Experimental and database-transferred electron-density analysis and evaluation of electrostatic forces in coumarin-102 dye

The electron-density distribution of a new crystal form of coumarin-102, a laser dye, has been investigated using the Hansen–Coppens multipolar atom model. The charge density was refined versus high-resolution X-ray diffraction data collected at 100 K and was also constructed by transferring the charge density from the Experimental Library of Multipolar Atom Model (ELMAM2). The topology of the refined charge density has been analysed within the Bader `Atoms In Molecules' theory framework. Deformation electron-density peak heights and topological features indicate that the chromen-2-one ring system has a delocalized π-electron cloud in resonance with the N (amino) atom. The molecular electrostatic potential was estimated from both experimental and transferred multipolar models; it reveals an asymmetric character of the charge distribution across the molecule. This polarization effect is due to a substantial charge delocalization within the molecule. The molecular dipole moments derived from the experimental and transferred multipolar models are also compared with the liquid and gas-phase dipole moments. The substantial molecular dipole moment enhancements observed in the crystal environment originate from the crystal field and from intermolecular charge transfer induced and controlled by C—H...O and C—H...N intermolecular hydrogen bonds. The atomic forces were integrated over the atomic basins and compared for the two electron-density models.

Computing details

Data collection: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.42 (release 29-05-2009); cell refinement: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.42 (release 29-05-2009); data reduction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.42 (release 29-05-2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELX97 (Sheldrick, 2008) MoPro (Jelsch et al., 2005); molecular graphics: ORTEP (Farrugia, 1997) PLATON (Spek, 2003) MoPro (Jelsch et al., 2005); software used to prepare material for publication: MoPro (Jelsch et al., 2005).

Figures

8-methyl-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo(de)anthracen-10-one

Crystal data

C16H17NO2	F(000) = 544
Mr = 255.30	Dx = 1.370 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 77717 reflections
a = 8.5755 (3) Å	θ = 2.7–51.2°
b = 10.1627 (3) Å	µ = 0.09 mm^−1
c = 14.2676 (2) Å	T = 100 K
β = 95.249 (2)°	Parallelepiped, yellow
V = 1238.21 (6) Å^3	0.92 × 0.65 × 0.33 mm
Z = 4

Data collection

Oxford diffraction Xcalibur 4-circles diffractometer	12801 independent reflections
Radiation source: fine-focus sealed tube	9801 reflections with > 2.0σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 51.2°, θmin = 2.7°
Absorption correction: analytical Oxford Diffraction, (Clark & Reid, 1995)	h = −18→18
Tmin = 0.943, Tmax = 0.975	k = 0→22
77717 measured reflections	l = 0→31

Refinement

Refinement on F	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.017	Weighting scheme based on measured s.u.'s
S = 1.91	(Δ/σ)max < 0.001
12801 reflections	Δρmax = 0.37 e Å^−3
612 parameters	Δρmin = −0.23 e Å^−3
343 restraints	Extinction correction: Isotropic Gaussian
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.43316

Special details

Refinement. Refinement of F¹ against reflections. The threshold expression of F² > σ(F²) is used for calculating R-factors(gt) 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.62321 (3)	0.54842 (2)	−0.17206 (2)	0.0134 (2)
O11	0.56277 (4)	0.65946 (3)	−0.30357 (2)	0.0189 (2)
C2	0.63367 (2)	0.66057 (2)	−0.22535 (1)	0.0139 (1)
C3	0.72648 (2)	0.76777 (2)	−0.18394 (2)	0.0149 (1)
H3	0.7345 (5)	0.8542 (4)	−0.2276 (2)	0.03315
C4	0.80212 (2)	0.75924 (2)	−0.09539 (2)	0.0131 (1)
C5	0.86283 (2)	0.62046 (2)	0.04932 (1)	0.0122 (1)
H5	0.9344 (5)	0.6994 (3)	0.0810 (2)	0.02768
C6	0.84666 (2)	0.50407 (2)	0.09709 (1)	0.0113 (1)
C7	0.75060 (2)	0.40135 (2)	0.05468 (1)	0.0106 (1)
C8	0.67611 (2)	0.41815 (2)	−0.03711 (1)	0.0108 (1)
C9	0.69769 (2)	0.53672 (2)	−0.08279 (1)	0.0108 (1)
C10	0.78880 (2)	0.64072 (2)	−0.04210 (1)	0.0114 (1)
C23	0.89940 (3)	0.87153 (2)	−0.05449 (2)	0.0185 (1)
H23A	0.8977 (4)	0.9510 (3)	−0.1022 (3)	0.04044
H23B	1.0173 (3)	0.8416 (3)	−0.0385 (3)	0.03777
H23C	0.8563 (4)	0.9053 (3)	0.0086 (2)	0.03756
C12	0.92625 (2)	0.48213 (2)	0.19428 (1)	0.0136 (1)
H12A	0.9553 (4)	0.5749 (3)	0.2296 (1)	0.03039
H12B	1.0365 (3)	0.4284 (4)	0.1910 (1)	0.02988
C13	0.81734 (3)	0.40229 (2)	0.25129 (1)	0.0155 (1)
H13A	0.8726 (4)	0.3868 (2)	0.3224 (2)	0.03380
H13B	0.7080 (3)	0.4562 (2)	0.2558 (3)	0.03077
C14	0.78469 (3)	0.27096 (2)	0.20253 (1)	0.0163 (1)
H14A	0.8900 (4)	0.2104 (3)	0.2083 (2)	0.03182
H14B	0.6934 (5)	0.2182 (3)	0.2360 (2)	0.03299
C16	0.64863 (3)	0.17364 (2)	0.06024 (2)	0.0150 (1)
H16A	0.5307 (4)	0.1724 (4)	0.0827 (2)	0.03192
H16B	0.7079 (5)	0.0840 (3)	0.0871 (2)	0.03239
C17	0.64245 (3)	0.17673 (2)	−0.04651 (1)	0.0145 (1)
H17A	0.5682 (5)	0.0975 (2)	−0.0765 (1)	0.03260
H17B	0.7602 (4)	0.1628 (3)	−0.0687 (1)	0.02937
C18	0.57795 (2)	0.30898 (2)	−0.08314 (1)	0.0132 (1)
H18A	0.5792 (5)	0.3123 (1)	−0.1596 (2)	0.02879
H18B	0.4559 (3)	0.3184 (1)	−0.0680 (3)	0.02929
N15	0.73229 (2)	0.28657 (2)	0.10296 (1)	0.0136 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0149 (8)	0.0134 (8)	0.0115 (8)	−0.00045 (6)	−0.00098 (9)	0.00120 (6)
O11	0.0220 (8)	0.0207 (8)	0.0136 (8)	0.00261 (9)	−0.0018 (1)	0.00386 (8)
C2	0.0146 (7)	0.0142 (7)	0.0127 (8)	0.00244 (5)	0.00118 (9)	0.00238 (5)
C3	0.0156 (7)	0.0123 (7)	0.0170 (8)	0.00174 (5)	0.00216 (9)	0.00331 (6)
H3	0.0423	0.0237	0.0334	−0.0012	0.0027	0.0120
C4	0.0128 (7)	0.0099 (7)	0.0167 (7)	0.00050 (5)	0.00232 (9)	0.00078 (5)
C5	0.0120 (7)	0.0107 (7)	0.0135 (7)	−0.00099 (5)	0.000023 (8)	−0.00149 (5)
H5	0.0290	0.0221	0.0307	−0.0080	−0.0042	−0.0050
C6	0.0113 (7)	0.0110 (7)	0.0112 (7)	−0.00044 (5)	−0.00053 (8)	−0.00120 (5)
C7	0.0112 (7)	0.0098 (7)	0.0105 (7)	−0.00060 (5)	−0.000018 (8)	−0.00049 (5)
C8	0.0115 (7)	0.0103 (7)	0.0105 (7)	−0.00114 (5)	−0.00032 (8)	−0.00030 (5)
C9	0.0110 (7)	0.0105 (7)	0.0108 (7)	−0.00030 (5)	0.00034 (8)	0.00031 (5)
C10	0.0116 (7)	0.0099 (7)	0.0128 (7)	−0.00055 (5)	0.00093 (8)	−0.00012 (5)
C23	0.0193 (8)	0.0110 (7)	0.0252 (8)	−0.00224 (6)	0.00121 (10)	0.00028 (7)
H23A	0.0517	0.0249	0.0440	−0.0077	0.0004	0.0117
H23B	0.0237	0.0303	0.0582	0.0012	−0.0017	−0.0036
H23C	0.0415	0.0348	0.0381	−0.0076	0.0130	−0.0109
C12	0.0128 (7)	0.0150 (7)	0.0125 (8)	0.00081 (5)	−0.00148 (8)	−0.00217 (5)
H12A	0.0383	0.0247	0.0273	−0.0041	−0.0018	−0.0079
H12B	0.0256	0.0336	0.0301	0.0090	0.0003	0.0006
C13	0.0182 (7)	0.0169 (8)	0.0112 (7)	0.00066 (6)	0.00047 (9)	−0.00124 (6)
H13A	0.0427	0.0381	0.0189	−0.0006	−0.0063	0.0026
H13B	0.0271	0.0310	0.0345	0.0041	0.0043	−0.0014
C14	0.0221 (7)	0.0142 (7)	0.0121 (8)	−0.00037 (7)	−0.00074 (9)	0.00148 (6)
H14A	0.0330	0.0314	0.0299	0.0090	−0.0027	−0.0002
H14B	0.0375	0.0350	0.0273	−0.0089	0.0073	0.0039
C16	0.0182 (8)	0.0121 (7)	0.0145 (8)	−0.00316 (6)	0.00079 (9)	0.00072 (6)
H16A	0.0274	0.0357	0.0333	−0.0071	0.0063	−0.0017
H16B	0.0428	0.0209	0.0323	0.0034	−0.0030	0.0037
C17	0.0170 (7)	0.0116 (7)	0.0145 (8)	−0.00099 (5)	−0.00020 (9)	−0.00187 (5)
H17A	0.0398	0.0229	0.0336	−0.0114	−0.0049	−0.0034
H17B	0.0269	0.0313	0.0303	0.0025	0.0042	0.0014
C18	0.0136 (7)	0.0124 (8)	0.0133 (7)	−0.00199 (5)	−0.00141 (9)	−0.00049 (5)
H18A	0.0390	0.0288	0.0182	−0.0028	0.0004	−0.0015
H18B	0.0206	0.0298	0.0378	−0.0030	0.0044	−0.0019
N15	0.0179 (8)	0.0112 (7)	0.0112 (7)	−0.00210 (5)	−0.00097 (9)	0.00087 (5)

Geometric parameters (Å, º)

O1—C2	1.3776 (3)	C23—H23B	1.061 (3)
O1—C9	1.3768 (3)	C12—C13	1.5269 (3)
O11—C2	1.2211 (4)	C12—H12A	1.087 (3)
C2—C3	1.4434 (3)	C12—H12B	1.096 (3)
C3—C4	1.3692 (3)	C13—C14	1.5192 (3)
C3—H3	1.083 (4)	C13—H13A	1.091 (3)
C4—C10	1.4344 (3)	C13—H13B	1.093 (3)
C4—C23	1.4999 (3)	C14—N15	1.4589 (3)
C5—C6	1.3785 (3)	C14—H14A	1.090 (3)
C5—C10	1.4126 (3)	C14—H14B	1.094 (3)
C5—H5	1.083 (4)	C16—N15	1.4572 (3)
C6—C7	1.4295 (2)	C16—C17	1.5195 (3)
C6—C12	1.5051 (3)	C16—H16A	1.089 (3)
C7—N15	1.3710 (3)	C16—H16B	1.095 (3)
C7—C8	1.4140 (3)	C17—C18	1.5273 (3)
C8—C9	1.3903 (2)	C17—H17A	1.089 (3)
C8—C18	1.5066 (3)	C17—H17B	1.095 (3)
C9—C10	1.4077 (3)	C18—H18B	1.092 (3)
C23—H23A	1.056 (3)	C18—H18A	1.092 (3)
C23—H23C	1.061 (3)
O1—C2—O11	116.40 (3)	C9—C8—C18	121.80 (2)
O1—C2—C3	117.38 (2)	C10—C4—C23	120.07 (2)
O1—C9—C8	115.98 (2)	H23A—C23—H23C	108.4 (3)
O1—C9—C10	120.64 (2)	H23A—C23—H23B	108.4 (2)
O11—C2—C3	126.22 (3)	H23B—C23—H23C	108.0 (3)
C2—O1—C9	122.27 (2)	C12—C13—C14	108.60 (2)
C2—C3—C4	121.79 (2)	C12—C13—H13A	109.7 (1)
C2—C3—H3	116.0 (1)	C12—C13—H13B	109.6 (1)
C3—C4—C10	119.23 (2)	H12A—C12—C13	109.9 (1)
C3—C4—C23	120.70 (2)	H12A—C12—H12B	106.8 (3)
H3—C3—C4	122.2 (1)	H12B—C12—C13	109.3 (1)
C4—C10—C9	118.68 (2)	C13—C14—N15	112.20 (2)
C4—C10—C5	124.12 (2)	C13—C14—H14A	110.2 (2)
C4—C23—H23A	110.9 (2)	C13—C14—H14B	109.9 (2)
C4—C23—H23C	110.6 (2)	H13A—C13—C14	110.2 (1)
C4—C23—H23B	110.6 (2)	H13A—C13—H13B	108.6 (3)
C5—C6—C7	119.84 (2)	H13B—C13—C14	110.1 (1)
C5—C6—C12	121.67 (2)	C14—N15—C16	114.69 (2)
C5—C10—C9	117.19 (2)	H14A—C14—N15	108.3 (2)
H5—C5—C6	120.6 (1)	H14A—C14—H14B	108.1 (3)
H5—C5—C10	117.8 (1)	H14B—C14—N15	108.0 (2)
C6—C7—N15	119.78 (2)	C16—C17—C18	109.85 (2)
C6—C7—C8	119.86 (2)	C16—C17—H17A	110.1 (1)
C6—C12—C13	108.76 (1)	C16—C17—H17B	109.8 (1)
C6—C12—H12A	111.3 (1)	H16A—C16—N15	108.7 (2)
C6—C12—H12B	110.8 (1)	H16A—C16—C17	110.3 (2)
C6—C5—C10	121.64 (2)	H16A—C16—H16B	107.6 (4)
C7—N15—C16	122.32 (2)	H16B—C16—N15	108.3 (2)
C7—N15—C14	122.85 (2)	H16B—C16—C17	109.9 (2)
C7—C8—C9	118.07 (2)	C17—C16—N15	111.94 (2)
C7—C8—C18	120.12 (2)	C17—C18—H18B	109.4 (1)
C7—C6—C12	118.49 (2)	C17—C18—H18A	109.4 (1)
C8—C9—C10	123.37 (2)	H17A—C17—C18	109.6 (1)
C8—C7—N15	120.35 (2)	H17A—C17—H17B	108.2 (3)
C8—C18—C17	109.18 (2)	H17B—C17—C18	109.2 (1)
C8—C18—H18B	110.9 (1)	H18A—C18—H18B	107.0 (3)
C8—C18—H18A	110.9 (1)
O1—C2—C3—C4	0.24 (2)	C7—C6—C5—C10	−1.19 (2)
O1—C2—C3—H3	179.0 (3)	C8—C7—N15—C16	5.55 (2)
O1—C9—C8—C7	179.85 (2)	C8—C7—N15—C14	−169.91 (2)
O1—C9—C8—C18	0.42 (2)	C8—C7—C6—C12	−179.06 (2)
O1—C9—C10—C4	0.19 (2)	C8—C18—C17—C16	55.74 (2)
O1—C9—C10—C5	−179.31 (2)	C8—C18—C17—H17A	176.8 (2)
O11—C2—O1—C9	179.89 (3)	C8—C18—C17—H17B	−64.7 (2)
O11—C2—C3—C4	−179.84 (3)	C9—C8—C7—N15	179.61 (2)
O11—C2—C3—H3	−1.0 (1)	C9—C8—C18—C17	149.33 (2)
C2—O1—C9—C8	179.70 (2)	C9—C8—C18—H18B	−90.0 (1)
C2—O1—C9—C10	−0.03 (2)	C9—C8—C18—H18A	28.67 (8)
C2—C3—C4—C10	−0.09 (2)	C9—C10—C4—C23	−179.47 (2)
C2—C3—C4—C23	179.25 (2)	C10—C9—C8—C18	−179.85 (2)
C3—C2—O1—C9	−0.18 (2)	C10—C4—C23—H23A	179.8 (2)
C3—C4—C10—C9	−0.12 (2)	C10—C4—C23—H23C	−60.0 (2)
C3—C4—C10—C5	179.33 (2)	C10—C4—C23—H23B	59.6 (2)
C3—C4—C23—H23A	0.4 (2)	C10—C5—C6—C12	179.64 (2)
C3—C4—C23—H23C	120.7 (2)	C12—C6—C7—N15	0.39 (2)
C3—C4—C23—H23B	−119.8 (2)	C12—C13—C14—N15	−51.35 (2)
H3—C3—C4—C10	−178.8 (3)	C12—C13—C14—H14A	69.4 (2)
H3—C3—C4—C23	0.5 (1)	C12—C13—C14—H14B	−171.5 (2)
C4—C10—C9—C8	−179.53 (2)	H12A—C12—C13—C14	−177.5 (2)
C4—C10—C5—C6	−179.61 (2)	H12A—C12—C13—H13A	−57.0 (2)
C4—C10—C5—H5	−0.2 (1)	H12A—C12—C13—H13B	62.1 (2)
C5—C6—C7—N15	−178.80 (2)	H12B—C12—C13—C14	−60.6 (2)
C5—C6—C7—C8	1.75 (2)	H12B—C12—C13—H13A	59.9 (3)
C5—C6—C12—C13	143.13 (2)	H12B—C12—C13—H13B	179.0 (3)
C5—C6—C12—H12A	21.96 (8)	C13—C14—N15—C16	−159.64 (2)
C5—C6—C12—H12B	−96.8 (1)	H13A—C13—C14—N15	−171.5 (2)
C5—C10—C9—C8	0.98 (2)	H13A—C13—C14—H14A	−50.8 (3)
C5—C10—C4—C23	−0.02 (2)	H13A—C13—C14—H14B	68.3 (2)
H5—C5—C6—C7	179.4 (3)	H13B—C13—C14—N15	68.7 (2)
H5—C5—C6—C12	0.2 (1)	H13B—C13—C14—H14A	−170.5 (3)
H5—C5—C10—C9	179.3 (3)	H13B—C13—C14—H14B	−51.5 (3)
C6—C7—N15—C16	−173.89 (2)	C14—N15—C16—C17	−162.02 (2)
C6—C7—N15—C14	10.64 (2)	C14—N15—C16—H16A	75.9 (2)
C6—C7—C8—C9	−0.95 (2)	C14—N15—C16—H16B	−40.7 (2)
C6—C7—C8—C18	178.49 (2)	H14A—C14—N15—C16	78.5 (2)
C6—C12—C13—C14	60.39 (2)	H14B—C14—N15—C16	−38.4 (2)
C6—C12—C13—H13A	−179.1 (2)	C16—C17—C18—H18B	−65.8 (2)
C6—C12—C13—H13B	−59.9 (2)	C16—C17—C18—H18A	177.3 (2)
C6—C5—C10—C9	−0.14 (2)	H16A—C16—C17—C18	68.4 (2)
C7—N15—C16—C17	22.17 (2)	H16A—C16—C17—H17A	−52.4 (3)
C7—N15—C16—H16A	−99.9 (2)	H16A—C16—C17—H17B	−171.4 (3)
C7—N15—C16—H16B	143.5 (2)	H16B—C16—C17—C18	−173.1 (2)
C7—N15—C14—C13	16.14 (2)	H16B—C16—C17—H17A	66.1 (2)
C7—N15—C14—H14A	−105.7 (2)	H16B—C16—C17—H17B	−53.0 (3)
C7—N15—C14—H14B	137.4 (2)	H17A—C17—C16—N15	−173.6 (2)
C7—C8—C9—C10	−0.42 (2)	H17A—C17—C18—H18B	55.3 (3)
C7—C8—C18—C17	−30.09 (2)	H17A—C17—C18—H18A	−61.6 (2)
C7—C8—C18—H18B	90.6 (2)	H17B—C17—C16—N15	67.4 (2)
C7—C8—C18—H18A	−150.7 (2)	H17B—C17—C18—H18B	173.7 (3)
C7—C6—C12—C13	−36.04 (2)	H17B—C17—C18—H18A	56.8 (3)
C7—C6—C12—H12A	−157.2 (2)	C18—C8—C7—N15	−0.95 (2)
C7—C6—C12—H12B	84.0 (2)	C18—C17—C16—N15	−52.77 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18A···O1	1.092 (3)	2.438 (1)	2.7878 (4)	96.86 (9)
C5—H5···O11^i	1.083 (4)	2.377 (4)	3.4189 (5)	160.8 (3)
C17—H17B···O11^ii	1.095 (3)	2.477 (2)	3.4620 (7)	149.1 (2)
C23—H23A···O11^iii	1.056 (3)	2.548 (3)	3.5900 (5)	169.0 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+3/2, y−1/2, −z−1/2; (iii) −x+3/2, y+1/2, −z−1/2.