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The title adduct, C7H6N2S·C12H10O4, is formed via N—H...O and N—H...N hydrogen-bonding interactions, which gener­ate a tetrameric unit with a pseudo-centre of symmetry. The tetramer further packs through parallel-displaced π–π stacking interactions along the a direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017207/fg1703sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017207/fg1703Isup2.hkl
Contains datablock I

CCDC reference: 199528

Comment top

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 ππ 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 ππ 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].

Experimental top

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 (CO), 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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title adduct, showing displacement ellipsoids at the 30% probability level. Two independent adducts were found in the asymmetric unit, labelled as A (right) and B (left), which generate the tetrameric unit by hydorgen-bonding interactions.
[Figure 2] Fig. 2. A stereoview of the title adduct, showing the ππ-stacking interactions that propagate along the a direction.
[Figure 3] Fig. 3. The individual overlap for complexes (a) 1A···2A and (b) 1B···2B.
(I) top
Crystal data top
C12H10O4·C7H6N2SF(000) = 768
Mr = 368.40Dx = 1.367 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 600 reflections
a = 9.360 (2) Åθ = 20–25°
b = 9.109 (2) ŵ = 0.21 mm1
c = 21.242 (4) ÅT = 293 K
β = 98.78 (3)°Prism, yellow
V = 1789.9 (7) Å30.38 × 0.20 × 0.09 mm
Z = 4
Data collection top
Bruker Smart Area Detector
diffractometer
8179 independent reflections
Radiation source: fine-focus sealed tube5785 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 3 pixels mm-1θmax = 28.0°, θmin = 1.9°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
SADABS (Sheldrick, 1997)
k = 1111
Tmin = 0.95, Tmax = 0.97l = 2727
20092 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-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 reflectionsΔρmax = 0.54 e Å3
472 parametersΔρmin = 0.18 e Å3
2 restraintsAbsolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.39 (7) with 3880 Friedel pairs
Crystal data top
C12H10O4·C7H6N2SV = 1789.9 (7) Å3
Mr = 368.40Z = 4
Monoclinic, PcMo Kα radiation
a = 9.360 (2) ŵ = 0.21 mm1
b = 9.109 (2) ÅT = 293 K
c = 21.242 (4) Å0.38 × 0.20 × 0.09 mm
β = 98.78 (3)°
Data collection top
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 = 0.97Rint = 0.033
20092 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.131Δρmax = 0.54 e Å3
S = 1.00Δρmin = 0.18 e Å3
8179 reflectionsAbsolute structure: Flack, H. D. (1983), Acta Cryst. A39, 876-881
472 parametersAbsolute structure parameter: 0.39 (7) with 3880 Friedel pairs
2 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.0086 (3)0.1474 (3)0.34509 (10)0.0640 (6)
O2A0.1487 (3)0.0016 (3)0.39873 (15)0.0879 (9)
O11A0.0601 (3)0.1657 (3)0.49650 (14)0.0628 (8)
O12A0.1484 (3)0.0906 (2)0.52396 (11)0.0598 (6)
C2A0.0296 (3)0.0483 (4)0.39433 (16)0.0571 (8)
C3A0.0778 (3)0.0234 (3)0.43619 (14)0.0485 (7)
C4A0.2038 (3)0.0962 (3)0.42656 (14)0.0490 (7)
H4A0.27080.07900.45390.059*
C5A0.3694 (4)0.2773 (4)0.3642 (2)0.0678 (11)
H5A0.43820.26450.39100.081*
C6A0.3975 (5)0.3706 (5)0.3149 (3)0.0755 (13)
H6A0.48420.42230.30790.091*
C7A0.2953 (6)0.3889 (5)0.2744 (2)0.0784 (15)
H7A0.31460.45350.24020.094*
C8A0.1646 (6)0.3129 (5)0.2836 (2)0.0715 (12)
H8A0.09660.32440.25630.086*
C9A0.1408 (5)0.2186 (4)0.33601 (18)0.0551 (10)
C10A0.2385 (4)0.1979 (4)0.37652 (19)0.0527 (9)
C11A0.0453 (4)0.0879 (4)0.48779 (17)0.0443 (8)
C13A0.1377 (4)0.2022 (4)0.57310 (19)0.0636 (9)
H13A0.13900.29950.55450.076*
H13B0.04890.19070.60290.076*
C14A0.2669 (5)0.1802 (5)0.6062 (2)0.0839 (12)
H14A0.25890.08760.62800.126*
H14B0.35330.18120.57530.126*
H14C0.27120.25790.63640.126*
O1B1.0109 (2)0.8902 (3)0.65672 (11)0.0644 (6)
O2B0.8518 (3)0.7431 (4)0.60243 (16)0.0919 (9)
O11B0.9365 (3)0.5862 (3)0.50148 (15)0.0660 (8)
O12B1.1477 (3)0.6580 (2)0.47562 (11)0.0579 (6)
C2B0.9693 (4)0.7963 (4)0.60586 (17)0.0604 (8)
C3B1.0752 (3)0.7740 (3)0.56242 (14)0.0455 (6)
C4B1.1979 (3)0.8517 (3)0.57014 (13)0.0481 (6)
H4B1.26170.83960.54100.058*
C5B1.3628 (4)1.0354 (4)0.63199 (18)0.0578 (9)
H5B1.42811.03000.60320.069*
C6B1.3910 (5)1.1237 (5)0.6847 (2)0.0705 (12)
H6B1.47591.17830.69160.085*
C7B1.2955 (6)1.1320 (5)0.7272 (2)0.0722 (12)
H7B1.31671.19230.76270.087*
C8B1.1707 (5)1.0542 (5)0.7187 (2)0.0668 (11)
H8B1.10721.06090.74830.080*
C9B1.1381 (4)0.9648 (4)0.66597 (18)0.0504 (9)
C10B1.2349 (4)0.9535 (4)0.62197 (17)0.0487 (9)
C11B1.0415 (4)0.6619 (4)0.51027 (19)0.0490 (9)
C13B1.1379 (4)0.5441 (4)0.42722 (16)0.0601 (9)
H13C1.04820.55330.39790.072*
H13D1.14090.44780.44680.072*
C14B1.2659 (5)0.5644 (5)0.3924 (2)0.0801 (12)
H14D1.35380.55020.42160.120*
H14E1.26440.66190.37510.120*
H14F1.26090.49410.35850.120*
S21A0.43633 (9)0.10069 (9)0.35927 (4)0.0578 (2)
N22A0.3653 (3)0.2150 (3)0.46741 (13)0.0663 (8)
H22A0.37870.26920.50090.080*
H22B0.28890.16170.45940.080*
N23A0.5821 (3)0.2903 (3)0.43606 (12)0.0520 (6)
C22A0.4632 (3)0.2135 (3)0.42785 (15)0.0498 (7)
C24A0.7972 (4)0.3229 (4)0.38342 (19)0.0544 (9)
H24A0.83920.39020.41360.065*
C25A0.8662 (5)0.2819 (5)0.3342 (2)0.0649 (11)
H25A0.95800.31890.33230.078*
C26A0.8042 (5)0.1870 (5)0.2867 (2)0.0648 (11)
H26A0.85280.16520.25280.078*
C27A0.6713 (5)0.1247 (5)0.28944 (18)0.0605 (10)
H27A0.62960.05940.25830.073*
C28A0.6013 (4)0.1630 (4)0.34039 (16)0.0481 (8)
C29A0.6632 (3)0.2623 (3)0.38762 (15)0.0457 (7)
S21B0.55791 (9)0.65976 (9)0.63805 (4)0.0560 (2)
N22B0.6346 (3)0.5354 (3)0.53262 (14)0.0677 (8)
H22C0.62320.47690.50050.081*
H22D0.70950.59130.53950.081*
N23B0.4198 (3)0.4584 (3)0.56498 (12)0.0514 (6)
C22B0.5365 (3)0.5394 (3)0.57181 (15)0.0503 (7)
C24B0.2041 (5)0.4275 (4)0.6165 (2)0.0587 (10)
H24B0.16440.35770.58700.070*
C25B0.1301 (5)0.4714 (5)0.6656 (2)0.0615 (11)
H25B0.04050.43060.66880.074*
C26B0.1891 (5)0.5752 (5)0.7095 (2)0.0705 (12)
H26B0.13810.60400.74180.085*
C27B0.3232 (5)0.6372 (5)0.70617 (19)0.0612 (10)
H27B0.36390.70510.73640.073*
C28B0.3948 (4)0.5952 (4)0.65675 (18)0.0515 (9)
C29B0.3376 (4)0.4895 (4)0.61244 (16)0.0490 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0690 (14)0.0727 (15)0.0552 (12)0.0056 (12)0.0250 (11)0.0092 (11)
O2A0.0637 (17)0.099 (2)0.110 (2)0.0263 (15)0.0414 (17)0.0341 (18)
O11A0.0549 (16)0.0701 (17)0.0646 (17)0.0146 (13)0.0127 (12)0.0149 (12)
O12A0.0533 (13)0.0684 (15)0.0614 (15)0.0091 (10)0.0207 (12)0.0145 (11)
C2A0.0510 (18)0.063 (2)0.0607 (19)0.0103 (15)0.0184 (15)0.0041 (16)
C3A0.0441 (15)0.0494 (16)0.0529 (17)0.0047 (13)0.0107 (13)0.0057 (13)
C4A0.0455 (15)0.0499 (15)0.0521 (16)0.0005 (14)0.0097 (13)0.0029 (14)
C5A0.060 (2)0.060 (2)0.083 (3)0.0039 (19)0.010 (2)0.001 (2)
C6A0.071 (3)0.060 (2)0.090 (4)0.010 (2)0.003 (3)0.001 (2)
C7A0.105 (4)0.055 (2)0.067 (3)0.008 (2)0.017 (3)0.0061 (18)
C8A0.098 (3)0.064 (2)0.052 (2)0.000 (2)0.011 (2)0.0057 (18)
C9A0.064 (3)0.049 (2)0.050 (2)0.0034 (18)0.002 (2)0.0014 (17)
C10A0.059 (2)0.0480 (17)0.0491 (19)0.0035 (16)0.0029 (17)0.0051 (15)
C11A0.0436 (18)0.0457 (18)0.0437 (18)0.0023 (13)0.0065 (14)0.0020 (12)
C13A0.056 (2)0.066 (2)0.068 (2)0.0014 (18)0.0100 (18)0.0133 (18)
C14A0.072 (3)0.114 (3)0.071 (3)0.006 (2)0.028 (2)0.023 (2)
O1B0.0614 (13)0.0739 (15)0.0636 (13)0.0103 (11)0.0275 (11)0.0123 (12)
O2B0.0589 (16)0.117 (2)0.109 (2)0.0326 (15)0.0427 (16)0.0346 (19)
O11B0.0504 (16)0.0702 (17)0.0782 (19)0.0142 (13)0.0120 (13)0.0157 (13)
O12B0.0548 (13)0.0639 (14)0.0579 (14)0.0080 (10)0.0176 (11)0.0126 (10)
C2B0.057 (2)0.063 (2)0.064 (2)0.0064 (15)0.0203 (16)0.0056 (16)
C3B0.0423 (15)0.0515 (16)0.0428 (15)0.0044 (12)0.0069 (12)0.0040 (13)
C4B0.0431 (15)0.0573 (17)0.0447 (15)0.0019 (13)0.0098 (12)0.0014 (14)
C5B0.0489 (18)0.066 (2)0.057 (2)0.0087 (17)0.0024 (16)0.0028 (18)
C6B0.068 (3)0.060 (2)0.075 (3)0.0062 (19)0.015 (2)0.009 (2)
C7B0.088 (3)0.062 (2)0.062 (3)0.002 (2)0.005 (2)0.0122 (19)
C8B0.075 (3)0.072 (2)0.057 (2)0.010 (2)0.018 (2)0.0082 (19)
C9B0.052 (2)0.052 (2)0.047 (2)0.0018 (17)0.0090 (17)0.0066 (17)
C10B0.048 (2)0.0475 (17)0.0495 (19)0.0052 (15)0.0050 (15)0.0042 (14)
C11B0.0401 (19)0.051 (2)0.055 (2)0.0005 (14)0.0035 (15)0.0025 (14)
C13B0.062 (2)0.067 (2)0.051 (2)0.0034 (18)0.0107 (16)0.0117 (16)
C14B0.077 (3)0.097 (3)0.071 (3)0.003 (2)0.027 (2)0.015 (2)
S21A0.0506 (4)0.0694 (5)0.0539 (5)0.0078 (4)0.0095 (3)0.0125 (4)
N22A0.0520 (15)0.083 (2)0.0697 (18)0.0171 (14)0.0278 (14)0.0226 (15)
N23A0.0478 (14)0.0565 (14)0.0531 (14)0.0028 (11)0.0118 (11)0.0089 (12)
C22A0.0423 (15)0.0525 (17)0.0554 (17)0.0004 (13)0.0098 (13)0.0058 (13)
C24A0.0505 (19)0.058 (2)0.055 (2)0.0040 (16)0.0102 (16)0.0003 (16)
C25A0.055 (3)0.066 (3)0.076 (3)0.000 (2)0.020 (2)0.003 (2)
C26A0.071 (3)0.075 (2)0.054 (2)0.011 (2)0.028 (2)0.0024 (19)
C27A0.061 (2)0.072 (2)0.051 (2)0.0042 (19)0.0152 (18)0.0097 (18)
C28A0.0434 (18)0.059 (2)0.0410 (19)0.0030 (14)0.0050 (14)0.0046 (14)
C29A0.0424 (17)0.0473 (17)0.0477 (17)0.0056 (13)0.0076 (14)0.0024 (13)
S21B0.0506 (4)0.0605 (5)0.0558 (5)0.0030 (4)0.0043 (3)0.0106 (4)
N22B0.0505 (15)0.082 (2)0.0746 (19)0.0153 (14)0.0217 (14)0.0228 (16)
N23B0.0460 (14)0.0546 (14)0.0553 (14)0.0035 (11)0.0135 (11)0.0092 (12)
C22B0.0469 (16)0.0534 (17)0.0501 (16)0.0017 (14)0.0062 (13)0.0050 (14)
C24B0.061 (2)0.056 (2)0.063 (2)0.0039 (17)0.0231 (18)0.0032 (17)
C25B0.061 (3)0.067 (3)0.063 (3)0.000 (2)0.031 (2)0.013 (2)
C26B0.081 (3)0.087 (3)0.051 (2)0.013 (2)0.032 (2)0.009 (2)
C27B0.070 (3)0.069 (2)0.044 (2)0.008 (2)0.0048 (18)0.0022 (17)
C28B0.055 (2)0.050 (2)0.049 (2)0.0098 (15)0.0049 (16)0.0059 (15)
C29B0.053 (2)0.0460 (17)0.0486 (18)0.0074 (14)0.0110 (15)0.0048 (14)
Geometric parameters (Å, º) top
O1A—C9A1.384 (5)C7B—H7B0.9300
O1A—C2A1.386 (4)C8B—C9B1.381 (5)
O2A—C2A1.195 (4)C8B—H8B0.9300
O11A—C11A1.206 (4)C9B—C10B1.401 (5)
O12A—C11A1.322 (4)C13B—C14B1.512 (5)
O12A—C13A1.450 (4)C13B—H13C0.9700
C2A—C3A1.458 (4)C13B—H13D0.9700
C3A—C4A1.342 (4)C14B—H14D0.9600
C3A—C11A1.490 (5)C14B—H14E0.9600
C4A—C10A1.410 (5)C14B—H14F0.9600
C4A—H4A0.9300S21A—C28A1.748 (4)
C5A—C6A1.344 (6)S21A—C22A1.769 (3)
C5A—C10A1.412 (6)N22A—C22A1.334 (4)
C5A—H5A0.9300N22A—H22A0.8600
C6A—C7A1.391 (7)N22A—H22B0.8600
C6A—H6A0.9300N23A—C22A1.303 (4)
C7A—C8A1.393 (7)N23A—C29A1.393 (4)
C7A—H7A0.9300C24A—C25A1.363 (6)
C8A—C9A1.397 (6)C24A—C29A1.385 (5)
C8A—H8A0.9300C24A—H24A0.9300
C9A—C10A1.361 (6)C25A—C26A1.386 (6)
C13A—C14A1.503 (6)C25A—H25A0.9300
C13A—H13A0.9700C26A—C27A1.377 (6)
C13A—H13B0.9700C26A—H26A0.9300
C14A—H14A0.9600C27A—C28A1.392 (5)
C14A—H14B0.9600C27A—H27A0.9300
C14A—H14C0.9600C28A—C29A1.408 (5)
O1B—C9B1.359 (5)S21B—C28B1.737 (4)
O1B—C2B1.387 (4)S21B—C22B1.771 (3)
O2B—C2B1.194 (4)N22B—C22B1.331 (4)
O11B—C11B1.192 (4)N22B—H22C0.8600
O12B—C11B1.324 (5)N22B—H22D0.8600
O12B—C13B1.453 (4)N23B—C22B1.308 (4)
C2B—C3B1.467 (4)N23B—C29B1.388 (4)
C3B—C4B1.338 (4)C24B—C29B1.386 (5)
C3B—C11B1.504 (5)C24B—C25B1.396 (6)
C4B—C10B1.440 (5)C24B—H24B0.9300
C4B—H4B0.9300C25B—C26B1.382 (6)
C5B—C6B1.371 (5)C25B—H25B0.9300
C5B—C10B1.399 (5)C26B—C27B1.389 (6)
C5B—H5B0.9300C26B—H26B0.9300
C6B—C7B1.366 (6)C27B—C28B1.383 (6)
C6B—H6B0.9300C27B—H27B0.9300
C7B—C8B1.355 (7)C28B—C29B1.395 (5)
C9A—O1A—C2A122.2 (3)C5B—C10B—C9B119.0 (3)
C11A—O12A—C13A117.1 (3)C5B—C10B—C4B124.0 (4)
O2A—C2A—O1A115.9 (3)C9B—C10B—C4B116.9 (3)
O2A—C2A—C3A128.0 (3)O11B—C11B—O12B124.6 (4)
O1A—C2A—C3A116.0 (3)O11B—C11B—C3B125.7 (4)
C4A—C3A—C2A120.1 (3)O12B—C11B—C3B109.7 (3)
C4A—C3A—C11A121.7 (3)O12B—C13B—C14B106.9 (3)
C2A—C3A—C11A118.2 (3)O12B—C13B—H13C110.4
C3A—C4A—C10A122.4 (3)C14B—C13B—H13C110.4
C3A—C4A—H4A118.8O12B—C13B—H13D110.4
C10A—C4A—H4A118.8C14B—C13B—H13D110.4
C6A—C5A—C10A122.0 (4)H13C—C13B—H13D108.6
C6A—C5A—H5A119.0C13B—C14B—H14D109.5
C10A—C5A—H5A119.0C13B—C14B—H14E109.5
C5A—C6A—C7A119.1 (4)H14D—C14B—H14E109.5
C5A—C6A—H6A120.5C13B—C14B—H14F109.5
C7A—C6A—H6A120.5H14D—C14B—H14F109.5
C6A—C7A—C8A121.7 (4)H14E—C14B—H14F109.5
C6A—C7A—H7A119.1C28A—S21A—C22A88.91 (16)
C8A—C7A—H7A119.1C22A—N22A—H22A120.0
C7A—C8A—C9A116.6 (5)C22A—N22A—H22B120.0
C7A—C8A—H8A121.7H22A—N22A—H22B120.0
C9A—C8A—H8A121.7C22A—N23A—C29A110.7 (3)
C10A—C9A—O1A121.3 (3)N23A—C22A—N22A124.4 (3)
C10A—C9A—C8A123.3 (4)N23A—C22A—S21A115.7 (2)
O1A—C9A—C8A115.4 (4)N22A—C22A—S21A120.0 (2)
C9A—C10A—C4A117.9 (3)C25A—C24A—C29A118.7 (4)
C9A—C10A—C5A117.3 (4)C25A—C24A—H24A120.7
C4A—C10A—C5A124.7 (4)C29A—C24A—H24A120.7
O11A—C11A—O12A123.5 (3)C24A—C25A—C26A122.3 (4)
O11A—C11A—C3A125.7 (3)C24A—C25A—H25A118.8
O12A—C11A—C3A110.8 (3)C26A—C25A—H25A118.8
O12A—C13A—C14A105.7 (3)C27A—C26A—C25A120.5 (4)
O12A—C13A—H13A110.6C27A—C26A—H26A119.8
C14A—C13A—H13A110.6C25A—C26A—H26A119.8
O12A—C13A—H13B110.6C26A—C27A—C28A117.7 (4)
C14A—C13A—H13B110.6C26A—C27A—H27A121.1
H13A—C13A—H13B108.7C28A—C27A—H27A121.1
C13A—C14A—H14A109.5C27A—C28A—C29A121.6 (3)
C13A—C14A—H14B109.5C27A—C28A—S21A129.3 (3)
H14A—C14A—H14B109.5C29A—C28A—S21A109.1 (3)
C13A—C14A—H14C109.5C24A—C29A—N23A125.2 (3)
H14A—C14A—H14C109.5C24A—C29A—C28A119.2 (3)
H14B—C14A—H14C109.5N23A—C29A—C28A115.6 (3)
C9B—O1B—C2B123.8 (3)C28B—S21B—C22B88.59 (16)
C11B—O12B—C13B116.2 (3)C22B—N22B—H22C120.0
O2B—C2B—O1B116.4 (3)C22B—N22B—H22D120.0
O2B—C2B—C3B127.6 (3)H22C—N22B—H22D120.0
O1B—C2B—C3B116.1 (3)C22B—N23B—C29B110.5 (3)
C4B—C3B—C2B120.0 (3)N23B—C22B—N22B124.0 (3)
C4B—C3B—C11B121.9 (3)N23B—C22B—S21B115.4 (2)
C2B—C3B—C11B118.1 (3)N22B—C22B—S21B120.6 (2)
C3B—C4B—C10B122.4 (3)C29B—C24B—C25B119.0 (4)
C3B—C4B—H4B118.8C29B—C24B—H24B120.5
C10B—C4B—H4B118.8C25B—C24B—H24B120.5
C6B—C5B—C10B119.4 (4)C26B—C25B—C24B120.5 (4)
C6B—C5B—H5B120.3C26B—C25B—H25B119.8
C10B—C5B—H5B120.3C24B—C25B—H25B119.8
C7B—C6B—C5B120.6 (4)C25B—C26B—C27B121.0 (4)
C7B—C6B—H6B119.7C25B—C26B—H26B119.5
C5B—C6B—H6B119.7C27B—C26B—H26B119.5
C8B—C7B—C6B121.4 (4)C28B—C27B—C26B118.3 (4)
C8B—C7B—H7B119.3C28B—C27B—H27B120.9
C6B—C7B—H7B119.3C26B—C27B—H27B120.9
C7B—C8B—C9B119.7 (4)C27B—C28B—C29B121.5 (4)
C7B—C8B—H8B120.1C27B—C28B—S21B128.6 (3)
C9B—C8B—H8B120.1C29B—C28B—S21B109.9 (3)
O1B—C9B—C8B119.5 (4)C24B—C29B—N23B124.6 (3)
O1B—C9B—C10B120.5 (3)C24B—C29B—C28B119.7 (4)
C8B—C9B—C10B120.0 (4)N23B—C29B—C28B115.6 (3)
C9A—O1A—C2A—O2A177.1 (3)O1B—C9B—C10B—C4B4.6 (5)
C9A—O1A—C2A—C3A0.0 (4)C8B—C9B—C10B—C4B176.4 (3)
O2A—C2A—C3A—C4A175.6 (4)C3B—C4B—C10B—C5B179.3 (3)
O1A—C2A—C3A—C4A1.1 (4)C3B—C4B—C10B—C9B2.1 (4)
O2A—C2A—C3A—C11A6.4 (5)C13B—O12B—C11B—O11B5.2 (5)
O1A—C2A—C3A—C11A176.8 (3)C13B—O12B—C11B—C3B173.9 (3)
C2A—C3A—C4A—C10A0.2 (4)C4B—C3B—C11B—O11B178.0 (3)
C11A—C3A—C4A—C10A177.7 (3)C2B—C3B—C11B—O11B1.6 (5)
C10A—C5A—C6A—C7A0.6 (7)C4B—C3B—C11B—O12B1.1 (4)
C5A—C6A—C7A—C8A0.0 (7)C2B—C3B—C11B—O12B179.3 (3)
C6A—C7A—C8A—C9A0.6 (7)C11B—O12B—C13B—C14B177.8 (3)
C2A—O1A—C9A—C10A2.1 (5)C29A—N23A—C22A—N22A178.5 (3)
C2A—O1A—C9A—C8A178.8 (3)C29A—N23A—C22A—S21A0.9 (3)
C7A—C8A—C9A—C10A0.7 (6)C28A—S21A—C22A—N23A0.2 (3)
C7A—C8A—C9A—O1A178.4 (3)C28A—S21A—C22A—N22A179.3 (3)
O1A—C9A—C10A—C4A2.9 (5)C29A—C24A—C25A—C26A2.9 (6)
C8A—C9A—C10A—C4A178.0 (3)C24A—C25A—C26A—C27A3.0 (6)
O1A—C9A—C10A—C5A178.9 (3)C25A—C26A—C27A—C28A1.3 (6)
C8A—C9A—C10A—C5A0.2 (6)C26A—C27A—C28A—C29A0.3 (5)
C3A—C4A—C10A—C9A1.8 (5)C26A—C27A—C28A—S21A177.9 (3)
C3A—C4A—C10A—C5A179.9 (3)C22A—S21A—C28A—C27A178.9 (3)
C6A—C5A—C10A—C9A0.5 (6)C22A—S21A—C28A—C29A0.5 (2)
C6A—C5A—C10A—C4A178.6 (4)C25A—C24A—C29A—N23A178.0 (3)
C13A—O12A—C11A—O11A5.2 (4)C25A—C24A—C29A—C28A1.3 (5)
C13A—O12A—C11A—C3A175.0 (3)C22A—N23A—C29A—C24A177.9 (3)
C4A—C3A—C11A—O11A174.0 (3)C22A—N23A—C29A—C28A1.4 (4)
C2A—C3A—C11A—O11A3.9 (4)C27A—C28A—C29A—C24A0.3 (5)
C4A—C3A—C11A—O12A6.2 (4)S21A—C28A—C29A—C24A178.2 (3)
C2A—C3A—C11A—O12A175.9 (3)C27A—C28A—C29A—N23A179.7 (3)
C11A—O12A—C13A—C14A179.9 (3)S21A—C28A—C29A—N23A1.2 (3)
C9B—O1B—C2B—O2B176.9 (4)C29B—N23B—C22B—N22B178.8 (3)
C9B—O1B—C2B—C3B3.0 (4)C29B—N23B—C22B—S21B1.0 (3)
O2B—C2B—C3B—C4B174.5 (4)C28B—S21B—C22B—N23B0.6 (2)
O1B—C2B—C3B—C4B5.5 (4)C28B—S21B—C22B—N22B179.1 (3)
O2B—C2B—C3B—C11B6.0 (5)C29B—C24B—C25B—C26B0.0 (6)
O1B—C2B—C3B—C11B174.1 (3)C24B—C25B—C26B—C27B0.5 (6)
C2B—C3B—C4B—C10B3.0 (4)C25B—C26B—C27B—C28B1.7 (6)
C11B—C3B—C4B—C10B176.5 (3)C26B—C27B—C28B—C29B2.3 (5)
C10B—C5B—C6B—C7B0.0 (6)C26B—C27B—C28B—S21B176.5 (3)
C5B—C6B—C7B—C8B0.1 (7)C22B—S21B—C28B—C27B178.9 (3)
C6B—C7B—C8B—C9B0.3 (6)C22B—S21B—C28B—C29B0.0 (2)
C2B—O1B—C9B—C8B179.0 (3)C25B—C24B—C29B—N23B178.1 (3)
C2B—O1B—C9B—C10B2.0 (5)C25B—C24B—C29B—C28B0.6 (6)
C7B—C8B—C9B—O1B178.1 (4)C22B—N23B—C29B—C24B176.6 (3)
C7B—C8B—C9B—C10B0.8 (5)C22B—N23B—C29B—C28B1.0 (4)
C6B—C5B—C10B—C9B0.5 (5)C27B—C28B—C29B—C24B1.8 (5)
C6B—C5B—C10B—C4B176.7 (3)S21B—C28B—C29B—C24B177.2 (3)
O1B—C9B—C10B—C5B178.0 (3)C27B—C28B—C29B—N23B179.5 (3)
C8B—C9B—C10B—C5B0.9 (5)S21B—C28B—C29B—N23B0.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N22A—H22B···O2A0.862.233.019 (4)152
N22A—H22B···O11A0.862.393.047 (4)133
N22B—H22D···O2B0.862.222.998 (4)150
N22B—H22D···O11B0.862.393.034 (4)133
N22A—H22A···N23B0.862.193.024 (4)163
N22B—H22C···N23A0.862.183.021 (4)166

Experimental details

Crystal data
Chemical formulaC12H10O4·C7H6N2S
Mr368.40
Crystal system, space groupMonoclinic, Pc
Temperature (K)293
a, b, c (Å)9.360 (2), 9.109 (2), 21.242 (4)
β (°) 98.78 (3)
V3)1789.9 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.38 × 0.20 × 0.09
Data collection
DiffractometerBruker Smart Area Detector
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 1997)
Tmin, Tmax0.95, 0.97
No. of measured, independent and
observed [I > 2σ(I)] reflections
20092, 8179, 5785
Rint0.033
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.131, 1.00
No. of reflections8179
No. of parameters472
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.18
Absolute structureFlack, H. D. (1983), Acta Cryst. A39, 876-881
Absolute structure parameter0.39 (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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N22A—H22B···O2A0.862.233.019 (4)152
N22A—H22B···O11A0.862.393.047 (4)133
N22B—H22D···O2B0.862.222.998 (4)150
N22B—H22D···O11B0.862.393.034 (4)133
N22A—H22A···N23B0.862.193.024 (4)163
N22B—H22C···N23A0.862.183.021 (4)166
 

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