6,8-Di­chloro-4-oxochromene-3-carbalde­hyde

Ishikawa, Y.; Motohashi, Y.

doi:10.1107/S1600536813022228

organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1416

doi:10.1107/S1600536813022228

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6,8-Dichloro-4-oxochromene-3-carbaldehyde

Yoshinobu Ishikawa ^a ^* and Yuya Motohashi ^a

^aSchool of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan
^*Correspondence e-mail: ishi206@u-shizuoka-ken.ac.jp

(Received 19 July 2013; accepted 8 August 2013; online 14 August 2013)

The asymmetric unit of the title compound, C₁₀H₄Cl₂O₃, contain two essentially planar independent molecules (mean atomic deviations from the corresponding least-square planes are 0.041 and 0.045 Å for molecules 1 and 2, respectively). In the crystal, molecules are linked through a pair of halogen bonds [Cl⋯O separations are 3.044 (5) and 3.033 (6) Å, C—Cl⋯O angles are 160.4 (3) and 162.8 (3)°, and C=O⋯Cl angles are 138.7 (4) and 139.6 (4)°, respectively, in molecules 1 and 2] and C—H⋯O hydrogen bonds into slightly folded bands [the dihedral angle between the planes of neighboring molecules is 8.6 (2)°] along the c-axis direction.

Related literature

For the biological activity of the title and related compounds, see: Shim et al. (2003 ); Kawase et al. (2007 ); Dückert et al. (2012 ). For related structures, see: Ishikawa et al. (2013a ,b ). For halogen bonding, see: Auffinger et al. (2004 ); Metrangolo et al. (2005 ); Wilcken et al. (2013 ).

Experimental

Crystal data

C₁₀H₄Cl₂O₃
M_r = 243.05
Triclinic, $[P \overline 1]$
a = 8.288 (8) Å
b = 8.325 (7) Å
c = 13.706 (7) Å
α = 96.55 (6)°
β = 92.23 (7)°
γ = 101.98 (7)°
V = 917.2 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 100 K
0.42 × 0.22 × 0.08 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.841, T_max = 0.947
5130 measured reflections
4203 independent reflections
2596 reflections with F² > 2σ(F²)
R_int = 0.057
3 standard reflections every 150 reflections intensity decay: 4.9%

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.212
S = 1.10
4203 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4bⁱ—H2bⁱ⋯O2a	0.95	2.35	3.246 (8)	157
C4a—H2a⋯O2bⁱ	0.95	2.35	3.259 (8)	160
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: WinAFC (Rigaku, 1999 $[Rigaku (1999). WinAFC Diffractometer Control Software. Rigaku Corporation, Tokyo, Japan.]$ ); cell refinement: WinAFC; data reduction: WinAFC; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536813022228/ld2111sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813022228/ld2111Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813022228/ld2111Isup3.cml

checkCIF report

Comment top

6,8-Dichloro-3-formylchromone shows many biological functions such as protein tyrosine phosphatase inhibitory (Shim et al. 2003), tumor cell-cytotoxic, anti-HIV, anti-Helicobacter pylori, and urease inhibitory activities (Kawase et al. 2007). In addition, it is used as a starting material for the synthesis of biologically relevant molecules (Dückert et al. 2012).

The title compound, C₁₀H₄Cl₂O₃, crystallizes with two independent molecules in the asymmetric unit (Fig. 1). The mean deviations from the least-square planes for all atoms of molecule 1 and 2 are 0.0410 Å and 0.0449 Å, respectively. In addition, the largest deviations of molecule 1 and 2 are 0.1512 (17) Å for Cl1a and -0.0973 Å for H4b, respectively. This means that all atoms of each molecule are essentially coplanar.

In the crystal, the molecules 1 and 2 are linked to each other through intermolecular interactions of the Cl atoms at the 8-position with the O atoms of the formyl groups [Cl2a···O3bⁱ; 3.033 (6) Å, Cl2bⁱ···O3a; 3.044 (5) Å, C7a–Cl2a···O3bⁱ = 160.4 (3)°, C7bⁱ–Cl2bⁱ···O3a =162.8 (3)°, C10a–O3a···Cl2bⁱ = 138.7 (4)°, C10bⁱ–O3bⁱ···Cl2a = 139.6 (4)° (i): -x + 1, -y + 1, -z + 1], and the carbonyl O atoms at the 4-position with the C–H atoms at the 5-position. The short contacts and the geometries involved in the Cl atoms fall into halogen bonding (Auffinger et al. 2004). Due to these halogen and hydrogen bonds, the molecules form wavy bands along c axis, as shown in Fig. 2.

Halogen bonds have been found to occur in organic, inorganic, and biological systems, and have recently attracted much attention in medicinal chemistry, chemical biology, and supramolecular chemistry (Auffinger et al. 2004, Metrangolo et al. 2005, Wilcken et al. 2013). Our analysis suggests that the strong inhibitory activity of the title compound against urease may be attributable to the halogen bond observed in the crystal, because 3-formylchromones without any halogen atom at the 8-position in the literature do not show the urease inhibitory activity (Kawase et al. 2007).

Related literature top

For the biological activity of the title and related compounds, see: Shim et al. (2003); Kawase et al. (2007); Dückert et al. (2012). For related structures, see: Ishikawa et al. (2013a,b). For halogen bonding, see: Auffinger et al. (2004); Metrangolo et al. (2005); Wilcken et al. (2013).

Experimental top

Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a 2-butanone solution of commercially available 6,8-dichloro-3-formylchromone at room temperature.

Computing details top

Data collection: WinAFC (Rigaku, 1999); cell refinement: WinAFC (Rigaku, 1999); data reduction: WinAFC (Rigaku, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are shown as small spheres of arbitrary radius.
	Fig. 2. A view of the intermolecular interactions of the title compound, represented as dashed green lines for Cl···O and dashed magenta lines for C–H···O interactions.

6,8-Dichloro-4-oxochromene-3-carbaldehyde top

Crystal data top

C₁₀H₄Cl₂O₃	Z = 4
M_r = 243.05	F(000) = 488.00
Triclinic, P1	D_x = 1.760 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.288 (8) Å	Cell parameters from 23 reflections
b = 8.325 (7) Å	θ = 15.2–17.4°
c = 13.706 (7) Å	µ = 0.68 mm⁻¹
α = 96.55 (6)°	T = 100 K
β = 92.23 (7)°	Prismatic, colourless
γ = 101.98 (7)°	0.42 × 0.22 × 0.08 mm
V = 917.2 (13) Å³

Data collection top

Rigaku AFC-7R diffractometer	R_int = 0.057
ω–2θ scans	θ_max = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −10→6
T_min = 0.841, T_max = 0.947	k = −10→10
5130 measured reflections	l = −17→17
4203 independent reflections	3 standard reflections every 150 reflections
2596 reflections with F² > 2σ(F²)	intensity decay: 4.9%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0531P)² + 6.620P] where P = (F_o² + 2F_c²)/3
4203 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.79 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₀H₄Cl₂O₃	γ = 101.98 (7)°
M_r = 243.05	V = 917.2 (13) Å³
Triclinic, P1	Z = 4
a = 8.288 (8) Å	Mo Kα radiation
b = 8.325 (7) Å	µ = 0.68 mm⁻¹
c = 13.706 (7) Å	T = 100 K
α = 96.55 (6)°	0.42 × 0.22 × 0.08 mm
β = 92.23 (7)°

Data collection top

Rigaku AFC-7R diffractometer	2596 reflections with F² > 2σ(F²)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.057
T_min = 0.841, T_max = 0.947	3 standard reflections every 150 reflections
5130 measured reflections	intensity decay: 4.9%
4203 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.212	H-atom parameters constrained
S = 1.10	Δρ_max = 0.70 e Å⁻³
4203 reflections	Δρ_min = −0.79 e Å⁻³
271 parameters

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Cl1a	0.9284 (2)	0.7180 (2)	−0.05206 (12)	0.0275 (4)
Cl2a	0.8997 (2)	0.60177 (19)	0.32529 (11)	0.0243 (4)
Cl1b	0.8654 (3)	1.0637 (2)	0.20783 (12)	0.0293 (4)
Cl2b	0.7665 (2)	1.01839 (19)	0.59010 (11)	0.0246 (4)
O1a	0.6255 (6)	0.3339 (5)	0.2521 (3)	0.0218 (10)
O2a	0.4506 (6)	0.1743 (6)	−0.0336 (4)	0.0277 (11)
O3a	0.2398 (7)	−0.0767 (6)	0.1869 (4)	0.0319 (12)
O1b	0.4940 (6)	0.7493 (6)	0.5162 (3)	0.0219 (10)
O2b	0.3559 (6)	0.5491 (6)	0.2305 (3)	0.0291 (11)
O3b	0.1021 (7)	0.3424 (6)	0.4522 (4)	0.0326 (12)
C1a	0.4980 (8)	0.2042 (8)	0.2288 (5)	0.0221 (13)
C2a	0.4342 (8)	0.1454 (8)	0.1358 (5)	0.0197 (13)
C3a	0.5023 (8)	0.2255 (8)	0.0520 (5)	0.0217 (13)
C4a	0.7126 (9)	0.4638 (8)	0.0063 (5)	0.0242 (14)
C5a	0.8382 (8)	0.5956 (8)	0.0344 (5)	0.0201 (13)
C6a	0.9020 (8)	0.6399 (8)	0.1321 (5)	0.0202 (13)
C7a	0.8290 (8)	0.5497 (8)	0.2026 (5)	0.0197 (13)
C8a	0.6945 (8)	0.4171 (8)	0.1770 (5)	0.0202 (13)
C9a	0.6370 (9)	0.3695 (8)	0.0784 (5)	0.0207 (13)
C10a	0.2954 (9)	−0.0026 (8)	0.1204 (5)	0.0250 (14)
C1b	0.3630 (8)	0.6197 (8)	0.4918 (5)	0.0220 (13)
C2b	0.3130 (8)	0.5479 (8)	0.4003 (5)	0.0217 (13)
C3b	0.3958 (8)	0.6127 (8)	0.3161 (5)	0.0214 (13)
C4b	0.6216 (8)	0.8361 (8)	0.2689 (5)	0.0220 (13)
C5b	0.7526 (8)	0.9654 (8)	0.2961 (5)	0.0227 (14)
C6b	0.8016 (9)	1.0234 (8)	0.3958 (5)	0.0234 (14)
C7b	0.7127 (8)	0.9495 (8)	0.4674 (5)	0.0217 (13)
C8b	0.5792 (8)	0.8170 (8)	0.4411 (5)	0.0188 (13)
C9b	0.5333 (8)	0.7557 (8)	0.3414 (5)	0.0190 (13)
C10b	0.1768 (9)	0.4034 (8)	0.3852 (5)	0.0238 (14)
H1a	0.4491	0.1499	0.2811	0.0265*
H2a	0.6755	0.4349	−0.0611	0.0290*
H3a	0.9933	0.7302	0.1493	0.0243*
H4a	0.2484	−0.0406	0.0555	0.0300*
H1b	0.3024	0.5769	0.5440	0.0264*
H2b	0.5904	0.8006	0.2012	0.0264*
H3b	0.8945	1.1120	0.4131	0.0281*
H4b	0.1440	0.3536	0.3196	0.0286*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1a	0.0338 (9)	0.0277 (9)	0.0216 (8)	0.0044 (7)	0.0053 (7)	0.0088 (6)
Cl2a	0.0312 (9)	0.0231 (8)	0.0166 (7)	0.0037 (7)	−0.0028 (6)	−0.0007 (6)
Cl1b	0.0345 (10)	0.0287 (9)	0.0246 (8)	0.0034 (8)	0.0082 (7)	0.0071 (7)
Cl2b	0.0311 (9)	0.0232 (8)	0.0171 (7)	0.0031 (7)	−0.0008 (6)	−0.0016 (6)
O1a	0.034 (3)	0.019 (3)	0.012 (2)	0.0034 (19)	0.0043 (18)	0.0014 (16)
O2a	0.035 (3)	0.032 (3)	0.014 (3)	0.005 (3)	−0.0023 (19)	−0.0005 (18)
O3a	0.037 (3)	0.030 (3)	0.023 (3)	−0.005 (3)	0.006 (2)	0.002 (2)
O1b	0.029 (3)	0.021 (3)	0.014 (2)	0.0013 (19)	0.0014 (18)	0.0028 (17)
O2b	0.035 (3)	0.035 (3)	0.014 (3)	0.003 (3)	−0.0017 (19)	−0.0023 (19)
O3b	0.036 (3)	0.032 (3)	0.025 (3)	−0.007 (3)	−0.002 (3)	0.005 (2)
C1a	0.025 (4)	0.022 (4)	0.020 (3)	0.006 (3)	0.001 (3)	0.004 (3)
C2a	0.020 (4)	0.021 (3)	0.018 (3)	0.005 (3)	0.003 (3)	0.001 (3)
C3a	0.026 (4)	0.020 (3)	0.019 (3)	0.007 (3)	−0.001 (3)	−0.001 (3)
C4a	0.033 (4)	0.025 (4)	0.013 (3)	0.003 (3)	0.003 (3)	0.004 (3)
C5a	0.028 (4)	0.019 (3)	0.017 (3)	0.010 (3)	0.007 (3)	0.006 (3)
C6a	0.025 (4)	0.017 (3)	0.019 (3)	0.004 (3)	0.003 (3)	0.002 (3)
C7a	0.025 (4)	0.020 (3)	0.014 (3)	0.006 (3)	−0.001 (3)	−0.001 (3)
C8a	0.024 (4)	0.019 (3)	0.017 (3)	0.004 (3)	0.002 (3)	0.004 (3)
C9a	0.030 (4)	0.018 (3)	0.015 (3)	0.009 (3)	0.002 (3)	0.001 (3)
C10a	0.030 (4)	0.019 (3)	0.024 (4)	0.004 (3)	−0.002 (3)	−0.001 (3)
C1b	0.027 (4)	0.019 (3)	0.021 (3)	0.006 (3)	0.004 (3)	0.002 (3)
C2b	0.023 (4)	0.025 (4)	0.018 (3)	0.007 (3)	−0.001 (3)	0.002 (3)
C3b	0.028 (4)	0.022 (4)	0.017 (3)	0.011 (3)	−0.000 (3)	0.002 (3)
C4b	0.027 (4)	0.021 (3)	0.018 (3)	0.004 (3)	0.004 (3)	0.002 (3)
C5b	0.028 (4)	0.023 (4)	0.022 (4)	0.012 (3)	0.006 (3)	0.008 (3)
C6b	0.027 (4)	0.020 (4)	0.022 (4)	0.004 (3)	−0.003 (3)	0.001 (3)
C7b	0.026 (4)	0.024 (4)	0.016 (3)	0.010 (3)	−0.000 (3)	0.001 (3)
C8b	0.023 (4)	0.024 (4)	0.014 (3)	0.013 (3)	0.005 (3)	0.006 (3)
C9b	0.020 (3)	0.023 (3)	0.017 (3)	0.013 (3)	0.000 (3)	0.003 (3)
C10b	0.031 (4)	0.019 (3)	0.020 (3)	0.004 (3)	0.004 (3)	0.000 (3)

Geometric parameters (Å, º) top

Cl1a—C5a	1.740 (7)	C7a—C8a	1.398 (8)
Cl2a—C7a	1.735 (6)	C8a—C9a	1.401 (9)
Cl1b—C5b	1.733 (7)	C1b—C2b	1.338 (9)
Cl2b—C7b	1.723 (6)	C2b—C3b	1.464 (9)
O1a—C1a	1.344 (7)	C2b—C10b	1.458 (9)
O1a—C8a	1.381 (8)	C3b—C9b	1.465 (8)
O2a—C3a	1.229 (8)	C4b—C5b	1.367 (9)
O3a—C10a	1.210 (9)	C4b—C9b	1.405 (9)
O1b—C1b	1.363 (7)	C5b—C6b	1.411 (9)
O1b—C8b	1.379 (8)	C6b—C7b	1.376 (10)
O2b—C3b	1.233 (7)	C7b—C8b	1.393 (8)
O3b—C10b	1.227 (9)	C8b—C9b	1.412 (8)
C1a—C2a	1.356 (9)	C1a—H1a	0.950
C2a—C3a	1.467 (9)	C4a—H2a	0.950
C2a—C10a	1.490 (9)	C6a—H3a	0.950
C3a—C9a	1.459 (9)	C10a—H4a	0.950
C4a—C5a	1.355 (9)	C1b—H1b	0.950
C4a—C9a	1.416 (9)	C4b—H2b	0.950
C5a—C6a	1.401 (9)	C6b—H3b	0.950
C6a—C7a	1.373 (9)	C10b—H4b	0.950

C1a—O1a—C8a	118.3 (5)	C5b—C4b—C9b	119.9 (6)
C1b—O1b—C8b	118.1 (5)	Cl1b—C5b—C4b	120.6 (5)
O1a—C1a—C2a	124.6 (6)	Cl1b—C5b—C6b	117.6 (5)
C1a—C2a—C3a	120.4 (6)	C4b—C5b—C6b	121.9 (6)
C1a—C2a—C10a	118.9 (6)	C5b—C6b—C7b	118.9 (6)
C3a—C2a—C10a	120.7 (6)	Cl2b—C7b—C6b	120.4 (5)
O2a—C3a—C2a	122.6 (6)	Cl2b—C7b—C8b	119.6 (5)
O2a—C3a—C9a	122.9 (6)	C6b—C7b—C8b	120.0 (6)
C2a—C3a—C9a	114.5 (5)	O1b—C8b—C7b	117.3 (5)
C5a—C4a—C9a	119.4 (6)	O1b—C8b—C9b	121.6 (5)
Cl1a—C5a—C4a	120.3 (5)	C7b—C8b—C9b	121.1 (6)
Cl1a—C5a—C6a	117.0 (5)	C3b—C9b—C4b	121.9 (6)
C4a—C5a—C6a	122.7 (6)	C3b—C9b—C8b	119.8 (6)
C5a—C6a—C7a	118.3 (6)	C4b—C9b—C8b	118.2 (5)
Cl2a—C7a—C6a	120.3 (5)	O3b—C10b—C2b	123.8 (6)
Cl2a—C7a—C8a	119.0 (5)	O1a—C1a—H1a	117.700
C6a—C7a—C8a	120.6 (6)	C2a—C1a—H1a	117.702
O1a—C8a—C7a	117.4 (5)	C5a—C4a—H2a	120.314
O1a—C8a—C9a	122.2 (5)	C9a—C4a—H2a	120.307
C7a—C8a—C9a	120.4 (6)	C5a—C6a—H3a	120.850
C3a—C9a—C4a	121.6 (6)	C7a—C6a—H3a	120.844
C3a—C9a—C8a	119.9 (6)	O3a—C10a—H4a	118.481
C4a—C9a—C8a	118.5 (6)	C2a—C10a—H4a	118.489
O3a—C10a—C2a	123.0 (6)	O1b—C1b—H1b	117.382
O1b—C1b—C2b	125.2 (6)	C2b—C1b—H1b	117.374
C1b—C2b—C3b	120.2 (6)	C5b—C4b—H2b	120.070
C1b—C2b—C10b	119.4 (6)	C9b—C4b—H2b	120.068
C3b—C2b—C10b	120.3 (6)	C5b—C6b—H3b	120.568
O2b—C3b—C2b	122.6 (6)	C7b—C6b—H3b	120.567
O2b—C3b—C9b	122.5 (6)	O3b—C10b—H4b	118.104
C2b—C3b—C9b	114.9 (5)	C2b—C10b—H4b	118.102

C1a—O1a—C8a—C7a	−178.8 (6)	O1a—C8a—C9a—C3a	−1.4 (10)
C1a—O1a—C8a—C9a	−0.7 (9)	O1a—C8a—C9a—C4a	178.7 (6)
C8a—O1a—C1a—C2a	1.9 (10)	C7a—C8a—C9a—C3a	176.7 (6)
C8a—O1a—C1a—H1a	−178.1	C7a—C8a—C9a—C4a	−3.2 (10)
C1b—O1b—C8b—C7b	180.0 (6)	O1b—C1b—C2b—C3b	−2.9 (11)
C1b—O1b—C8b—C9b	0.3 (9)	O1b—C1b—C2b—C10b	176.3 (6)
C8b—O1b—C1b—C2b	2.5 (10)	H1b—C1b—C2b—C3b	177.1
C8b—O1b—C1b—H1b	−177.5	H1b—C1b—C2b—C10b	−3.7
O1a—C1a—C2a—C3a	−1.0 (11)	C1b—C2b—C3b—O2b	178.7 (7)
O1a—C1a—C2a—C10a	178.3 (6)	C1b—C2b—C3b—C9b	0.7 (10)
H1a—C1a—C2a—C3a	179.0	C1b—C2b—C10b—O3b	0.7 (11)
H1a—C1a—C2a—C10a	−1.7	C1b—C2b—C10b—H4b	−179.3
C1a—C2a—C3a—O2a	178.4 (7)	C3b—C2b—C10b—O3b	179.9 (7)
C1a—C2a—C3a—C9a	−1.1 (10)	C3b—C2b—C10b—H4b	−0.1
C1a—C2a—C10a—O3a	−2.4 (11)	C10b—C2b—C3b—O2b	−0.4 (11)
C1a—C2a—C10a—H4a	177.6	C10b—C2b—C3b—C9b	−178.5 (6)
C3a—C2a—C10a—O3a	176.9 (7)	O2b—C3b—C9b—C4b	4.2 (11)
C3a—C2a—C10a—H4a	−3.1	O2b—C3b—C9b—C8b	−176.2 (6)
C10a—C2a—C3a—O2a	−0.9 (11)	C2b—C3b—C9b—C4b	−177.7 (6)
C10a—C2a—C3a—C9a	179.7 (6)	C2b—C3b—C9b—C8b	1.8 (9)
O2a—C3a—C9a—C4a	2.6 (11)	C5b—C4b—C9b—C3b	−177.7 (6)
O2a—C3a—C9a—C8a	−177.3 (6)	C5b—C4b—C9b—C8b	2.7 (10)
C2a—C3a—C9a—C4a	−178.0 (6)	C9b—C4b—C5b—Cl1b	178.8 (6)
C2a—C3a—C9a—C8a	2.2 (10)	C9b—C4b—C5b—C6b	−0.9 (11)
C5a—C4a—C9a—C3a	−179.4 (6)	H2b—C4b—C5b—Cl1b	−1.2
C5a—C4a—C9a—C8a	0.5 (11)	H2b—C4b—C5b—C6b	179.1
C9a—C4a—C5a—Cl1a	−177.7 (6)	H2b—C4b—C9b—C3b	2.3
C9a—C4a—C5a—C6a	2.5 (11)	H2b—C4b—C9b—C8b	−177.3
H2a—C4a—C5a—Cl1a	2.3	Cl1b—C5b—C6b—C7b	179.0 (5)
H2a—C4a—C5a—C6a	−177.5	Cl1b—C5b—C6b—H3b	−1.0
H2a—C4a—C9a—C3a	0.6	C4b—C5b—C6b—C7b	−1.3 (11)
H2a—C4a—C9a—C8a	−179.5	C4b—C5b—C6b—H3b	178.6
Cl1a—C5a—C6a—C7a	177.5 (5)	C5b—C6b—C7b—Cl2b	−179.1 (6)
Cl1a—C5a—C6a—H3a	−2.5	C5b—C6b—C7b—C8b	1.6 (11)
C4a—C5a—C6a—C7a	−2.7 (11)	H3b—C6b—C7b—Cl2b	0.9
C4a—C5a—C6a—H3a	177.3	H3b—C6b—C7b—C8b	−178.4
C5a—C6a—C7a—Cl2a	−178.6 (6)	Cl2b—C7b—C8b—O1b	1.3 (9)
C5a—C6a—C7a—C8a	−0.1 (10)	Cl2b—C7b—C8b—C9b	−179.0 (5)
H3a—C6a—C7a—Cl2a	1.4	C6b—C7b—C8b—O1b	−179.3 (6)
H3a—C6a—C7a—C8a	179.9	C6b—C7b—C8b—C9b	0.3 (11)
Cl2a—C7a—C8a—O1a	−0.3 (9)	O1b—C8b—C9b—C3b	−2.4 (10)
Cl2a—C7a—C8a—C9a	−178.5 (5)	O1b—C8b—C9b—C4b	177.2 (6)
C6a—C7a—C8a—O1a	−178.8 (6)	C7b—C8b—C9b—C3b	178.0 (6)
C6a—C7a—C8a—C9a	3.0 (10)	C7b—C8b—C9b—C4b	−2.5 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4bⁱ—H2bⁱ···O2a	0.95	2.35	3.246 (8)	157
C4a—H2a···O2bⁱ	0.95	2.35	3.259 (8)	160

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4bⁱ—H2bⁱ···O2a	0.95	2.349	3.246 (8)	157
C4a—H2a···O2bⁱ	0.95	2.349	3.259 (8)	160

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

We acknowledge the University of Shizuoka for instrumental support.

References

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