
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000709/om6124sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000709/om6124Isup2.hkl |
CCDC reference: 204687
Coumarin 500 was crystallized as received (Exiton Inc.) by slow evaporation in acetonitrile.
The H atoms on C3, C5, C6, C8 and N13 were included in their calculated positions as riding atoms. Distance and angle restraints were applied to the ethyl H atoms on the disordered C14 and C15 atoms.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1998); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN ((Molecular Structure Corporation, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: TEXSAN.
C12H10F3NO2 | Z = 2 |
Mr = 257.21 | F(000) = 264 |
Triclinic, P1 | Dx = 1.521 Mg m−3 |
a = 10.567 (6) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.856 (2) Å | Cell parameters from 20 reflections |
c = 4.6321 (11) Å | θ = 30.2–39.4° |
α = 93.303 (18)° | µ = 0.14 mm−1 |
β = 100.25 (3)° | T = 296 K |
γ = 99.14 (3)° | Needle, colorless |
V = 561.6 (4) Å3 | 0.90 × 0.30 × 0.10 mm |
Rigaku AFC-6S diffractometer | 965 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 30.0°, θmin = 2.9° |
2θ/ω scans | h = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→16 |
Tmin = 0.887, Tmax = 0.987 | l = −6→6 |
3292 measured reflections | 3 standard reflections every 150 reflections |
3126 independent reflections | intensity decay: 2.2% |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0477P)2] where P = (Fo2 + 2Fc2)/3 |
3126 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.20 e Å−3 |
2 restraints | Δρmin = −0.19 e Å−3 |
C12H10F3NO2 | γ = 99.14 (3)° |
Mr = 257.21 | V = 561.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.567 (6) Å | Mo Kα radiation |
b = 11.856 (2) Å | µ = 0.14 mm−1 |
c = 4.6321 (11) Å | T = 296 K |
α = 93.303 (18)° | 0.90 × 0.30 × 0.10 mm |
β = 100.25 (3)° |
Rigaku AFC-6S diffractometer | 965 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.061 |
Tmin = 0.887, Tmax = 0.987 | 3 standard reflections every 150 reflections |
3292 measured reflections | intensity decay: 2.2% |
3126 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 2 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | Δρmax = 0.20 e Å−3 |
3126 reflections | Δρmin = −0.19 e Å−3 |
182 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 | Occ. (<1) | |
F1 | 0.9049 (2) | 1.03223 (18) | 1.2323 (5) | 0.0730 (7) | |
F2 | 0.8126 (2) | 1.01490 (17) | 0.7811 (4) | 0.0735 (7) | |
F3 | 0.7054 (2) | 1.05216 (17) | 1.1149 (5) | 0.0733 (7) | |
O1 | 0.6623 (2) | 0.63630 (18) | 1.1197 (5) | 0.0518 (6) | |
O11 | 0.8178 (2) | 0.6369 (2) | 1.5052 (5) | 0.0676 (8) | |
N13 | 0.3057 (3) | 0.6034 (3) | 0.3366 (6) | 0.0619 (9) | |
H13 | 0.2854 | 0.5250 | 0.3826 | 0.074* | |
C2 | 0.7702 (3) | 0.6919 (3) | 1.3156 (8) | 0.0506 (9) | |
C3 | 0.8152 (3) | 0.8090 (3) | 1.2752 (7) | 0.0501 (9) | |
H3A | 0.8917 | 0.8481 | 1.3942 | 0.060* | |
C4 | 0.7484 (3) | 0.8644 (3) | 1.0654 (7) | 0.0443 (8) | |
C5 | 0.5556 (4) | 0.8521 (3) | 0.6407 (7) | 0.0522 (9) | |
H5A | 0.5777 | 0.9288 | 0.6077 | 0.063* | |
C6 | 0.4490 (3) | 0.7871 (3) | 0.4675 (7) | 0.0512 (9) | |
H6A | 0.3998 | 0.8202 | 0.3192 | 0.061* | |
C7 | 0.4106 (3) | 0.6711 (3) | 0.5058 (7) | 0.0461 (9) | |
C8 | 0.4869 (3) | 0.6239 (3) | 0.7312 (7) | 0.0488 (9) | |
H8A | 0.4645 | 0.5473 | 0.7645 | 0.059* | |
C9 | 0.5939 (3) | 0.6909 (3) | 0.9018 (7) | 0.0424 (8) | |
C10 | 0.6337 (3) | 0.8064 (3) | 0.8684 (7) | 0.0406 (8) | |
C12 | 0.7930 (4) | 0.9901 (3) | 1.0496 (8) | 0.0548 (10) | |
C14A | 0.2146 (7) | 0.6327 (6) | 0.0982 (17) | 0.050 (2) | 0.725 (8) |
H14A | 0.1765 | 0.5645 | −0.0336 | 0.060* | 0.725 (8) |
H14B | 0.2601 | 0.6876 | −0.0118 | 0.060* | 0.725 (8) |
C15A | 0.1072 (7) | 0.6833 (7) | 0.2058 (16) | 0.091 (3) | 0.725 (8) |
H15A | 0.0510 | 0.7065 | 0.0416 | 0.137* | 0.725 (8) |
H15B | 0.1449 | 0.7487 | 0.3435 | 0.137* | 0.725 (8) |
H15C | 0.0574 | 0.6269 | 0.3008 | 0.137* | 0.725 (8) |
C14B | 0.206 (2) | 0.6776 (14) | 0.149 (6) | 0.071 (8) | 0.275 (8) |
H14C | 0.1858 | 0.7388 | 0.2730 | 0.086* | 0.275 (8) |
H14D | 0.2396 | 0.7092 | −0.0157 | 0.086* | 0.275 (8) |
C15B | 0.0882 (15) | 0.5834 (16) | 0.048 (4) | 0.093 (7) | 0.275 (8) |
H15D | 0.0313 | 0.6063 | −0.1150 | 0.140* | 0.275 (8) |
H15E | 0.0422 | 0.5700 | 0.2074 | 0.140* | 0.275 (8) |
H15F | 0.1169 | 0.5143 | −0.0112 | 0.140* | 0.275 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0799 (16) | 0.0610 (13) | 0.0660 (14) | −0.0076 (11) | −0.0007 (12) | 0.0059 (11) |
F2 | 0.1062 (18) | 0.0621 (14) | 0.0498 (13) | −0.0040 (12) | 0.0229 (12) | 0.0100 (10) |
F3 | 0.0953 (17) | 0.0525 (13) | 0.0788 (15) | 0.0264 (12) | 0.0225 (13) | 0.0048 (11) |
O1 | 0.0550 (15) | 0.0466 (14) | 0.0512 (14) | 0.0084 (12) | 0.0011 (12) | 0.0121 (12) |
O11 | 0.0688 (18) | 0.0682 (17) | 0.0622 (17) | 0.0166 (14) | −0.0080 (13) | 0.0259 (14) |
N13 | 0.062 (2) | 0.060 (2) | 0.057 (2) | 0.0054 (17) | −0.0039 (17) | 0.0165 (16) |
C2 | 0.050 (2) | 0.049 (2) | 0.054 (2) | 0.0126 (18) | 0.0107 (19) | 0.0074 (18) |
C3 | 0.050 (2) | 0.050 (2) | 0.047 (2) | 0.0049 (17) | 0.0045 (17) | 0.0013 (16) |
C4 | 0.052 (2) | 0.043 (2) | 0.0411 (19) | 0.0112 (17) | 0.0165 (17) | 0.0040 (16) |
C5 | 0.065 (2) | 0.045 (2) | 0.052 (2) | 0.0170 (19) | 0.0175 (19) | 0.0132 (17) |
C6 | 0.051 (2) | 0.057 (2) | 0.048 (2) | 0.0171 (19) | 0.0043 (18) | 0.0178 (18) |
C7 | 0.045 (2) | 0.048 (2) | 0.045 (2) | 0.0052 (17) | 0.0092 (17) | 0.0089 (16) |
C8 | 0.055 (2) | 0.045 (2) | 0.048 (2) | 0.0106 (18) | 0.0091 (18) | 0.0139 (17) |
C9 | 0.044 (2) | 0.050 (2) | 0.0366 (19) | 0.0158 (17) | 0.0077 (16) | 0.0102 (16) |
C10 | 0.048 (2) | 0.0369 (19) | 0.0409 (19) | 0.0099 (16) | 0.0135 (17) | 0.0108 (15) |
C12 | 0.062 (3) | 0.053 (2) | 0.047 (2) | 0.004 (2) | 0.010 (2) | −0.0004 (18) |
C14A | 0.049 (4) | 0.042 (4) | 0.059 (4) | 0.008 (3) | 0.009 (3) | 0.011 (3) |
C15A | 0.059 (5) | 0.116 (7) | 0.105 (6) | 0.030 (5) | 0.016 (4) | 0.014 (5) |
C14B | 0.072 (15) | 0.031 (11) | 0.096 (16) | 0.013 (10) | −0.025 (12) | 0.000 (10) |
C15B | 0.052 (11) | 0.105 (15) | 0.105 (15) | −0.010 (10) | −0.019 (9) | 0.028 (12) |
F1—C12 | 1.331 (4) | C6—C7 | 1.402 (5) |
F2—C12 | 1.338 (4) | C6—H6A | 0.9300 |
F3—C12 | 1.334 (4) | C7—C8 | 1.401 (4) |
O1—C2 | 1.372 (4) | C8—C9 | 1.363 (4) |
O1—C9 | 1.387 (4) | C8—H8A | 0.9303 |
O11—C2 | 1.209 (4) | C9—C10 | 1.392 (4) |
N13—C7 | 1.350 (4) | C14A—C15A | 1.510 (8) |
N13—C14A | 1.427 (8) | C14A—H14A | 0.9700 |
N13—C14B | 1.64 (2) | C14A—H14B | 0.9700 |
N13—H13 | 0.9650 | C15A—H15A | 0.9600 |
C2—C3 | 1.429 (5) | C15A—H15B | 0.9600 |
C3—C4 | 1.360 (4) | C15A—H15C | 0.9600 |
C3—H3A | 0.9301 | C14B—C15B | 1.515 (17) |
C4—C10 | 1.430 (4) | C14B—H14C | 0.9700 |
C4—C12 | 1.500 (5) | C14B—H14D | 0.9700 |
C5—C6 | 1.356 (5) | C15B—H15D | 0.9600 |
C5—C10 | 1.409 (4) | C15B—H15E | 0.9600 |
C5—H5A | 0.9306 | C15B—H15F | 0.9600 |
C2—O1—C9 | 122.7 (3) | C9—C10—C4 | 116.9 (3) |
C7—N13—C14A | 128.7 (4) | C5—C10—C4 | 127.6 (3) |
C7—N13—C14B | 112.5 (6) | F1—C12—F3 | 106.5 (3) |
C14A—N13—C14B | 21.0 (8) | F1—C12—F2 | 105.6 (3) |
C7—N13—H13 | 117.7 | F3—C12—F2 | 106.3 (3) |
C14A—N13—H13 | 113.5 | F1—C12—C4 | 113.5 (3) |
C14B—N13—H13 | 126.9 | F3—C12—C4 | 111.8 (3) |
O11—C2—O1 | 116.8 (3) | F2—C12—C4 | 112.6 (3) |
O11—C2—C3 | 126.5 (3) | N13—C14A—C15A | 111.6 (6) |
O1—C2—C3 | 116.7 (3) | N13—C14A—H14A | 109.3 |
C4—C3—C2 | 121.3 (3) | C15A—C14A—H14A | 109.3 |
C4—C3—H3A | 119.3 | N13—C14A—H14B | 109.3 |
C2—C3—H3A | 119.4 | C15A—C14A—H14B | 109.3 |
C3—C4—C10 | 121.3 (3) | H14A—C14A—H14B | 108.0 |
C3—C4—C12 | 119.2 (3) | C14A—C15A—H15A | 109.5 |
C10—C4—C12 | 119.5 (3) | C14A—C15A—H15B | 109.5 |
C6—C5—C10 | 121.7 (3) | H15A—C15A—H15B | 109.5 |
C6—C5—H5A | 119.0 | C14A—C15A—H15C | 109.5 |
C10—C5—H5A | 119.3 | H15A—C15A—H15C | 109.5 |
C5—C6—C7 | 121.8 (3) | H15B—C15A—H15C | 109.5 |
C5—C6—H6A | 119.3 | C15B—C14B—N13 | 99.5 (12) |
C7—C6—H6A | 118.9 | C15B—C14B—H14C | 111.9 |
N13—C7—C8 | 119.0 (3) | N13—C14B—H14C | 111.9 |
N13—C7—C6 | 123.5 (3) | C15B—C14B—H14D | 111.9 |
C8—C7—C6 | 117.5 (3) | N13—C14B—H14D | 111.9 |
C9—C8—C7 | 119.7 (3) | H14C—C14B—H14D | 109.6 |
C9—C8—H8A | 120.2 | C14B—C15B—H15D | 109.5 |
C7—C8—H8A | 120.1 | C14B—C15B—H15E | 109.5 |
C8—C9—O1 | 115.1 (3) | H15D—C15B—H15E | 109.5 |
C8—C9—C10 | 123.9 (3) | C14B—C15B—H15F | 109.5 |
O1—C9—C10 | 121.0 (3) | H15D—C15B—H15F | 109.5 |
C9—C10—C5 | 115.6 (3) | H15E—C15B—H15F | 109.5 |
C9—O1—C2—O11 | 176.4 (3) | O1—C9—C10—C5 | −179.5 (3) |
C9—O1—C2—C3 | −3.6 (4) | C8—C9—C10—C4 | −179.9 (3) |
O11—C2—C3—C4 | −175.5 (3) | O1—C9—C10—C4 | 0.9 (4) |
O1—C2—C3—C4 | 4.5 (5) | C6—C5—C10—C9 | 0.1 (5) |
C2—C3—C4—C10 | −2.7 (5) | C6—C5—C10—C4 | 179.6 (3) |
C2—C3—C4—C12 | 174.6 (3) | C3—C4—C10—C9 | −0.1 (5) |
C10—C5—C6—C7 | 0.1 (5) | C12—C4—C10—C9 | −177.3 (3) |
C14A—N13—C7—C8 | 179.7 (4) | C3—C4—C10—C5 | −179.5 (3) |
C14B—N13—C7—C8 | 164.1 (11) | C12—C4—C10—C5 | 3.2 (5) |
C14A—N13—C7—C6 | −0.9 (7) | C3—C4—C12—F1 | 6.4 (5) |
C14B—N13—C7—C6 | −16.5 (12) | C10—C4—C12—F1 | −176.3 (3) |
C5—C6—C7—N13 | −179.5 (4) | C3—C4—C12—F3 | −114.1 (4) |
C5—C6—C7—C8 | −0.1 (5) | C10—C4—C12—F3 | 63.2 (4) |
N13—C7—C8—C9 | 179.3 (3) | C3—C4—C12—F2 | 126.4 (3) |
C6—C7—C8—C9 | −0.2 (5) | C10—C4—C12—F2 | −56.3 (4) |
C7—C8—C9—O1 | 179.6 (3) | C7—N13—C14A—C15A | −84.9 (7) |
C7—C8—C9—C10 | 0.4 (5) | C14B—N13—C14A—C15A | −41 (3) |
C2—O1—C9—C8 | −178.2 (3) | C7—N13—C14B—C15B | −166.9 (13) |
C2—O1—C9—C10 | 1.0 (4) | C14A—N13—C14B—C15B | 48.9 (19) |
C8—C9—C10—C5 | −0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O11i | 0.96 | 2.19 | 3.124 (4) | 163 |
C8—H8A···O1i | 0.93 | 2.51 | 3.401 (4) | 161 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C12H10F3NO2 |
Mr | 257.21 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.567 (6), 11.856 (2), 4.6321 (11) |
α, β, γ (°) | 93.303 (18), 100.25 (3), 99.14 (3) |
V (Å3) | 561.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.90 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.887, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3292, 3126, 965 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.168, 0.90 |
No. of reflections | 3126 |
No. of parameters | 182 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.19 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1998), MSC/AFC Diffractometer Control Software, TEXSAN ((Molecular Structure Corporation, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN.
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O11i | 0.96 | 2.19 | 3.124 (4) | 163 |
C8—H8A···O1i | 0.93 | 2.51 | 3.401 (4) | 161 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
The title compound, (I), a laser dye aminocoumarin compound, has been found to be very useful with various laser pump sources exhibiting a lasing maximum in the range 470–522 nm (Bos, 1981; Alcock et al., 1978; Eschrich & Morgan, 1985; Gunthals & Nibler, 1979). Bond lengths and angles in the rigid coumarin ring system (Fig. 1) are similar to those observed in the structurally related 7-amino (coumarin 151 or 490; Selladauri & Subramanian, 1992), 7-dimethylamino polymorphs (coumarin 152 A and 152B; Jasinski & Paight, 1994; Chinnakali et al., 1990), and 7-diethylamino (coumarin 466; Yufit et al., 1991), as well as the −6-methyl-7-dimethylamino (Coumarin 307; Chinnakali et al., 1992) −4-trifluoromethyl coumarin molecules except for C14A—C15A, C14B—C15B [1.510 (8) and 1.515 (17) Å] which has disorder on C15 and has been modeled with a restrained C14—C15 bond length (1.52 Å). The benzene and pyrone rings are planar (r.m.s. deviation = 0.0012 and 0.0137) and the angle between the least-squares planes of the rings is 0.65 (18)°.
The amino N atom, N13, trifluoromethyl carbon, C12, and carboxyl oxygen, O11, all extend from the coumarin ring in a planar fashion, with maximum deviations of −0.013 (4), 0.069 (5) and 0.096 (4) Å, respectively. The ethyl group is essentially perpendicular to the plane of the coumarin ring [C7—N13—C14A—C15A = −84.8 (7)° and C7—N13—C14B—C15B = −166.9 (13)°].
A packing diagram of the molecule (Fig. 2) indicates that the asymmetric units are stacked in layers along the c axis, with the parallel least-squares planes of the coumarin rings perpendicular to the axis and a closest contact interlayer spacing of 3.64 (2) Å. Intermolecular hydrogen-bonding interactions are outlined in Table 1.
In three of the four of the structurally related aminocoumarin systems mentioned earlier (coumarin 151, 152 A and 152B, and 307) crystallization also occurs in the triclinic (P1) space group, while coumarin 466 crystallizes in the P21/n space group. In all of these systems, the molecules stack with the asymmetric least-squares planes of the coumarin rings in a similar parallel fashion to that of the title compound.