Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045515/at2400sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045515/at2400Isup2.hkl |
CCDC reference: 654266
The reaction mixture containing 3-ethoxycarbonylaminophenol (1.81 g, 10 mmol), acetoacetic ester (1.3 ml, 10 mmol) and phosphoric acid (5.3 ml) was stirred at 343–353 K for 12 h, and then poured into the water. The solid obtained was filtered off, washed with water and dried at room temperature. Colourless crystals of (I) suitable for X-ray structure analysis were obtained by slow evaporation of a solution of ethanol–petroleum (1:1) with the crude product over three weeks.
H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic), 0.97 Å (methylene), 0.96 Å (methyl) and N—H = 0.86 Å (amino), and refined in riding mode with Uiso(H) = 1.5Ueq(C) (methyl) and Uiso(H) = 1.2Ueq(C,N)(aromatic, methylene and amino).
Some aminocoumarin derivatives are known to be a category of important fluorogenic dyes (Lemieux et al., 2003; Zhao et al., 2004). The hydrogen bonding interaction in the self-association of some coumarin derivatives in the solid state (Aazam et al., 2006; Hamaker & McCully, 2006; Yang et al., 2006; Yang et al., 2007) have been decribed. Here, we report the crystal structure of (I).
Compound (I) crystallizes in monoclinic space group P21/c with the two independent molecules in the asymmetric unit. The molecules A and B have a similar conformation (Fig. 1). Two coumarin moieties in (I) are nearly planar, and the dihedral angles between the pyrone and the benzene rings are 1.4 (1)° and 0.9 (1)° in molecules A and B, respectively. Geometric parameters are normal (Allen et al., 1987) in molecules A and B. In the selected asymmetric unit, each of the independent molecules there is an intramolecular C—H···O hydrogen bond, defining an S(6) motif (Bernstein et al., 1995), and the molecules A and B are linked by one N—H···O hydrogen bond (Table 1 and Fig.1).
In the crystal structure of (I), atom N1A and C6A in the molecule A at (x, y, z) act as hydrogen-bond donors to atom O2B in the molecule B at (1 + x, 1/2 - y, 3/2 + z), forming a C22(12)[R21(6)] chain of rings (Bernstein et al., 1995). Similarly, the atom C2A in the molecule A at (x, y, z) acts as hydrogen-bond donor to the atom O4B in the molecule B at (1 - x, 1/2 + y, 1/2 - z), thus generating a C22(14) chain. The combination of these chains generates R44(36)[R21(6)R44(32)] and R88(60)[R21(6)R88(56)] rings (Table 1 and Fig. 2).
The molecules are also linked by C—H···π interactions [C13A···Cg1 Aiii = 3.637 (4) Å, C13—H13C···Cg1 Aiii = 147°, where Cg1 A is the centroid of the ring C4A–C9A, symmetry code: (iii) x, 1/2 - y, 1/2 + z], resulting in a three-dimensional structure.
For related literature, see: Aazam et al. (2006); Allen et al. (1987); Bernstein et al. (1995); Hamaker & McCully (2006); Lemieux et al. (2003); Yang et al. (2006, 2007); Zhao et al. (2004).
Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
C13H13NO4 | F(000) = 1040 |
Mr = 247.24 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2636 reflections |
a = 11.366 (1) Å | θ = 2.5–24.0° |
b = 24.875 (2) Å | µ = 0.10 mm−1 |
c = 9.0750 (11) Å | T = 298 K |
β = 112.425 (2)° | Block, colourless |
V = 2371.7 (4) Å3 | 0.58 × 0.50 × 0.31 mm |
Z = 8 |
Siemens SMART 1000 CCD area-detector diffractometer | 4185 independent reflections |
Radiation source: fine-focus sealed tube | 2261 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
φ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.942, Tmax = 0.969 | k = −25→29 |
11821 measured reflections | l = −10→7 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.9292P] where P = (Fo2 + 2Fc2)/3 |
4185 reflections | (Δ/σ)max < 0.001 |
329 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C13H13NO4 | V = 2371.7 (4) Å3 |
Mr = 247.24 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.366 (1) Å | µ = 0.10 mm−1 |
b = 24.875 (2) Å | T = 298 K |
c = 9.0750 (11) Å | 0.58 × 0.50 × 0.31 mm |
β = 112.425 (2)° |
Siemens SMART 1000 CCD area-detector diffractometer | 4185 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2261 reflections with I > 2σ(I) |
Tmin = 0.942, Tmax = 0.969 | Rint = 0.076 |
11821 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.24 e Å−3 |
4185 reflections | Δρmin = −0.20 e Å−3 |
329 parameters |
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 | ||
N1A | 0.9015 (2) | 0.28355 (9) | 0.8953 (3) | 0.0481 (7) | |
H1A | 0.9571 | 0.2848 | 0.9914 | 0.058* | |
N1B | 0.5937 (2) | 0.15407 (9) | 0.4348 (3) | 0.0456 (7) | |
H1B | 0.6510 | 0.1692 | 0.5157 | 0.055* | |
O1A | 0.6168 (2) | 0.38887 (8) | 0.4701 (2) | 0.0600 (6) | |
O2A | 0.4820 (2) | 0.43292 (10) | 0.2653 (3) | 0.0832 (9) | |
O3A | 0.9400 (2) | 0.19733 (8) | 0.9377 (2) | 0.0539 (6) | |
O4A | 0.7880 (2) | 0.22272 (8) | 0.7035 (2) | 0.0594 (6) | |
O1B | 0.25690 (18) | 0.18418 (7) | −0.0695 (2) | 0.0465 (5) | |
O2B | 0.1001 (2) | 0.19225 (9) | −0.3016 (2) | 0.0597 (6) | |
O3B | 0.68274 (18) | 0.07941 (8) | 0.5614 (2) | 0.0513 (6) | |
O4B | 0.5105 (2) | 0.07233 (8) | 0.3349 (3) | 0.0700 (7) | |
C1A | 0.5710 (3) | 0.43702 (14) | 0.3906 (4) | 0.0595 (9) | |
C2A | 0.6316 (3) | 0.48530 (13) | 0.4690 (4) | 0.0589 (9) | |
H2A | 0.6024 | 0.5179 | 0.4178 | 0.071* | |
C3A | 0.7279 (3) | 0.48639 (12) | 0.6116 (4) | 0.0498 (8) | |
C4A | 0.7739 (3) | 0.43540 (11) | 0.6909 (3) | 0.0412 (7) | |
C5A | 0.8744 (3) | 0.42925 (12) | 0.8372 (4) | 0.0492 (8) | |
H5A | 0.9158 | 0.4597 | 0.8920 | 0.059* | |
C6A | 0.9145 (3) | 0.37971 (12) | 0.9033 (3) | 0.0480 (8) | |
H6A | 0.9810 | 0.3771 | 1.0023 | 0.058* | |
C7A | 0.8560 (3) | 0.33308 (11) | 0.8226 (3) | 0.0425 (8) | |
C8A | 0.7551 (3) | 0.33765 (12) | 0.6777 (3) | 0.0491 (8) | |
H8A | 0.7134 | 0.3072 | 0.6233 | 0.059* | |
C9A | 0.7171 (3) | 0.38830 (12) | 0.6150 (3) | 0.0460 (8) | |
C10A | 0.7875 (3) | 0.53776 (13) | 0.6904 (4) | 0.0713 (11) | |
H10A | 0.7475 | 0.5675 | 0.6221 | 0.107* | |
H10B | 0.8766 | 0.5374 | 0.7101 | 0.107* | |
H10C | 0.7764 | 0.5414 | 0.7897 | 0.107* | |
C11A | 0.8682 (3) | 0.23365 (12) | 0.8320 (4) | 0.0446 (8) | |
C12A | 0.9173 (3) | 0.14170 (11) | 0.8869 (4) | 0.0572 (9) | |
H12A | 0.9315 | 0.1363 | 0.7891 | 0.069* | |
H12B | 0.8305 | 0.1314 | 0.8688 | 0.069* | |
C13A | 1.0104 (3) | 0.10912 (12) | 1.0206 (4) | 0.0620 (10) | |
H13A | 1.0956 | 0.1202 | 1.0383 | 0.093* | |
H13B | 1.0005 | 0.0717 | 0.9927 | 0.093* | |
H13C | 0.9945 | 0.1147 | 1.1161 | 0.093* | |
C1B | 0.1758 (3) | 0.21595 (13) | −0.1872 (3) | 0.0455 (8) | |
C2B | 0.1863 (3) | 0.27277 (12) | −0.1633 (3) | 0.0468 (8) | |
H2B | 0.1308 | 0.2949 | −0.2417 | 0.056* | |
C3B | 0.2722 (3) | 0.29573 (11) | −0.0336 (3) | 0.0417 (7) | |
C4B | 0.3577 (3) | 0.26164 (11) | 0.0885 (3) | 0.0376 (7) | |
C5B | 0.4538 (3) | 0.27906 (12) | 0.2297 (3) | 0.0469 (8) | |
H5B | 0.4667 | 0.3157 | 0.2490 | 0.056* | |
C6B | 0.5295 (3) | 0.24323 (12) | 0.3404 (4) | 0.0496 (8) | |
H6B | 0.5920 | 0.2560 | 0.4338 | 0.060* | |
C7B | 0.5137 (3) | 0.18778 (11) | 0.3146 (3) | 0.0400 (7) | |
C8B | 0.4216 (3) | 0.16943 (11) | 0.1753 (3) | 0.0424 (8) | |
H8B | 0.4100 | 0.1327 | 0.1551 | 0.051* | |
C9B | 0.3470 (3) | 0.20605 (11) | 0.0665 (3) | 0.0381 (7) | |
C10B | 0.2786 (3) | 0.35549 (12) | −0.0124 (4) | 0.0608 (10) | |
H10D | 0.2132 | 0.3721 | −0.1019 | 0.091* | |
H10E | 0.3603 | 0.3682 | −0.0052 | 0.091* | |
H10F | 0.2663 | 0.3646 | 0.0836 | 0.091* | |
C11B | 0.5883 (3) | 0.09907 (12) | 0.4339 (4) | 0.0470 (8) | |
C12B | 0.6840 (3) | 0.02102 (12) | 0.5736 (4) | 0.0608 (10) | |
H12C | 0.6739 | 0.0049 | 0.4722 | 0.073* | |
H12D | 0.6148 | 0.0089 | 0.6030 | 0.073* | |
C13B | 0.8085 (3) | 0.00531 (14) | 0.6981 (4) | 0.0806 (12) | |
H13D | 0.8760 | 0.0161 | 0.6655 | 0.121* | |
H13F | 0.8109 | −0.0330 | 0.7124 | 0.121* | |
H13E | 0.8189 | 0.0227 | 0.7968 | 0.121* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0580 (17) | 0.0410 (15) | 0.0322 (14) | −0.0013 (13) | 0.0027 (12) | −0.0006 (11) |
N1B | 0.0447 (15) | 0.0375 (14) | 0.0396 (15) | −0.0048 (12) | −0.0006 (12) | 0.0000 (11) |
O1A | 0.0583 (14) | 0.0525 (14) | 0.0496 (14) | 0.0015 (12) | −0.0013 (11) | 0.0056 (11) |
O2A | 0.0740 (17) | 0.0756 (19) | 0.0654 (17) | 0.0060 (14) | −0.0123 (14) | 0.0118 (13) |
O3A | 0.0693 (15) | 0.0388 (12) | 0.0426 (12) | 0.0008 (11) | 0.0088 (11) | 0.0012 (10) |
O4A | 0.0624 (14) | 0.0488 (13) | 0.0476 (14) | −0.0058 (11) | −0.0007 (12) | −0.0027 (10) |
O1B | 0.0519 (12) | 0.0405 (12) | 0.0348 (11) | −0.0050 (10) | 0.0027 (10) | −0.0013 (9) |
O2B | 0.0616 (14) | 0.0591 (14) | 0.0399 (13) | −0.0086 (12) | −0.0013 (11) | −0.0006 (11) |
O3B | 0.0499 (13) | 0.0380 (12) | 0.0526 (13) | 0.0032 (10) | 0.0045 (11) | 0.0043 (10) |
O4B | 0.0766 (16) | 0.0415 (13) | 0.0597 (15) | −0.0072 (12) | −0.0101 (13) | −0.0020 (11) |
C1A | 0.052 (2) | 0.063 (2) | 0.053 (2) | 0.0091 (19) | 0.0067 (18) | 0.0127 (18) |
C2A | 0.061 (2) | 0.047 (2) | 0.063 (2) | 0.0050 (18) | 0.0177 (19) | 0.0125 (17) |
C3A | 0.0500 (19) | 0.0433 (19) | 0.057 (2) | 0.0040 (16) | 0.0212 (17) | 0.0067 (15) |
C4A | 0.0407 (18) | 0.0414 (18) | 0.0422 (18) | 0.0037 (15) | 0.0164 (15) | 0.0005 (14) |
C5A | 0.051 (2) | 0.0458 (19) | 0.046 (2) | −0.0012 (16) | 0.0137 (16) | −0.0025 (15) |
C6A | 0.0511 (19) | 0.0476 (19) | 0.0374 (17) | 0.0012 (16) | 0.0079 (15) | −0.0015 (15) |
C7A | 0.0446 (18) | 0.0423 (18) | 0.0380 (17) | 0.0011 (15) | 0.0128 (15) | 0.0032 (14) |
C8A | 0.0499 (19) | 0.0423 (19) | 0.0457 (19) | −0.0047 (16) | 0.0078 (16) | −0.0016 (14) |
C9A | 0.0425 (18) | 0.0485 (19) | 0.0399 (18) | 0.0024 (16) | 0.0079 (15) | 0.0045 (15) |
C10A | 0.079 (3) | 0.045 (2) | 0.084 (3) | −0.003 (2) | 0.024 (2) | 0.0048 (18) |
C11A | 0.0451 (18) | 0.0440 (19) | 0.0391 (19) | 0.0004 (16) | 0.0097 (16) | 0.0007 (15) |
C12A | 0.080 (2) | 0.0373 (18) | 0.052 (2) | −0.0050 (18) | 0.0219 (19) | −0.0014 (15) |
C13A | 0.078 (2) | 0.0411 (19) | 0.064 (2) | 0.0036 (18) | 0.0241 (19) | 0.0051 (16) |
C1B | 0.0435 (19) | 0.054 (2) | 0.0331 (17) | −0.0028 (16) | 0.0077 (15) | 0.0007 (15) |
C2B | 0.0481 (19) | 0.0461 (19) | 0.0407 (18) | 0.0031 (16) | 0.0107 (15) | 0.0085 (14) |
C3B | 0.0447 (18) | 0.0388 (17) | 0.0427 (18) | −0.0023 (15) | 0.0180 (15) | 0.0007 (14) |
C4B | 0.0383 (17) | 0.0345 (17) | 0.0405 (17) | −0.0022 (14) | 0.0157 (14) | −0.0018 (13) |
C5B | 0.0529 (19) | 0.0344 (17) | 0.0488 (19) | −0.0072 (15) | 0.0142 (16) | −0.0049 (14) |
C6B | 0.0473 (19) | 0.0439 (19) | 0.0439 (19) | −0.0073 (16) | 0.0020 (15) | −0.0069 (15) |
C7B | 0.0380 (16) | 0.0389 (17) | 0.0392 (17) | 0.0002 (14) | 0.0102 (14) | −0.0023 (13) |
C8B | 0.0461 (18) | 0.0336 (16) | 0.0423 (18) | −0.0025 (14) | 0.0112 (15) | −0.0044 (13) |
C9B | 0.0378 (17) | 0.0403 (17) | 0.0320 (16) | −0.0044 (14) | 0.0086 (13) | −0.0054 (13) |
C10B | 0.069 (2) | 0.0387 (19) | 0.066 (2) | 0.0035 (18) | 0.0171 (19) | 0.0040 (16) |
C11B | 0.0415 (18) | 0.047 (2) | 0.045 (2) | −0.0008 (17) | 0.0082 (16) | 0.0032 (15) |
C12B | 0.070 (2) | 0.0381 (19) | 0.062 (2) | 0.0033 (18) | 0.0114 (19) | 0.0026 (16) |
C13B | 0.078 (3) | 0.057 (2) | 0.084 (3) | 0.014 (2) | 0.005 (2) | 0.011 (2) |
N1A—C11A | 1.359 (3) | N1B—C11B | 1.369 (4) |
N1A—C7A | 1.400 (3) | N1B—C7B | 1.401 (3) |
N1A—H1A | 0.8600 | N1B—H1B | 0.8600 |
O1A—C9A | 1.373 (3) | O1B—C1B | 1.365 (3) |
O1A—C1A | 1.393 (4) | O1B—C9B | 1.380 (3) |
O2A—C1A | 1.204 (4) | O2B—C1B | 1.218 (3) |
O3A—C11A | 1.344 (3) | O3B—C11B | 1.335 (3) |
O3A—C12A | 1.450 (3) | O3B—C12B | 1.456 (3) |
O4A—C11A | 1.206 (3) | O4B—C11B | 1.194 (3) |
C1A—C2A | 1.431 (4) | C1B—C2B | 1.428 (4) |
C2A—C3A | 1.339 (4) | C2B—C3B | 1.337 (4) |
C2A—H2A | 0.9300 | C2B—H2B | 0.9300 |
C3A—C4A | 1.453 (4) | C3B—C4B | 1.439 (4) |
C3A—C10A | 1.494 (4) | C3B—C10B | 1.497 (4) |
C4A—C9A | 1.387 (4) | C4B—C9B | 1.396 (4) |
C4A—C5A | 1.391 (4) | C4B—C5B | 1.398 (4) |
C5A—C6A | 1.370 (4) | C5B—C6B | 1.373 (4) |
C5A—H5A | 0.9300 | C5B—H5B | 0.9300 |
C6A—C7A | 1.397 (4) | C6B—C7B | 1.399 (4) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.381 (4) | C7B—C8B | 1.376 (3) |
C8A—C9A | 1.382 (4) | C8B—C9B | 1.373 (4) |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C10A—H10A | 0.9600 | C10B—H10D | 0.9600 |
C10A—H10B | 0.9600 | C10B—H10E | 0.9600 |
C10A—H10C | 0.9600 | C10B—H10F | 0.9600 |
C12A—C13A | 1.507 (4) | C12B—C13B | 1.487 (4) |
C12A—H12A | 0.9700 | C12B—H12C | 0.9700 |
C12A—H12B | 0.9700 | C12B—H12D | 0.9700 |
C13A—H13A | 0.9600 | C13B—H13D | 0.9600 |
C13A—H13B | 0.9600 | C13B—H13F | 0.9600 |
C13A—H13C | 0.9600 | C13B—H13E | 0.9600 |
C11A—N1A—C7A | 127.7 (2) | C11B—N1B—C7B | 125.4 (2) |
C11A—N1A—H1A | 116.2 | C11B—N1B—H1B | 117.3 |
C7A—N1A—H1A | 116.2 | C7B—N1B—H1B | 117.3 |
C9A—O1A—C1A | 121.0 (2) | C1B—O1B—C9B | 121.4 (2) |
C11A—O3A—C12A | 115.4 (2) | C11B—O3B—C12B | 114.4 (2) |
O2A—C1A—O1A | 115.5 (3) | O2B—C1B—O1B | 115.7 (3) |
O2A—C1A—C2A | 127.7 (3) | O2B—C1B—C2B | 126.8 (3) |
O1A—C1A—C2A | 116.8 (3) | O1B—C1B—C2B | 117.5 (2) |
C3A—C2A—C1A | 123.9 (3) | C3B—C2B—C1B | 123.2 (3) |
C3A—C2A—H2A | 118.0 | C3B—C2B—H2B | 118.4 |
C1A—C2A—H2A | 118.0 | C1B—C2B—H2B | 118.4 |
C2A—C3A—C4A | 117.9 (3) | C2B—C3B—C4B | 118.5 (3) |
C2A—C3A—C10A | 122.3 (3) | C2B—C3B—C10B | 121.4 (3) |
C4A—C3A—C10A | 119.9 (3) | C4B—C3B—C10B | 120.1 (3) |
C9A—C4A—C5A | 116.0 (3) | C9B—C4B—C5B | 115.7 (2) |
C9A—C4A—C3A | 118.7 (3) | C9B—C4B—C3B | 118.5 (2) |
C5A—C4A—C3A | 125.3 (3) | C5B—C4B—C3B | 125.8 (3) |
C6A—C5A—C4A | 122.1 (3) | C6B—C5B—C4B | 121.5 (3) |
C6A—C5A—H5A | 119.0 | C6B—C5B—H5B | 119.3 |
C4A—C5A—H5A | 119.0 | C4B—C5B—H5B | 119.3 |
C5A—C6A—C7A | 120.4 (3) | C5B—C6B—C7B | 120.9 (3) |
C5A—C6A—H6A | 119.8 | C5B—C6B—H6B | 119.6 |
C7A—C6A—H6A | 119.8 | C7B—C6B—H6B | 119.6 |
C8A—C7A—C6A | 119.1 (3) | C8B—C7B—C6B | 119.0 (3) |
C8A—C7A—N1A | 123.0 (3) | C8B—C7B—N1B | 123.8 (3) |
C6A—C7A—N1A | 117.9 (2) | C6B—C7B—N1B | 117.2 (2) |
C7A—C8A—C9A | 118.9 (3) | C9B—C8B—C7B | 119.0 (3) |
C7A—C8A—H8A | 120.6 | C9B—C8B—H8B | 120.5 |
C9A—C8A—H8A | 120.6 | C7B—C8B—H8B | 120.5 |
O1A—C9A—C8A | 114.7 (3) | C8B—C9B—O1B | 115.2 (2) |
O1A—C9A—C4A | 121.7 (3) | C8B—C9B—C4B | 124.0 (2) |
C8A—C9A—C4A | 123.5 (3) | O1B—C9B—C4B | 120.9 (2) |
C3A—C10A—H10A | 109.5 | C3B—C10B—H10D | 109.5 |
C3A—C10A—H10B | 109.5 | C3B—C10B—H10E | 109.5 |
H10A—C10A—H10B | 109.5 | H10D—C10B—H10E | 109.5 |
C3A—C10A—H10C | 109.5 | C3B—C10B—H10F | 109.5 |
H10A—C10A—H10C | 109.5 | H10D—C10B—H10F | 109.5 |
H10B—C10A—H10C | 109.5 | H10E—C10B—H10F | 109.5 |
O4A—C11A—O3A | 124.6 (3) | O4B—C11B—O3B | 124.6 (3) |
O4A—C11A—N1A | 126.9 (3) | O4B—C11B—N1B | 125.4 (3) |
O3A—C11A—N1A | 108.5 (2) | O3B—C11B—N1B | 109.9 (3) |
O3A—C12A—C13A | 105.8 (2) | O3B—C12B—C13B | 107.4 (3) |
O3A—C12A—H12A | 110.6 | O3B—C12B—H12C | 110.2 |
C13A—C12A—H12A | 110.6 | C13B—C12B—H12C | 110.2 |
O3A—C12A—H12B | 110.6 | O3B—C12B—H12D | 110.2 |
C13A—C12A—H12B | 110.6 | C13B—C12B—H12D | 110.2 |
H12A—C12A—H12B | 108.7 | H12C—C12B—H12D | 108.5 |
C12A—C13A—H13A | 109.5 | C12B—C13B—H13D | 109.5 |
C12A—C13A—H13B | 109.5 | C12B—C13B—H13F | 109.5 |
H13A—C13A—H13B | 109.5 | H13D—C13B—H13F | 109.5 |
C12A—C13A—H13C | 109.5 | C12B—C13B—H13E | 109.5 |
H13A—C13A—H13C | 109.5 | H13D—C13B—H13E | 109.5 |
H13B—C13A—H13C | 109.5 | H13F—C13B—H13E | 109.5 |
C9A—O1A—C1A—O2A | −179.3 (3) | C9B—O1B—C1B—O2B | −179.9 (2) |
C9A—O1A—C1A—C2A | −1.3 (5) | C9B—O1B—C1B—C2B | −0.9 (4) |
O2A—C1A—C2A—C3A | 177.7 (4) | O2B—C1B—C2B—C3B | 179.9 (3) |
O1A—C1A—C2A—C3A | 0.0 (5) | O1B—C1B—C2B—C3B | 1.0 (5) |
C1A—C2A—C3A—C4A | 0.4 (5) | C1B—C2B—C3B—C4B | −0.4 (5) |
C1A—C2A—C3A—C10A | −179.1 (3) | C1B—C2B—C3B—C10B | −179.0 (3) |
C2A—C3A—C4A—C9A | 0.6 (5) | C2B—C3B—C4B—C9B | −0.2 (4) |
C10A—C3A—C4A—C9A | −180.0 (3) | C10B—C3B—C4B—C9B | 178.4 (3) |
C2A—C3A—C4A—C5A | 178.6 (3) | C2B—C3B—C4B—C5B | 179.0 (3) |
C10A—C3A—C4A—C5A | −1.9 (5) | C10B—C3B—C4B—C5B | −2.4 (5) |
C9A—C4A—C5A—C6A | −0.4 (5) | C9B—C4B—C5B—C6B | −1.8 (4) |
C3A—C4A—C5A—C6A | −178.5 (3) | C3B—C4B—C5B—C6B | 179.0 (3) |
C4A—C5A—C6A—C7A | 1.2 (5) | C4B—C5B—C6B—C7B | 0.7 (5) |
C5A—C6A—C7A—C8A | −1.8 (5) | C5B—C6B—C7B—C8B | 0.6 (5) |
C5A—C6A—C7A—N1A | 179.5 (3) | C5B—C6B—C7B—N1B | −179.1 (3) |
C11A—N1A—C7A—C8A | 8.8 (5) | C11B—N1B—C7B—C8B | −2.9 (5) |
C11A—N1A—C7A—C6A | −172.6 (3) | C11B—N1B—C7B—C6B | 176.8 (3) |
C6A—C7A—C8A—C9A | 1.6 (5) | C6B—C7B—C8B—C9B | −0.7 (4) |
N1A—C7A—C8A—C9A | −179.8 (3) | N1B—C7B—C8B—C9B | 179.0 (3) |
C1A—O1A—C9A—C8A | −178.1 (3) | C7B—C8B—C9B—O1B | −179.8 (2) |
C1A—O1A—C9A—C4A | 2.3 (4) | C7B—C8B—C9B—C4B | −0.6 (5) |
C7A—C8A—C9A—O1A | 179.5 (3) | C1B—O1B—C9B—C8B | 179.6 (3) |
C7A—C8A—C9A—C4A | −0.9 (5) | C1B—O1B—C9B—C4B | 0.3 (4) |
C5A—C4A—C9A—O1A | 179.9 (3) | C5B—C4B—C9B—C8B | 1.8 (4) |
C3A—C4A—C9A—O1A | −1.9 (4) | C3B—C4B—C9B—C8B | −178.9 (3) |
C5A—C4A—C9A—C8A | 0.3 (5) | C5B—C4B—C9B—O1B | −179.0 (2) |
C3A—C4A—C9A—C8A | 178.5 (3) | C3B—C4B—C9B—O1B | 0.3 (4) |
C12A—O3A—C11A—O4A | 1.1 (4) | C12B—O3B—C11B—O4B | −0.7 (5) |
C12A—O3A—C11A—N1A | −179.1 (3) | C12B—O3B—C11B—N1B | 178.8 (3) |
C7A—N1A—C11A—O4A | −4.1 (5) | C7B—N1B—C11B—O4B | −4.2 (5) |
C7A—N1A—C11A—O3A | 176.1 (3) | C7B—N1B—C11B—O3B | 176.3 (2) |
C11A—O3A—C12A—C13A | 178.2 (3) | C11B—O3B—C12B—C13B | 167.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8A—H8A···O4A | 0.93 | 2.28 | 2.881 (4) | 122 |
C8B—H8B···O4B | 0.93 | 2.19 | 2.799 (3) | 122 |
N1B—H1B···O4A | 0.86 | 2.25 | 3.104 (3) | 170 |
N1A—H1A···O2Bi | 0.86 | 2.04 | 2.878 (3) | 164 |
C6A—H6A···O2Bi | 0.93 | 2.48 | 3.243 (4) | 140 |
C2A—H2A···O4Bii | 0.93 | 2.55 | 3.392 (4) | 151 |
C13A—H13C···Cg1Aiii | 0.96 | 2.79 | 3.637 (4) | 147 |
Symmetry codes: (i) x+1, −y+1/2, z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H13NO4 |
Mr | 247.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.366 (1), 24.875 (2), 9.0750 (11) |
β (°) | 112.425 (2) |
V (Å3) | 2371.7 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.58 × 0.50 × 0.31 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.942, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11821, 4185, 2261 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.144, 1.02 |
No. of reflections | 4185 |
No. of parameters | 329 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
C8A—H8A···O4A | 0.93 | 2.28 | 2.881 (4) | 122.0 |
C8B—H8B···O4B | 0.93 | 2.19 | 2.799 (3) | 122.1 |
N1B—H1B···O4A | 0.86 | 2.25 | 3.104 (3) | 169.6 |
N1A—H1A···O2Bi | 0.86 | 2.04 | 2.878 (3) | 164.2 |
C6A—H6A···O2Bi | 0.93 | 2.48 | 3.243 (4) | 139.7 |
C2A—H2A···O4Bii | 0.93 | 2.55 | 3.392 (4) | 150.9 |
C13A—H13C···Cg1Aiii | 0.96 | 2.79 | 3.637 (4) | 147.0 |
Symmetry codes: (i) x+1, −y+1/2, z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2. |
Some aminocoumarin derivatives are known to be a category of important fluorogenic dyes (Lemieux et al., 2003; Zhao et al., 2004). The hydrogen bonding interaction in the self-association of some coumarin derivatives in the solid state (Aazam et al., 2006; Hamaker & McCully, 2006; Yang et al., 2006; Yang et al., 2007) have been decribed. Here, we report the crystal structure of (I).
Compound (I) crystallizes in monoclinic space group P21/c with the two independent molecules in the asymmetric unit. The molecules A and B have a similar conformation (Fig. 1). Two coumarin moieties in (I) are nearly planar, and the dihedral angles between the pyrone and the benzene rings are 1.4 (1)° and 0.9 (1)° in molecules A and B, respectively. Geometric parameters are normal (Allen et al., 1987) in molecules A and B. In the selected asymmetric unit, each of the independent molecules there is an intramolecular C—H···O hydrogen bond, defining an S(6) motif (Bernstein et al., 1995), and the molecules A and B are linked by one N—H···O hydrogen bond (Table 1 and Fig.1).
In the crystal structure of (I), atom N1A and C6A in the molecule A at (x, y, z) act as hydrogen-bond donors to atom O2B in the molecule B at (1 + x, 1/2 - y, 3/2 + z), forming a C22(12)[R21(6)] chain of rings (Bernstein et al., 1995). Similarly, the atom C2A in the molecule A at (x, y, z) acts as hydrogen-bond donor to the atom O4B in the molecule B at (1 - x, 1/2 + y, 1/2 - z), thus generating a C22(14) chain. The combination of these chains generates R44(36)[R21(6)R44(32)] and R88(60)[R21(6)R88(56)] rings (Table 1 and Fig. 2).
The molecules are also linked by C—H···π interactions [C13A···Cg1 Aiii = 3.637 (4) Å, C13—H13C···Cg1 Aiii = 147°, where Cg1 A is the centroid of the ring C4A–C9A, symmetry code: (iii) x, 1/2 - y, 1/2 + z], resulting in a three-dimensional structure.