Trans-cinnamic acid and coumarin-3-carboxylic acid: experimental charge-density studies to shed light on [2 + 2] cycloaddition reactions

Howard, J.A.K.; Mahon, M.F.; Raithby, P.R.; Sparkes, H.A.

doi:10.1107/S0108768109001566

Trans-cinnamic acid and coumarin-3-carboxylic acid: experimental charge-density studies to shed light on [2 + 2] cycloaddition reactions

J. A. K. Howard, M. F. Mahon, P. R. Raithby and H. A. Sparkes

As part of an ongoing series of experimental charge-density investigations into the intra- and intermolecular interactions present in compounds which undergo solid-state [2 + 2] cycloaddition reactions, the charge-density analyses of trans-cinnamic acid and coumarin-3-carboxylic acid are reported. Thus, high-resolution single-crystal X-ray diffraction data were recorded at 100 K for trans-cinnamic acid (sin θ/λ_max = 1.03 Å⁻¹) and coumarin-3-carboxylic acid (sin θ/λ_max = 1.19 Å⁻¹). In addition to the anticipated O—H

O hydrogen bonds weak C—H

O interactions were identified in both structures along with very weak intermolecular interactions between pairs of molecules that undergo solid-state [2 + 2] cycloaddition reactions upon irradiation.

Keywords: charge density; X-ray diffraction; solid-state [2 + 2] cycloaddition.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768109001566/so5021sup1.cif Contains datablocks 2a, publication_text, 1a
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768109001566/so50211asup2.hkl Contains datablock 1a
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768109001566/so50212asup3.hkl Contains datablock 2a
	Portable Document Format (PDF) file https://doi.org/10.1107/S0108768109001566/so5021sup4.pdf Hirshfeld analysis results and extra figures

CCDC references: 737459; 737460

Computing details top

For both compounds, data collection: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43); cell refinement: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43); data reduction: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (1a); SHELXS97 (Sheldrick, 1998) for (2a). For both compounds, program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).

Figures top

(1a) top

Crystal data top

C₉H₈O₂	F(000) = 312
M_r = 148.15	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 38572 reflections
a = 5.5504 (1) Å	θ = 2.3–49.3°
b = 17.5427 (1) Å	µ = 0.09 mm⁻¹
c = 7.7161 (1) Å	T = 100 K
β = 96.296 (1)°	Block, colourless
V = 746.78 (2) Å³	0.57 × 0.36 × 0.10 mm
Z = 4

Data collection top

Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer	6591 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4859 reflections with I > 3 σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 10.3317 pixels mm^-1	θ_max = 46.5°, θ_min = 2.3°
ω scans	h = −11→9
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −35→34
T_min = 0.911, T_max = 0.990	l = −15→15
70528 measured reflections

Refinement top

Refinement on F	0 restraints
Least-squares matrix: full	Only H-atom displacement parameters refined
R[F² > 2σ(F²)] = 0.018	w1 = 1/[s²(F_o)]
wR(F²) = 0.014	(Δ/σ)_max < 0.001
S = 1.74	Δρ_max = 0.13 e Å⁻³
4859 reflections	Δρ_min = −0.13 e Å⁻³
295 parameters

Crystal data top

C₉H₈O₂	V = 746.78 (2) Å³
M_r = 148.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.5504 (1) Å	µ = 0.09 mm⁻¹
b = 17.5427 (1) Å	T = 100 K
c = 7.7161 (1) Å	0.57 × 0.36 × 0.10 mm
β = 96.296 (1)°

Data collection top

Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer	6591 independent reflections
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	4859 reflections with I > 3 σ(I)
T_min = 0.911, T_max = 0.990	R_int = 0.023
70528 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.014	Only H-atom displacement parameters refined
S = 1.74	Δρ_max = 0.13 e Å⁻³
4859 reflections	Δρ_min = −0.13 e Å⁻³
295 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O(1)	0.26803 (7)	0.04975 (2)	0.58236 (4)	0.022
O(2)	−0.05071 (7)	0.00677 (2)	0.71005 (4)	0.021
C(1)	0.53321 (5)	0.119200 (14)	1.22626 (3)	0.018
C(2)	0.66266 (6)	0.148390 (16)	1.37622 (3)	0.023
C(3)	0.87407 (6)	0.190256 (16)	1.36564 (4)	0.023
C(4)	0.95498 (5)	0.203295 (15)	1.20338 (4)	0.021
C(5)	0.82592 (5)	0.174013 (14)	1.05311 (3)	0.018
C(6)	0.61359 (4)	0.131561 (12)	1.06228 (3)	0.015
C(7)	0.48321 (5)	0.102155 (13)	0.90102 (3)	0.016
C(8)	0.27040 (5)	0.064820 (14)	0.88698 (3)	0.016
C(9)	0.15126 (5)	0.038215 (14)	0.71843 (3)	0.016
H(1A)	0.174598	0.027214	0.47475	0.037
H(1)	0.373282	0.085046	1.235688	0.035
H(2)	0.598173	0.138129	1.501213	0.043
H(3)	0.975137	0.212849	1.481918	0.04
H(4)	1.117938	0.23573	1.192203	0.042
H(5)	0.89459	0.184165	0.929506	0.035
H(7)	0.570981	0.113595	0.785568	0.031
H(8)	0.179864	0.054076	1.001513	0.033

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O(1)	0.02249 (14)	0.03106 (15)	0.01370 (11)	−0.00881 (12)	0.00264 (10)	−0.00048 (10)
O(2)	0.01632 (12)	0.03081 (14)	0.01686 (10)	−0.00703 (11)	0.00132 (9)	−0.00244 (10)
C(1)	0.01862 (10)	0.02038 (9)	0.01571 (9)	−0.00558 (8)	0.00264 (8)	−0.00201 (7)
C(2)	0.02602 (13)	0.02506 (11)	0.01650 (9)	−0.00874 (10)	0.00237 (9)	−0.00422 (8)
C(3)	0.02465 (13)	0.02234 (11)	0.02113 (10)	−0.00771 (9)	−0.00098 (10)	−0.00361 (9)
C(4)	0.01763 (11)	0.02044 (10)	0.02434 (11)	−0.00563 (8)	−0.00030 (9)	0.00010 (9)
C(5)	0.01480 (9)	0.01875 (9)	0.01960 (9)	−0.00248 (8)	0.00183 (8)	0.00148 (8)
C(6)	0.01417 (9)	0.01494 (8)	0.01537 (8)	−0.00119 (7)	0.00151 (7)	−0.00013 (7)
C(7)	0.01570 (9)	0.01803 (9)	0.01444 (8)	−0.00178 (7)	0.00107 (7)	0.00037 (7)
C(8)	0.01544 (9)	0.01899 (9)	0.01456 (8)	−0.00209 (8)	0.00159 (7)	−0.00100 (7)
C(9)	0.01513 (10)	0.01985 (9)	0.01421 (8)	−0.00228 (8)	0.00106 (7)	−0.00031 (7)
H(1A)	0.037515	0.051737	0.021435	−0.002839	0.001308	−0.014456
H(1)	0.03357	0.04322	0.029741	−0.004083	0.00739	−0.017817
H(2)	0.046617	0.058975	0.023448	−0.005678	0.0077	−0.02197
H(3)	0.040804	0.047255	0.030753	−0.007344	−0.00534	−0.015975
H(4)	0.040024	0.043308	0.041776	−0.001222	0.001428	−0.01691
H(5)	0.02995	0.047221	0.028783	0.001654	0.00817	−0.01242
H(7)	0.027602	0.042709	0.023682	0.00213	0.008611	−0.008558
H(8)	0.032889	0.043891	0.024479	−0.003164	0.010216	−0.008228

Geometric parameters (Å, º) top

O(1)—C(9)	1.3087 (4)	C(4)—C(5)	1.3926 (4)
O(1)—H(1A)	1.0100	C(4)—H(4)	1.0800
O(2)—C(9)	1.2447 (4)	C(5)—C(6)	1.4024 (3)
C(1)—C(2)	1.3911 (3)	C(5)—H(5)	1.0800
C(1)—C(6)	1.4038 (3)	C(6)—C(7)	1.4630 (3)
C(1)—H(1)	1.0800	C(7)—C(8)	1.3446 (3)
C(2)—C(3)	1.3943 (4)	C(7)—H(7)	1.0800
C(2)—H(2)	1.0800	C(8)—C(9)	1.4690 (3)
C(3)—C(4)	1.3946 (4)	C(8)—H(8)	1.0800
C(3)—H(3)	1.0800

C(9)—O(1)—H(1A)	110.14	C(4)—C(5)—H(5)	118.38
C(2)—C(1)—C(6)	120.44 (2)	C(6)—C(5)—H(5)	120.80
C(2)—C(1)—H(1)	120.10	C(1)—C(6)—C(5)	118.64 (2)
C(6)—C(1)—H(1)	119.42	C(1)—C(6)—C(7)	122.39 (2)
C(1)—C(2)—C(3)	120.43 (3)	C(5)—C(6)—C(7)	118.97 (2)
C(1)—C(2)—H(2)	119.34	C(6)—C(7)—C(8)	126.05 (2)
C(3)—C(2)—H(2)	120.24	C(6)—C(7)—H(7)	114.22
C(2)—C(3)—C(4)	119.66 (3)	C(8)—C(7)—H(7)	119.72
C(2)—C(3)—H(3)	120.56	C(7)—C(8)—C(9)	122.16 (2)
C(4)—C(3)—H(3)	119.77	C(7)—C(8)—H(8)	120.17
C(3)—C(4)—C(5)	120.01 (2)	C(9)—C(8)—H(8)	117.67
C(3)—C(4)—H(4)	120.87	O(1)—C(9)—O(2)	123.32 (3)
C(5)—C(4)—H(4)	119.12	O(1)—C(9)—C(8)	116.54 (3)
C(4)—C(5)—C(6)	120.81 (2)	O(2)—C(9)—C(8)	120.15 (2)

H(1A)—O(1)—C(9)—O(2)	−2.92	C(3)—C(4)—C(5)—H(5)	−178.93
H(1A)—O(1)—C(9)—C(8)	177.31	H(4)—C(4)—C(5)—C(6)	179.95
C(6)—C(1)—C(2)—C(3)	−0.05 (3)	H(4)—C(4)—C(5)—H(5)	0.74
C(2)—C(1)—C(6)—C(5)	−0.20 (2)	C(4)—C(5)—C(6)—C(1)	0.09 (2)
C(2)—C(1)—C(6)—C(7)	−179.85 (4)	C(4)—C(5)—C(6)—C(7)	179.75 (4)
C(6)—C(1)—C(2)—H(2)	−179.82	H(5)—C(5)—C(6)—C(1)	179.28
H(1)—C(1)—C(2)—C(3)	177.72	H(5)—C(5)—C(6)—C(7)	−1.06
H(1)—C(1)—C(2)—H(2)	−2.05	C(1)—C(6)—C(7)—C(8)	4.06 (2)
H(1)—C(1)—C(6)—C(5)	−177.99	C(1)—C(6)—C(7)—H(7)	−177.03
H(1)—C(1)—C(6)—C(7)	2.36	C(5)—C(6)—C(7)—C(8)	−175.58 (4)
C(1)—C(2)—C(3)—C(4)	0.43 (3)	C(5)—C(6)—C(7)—H(7)	3.32
C(1)—C(2)—C(3)—H(3)	−179.84	C(6)—C(7)—C(8)—C(9)	179.17 (4)
H(2)—C(2)—C(3)—C(4)	−179.81	C(6)—C(7)—C(8)—H(8)	−0.02
H(2)—C(2)—C(3)—H(3)	−0.07	H(7)—C(7)—C(8)—C(9)	0.32
C(2)—C(3)—C(4)—C(5)	−0.54 (3)	H(7)—C(7)—C(8)—H(8)	−178.87
C(2)—C(3)—C(4)—H(4)	179.80	C(7)—C(8)—C(9)—O(1)	2.88 (3)
H(3)—C(3)—C(4)—C(5)	179.72	C(7)—C(8)—C(9)—O(2)	−176.90 (4)
H(3)—C(3)—C(4)—H(4)	0.06	H(8)—C(8)—C(9)—O(1)	−177.91
C(3)—C(4)—C(5)—C(6)	0.28 (3)	H(8)—C(8)—C(9)—O(2)	2.31

(2a) top

Crystal data top

C₁₀H₆O₄	F(000) = 392
M_r = 190.15	D_x = 1.574 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 66859 reflections
a = 11.1992 (1) Å	θ = 3.1–67.4°
b = 5.4662 (1) Å	µ = 0.12 mm⁻¹
c = 13.7267 (2) Å	T = 100 K
β = 107.256 (1)°	Block, colourless
V = 802.49 (2) Å³	0.60 × 0.52 × 0.29 mm
Z = 4

Data collection top

Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer	11309 independent reflections
Radiation source: Enhance (Mo) X-ray Source	8933 reflections with I > 3 σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 10.3317 pixels mm^-1	θ_max = 57.8°, θ_min = 3.1°
CCD scans	h = −26→26
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.18 (release 23-07-2008 CrysAlis171 .NET) (compiled Jul 23 2008,18:57:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→13
T_min = 0.891, T_max = 0.965	l = −32→32
147662 measured reflections

Refinement top

Refinement on F	367 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.016	w1 = 1/[s²(F_o)]
wR(F²) = 0.014	(Δ/σ)_max < 0.001
S = 1.67	Δρ_max = 0.15 e Å⁻³
8933 reflections	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₀H₆O₄	V = 802.49 (2) Å³
M_r = 190.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.1992 (1) Å	µ = 0.12 mm⁻¹
b = 5.4662 (1) Å	T = 100 K
c = 13.7267 (2) Å	0.60 × 0.52 × 0.29 mm
β = 107.256 (1)°

Data collection top

Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer	11309 independent reflections
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.18 (release 23-07-2008 CrysAlis171 .NET) (compiled Jul 23 2008,18:57:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	8933 reflections with I > 3 σ(I)
T_min = 0.891, T_max = 0.965	R_int = 0.023
147662 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	367 parameters
wR(F²) = 0.014	0 restraints
S = 1.67	Δρ_max = 0.15 e Å⁻³
8933 reflections	Δρ_min = −0.14 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O(1)	0.900004 (14)	0.19923 (2)	0.254215 (12)	0.012
O(2)	0.772812 (16)	0.30671 (3)	0.341479 (13)	0.015
O(3)	0.73811 (2)	0.03092 (4)	0.483840 (17)	0.021
O(4)	0.856569 (19)	−0.29867 (3)	0.528735 (15)	0.018
C(1)	0.980824 (12)	0.03660 (2)	0.230834 (10)	0.011
C(2)	1.023635 (14)	0.09363 (2)	0.148238 (12)	0.014
C(3)	1.106404 (15)	−0.06761 (3)	0.123505 (12)	0.015
C(4)	1.146074 (15)	−0.28187 (3)	0.180257 (13)	0.015
C(5)	1.102190 (13)	−0.33595 (2)	0.262115 (12)	0.013
C(6)	1.017881 (12)	−0.17668 (2)	0.288303 (10)	0.01
C(7)	0.965884 (12)	−0.22503 (2)	0.369680 (10)	0.011
C(8)	0.881696 (12)	−0.06819 (2)	0.389306 (10)	0.01
C(9)	0.846586 (12)	0.15328 (2)	0.328619 (10)	0.011
C(10)	0.825109 (14)	−0.12314 (2)	0.472765 (11)	0.013
H(3A)	0.730201	0.162694	0.430715	0.028
H(2)	0.993041	0.256504	0.103211	0.031
H(3)	1.140067	−0.023708	0.059563	0.034
H(4)	1.209662	−0.408184	0.160928	0.034
H(5)	1.130951	−0.500765	0.306234	0.03
H(7)	0.9972	−0.384099	0.41704	0.027

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O(1)	0.01327 (4)	0.01043 (3)	0.01187 (4)	0.00072 (3)	0.00434 (4)	0.00192 (3)
O(2)	0.01680 (5)	0.01453 (4)	0.01584 (5)	0.00562 (4)	0.00607 (4)	0.00173 (4)
O(3)	0.02272 (7)	0.02447 (6)	0.01944 (7)	0.00838 (6)	0.01356 (6)	0.00555 (6)
O(4)	0.02317 (7)	0.01860 (5)	0.01627 (6)	0.00354 (5)	0.01083 (5)	0.00651 (5)
C(1)	0.01119 (4)	0.01108 (3)	0.00970 (4)	−0.00077 (3)	0.00339 (3)	0.00093 (3)
C(2)	0.01507 (5)	0.01562 (4)	0.01093 (5)	−0.00115 (4)	0.00496 (4)	0.00207 (3)
C(3)	0.01500 (5)	0.02008 (5)	0.01155 (5)	−0.00124 (4)	0.00617 (4)	0.00027 (4)
C(4)	0.01428 (5)	0.01830 (5)	0.01418 (5)	0.00077 (4)	0.00705 (4)	−0.00097 (4)
C(5)	0.01305 (4)	0.01357 (4)	0.01374 (5)	0.00170 (3)	0.00590 (4)	0.00054 (3)
C(6)	0.01067 (4)	0.01085 (3)	0.01042 (4)	0.00028 (3)	0.00399 (3)	0.00078 (3)
C(7)	0.01184 (4)	0.01060 (3)	0.01063 (4)	0.00094 (3)	0.00431 (3)	0.00171 (3)
C(8)	0.01086 (4)	0.01102 (3)	0.00964 (4)	0.00054 (3)	0.00363 (3)	0.00090 (3)
C(9)	0.01129 (4)	0.01056 (3)	0.01060 (4)	0.00117 (3)	0.00304 (3)	0.00062 (3)
C(10)	0.01415 (4)	0.01501 (4)	0.01128 (4)	0.00100 (3)	0.00576 (4)	0.00172 (3)
H(3A)	0.031528	0.029738	0.027646	0.006525	0.01482	0.008194
H(2)	0.037845	0.028009	0.028027	0.011656	0.013196	0.005116
H(3)	0.038669	0.042988	0.027274	0.006083	0.021361	0.001527
H(4)	0.035128	0.036847	0.036477	−0.000279	0.020954	0.011332
H(5)	0.03537	0.025363	0.031254	0.008469	0.013488	0.010856
H(7)	0.033469	0.022741	0.027266	0.010716	0.011966	0.007944

Geometric parameters (Å, º) top

O(1)—C(1)	1.3729 (2)	C(3)—H(3)	1.0800
O(1)—C(9)	1.3515 (2)	C(4)—C(5)	1.3853 (2)
O(2)—C(9)	1.2263 (2)	C(4)—H(4)	1.0800
O(3)—C(10)	1.3302 (2)	C(5)—C(6)	1.4071 (2)
O(3)—H(3A)	1.0100	C(5)—H(5)	1.0800
O(4)—C(10)	1.2142 (2)	C(6)—C(7)	1.4292 (2)
C(1)—C(2)	1.3910 (2)	C(7)—C(8)	1.3591 (2)
C(1)—C(6)	1.3998 (2)	C(7)—H(7)	1.0800
C(2)—C(3)	1.3921 (2)	C(8)—C(9)	1.4559 (2)
C(2)—H(2)	1.0800	C(8)—C(10)	1.4950 (2)
C(3)—C(4)	1.4038 (2)

C(1)—O(1)—C(9)	121.77 (1)	C(6)—C(5)—H(5)	118.94
C(10)—O(3)—H(3A)	106.22	C(1)—C(6)—C(5)	118.72 (1)
O(1)—C(1)—C(2)	117.13 (1)	C(1)—C(6)—C(7)	118.23 (1)
O(1)—C(1)—C(6)	120.89 (1)	C(5)—C(6)—C(7)	123.03 (1)
C(2)—C(1)—C(6)	121.99 (1)	C(6)—C(7)—C(8)	120.38 (1)
C(1)—C(2)—C(3)	118.18 (1)	C(6)—C(7)—H(7)	118.98
C(1)—C(2)—H(2)	121.58	C(8)—C(7)—H(7)	120.60
C(3)—C(2)—H(2)	120.23	C(7)—C(8)—C(9)	119.77 (1)
C(2)—C(3)—C(4)	121.12 (1)	C(7)—C(8)—C(10)	120.12 (1)
C(2)—C(3)—H(3)	118.41	C(9)—C(8)—C(10)	120.11 (1)
C(4)—C(3)—H(3)	120.47	O(1)—C(9)—O(2)	116.73 (1)
C(3)—C(4)—C(5)	119.88 (1)	O(1)—C(9)—C(8)	118.81 (1)
C(3)—C(4)—H(4)	121.35	O(2)—C(9)—C(8)	124.44 (1)
C(5)—C(4)—H(4)	118.77	O(3)—C(10)—O(4)	120.85 (2)
C(4)—C(5)—C(6)	120.10 (1)	O(3)—C(10)—C(8)	116.85 (1)
C(4)—C(5)—H(5)	120.95	O(4)—C(10)—C(8)	122.29 (1)

C(1)—O(1)—C(9)—O(2)	−177.83 (2)	H(3)—C(3)—C(4)—H(4)	−0.84
C(9)—O(1)—C(1)—C(2)	175.56 (2)	C(3)—C(4)—C(5)—C(6)	0.08 (1)
C(9)—O(1)—C(1)—C(6)	−4.49 (1)	C(3)—C(4)—C(5)—H(5)	179.41
C(1)—O(1)—C(9)—C(8)	3.66 (1)	H(4)—C(4)—C(5)—C(6)	−179.11
H(3A)—O(2)—C(9)—O(1)	176.76	H(4)—C(4)—C(5)—H(5)	0.22
C(9)—O(2)—H(3A)—O(3)	12.53	C(4)—C(5)—C(6)—C(1)	−0.61 (1)
H(3A)—O(2)—C(9)—C(8)	−4.82	C(4)—C(5)—C(6)—C(7)	177.96 (2)
C(10)—O(3)—H(3A)—O(2)	−8.67	H(5)—C(5)—C(6)—C(1)	−179.95
H(3A)—O(3)—C(10)—O(4)	178.28	H(5)—C(5)—C(6)—C(7)	−1.39
H(3A)—O(3)—C(10)—C(8)	−1.35	C(1)—C(6)—C(7)—C(8)	0.73 (1)
O(1)—C(1)—C(2)—C(3)	179.54 (2)	C(1)—C(6)—C(7)—H(7)	−176.92
O(1)—C(1)—C(2)—H(2)	−1.43	C(5)—C(6)—C(7)—C(8)	−177.84 (2)
O(1)—C(1)—C(6)—C(5)	−179.16 (2)	C(5)—C(6)—C(7)—H(7)	4.51
O(1)—C(1)—C(6)—C(7)	2.20 (1)	C(6)—C(7)—C(8)—C(9)	−1.47 (1)
C(6)—C(1)—C(2)—C(3)	−0.42 (1)	C(6)—C(7)—C(8)—C(10)	178.39 (2)
C(2)—C(1)—C(6)—C(5)	0.79 (1)	H(7)—C(7)—C(8)—C(9)	176.14
C(2)—C(1)—C(6)—C(7)	−177.84 (2)	H(7)—C(7)—C(8)—C(10)	−4.00
C(6)—C(1)—C(2)—H(2)	178.62	C(7)—C(8)—C(9)—O(1)	−0.67 (1)
C(1)—C(2)—C(3)—C(4)	−0.14 (1)	C(7)—C(8)—C(9)—O(2)	−179.05 (2)
C(1)—C(2)—C(3)—H(3)	−179.82	C(7)—C(8)—C(10)—O(3)	−176.21 (2)
H(2)—C(2)—C(3)—C(4)	−179.18	C(7)—C(8)—C(10)—O(4)	4.16 (2)
H(2)—C(2)—C(3)—H(3)	1.13	C(10)—C(8)—C(9)—O(1)	179.47 (2)
C(2)—C(3)—C(4)—C(5)	0.30 (1)	C(10)—C(8)—C(9)—O(2)	1.09 (1)
C(2)—C(3)—C(4)—H(4)	179.48	C(9)—C(8)—C(10)—O(3)	3.65 (2)
H(3)—C(3)—C(4)—C(5)	179.98	C(9)—C(8)—C(10)—O(4)	−175.98 (2)

Experimental details

	(1a)	(2a)
Crystal data
Chemical formula	C₉H₈O₂	C₁₀H₆O₄
M_r	148.15	190.15
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	100	100
a, b, c (Å)	5.5504 (1), 17.5427 (1), 7.7161 (1)	11.1992 (1), 5.4662 (1), 13.7267 (2)
β (°)	96.296 (1)	107.256 (1)
V (Å³)	746.78 (2)	802.49 (2)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.09	0.12
Crystal size (mm)	0.57 × 0.36 × 0.10	0.60 × 0.52 × 0.29

Data collection
Diffractometer	Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer	Goniometer Xcalibur, detector: Atlas (Gemini ultra Mo) diffractometer
Absorption correction	Multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	Multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.18 (release 23-07-2008 CrysAlis171 .NET) (compiled Jul 23 2008,18:57:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
T_min, T_max	0.911, 0.990	0.891, 0.965
No. of measured, independent and observed [I > 3 σ(I)] reflections	70528, 6591, 4859	147662, 11309, 8933
R_int	0.023	0.023
(sin θ/λ)_max (Å⁻¹)	1.020	1.190

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.014, 1.74	0.016, 0.014, 1.67
No. of reflections	4859	8933
No. of parameters	295	367
H-atom treatment	Only H-atom displacement parameters refined	?
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.13	0.15, −0.14

Computer programs: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.5 (release 18-04-2008 CrysAlis171 .NET) (compiled Apr 18 2008,18:17:43), SHELXS97 (Sheldrick, 1990), SHELXS97 (Sheldrick, 1998), Volkov et al., (2006).

Selected geometric parameters (Å, º) for (1a) top

O(1)—C(9)	1.3087 (4)	C(4)—C(5)	1.3926 (4)
O(2)—C(9)	1.2447 (4)	C(5)—C(6)	1.4024 (3)
C(1)—C(2)	1.3911 (3)	C(6)—C(7)	1.4630 (3)
C(1)—C(6)	1.4038 (3)	C(7)—C(8)	1.3446 (3)
C(2)—C(3)	1.3943 (4)	C(8)—C(9)	1.4690 (3)
C(3)—C(4)	1.3946 (4)

C(2)—C(1)—C(6)	120.44 (2)	C(5)—C(6)—C(7)	118.97 (2)
C(1)—C(2)—C(3)	120.43 (3)	C(6)—C(7)—C(8)	126.05 (2)
C(2)—C(3)—C(4)	119.66 (3)	C(7)—C(8)—C(9)	122.16 (2)
C(3)—C(4)—C(5)	120.01 (2)	O(1)—C(9)—O(2)	123.32 (3)
C(4)—C(5)—C(6)	120.81 (2)	O(1)—C(9)—C(8)	116.54 (3)
C(1)—C(6)—C(5)	118.64 (2)	O(2)—C(9)—C(8)	120.15 (2)
C(1)—C(6)—C(7)	122.39 (2)

H(1A)—O(1)—C(9)—O(2)	−2.92	C(3)—C(4)—C(5)—H(5)	−178.93
H(1A)—O(1)—C(9)—C(8)	177.31	H(4)—C(4)—C(5)—C(6)	179.95
C(6)—C(1)—C(2)—C(3)	−0.05 (3)	H(4)—C(4)—C(5)—H(5)	0.74
C(2)—C(1)—C(6)—C(5)	−0.20 (2)	C(4)—C(5)—C(6)—C(1)	0.09 (2)
C(2)—C(1)—C(6)—C(7)	−179.85 (4)	C(4)—C(5)—C(6)—C(7)	179.75 (4)
C(6)—C(1)—C(2)—H(2)	−179.82	H(5)—C(5)—C(6)—C(1)	179.28
H(1)—C(1)—C(2)—C(3)	177.72	H(5)—C(5)—C(6)—C(7)	−1.06
H(1)—C(1)—C(2)—H(2)	−2.05	C(1)—C(6)—C(7)—C(8)	4.06 (2)
H(1)—C(1)—C(6)—C(5)	−177.99	C(1)—C(6)—C(7)—H(7)	−177.03
H(1)—C(1)—C(6)—C(7)	2.36	C(5)—C(6)—C(7)—C(8)	−175.58 (4)
C(1)—C(2)—C(3)—C(4)	0.43 (3)	C(5)—C(6)—C(7)—H(7)	3.32
C(1)—C(2)—C(3)—H(3)	−179.84	C(6)—C(7)—C(8)—C(9)	179.17 (4)
H(2)—C(2)—C(3)—C(4)	−179.81	C(6)—C(7)—C(8)—H(8)	−0.02
H(2)—C(2)—C(3)—H(3)	−0.07	H(7)—C(7)—C(8)—C(9)	0.32
C(2)—C(3)—C(4)—C(5)	−0.54 (3)	H(7)—C(7)—C(8)—H(8)	−178.87
C(2)—C(3)—C(4)—H(4)	179.80	C(7)—C(8)—C(9)—O(1)	2.88 (3)
H(3)—C(3)—C(4)—C(5)	179.72	C(7)—C(8)—C(9)—O(2)	−176.90 (4)
H(3)—C(3)—C(4)—H(4)	0.06	H(8)—C(8)—C(9)—O(1)	−177.91
C(3)—C(4)—C(5)—C(6)	0.28 (3)	H(8)—C(8)—C(9)—O(2)	2.31

Selected geometric parameters (Å, º) for (2a) top

O(1)—C(1)	1.3729 (2)	C(3)—C(4)	1.4038 (2)
O(1)—C(9)	1.3515 (2)	C(4)—C(5)	1.3853 (2)
O(2)—C(9)	1.2263 (2)	C(5)—C(6)	1.4071 (2)
O(3)—C(10)	1.3302 (2)	C(6)—C(7)	1.4292 (2)
O(4)—C(10)	1.2142 (2)	C(7)—C(8)	1.3591 (2)
C(1)—C(2)	1.3910 (2)	C(8)—C(9)	1.4559 (2)
C(1)—C(6)	1.3998 (2)	C(8)—C(10)	1.4950 (2)
C(2)—C(3)	1.3921 (2)

C(1)—O(1)—C(9)	121.77 (1)	C(6)—C(7)—C(8)	120.38 (1)
O(1)—C(1)—C(2)	117.13 (1)	C(7)—C(8)—C(9)	119.77 (1)
O(1)—C(1)—C(6)	120.89 (1)	C(7)—C(8)—C(10)	120.12 (1)
C(2)—C(1)—C(6)	121.99 (1)	C(9)—C(8)—C(10)	120.11 (1)
C(1)—C(2)—C(3)	118.18 (1)	O(1)—C(9)—O(2)	116.73 (1)
C(2)—C(3)—C(4)	121.12 (1)	O(1)—C(9)—C(8)	118.81 (1)
C(3)—C(4)—C(5)	119.88 (1)	O(2)—C(9)—C(8)	124.44 (1)
C(4)—C(5)—C(6)	120.10 (1)	O(3)—C(10)—O(4)	120.85 (2)
C(1)—C(6)—C(5)	118.72 (1)	O(3)—C(10)—C(8)	116.85 (1)
C(1)—C(6)—C(7)	118.23 (1)	O(4)—C(10)—C(8)	122.29 (1)
C(5)—C(6)—C(7)	123.03 (1)

C(1)—O(1)—C(9)—O(2)	−177.83 (2)	H(3)—C(3)—C(4)—H(4)	−0.84
C(9)—O(1)—C(1)—C(2)	175.56 (2)	C(3)—C(4)—C(5)—C(6)	0.08 (1)
C(9)—O(1)—C(1)—C(6)	−4.49 (1)	C(3)—C(4)—C(5)—H(5)	179.41
C(1)—O(1)—C(9)—C(8)	3.66 (1)	H(4)—C(4)—C(5)—C(6)	−179.11
H(3A)—O(2)—C(9)—O(1)	176.76	H(4)—C(4)—C(5)—H(5)	0.22
C(9)—O(2)—H(3A)—O(3)	12.53	C(4)—C(5)—C(6)—C(1)	−0.61 (1)
H(3A)—O(2)—C(9)—C(8)	−4.82	C(4)—C(5)—C(6)—C(7)	177.96 (2)
C(10)—O(3)—H(3A)—O(2)	−8.67	H(5)—C(5)—C(6)—C(1)	−179.95
H(3A)—O(3)—C(10)—O(4)	178.28	H(5)—C(5)—C(6)—C(7)	−1.39
H(3A)—O(3)—C(10)—C(8)	−1.35	C(1)—C(6)—C(7)—C(8)	0.73 (1)
O(1)—C(1)—C(2)—C(3)	179.54 (2)	C(1)—C(6)—C(7)—H(7)	−176.92
O(1)—C(1)—C(2)—H(2)	−1.43	C(5)—C(6)—C(7)—C(8)	−177.84 (2)
O(1)—C(1)—C(6)—C(5)	−179.16 (2)	C(5)—C(6)—C(7)—H(7)	4.51
O(1)—C(1)—C(6)—C(7)	2.20 (1)	C(6)—C(7)—C(8)—C(9)	−1.47 (1)
C(6)—C(1)—C(2)—C(3)	−0.42 (1)	C(6)—C(7)—C(8)—C(10)	178.39 (2)
C(2)—C(1)—C(6)—C(5)	0.79 (1)	H(7)—C(7)—C(8)—C(9)	176.14
C(2)—C(1)—C(6)—C(7)	−177.84 (2)	H(7)—C(7)—C(8)—C(10)	−4.00
C(6)—C(1)—C(2)—H(2)	178.62	C(7)—C(8)—C(9)—O(1)	−0.67 (1)
C(1)—C(2)—C(3)—C(4)	−0.14 (1)	C(7)—C(8)—C(9)—O(2)	−179.05 (2)
C(1)—C(2)—C(3)—H(3)	−179.82	C(7)—C(8)—C(10)—O(3)	−176.21 (2)
H(2)—C(2)—C(3)—C(4)	−179.18	C(7)—C(8)—C(10)—O(4)	4.16 (2)
H(2)—C(2)—C(3)—H(3)	1.13	C(10)—C(8)—C(9)—O(1)	179.47 (2)
C(2)—C(3)—C(4)—C(5)	0.30 (1)	C(10)—C(8)—C(9)—O(2)	1.09 (1)
C(2)—C(3)—C(4)—H(4)	179.48	C(9)—C(8)—C(10)—O(3)	3.65 (2)
H(3)—C(3)—C(4)—C(5)	179.98	C(9)—C(8)—C(10)—O(4)	−175.98 (2)

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