reflections |
a = 9.360 (2) Å | θ = 20–25° |
b = 9.109 (2) Å | µ = 0.21 mm−1 |
c = 21.242 (4) Å | T = 293 K |
β = 98.78 (3)° | Prism, yellow |
V = 1789.9 (7) Å3 | 0.38 × 0.20 × 0.09 mm |
Z = 4 |
Bruker Smart Area Detector diffractometer | 8179 independent reflections |
Radiation source: fine-focus sealed tube | 5785 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 3 pixels mm-1 | θmax = 28.0°, θmin = 1.9° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan SADABS (Sheldrick, 1997) | k = −11→11 |
Tmin = 0.95, Tmax = 0.97 | l = −27→27 |
20092 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0688P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
8179 reflections | Δρmax = 0.54 e Å−3 |
472 parameters | Δρmin = −0.18 e Å−3 |
2 restraints | Absolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.39 (7) with 3880 Friedel pairs |
C12H10O4·C7H6N2S | V = 1789.9 (7) Å3 |
Mr = 368.40 | Z = 4 |
Monoclinic, Pc | Mo Kα radiation |
a = 9.360 (2) Å | µ = 0.21 mm−1 |
b = 9.109 (2) Å | T = 293 K |
c = 21.242 (4) Å | 0.38 × 0.20 × 0.09 mm |
β = 98.78 (3)° |
Bruker Smart Area Detector diffractometer | 8179 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1997) | 5785 reflections with I > 2σ(I) |
Tmin = 0.95, Tmax = 0.97 | Rint = 0.033 |
20092 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.131 | Δρmax = 0.54 e Å−3 |
S = 1.00 | Δρmin = −0.18 e Å−3 |
8179 reflections | Absolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
472 parameters | Absolute structure parameter: 0.39 (7) with 3880 Friedel pairs |
2 restraints |
Experimental. Diffractometer operator H. Höpfl scanwidth_degrees 0.7 low_scanspeed_degrees/min 16.1 high_scanspeed_degrees/min 60 Background measurement: Moving crystal and moving counter at the beginning and end of scan, each for 25% of total scan area. Crystal mounted on a glass fiber. |
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 | ||
O1A | −0.0086 (3) | −0.1474 (3) | 0.34509 (10) | 0.0640 (6) | |
O2A | 0.1487 (3) | 0.0016 (3) | 0.39873 (15) | 0.0879 (9) | |
O11A | 0.0601 (3) | 0.1657 (3) | 0.49650 (14) | 0.0628 (8) | |
O12A | −0.1484 (3) | 0.0906 (2) | 0.52396 (11) | 0.0598 (6) | |
C2A | 0.0296 (3) | −0.0483 (4) | 0.39433 (16) | 0.0571 (8) | |
C3A | −0.0778 (3) | −0.0234 (3) | 0.43619 (14) | 0.0485 (7) | |
C4A | −0.2038 (3) | −0.0962 (3) | 0.42656 (14) | 0.0490 (7) | |
H4A | −0.2708 | −0.0790 | 0.4539 | 0.059* | |
C5A | −0.3694 (4) | −0.2773 (4) | 0.3642 (2) | 0.0678 (11) | |
H5A | −0.4382 | −0.2645 | 0.3910 | 0.081* | |
C6A | −0.3975 (5) | −0.3706 (5) | 0.3149 (3) | 0.0755 (13) | |
H6A | −0.4842 | −0.4223 | 0.3079 | 0.091* | |
C7A | −0.2953 (6) | −0.3889 (5) | 0.2744 (2) | 0.0784 (15) | |
H7A | −0.3146 | −0.4535 | 0.2402 | 0.094* | |
C8A | −0.1646 (6) | −0.3129 (5) | 0.2836 (2) | 0.0715 (12) | |
H8A | −0.0966 | −0.3244 | 0.2563 | 0.086* | |
C9A | −0.1408 (5) | −0.2186 (4) | 0.33601 (18) | 0.0551 (10) | |
C10A | −0.2385 (4) | −0.1979 (4) | 0.37652 (19) | 0.0527 (9) | |
C11A | −0.0453 (4) | 0.0879 (4) | 0.48779 (17) | 0.0443 (8) | |
C13A | −0.1377 (4) | 0.2022 (4) | 0.57310 (19) | 0.0636 (9) | |
H13A | −0.1390 | 0.2995 | 0.5545 | 0.076* | |
H13B | −0.0489 | 0.1907 | 0.6029 | 0.076* | |
C14A | −0.2669 (5) | 0.1802 (5) | 0.6062 (2) | 0.0839 (12) | |
H14A | −0.2589 | 0.0876 | 0.6280 | 0.126* | |
H14B | −0.3533 | 0.1812 | 0.5753 | 0.126* | |
H14C | −0.2712 | 0.2579 | 0.6364 | 0.126* | |
O1B | 1.0109 (2) | 0.8902 (3) | 0.65672 (11) | 0.0644 (6) | |
O2B | 0.8518 (3) | 0.7431 (4) | 0.60243 (16) | 0.0919 (9) | |
O11B | 0.9365 (3) | 0.5862 (3) | 0.50148 (15) | 0.0660 (8) | |
O12B | 1.1477 (3) | 0.6580 (2) | 0.47562 (11) | 0.0579 (6) | |
C2B | 0.9693 (4) | 0.7963 (4) | 0.60586 (17) | 0.0604 (8) | |
C3B | 1.0752 (3) | 0.7740 (3) | 0.56242 (14) | 0.0455 (6) | |
C4B | 1.1979 (3) | 0.8517 (3) | 0.57014 (13) | 0.0481 (6) | |
H4B | 1.2617 | 0.8396 | 0.5410 | 0.058* | |
C5B | 1.3628 (4) | 1.0354 (4) | 0.63199 (18) | 0.0578 (9) | |
H5B | 1.4281 | 1.0300 | 0.6032 | 0.069* | |
C6B | 1.3910 (5) | 1.1237 (5) | 0.6847 (2) | 0.0705 (12) | |
H6B | 1.4759 | 1.1783 | 0.6916 | 0.085* | |
C7B | 1.2955 (6) | 1.1320 (5) | 0.7272 (2) | 0.0722 (12) | |
H7B | 1.3167 | 1.1923 | 0.7627 | 0.087* | |
C8B | 1.1707 (5) | 1.0542 (5) | 0.7187 (2) | 0.0668 (11) | |
H8B | 1.1072 | 1.0609 | 0.7483 | 0.080* | |
C9B | 1.1381 (4) | 0.9648 (4) | 0.66597 (18) | 0.0504 (9) | |
C10B | 1.2349 (4) | 0.9535 (4) | 0.62197 (17) | 0.0487 (9) | |
C11B | 1.0415 (4) | 0.6619 (4) | 0.51027 (19) | 0.0490 (9) | |
C13B | 1.1379 (4) | 0.5441 (4) | 0.42722 (16) | 0.0601 (9) | |
H13C | 1.0482 | 0.5533 | 0.3979 | 0.072* | |
H13D | 1.1409 | 0.4478 | 0.4468 | 0.072* | |
C14B | 1.2659 (5) | 0.5644 (5) | 0.3924 (2) | 0.0801 (12) | |
H14D | 1.3538 | 0.5502 | 0.4216 | 0.120* | |
H14E | 1.2644 | 0.6619 | 0.3751 | 0.120* | |
H14F | 1.2609 | 0.4941 | 0.3585 | 0.120* | |
S21A | 0.43633 (9) | 0.10069 (9) | 0.35927 (4) | 0.0578 (2) | |
N22A | 0.3653 (3) | 0.2150 (3) | 0.46741 (13) | 0.0663 (8) | |
H22A | 0.3787 | 0.2692 | 0.5009 | 0.080* | |
H22B | 0.2889 | 0.1617 | 0.4594 | 0.080* | |
N23A | 0.5821 (3) | 0.2903 (3) | 0.43606 (12) | 0.0520 (6) | |
C22A | 0.4632 (3) | 0.2135 (3) | 0.42785 (15) | 0.0498 (7) | |
C24A | 0.7972 (4) | 0.3229 (4) | 0.38342 (19) | 0.0544 (9) | |
H24A | 0.8392 | 0.3902 | 0.4136 | 0.065* | |
C25A | 0.8662 (5) | 0.2819 (5) | 0.3342 (2) | 0.0649 (11) | |
H25A | 0.9580 | 0.3189 | 0.3323 | 0.078* | |
C26A | 0.8042 (5) | 0.1870 (5) | 0.2867 (2) | 0.0648 (11) | |
H26A | 0.8528 | 0.1652 | 0.2528 | 0.078* | |
C27A | 0.6713 (5) | 0.1247 (5) | 0.28944 (18) | 0.0605 (10) | |
H27A | 0.6296 | 0.0594 | 0.2583 | 0.073* | |
C28A | 0.6013 (4) | 0.1630 (4) | 0.34039 (16) | 0.0481 (8) | |
C29A | 0.6632 (3) | 0.2623 (3) | 0.38762 (15) | 0.0457 (7) | |
S21B | 0.55791 (9) | 0.65976 (9) | 0.63805 (4) | 0.0560 (2) | |
N22B | 0.6346 (3) | 0.5354 (3) | 0.53262 (14) | 0.0677 (8) | |
H22C | 0.6232 | 0.4769 | 0.5005 | 0.081* | |
H22D | 0.7095 | 0.5913 | 0.5395 | 0.081* | |
N23B | 0.4198 (3) | 0.4584 (3) | 0.56498 (12) | 0.0514 (6) | |
C22B | 0.5365 (3) | 0.5394 (3) | 0.57181 (15) | 0.0503 (7) | |
C24B | 0.2041 (5) | 0.4275 (4) | 0.6165 (2) | 0.0587 (10) | |
H24B | 0.1644 | 0.3577 | 0.5870 | 0.070* | |
C25B | 0.1301 (5) | 0.4714 (5) | 0.6656 (2) | 0.0615 (11) | |
H25B | 0.0405 | 0.4306 | 0.6688 | 0.074* | |
C26B | 0.1891 (5) | 0.5752 (5) | 0.7095 (2) | 0.0705 (12) | |
H26B | 0.1381 | 0.6040 | 0.7418 | 0.085* | |
C27B | 0.3232 (5) | 0.6372 (5) | 0.70617 (19) | 0.0612 (10) | |
H27B | 0.3639 | 0.7051 | 0.7364 | 0.073* | |
C28B | 0.3948 (4) | 0.5952 (4) | 0.65675 (18) | 0.0515 (9) | |
C29B | 0.3376 (4) | 0.4895 (4) | 0.61244 (16) | 0.0490 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0690 (14) | 0.0727 (15) | 0.0552 (12) | −0.0056 (12) | 0.0250 (11) | −0.0092 (11) |
O2A | 0.0637 (17) | 0.099 (2) | 0.110 (2) | −0.0263 (15) | 0.0414 (17) | −0.0341 (18) |
O11A | 0.0549 (16) | 0.0701 (17) | 0.0646 (17) | −0.0146 (13) | 0.0127 (12) | −0.0149 (12) |
O12A | 0.0533 (13) | 0.0684 (15) | 0.0614 (15) | −0.0091 (10) | 0.0207 (12) | −0.0145 (11) |
C2A | 0.0510 (18) | 0.063 (2) | 0.0607 (19) | −0.0103 (15) | 0.0184 (15) | −0.0041 (16) |
C3A | 0.0441 (15) | 0.0494 (16) | 0.0529 (17) | 0.0047 (13) | 0.0107 (13) | 0.0057 (13) |
C4A | 0.0455 (15) | 0.0499 (15) | 0.0521 (16) | 0.0005 (14) | 0.0097 (13) | 0.0029 (14) |
C5A | 0.060 (2) | 0.060 (2) | 0.083 (3) | −0.0039 (19) | 0.010 (2) | −0.001 (2) |
C6A | 0.071 (3) | 0.060 (2) | 0.090 (4) | −0.010 (2) | −0.003 (3) | −0.001 (2) |
C7A | 0.105 (4) | 0.055 (2) | 0.067 (3) | −0.008 (2) | −0.017 (3) | −0.0061 (18) |
C8A | 0.098 (3) | 0.064 (2) | 0.052 (2) | 0.000 (2) | 0.011 (2) | −0.0057 (18) |
C9A | 0.064 (3) | 0.049 (2) | 0.050 (2) | −0.0034 (18) | 0.002 (2) | −0.0014 (17) |
C10A | 0.059 (2) | 0.0480 (17) | 0.0491 (19) | −0.0035 (16) | 0.0029 (17) | 0.0051 (15) |
C11A | 0.0436 (18) | 0.0457 (18) | 0.0437 (18) | 0.0023 (13) | 0.0065 (14) | 0.0020 (12) |
C13A | 0.056 (2) | 0.066 (2) | 0.068 (2) | 0.0014 (18) | 0.0100 (18) | −0.0133 (18) |
C14A | 0.072 (3) | 0.114 (3) | 0.071 (3) | 0.006 (2) | 0.028 (2) | −0.023 (2) |
O1B | 0.0614 (13) | 0.0739 (15) | 0.0636 (13) | −0.0103 (11) | 0.0275 (11) | −0.0123 (12) |
O2B | 0.0589 (16) | 0.117 (2) | 0.109 (2) | −0.0326 (15) | 0.0427 (16) | −0.0346 (19) |
O11B | 0.0504 (16) | 0.0702 (17) | 0.0782 (19) | −0.0142 (13) | 0.0120 (13) | −0.0157 (13) |
O12B | 0.0548 (13) | 0.0639 (14) | 0.0579 (14) | −0.0080 (10) | 0.0176 (11) | −0.0126 (10) |
C2B | 0.057 (2) | 0.063 (2) | 0.064 (2) | −0.0064 (15) | 0.0203 (16) | −0.0056 (16) |
C3B | 0.0423 (15) | 0.0515 (16) | 0.0428 (15) | −0.0044 (12) | 0.0069 (12) | 0.0040 (13) |
C4B | 0.0431 (15) | 0.0573 (17) | 0.0447 (15) | −0.0019 (13) | 0.0098 (12) | 0.0014 (14) |
C5B | 0.0489 (18) | 0.066 (2) | 0.057 (2) | −0.0087 (17) | 0.0024 (16) | 0.0028 (18) |
C6B | 0.068 (3) | 0.060 (2) | 0.075 (3) | −0.0062 (19) | −0.015 (2) | −0.009 (2) |
C7B | 0.088 (3) | 0.062 (2) | 0.062 (3) | 0.002 (2) | −0.005 (2) | −0.0122 (19) |
C8B | 0.075 (3) | 0.072 (2) | 0.057 (2) | 0.010 (2) | 0.018 (2) | −0.0082 (19) |
C9B | 0.052 (2) | 0.052 (2) | 0.047 (2) | 0.0018 (17) | 0.0090 (17) | 0.0066 (17) |
C10B | 0.048 (2) | 0.0475 (17) | 0.0495 (19) | 0.0052 (15) | 0.0050 (15) | 0.0042 (14) |
C11B | 0.0401 (19) | 0.051 (2) | 0.055 (2) | −0.0005 (14) | 0.0035 (15) | 0.0025 (14) |
C13B | 0.062 (2) | 0.067 (2) | 0.051 (2) | −0.0034 (18) | 0.0107 (16) | −0.0117 (16) |
C14B | 0.077 (3) | 0.097 (3) | 0.071 (3) | −0.003 (2) | 0.027 (2) | −0.015 (2) |
S21A | 0.0506 (4) | 0.0694 (5) | 0.0539 (5) | −0.0078 (4) | 0.0095 (3) | −0.0125 (4) |
N22A | 0.0520 (15) | 0.083 (2) | 0.0697 (18) | −0.0171 (14) | 0.0278 (14) | −0.0226 (15) |
N23A | 0.0478 (14) | 0.0565 (14) | 0.0531 (14) | −0.0028 (11) | 0.0118 (11) | −0.0089 (12) |
C22A | 0.0423 (15) | 0.0525 (17) | 0.0554 (17) | −0.0004 (13) | 0.0098 (13) | −0.0058 (13) |
C24A | 0.0505 (19) | 0.058 (2) | 0.055 (2) | −0.0040 (16) | 0.0102 (16) | 0.0003 (16) |
C25A | 0.055 (3) | 0.066 (3) | 0.076 (3) | 0.000 (2) | 0.020 (2) | 0.003 (2) |
C26A | 0.071 (3) | 0.075 (2) | 0.054 (2) | 0.011 (2) | 0.028 (2) | 0.0024 (19) |
C27A | 0.061 (2) | 0.072 (2) | 0.051 (2) | 0.0042 (19) | 0.0152 (18) | −0.0097 (18) |
C28A | 0.0434 (18) | 0.059 (2) | 0.0410 (19) | 0.0030 (14) | 0.0050 (14) | 0.0046 (14) |
C29A | 0.0424 (17) | 0.0473 (17) | 0.0477 (17) | 0.0056 (13) | 0.0076 (14) | 0.0024 (13) |
S21B | 0.0506 (4) | 0.0605 (5) | 0.0558 (5) | −0.0030 (4) | 0.0043 (3) | −0.0106 (4) |
N22B | 0.0505 (15) | 0.082 (2) | 0.0746 (19) | −0.0153 (14) | 0.0217 (14) | −0.0228 (16) |
N23B | 0.0460 (14) | 0.0546 (14) | 0.0553 (14) | −0.0035 (11) | 0.0135 (11) | −0.0092 (12) |
C22B | 0.0469 (16) | 0.0534 (17) | 0.0501 (16) | 0.0017 (14) | 0.0062 (13) | −0.0050 (14) |
C24B | 0.061 (2) | 0.056 (2) | 0.063 (2) | 0.0039 (17) | 0.0231 (18) | 0.0032 (17) |
C25B | 0.061 (3) | 0.067 (3) | 0.063 (3) | 0.000 (2) | 0.031 (2) | 0.013 (2) |
C26B | 0.081 (3) | 0.087 (3) | 0.051 (2) | 0.013 (2) | 0.032 (2) | 0.009 (2) |
C27B | 0.070 (3) | 0.069 (2) | 0.044 (2) | 0.008 (2) | 0.0048 (18) | −0.0022 (17) |
C28B | 0.055 (2) | 0.050 (2) | 0.049 (2) | 0.0098 (15) | 0.0049 (16) | 0.0059 (15) |
C29B | 0.053 (2) | 0.0460 (17) | 0.0486 (18) | 0.0074 (14) | 0.0110 (15) | 0.0048 (14) |
O1A—C9A | 1.384 (5) | C7B—H7B | 0.9300 |
O1A—C2A | 1.386 (4) | C8B—C9B | 1.381 (5) |
O2A—C2A | 1.195 (4) | C8B—H8B | 0.9300 |
O11A—C11A | 1.206 (4) | C9B—C10B | 1.401 (5) |
O12A—C11A | 1.322 (4) | C13B—C14B | 1.512 (5) |
O12A—C13A | 1.450 (4) | C13B—H13C | 0.9700 |
C2A—C3A | 1.458 (4) | C13B—H13D | 0.9700 |
C3A—C4A | 1.342 (4) | C14B—H14D | 0.9600 |
C3A—C11A | 1.490 (5) | C14B—H14E | 0.9600 |
C4A—C10A | 1.410 (5) | C14B—H14F | 0.9600 |
C4A—H4A | 0.9300 | S21A—C28A | 1.748 (4) |
C5A—C6A | 1.344 (6) | S21A—C22A | 1.769 (3) |
C5A—C10A | 1.412 (6) | N22A—C22A | 1.334 (4) |
C5A—H5A | 0.9300 | N22A—H22A | 0.8600 |
C6A—C7A | 1.391 (7) | N22A—H22B | 0.8600 |
C6A—H6A | 0.9300 | N23A—C22A | 1.303 (4) |
C7A—C8A | 1.393 (7) | N23A—C29A | 1.393 (4) |
C7A—H7A | 0.9300 | C24A—C25A | 1.363 (6) |
C8A—C9A | 1.397 (6) | C24A—C29A | 1.385 (5) |
C8A—H8A | 0.9300 | C24A—H24A | 0.9300 |
C9A—C10A | 1.361 (6) | C25A—C26A | 1.386 (6) |
C13A—C14A | 1.503 (6) | C25A—H25A | 0.9300 |
C13A—H13A | 0.9700 | C26A—C27A | 1.377 (6) |
C13A—H13B | 0.9700 | C26A—H26A | 0.9300 |
C14A—H14A | 0.9600 | C27A—C28A | 1.392 (5) |
C14A—H14B | 0.9600 | C27A—H27A | 0.9300 |
C14A—H14C | 0.9600 | C28A—C29A | 1.408 (5) |
O1B—C9B | 1.359 (5) | S21B—C28B | 1.737 (4) |
O1B—C2B | 1.387 (4) | S21B—C22B | 1.771 (3) |
O2B—C2B | 1.194 (4) | N22B—C22B | 1.331 (4) |
O11B—C11B | 1.192 (4) | N22B—H22C | 0.8600 |
O12B—C11B | 1.324 (5) | N22B—H22D | 0.8600 |
O12B—C13B | 1.453 (4) | N23B—C22B | 1.308 (4) |
C2B—C3B | 1.467 (4) | N23B—C29B | 1.388 (4) |
C3B—C4B | 1.338 (4) | C24B—C29B | 1.386 (5) |
C3B—C11B | 1.504 (5) | C24B—C25B | 1.396 (6) |
C4B—C10B | 1.440 (5) | C24B—H24B | 0.9300 |
C4B—H4B | 0.9300 | C25B—C26B | 1.382 (6) |
C5B—C6B | 1.371 (5) | C25B—H25B | 0.9300 |
C5B—C10B | 1.399 (5) | C26B—C27B | 1.389 (6) |
C5B—H5B | 0.9300 | C26B—H26B | 0.9300 |
C6B—C7B | 1.366 (6) | C27B—C28B | 1.383 (6) |
C6B—H6B | 0.9300 | C27B—H27B | 0.9300 |
C7B—C8B | 1.355 (7) | C28B—C29B | 1.395 (5) |
C9A—O1A—C2A | 122.2 (3) | C5B—C10B—C9B | 119.0 (3) |
C11A—O12A—C13A | 117.1 (3) | C5B—C10B—C4B | 124.0 (4) |
O2A—C2A—O1A | 115.9 (3) | C9B—C10B—C4B | 116.9 (3) |
O2A—C2A—C3A | 128.0 (3) | O11B—C11B—O12B | 124.6 (4) |
O1A—C2A—C3A | 116.0 (3) | O11B—C11B—C3B | 125.7 (4) |
C4A—C3A—C2A | 120.1 (3) | O12B—C11B—C3B | 109.7 (3) |
C4A—C3A—C11A | 121.7 (3) | O12B—C13B—C14B | 106.9 (3) |
C2A—C3A—C11A | 118.2 (3) | O12B—C13B—H13C | 110.4 |
C3A—C4A—C10A | 122.4 (3) | C14B—C13B—H13C | 110.4 |
C3A—C4A—H4A | 118.8 | O12B—C13B—H13D | 110.4 |
C10A—C4A—H4A | 118.8 | C14B—C13B—H13D | 110.4 |
C6A—C5A—C10A | 122.0 (4) | H13C—C13B—H13D | 108.6 |
C6A—C5A—H5A | 119.0 | C13B—C14B—H14D | 109.5 |
C10A—C5A—H5A | 119.0 | C13B—C14B—H14E | 109.5 |
C5A—C6A—C7A | 119.1 (4) | H14D—C14B—H14E | 109.5 |
C5A—C6A—H6A | 120.5 | C13B—C14B—H14F | 109.5 |
C7A—C6A—H6A | 120.5 | H14D—C14B—H14F | 109.5 |
C6A—C7A—C8A | 121.7 (4) | H14E—C14B—H14F | 109.5 |
C6A—C7A—H7A | 119.1 | C28A—S21A—C22A | 88.91 (16) |
C8A—C7A—H7A | 119.1 | C22A—N22A—H22A | 120.0 |
C7A—C8A—C9A | 116.6 (5) | C22A—N22A—H22B | 120.0 |
C7A—C8A—H8A | 121.7 | H22A—N22A—H22B | 120.0 |
C9A—C8A—H8A | 121.7 | C22A—N23A—C29A | 110.7 (3) |
C10A—C9A—O1A | 121.3 (3) | N23A—C22A—N22A | 124.4 (3) |
C10A—C9A—C8A | 123.3 (4) | N23A—C22A—S21A | 115.7 (2) |
O1A—C9A—C8A | 115.4 (4) | N22A—C22A—S21A | 120.0 (2) |
C9A—C10A—C4A | 117.9 (3) | C25A—C24A—C29A | 118.7 (4) |
C9A—C10A—C5A | 117.3 (4) | C25A—C24A—H24A | 120.7 |
C4A—C10A—C5A | 124.7 (4) | C29A—C24A—H24A | 120.7 |
O11A—C11A—O12A | 123.5 (3) | C24A—C25A—C26A | 122.3 (4) |
O11A—C11A—C3A | 125.7 (3) | C24A—C25A—H25A | 118.8 |
O12A—C11A—C3A | 110.8 (3) | C26A—C25A—H25A | 118.8 |
O12A—C13A—C14A | 105.7 (3) | C27A—C26A—C25A | 120.5 (4) |
O12A—C13A—H13A | 110.6 | C27A—C26A—H26A | 119.8 |
C14A—C13A—H13A | 110.6 | C25A—C26A—H26A | 119.8 |
O12A—C13A—H13B | 110.6 | C26A—C27A—C28A | 117.7 (4) |
C14A—C13A—H13B | 110.6 | C26A—C27A—H27A | 121.1 |
H13A—C13A—H13B | 108.7 | C28A—C27A—H27A | 121.1 |
C13A—C14A—H14A | 109.5 | C27A—C28A—C29A | 121.6 (3) |
C13A—C14A—H14B | 109.5 | C27A—C28A—S21A | 129.3 (3) |
H14A—C14A—H14B | 109.5 | C29A—C28A—S21A | 109.1 (3) |
C13A—C14A—H14C | 109.5 | C24A—C29A—N23A | 125.2 (3) |
H14A—C14A—H14C | 109.5 | C24A—C29A—C28A | 119.2 (3) |
H14B—C14A—H14C | 109.5 | N23A—C29A—C28A | 115.6 (3) |
C9B—O1B—C2B | 123.8 (3) | C28B—S21B—C22B | 88.59 (16) |
C11B—O12B—C13B | 116.2 (3) | C22B—N22B—H22C | 120.0 |
O2B—C2B—O1B | 116.4 (3) | C22B—N22B—H22D | 120.0 |
O2B—C2B—C3B | 127.6 (3) | H22C—N22B—H22D | 120.0 |
O1B—C2B—C3B | 116.1 (3) | C22B—N23B—C29B | 110.5 (3) |
C4B—C3B—C2B | 120.0 (3) | N23B—C22B—N22B | 124.0 (3) |
C4B—C3B—C11B | 121.9 (3) | N23B—C22B—S21B | 115.4 (2) |
C2B—C3B—C11B | 118.1 (3) | N22B—C22B—S21B | 120.6 (2) |
C3B—C4B—C10B | 122.4 (3) | C29B—C24B—C25B | 119.0 (4) |
C3B—C4B—H4B | 118.8 | C29B—C24B—H24B | 120.5 |
C10B—C4B—H4B | 118.8 | C25B—C24B—H24B | 120.5 |
C6B—C5B—C10B | 119.4 (4) | C26B—C25B—C24B | 120.5 (4) |
C6B—C5B—H5B | 120.3 | C26B—C25B—H25B | 119.8 |
C10B—C5B—H5B | 120.3 | C24B—C25B—H25B | 119.8 |
C7B—C6B—C5B | 120.6 (4) | C25B—C26B—C27B | 121.0 (4) |
C7B—C6B—H6B | 119.7 | C25B—C26B—H26B | 119.5 |
C5B—C6B—H6B | 119.7 | C27B—C26B—H26B | 119.5 |
C8B—C7B—C6B | 121.4 (4) | C28B—C27B—C26B | 118.3 (4) |
C8B—C7B—H7B | 119.3 | C28B—C27B—H27B | 120.9 |
C6B—C7B—H7B | 119.3 | C26B—C27B—H27B | 120.9 |
C7B—C8B—C9B | 119.7 (4) | C27B—C28B—C29B | 121.5 (4) |
C7B—C8B—H8B | 120.1 | C27B—C28B—S21B | 128.6 (3) |
C9B—C8B—H8B | 120.1 | C29B—C28B—S21B | 109.9 (3) |
O1B—C9B—C8B | 119.5 (4) | C24B—C29B—N23B | 124.6 (3) |
O1B—C9B—C10B | 120.5 (3) | C24B—C29B—C28B | 119.7 (4) |
C8B—C9B—C10B | 120.0 (4) | N23B—C29B—C28B | 115.6 (3) |
C9A—O1A—C2A—O2A | 177.1 (3) | O1B—C9B—C10B—C4B | −4.6 (5) |
C9A—O1A—C2A—C3A | 0.0 (4) | C8B—C9B—C10B—C4B | 176.4 (3) |
O2A—C2A—C3A—C4A | −175.6 (4) | C3B—C4B—C10B—C5B | 179.3 (3) |
O1A—C2A—C3A—C4A | 1.1 (4) | C3B—C4B—C10B—C9B | 2.1 (4) |
O2A—C2A—C3A—C11A | 6.4 (5) | C13B—O12B—C11B—O11B | −5.2 (5) |
O1A—C2A—C3A—C11A | −176.8 (3) | C13B—O12B—C11B—C3B | 173.9 (3) |
C2A—C3A—C4A—C10A | −0.2 (4) | C4B—C3B—C11B—O11B | 178.0 (3) |
C11A—C3A—C4A—C10A | 177.7 (3) | C2B—C3B—C11B—O11B | −1.6 (5) |
C10A—C5A—C6A—C7A | −0.6 (7) | C4B—C3B—C11B—O12B | −1.1 (4) |
C5A—C6A—C7A—C8A | 0.0 (7) | C2B—C3B—C11B—O12B | 179.3 (3) |
C6A—C7A—C8A—C9A | 0.6 (7) | C11B—O12B—C13B—C14B | 177.8 (3) |
C2A—O1A—C9A—C10A | −2.1 (5) | C29A—N23A—C22A—N22A | 178.5 (3) |
C2A—O1A—C9A—C8A | 178.8 (3) | C29A—N23A—C22A—S21A | −0.9 (3) |
C7A—C8A—C9A—C10A | −0.7 (6) | C28A—S21A—C22A—N23A | 0.2 (3) |
C7A—C8A—C9A—O1A | 178.4 (3) | C28A—S21A—C22A—N22A | −179.3 (3) |
O1A—C9A—C10A—C4A | 2.9 (5) | C29A—C24A—C25A—C26A | 2.9 (6) |
C8A—C9A—C10A—C4A | −178.0 (3) | C24A—C25A—C26A—C27A | −3.0 (6) |
O1A—C9A—C10A—C5A | −178.9 (3) | C25A—C26A—C27A—C28A | 1.3 (6) |
C8A—C9A—C10A—C5A | 0.2 (6) | C26A—C27A—C28A—C29A | 0.3 (5) |
C3A—C4A—C10A—C9A | −1.8 (5) | C26A—C27A—C28A—S21A | −177.9 (3) |
C3A—C4A—C10A—C5A | −179.9 (3) | C22A—S21A—C28A—C27A | 178.9 (3) |
C6A—C5A—C10A—C9A | 0.5 (6) | C22A—S21A—C28A—C29A | 0.5 (2) |
C6A—C5A—C10A—C4A | 178.6 (4) | C25A—C24A—C29A—N23A | 178.0 (3) |
C13A—O12A—C11A—O11A | 5.2 (4) | C25A—C24A—C29A—C28A | −1.3 (5) |
C13A—O12A—C11A—C3A | −175.0 (3) | C22A—N23A—C29A—C24A | −177.9 (3) |
C4A—C3A—C11A—O11A | −174.0 (3) | C22A—N23A—C29A—C28A | 1.4 (4) |
C2A—C3A—C11A—O11A | 3.9 (4) | C27A—C28A—C29A—C24A | −0.3 (5) |
C4A—C3A—C11A—O12A | 6.2 (4) | S21A—C28A—C29A—C24A | 178.2 (3) |
C2A—C3A—C11A—O12A | −175.9 (3) | C27A—C28A—C29A—N23A | −179.7 (3) |
C11A—O12A—C13A—C14A | 179.9 (3) | S21A—C28A—C29A—N23A | −1.2 (3) |
C9B—O1B—C2B—O2B | −176.9 (4) | C29B—N23B—C22B—N22B | −178.8 (3) |
C9B—O1B—C2B—C3B | 3.0 (4) | C29B—N23B—C22B—S21B | 1.0 (3) |
O2B—C2B—C3B—C4B | 174.5 (4) | C28B—S21B—C22B—N23B | −0.6 (2) |
O1B—C2B—C3B—C4B | −5.5 (4) | C28B—S21B—C22B—N22B | 179.1 (3) |
O2B—C2B—C3B—C11B | −6.0 (5) | C29B—C24B—C25B—C26B | 0.0 (6) |
O1B—C2B—C3B—C11B | 174.1 (3) | C24B—C25B—C26B—C27B | −0.5 (6) |
C2B—C3B—C4B—C10B | 3.0 (4) | C25B—C26B—C27B—C28B | 1.7 (6) |
C11B—C3B—C4B—C10B | −176.5 (3) | C26B—C27B—C28B—C29B | −2.3 (5) |
C10B—C5B—C6B—C7B | 0.0 (6) | C26B—C27B—C28B—S21B | 176.5 (3) |
C5B—C6B—C7B—C8B | −0.1 (7) | C22B—S21B—C28B—C27B | −178.9 (3) |
C6B—C7B—C8B—C9B | −0.3 (6) | C22B—S21B—C28B—C29B | 0.0 (2) |
C2B—O1B—C9B—C8B | −179.0 (3) | C25B—C24B—C29B—N23B | −178.1 (3) |
C2B—O1B—C9B—C10B | 2.0 (5) | C25B—C24B—C29B—C28B | −0.6 (6) |
C7B—C8B—C9B—O1B | −178.1 (4) | C22B—N23B—C29B—C24B | 176.6 (3) |
C7B—C8B—C9B—C10B | 0.8 (5) | C22B—N23B—C29B—C28B | −1.0 (4) |
C6B—C5B—C10B—C9B | 0.5 (5) | C27B—C28B—C29B—C24B | 1.8 (5) |
C6B—C5B—C10B—C4B | −176.7 (3) | S21B—C28B—C29B—C24B | −177.2 (3) |
O1B—C9B—C10B—C5B | 178.0 (3) | C27B—C28B—C29B—N23B | 179.5 (3) |
C8B—C9B—C10B—C5B | −0.9 (5) | S21B—C28B—C29B—N23B | 0.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N22A—H22B···O2A | 0.86 | 2.23 | 3.019 (4) | 152 |
N22A—H22B···O11A | 0.86 | 2.39 | 3.047 (4) | 133 |
N22B—H22D···O2B | 0.86 | 2.22 | 2.998 (4) | 150 |
N22B—H22D···O11B | 0.86 | 2.39 | 3.034 (4) | 133 |
N22A—H22A···N23B | 0.86 | 2.19 | 3.024 (4) | 163 |
N22B—H22C···N23A | 0.86 | 2.18 | 3.021 (4) | 166 |
Experimental details
Crystal data | |
Chemical formula | C12H10O4·C7H6N2S |
Mr | 368.40 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 293 |
a, b, c (Å) | 9.360 (2), 9.109 (2), 21.242 (4) |
β (°) | 98.78 (3) |
V (Å3) | 1789.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.38 × 0.20 × 0.09 |
Data collection | |
Diffractometer | Bruker Smart Area Detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1997) |
Tmin, Tmax | 0.95, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20092, 8179, 5785 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.131, 1.00 |
No. of reflections | 8179 |
No. of parameters | 472 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.18 |
Absolute structure | Flack, H. D. (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.39 (7) with 3880 Friedel pairs |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXL97 and WinGX2003 (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N22A—H22B···O2A | 0.86 | 2.23 | 3.019 (4) | 152 |
N22A—H22B···O11A | 0.86 | 2.39 | 3.047 (4) | 133 |
N22B—H22D···O2B | 0.86 | 2.22 | 2.998 (4) | 150 |
N22B—H22D···O11B | 0.86 | 2.39 | 3.034 (4) | 133 |
N22A—H22A···N23B | 0.86 | 2.19 | 3.024 (4) | 163 |
N22B—H22C···N23A | 0.86 | 2.18 | 3.021 (4) | 166 |
3-Carboxy coumarin derivatives have been reported as tautomerase (Orita et al., 2001), elastase (Doucet et al., 1999) and α chimotripsin inhibitors (Pochet et al., 1996), although so far little is known about the forces that regulate the molecular recognition interactions involved. We report here the molecular structure of the hydrogen-bonded adduct formed between 2-aminobenzothiazole, (I), and ethyl coumarin-3-carboxylate, (II).
The title adduct forms yellow monoclinic crystals (space group Pc, Z' = 2) whose molecular structure is depicted in Fig. 1. The asymmetric unit is a hydrogen-bonded tetramer composed of two molecules of (I) and two molecules of (II) (see Fig. 1 for the labelling scheme). Bond distances and angles are close to the reported values for the individual coumarin molecule (García-Báez et al., 2003) and other 2-aminobenzothiazole adducts (Armstrong et al., 1992). No comparison is performed with the molecular structure of compound (I) since, to our knowledge, the only report of it as a single compound is from X-ray powder diffraction data, where the R-factor is 16.4% (Goubitz et al., 2001).
The graph-set notation (Bernstein et al., 1995) Gda(n) (G = S for intramolecular rings, R for rings, C for chains and D for discrete patterns, a is the number of acceptors, d is the number of donors involved in hydrogen bonding, and n is the number of atoms in the pattern) is used to describe the hydrogen-bonding patterns throughout this paper. Molecules of (I) and (II) are linked via the intermolecular three-centered hydrogen-bonding interaction O2···H22···O11 (Steiner, 2002), which involves the 2-amino group of molecule (I) and both coumarin carboxy groups [N22A—H22B···O2A (Da), N22A—H22B···O11A (Db) and N22B—H22D···O2B (Dc), N22B—H22D···O11B (Dd)], thus forming the six-membered ring motifs R12(6)[DaDb] and R12(6)[DcDd] for the 1A···2A and 1B···2B hydrogen-bonded aggregates, respectively (Table 1). Two molecules of (I) are linked by complementary hydrogen-bonding interactions via the free H atom of the amino group and the pyridine-like N atom to form an eight-membered ring whose graph-set descriptor corresponds to an R22(8)[DeDf] motif (Fig. 1). It is noteworthy that this motif is also observed in the molecular structure of 2-aminobenzothiazole (Goubitz et al., 2001). The overall hydrogen-bonding arrangement leads to an essentially coplanar 2A···1A···1B···2B hydrogen-bonded pseudo-centrosymmetric tetramer [the angle between 1A···2A and 1B···2B planes is 3.2 (3)°], as shown in Fig. 1.
The tetrameric unit packs along the a direction, giving rise to a π-stacked zigzag arrangement (Fig. 2). The shortest intermolecular distances are C24A···C11A* of 3.267 (5) Å and C28A···C4A* of 3.352 (5) Å, and C24B···C11B# of 3.304 (6) Å and C28B···C4B# of 3.348 (5) Å [atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 + x, y, z) and (−1 + x, y, z), respectively], for 1A···2A and 1B···2B alternated π–π interactions, respectively (Figs. 3a and 3 b), which are considered to occur if the shortest C···C distance is below 4.8 Å (Singh & Thornton, 1990). However, the mean interplanar and the mean intercentroid distances between the 1-aromatic and 2-lactone rings are 3.38 (8) Å and 3.54 (3) Å, respectively, in agreement with strong parallel displaced or offset face-to-face interactions (Sinnokrot et al., 2002). A particular feature of this π–π interaction is that molecules of 1 and 2 are rotated by 110° in relation to their long axes (C22—C26 and C2—C6, respectively); this wide angle is probably related to the steric demand exerted by the hydrogen-bonded tetramer. Finally, the donor–acceptor nature of the title adduct was confirmed by the charge transfer band measured at 423 nm in the solid phase, which was obtained by digital subtraction (Bosch et al., 1998) from the electronic spectra of the individual components [λmax(1) = 361 nm and λmax(2) = 370 nm].