Diospyrin

Harrison, W.T.A.; Musgrave, O.C.

doi:10.1107/S0108270104007826

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 6| June 2004| Pages o399-o401

doi:10.1107/S0108270104007826

Diospyrin

William T. A. Harrison ^a ^* and Oliver C. Musgrave ^a

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 4 March 2004; accepted 31 March 2004; online 11 May 2004)

The structure of the title natural product, 1′,5-dihydroxy-3′,7-dimethyl-2,2′-binaphthalene-1,4,5′,8′-tetrone, C₂₂H₁₄O₆, confirms the atomic connectivity postulated on the basis of spectroscopic data. The geometric parameters are normal and the angle between the planes of the two ring systems is 59.74 (2)°. The crystal packing is influenced by O—H⋯O hydrogen bonds, and possible short C—H⋯O and π–π stacking interactions.

Comment

Diopyrin, C₂₂H₁₄O₆, (I), is an orange–red naphthoquinonylnaphthoquinone that is present in the heartwood of many species of Diospyros (persimmon) trees (Thomson, 1987 ). The potent antimycobacterial properties of diospyrin and its analogues have been investigated by various workers (Lall et al., 2003 , and references therein). Arguments based on NMR spectra (Sidhu & Pardhasaradhi, 1967 , 1970 ; Lillie & Musgrave, 1977 ) indicated that diospyrin has the structure shown in the scheme below, with a 6-2¹ linkage present between the naphthoquinonyl units, and a recent synthesis (Yoshida & Mori, 2000 ) has provided support for this hypothesis. However, the alternative 6-3¹ mode of linkage has never been conclusively disproved. We have now established crystallographically that diospyrin does indeed have the 6-2¹ structure (Fig. 1).

The geometric parameters for (I) (Table 1) are consistent with those reported for other naphthoquinone systems (Lynch & McClenaghan, 2002 ). In the crystal, the two ring systems (C1–C11/O1–O3, with an r.m.s. deviation from the least-squares plane of 0.048 Å, and C12–C22/O5/O6, with an r.m.s. deviation of 0.069 Å) are not coplanar, the angle between their least-squares planes being 59.74 (2)°. The length of the inter-ring C9—C12 bond [1.494 (3) Å] suggests that it is essentially a single bond. A somewhat surprising feature is that the bulky C11 methyl group lies close to atom O4 rather than, as might be expected, close to the much smaller H atom attached to atom C13. As a result, atom O4 is significantly displaced [by 0.387 (3) Å] from the least-squares plane of its naphthoquinonyl unit (C12–C22/O5/O6). Conversely, atom C11 shows no significant deviation [displacement = 0.018 (2) Å] from the C1–C11/O1–O3 least-squares plane.

Both OH groups participate in bifurcated intra/intermolecular hydrogen bonds to C=O acceptors (Table 2). The intramolecular O—H⋯O bonds are much shorter and stronger than the intermolecular links. This difference results in an `unbalanced' hydrogen-bonding network, in which atoms O2 and O5 accept two hydrogen bonds each (one intramolecular and one intermolecular), and atoms O1 and O4 do not accept any conventional hydrogen bonds. Together (Fig. 2), the O—H⋯O bonds generate infinite [010] stacks of molecules of (I), generated by a 2₁ screw axis. A PLATON (Spek, 2003 ) analysis of (I) indicated the possible presence of two short C—H⋯O interactions arising from methyl group H atoms (Table 2), although such interactions are expected to be very weak for such `unactivated' bonds (Desiraju & Steiner, 1999 ). Interestingly, the acceptor atoms are the `underbonded' atoms O1 and O4 (see above). If they are not merely packing artefacts, these C—H⋯O interactions may provide some coherence between adjacent [010] stacks of molecules in the a direction. Possible π–π stacking interactions, with a centroid–centroid separation of less than 4.0 Å, are listed in Table 3. The relatively large value of Δ in each case suggests that these interactions are weak.

The structure shown in Fig. 1 is dissymmetric, but crystal symmetry generates a racemic mixture that is consistent with the lack of optical activity shown by (I) in solution (Lillie et al., 1976 ). The interconversion of the two enantiomeric forms would be expected to occur readily in solution by analogy with the behaviour of trisubstituted biphenyls such as (II) (Adams & Teeter, 1940 ), which undergo rapid racemization in solution. The crystal packing of (I) is shown in Fig. 3.

Figure 1
The asymmetric unit of (I

) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are indicated by dashed lines.

Figure 2
A detail of (I

), showing the [010] stacking resulting from O—H⋯O hydrogen bonds (50% probability displacement ellipsoids). [Symmetry codes: (ii) $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{1 \over 2}]$ − z; (ix) x, 1 + y, z.]

Figure 3
The crystal packing of (I

), projected on to (010) (H atoms have been omitted for clarity).

Experimental

Diospyrin was isolated from Diospyros montana (cf. Lillie et al., 1976) and recrystallized from chloroform as an intense orange powder accompanied by one or two well faceted orange plates.

Crystal data

C₂₂H₁₄O₆
M_r = 374.33
Monoclinic, P2₁/n
a = 13.5603 (10) Å
b = 7.8549 (6) Å
c = 15.8121 (11) Å
β = 101.063 (2)°
V = 1652.9 (2) Å³
Z = 4
D_x = 1.504 Mg m⁻³
Mo Kα radiation
Cell parameters from 2069 reflections
θ = 2.6–25.5°
μ = 0.11 mm⁻¹
T = 293 (2) K
Plate, orange
0.36 × 0.29 × 0.05 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.920, T_max = 0.995
10 116 measured reflections
3091 independent reflections
1739 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 25.6°
h = −16 → 14
k = −9 → 8
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 0.92
3091 reflections
255 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.069P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Selected interatomic distances (Å)

O1—C1	1.214 (3)
O2—C4	1.232 (3)
O3—C10	1.341 (2)
O4—C17	1.218 (2)
O5—C14	1.233 (2)
O6—C18	1.340 (2)
C1—C2	1.471 (3)
C1—C6	1.483 (3)
C2—C3	1.320 (3)
C3—C4	1.480 (3)
C4—C5	1.452 (3)
C5—C10	1.407 (3)
C5—C6	1.409 (3)
C6—C7	1.370 (3)
C7—C8	1.397 (3)
C8—C9	1.391 (3)
C8—C11	1.499 (3)
C9—C10	1.404 (3)
C9—C12	1.494 (3)
C12—C13	1.337 (3)
C12—C17	1.485 (3)
C13—C14	1.468 (3)
C14—C15	1.454 (3)
C15—C18	1.402 (3)
C15—C16	1.408 (3)
C16—C21	1.378 (3)
C16—C17	1.487 (3)
C18—C19	1.381 (3)
C19—C20	1.379 (3)
C20—C21	1.396 (3)
C20—C22	1.504 (3)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O2	0.96	1.77	2.607 (2)	144
O3—H1⋯O5ⁱ	0.96	2.40	2.986 (2)	119
O6—H2⋯O5	0.99	1.78	2.630 (2)	142
O6—H2⋯O2ⁱⁱ	0.99	2.36	2.980 (2)	120
C11—H6⋯O4ⁱⁱⁱ	0.96	2.38	3.331 (3)	170
C22—H12⋯O1^iv	0.96	2.52	3.415 (3)	156
Symmetry codes: (i) $[{\script{1\over 2}}-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ ; (ii) $[{\script{1\over 2}}-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]$ ; (iii) $[{\script{3\over 2}}-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]$ ; (iv) $[{\script{3\over 2}}-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ .

Table 3
π–π stacking interactions in (I)

Cg1 is the centroid of the C1–C6 ring, Cg2 is the centroid of the C5–C10 ring, Cg3 is the centroid of the C12–C17 ring and Cg4 is the centroid of the C15/C16/C18–C21 ring. φ is the dihedral angle (°) between the planes of the rings, d is the distance (Å) between the ring centroids and Δ is the displacement (Å) of the centroid of ring 2 relative to the intersection point of the normal to the centroid of ring 1 and the least-squares plane of ring 2.

Ring 1	Ring 2	φ	d	Δ
Cg1	Cg2^v	0.0	3.9219 (14)	2.15
Cg1	Cg2^vi	2.9	3.7161 (14)	1.17
Cg3	Cg4^vii	4.5	3.9486 (14)	2.02
Cg4	Cg4^viii	0.0	3.6772 (14)	1.36
Symmetry codes: (v) 1 -x, -y, -z; (vi) 1 -x, 1-y, -z; (vii) 1 -x, 1-y, 1-z; (viii) 1 -x, -y, 1-z.

H atoms bonded to O atoms were found in difference maps and refined as riding. H atoms bonded to C atoms were placed in calculated positions (C—H = 0.96–0.98 Å) and refined as riding, allowing for free rotation of the rigid methyl groups. U_iso(H) values were constrained to be 1.2U_eq(attached atom) [1.5U_eq(C) for methyl H atoms].

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270104007826/hj1005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104007826/hj1005Isup2.hkl

Comment top

Diopyrin, C₂₂H₁₄O₆, (I), is an orange–red naphthoquinonylnaphthoquinone that is present in the heartwood of many species of Diospyros (persimmon) trees (Thomson, 1987). The potent antimycobacterial properties of diospyrin and its analogues have been investigated by various workers (Lall et al., 2003, and references therein). Arguments based on NMR spectra (Sidhu & Pardhasaradhi, 1967, 1970; Lillie & Musgrave, 1977) indicated that diospyrin has the structure shown in the scheme below, with a (6–2¹) linkage present between the naphthoquinonyl units, and a recent synthesis (Yoshida & Mori, 2000) has provided support for this hypothesis. However, the alternative (6–3¹) mode of linkage has never been conclusively disproved. We have now established crystallographically that diospyrin does indeed have the structure shown (Fig. 1).

The geometric parameters for (I) (Table 1) are consistent with those reported for other naphthoquinone systems (Lynch & McClenaghan, 2002). In the crystal, the two ring systems (C1–C11/O1–O3, with an r.m.s. deviation from the least-squares plane of 0.048 Å, and C12–C22/O5/O6, with an r.m.s. deviation of 0.069 Å) are not coplanar, the angle between their least-squares planes being 59.74 (2)°. The inter-ring C9—C12 bond length [1.494 (3) Å] suggests that it is essentially a single bond. A somewhat surprising feature is that the bulky C11 methyl group lies close to the atom O4 rather than, as might be expected, close to the much smaller H atom attached to atom C13. As a result, atom O4 is significantly displaced [by 0.387 (3) Å] from the least-squares plane of its naphthoquinonyl unit (C12–C22/O5/O6). Conversely, atom C11 shows no significant deviation [displacement = 0.018 (2) Å] from the C1–C11/O1–O3 least-squares plane.

Both OH groups participate in bifurcated intra/intermolecular hydrogen bonds to C=O acceptors (Table 2). The intramolecular O—H···O bonds are much shorter and stronger than the intermolecular links. This results in an `unbalanced' hydrogen-bonding network, in which atoms O2 and O5 accept two hydrogen bonds each (one intramolecular and one intermolecular), and atoms O1 and O4 do not accept any conventional hydrogen bonds. Together (Fig. 2), the O—H···O bonds generate infinite [010] stacks of molecules of (I), generated by a 2₁ screw axis. A PLATON (Spek, 2003) analysis of (I) indicated the possible presence of two short C—H···O interactions arising from methyl group H atoms (Table 2), although such interactions are expected to be very weak for such `unactivated' bonds (Desiraju & Steiner, 1999). Interestingly, the acceptor atoms are the `underbonded' atoms O1 and O4 (see above). If they are not merely packing artefacts, these C—H···O interactions may provide some coherence between adjacent [010] stacks of molecules in the a direction. Possible π–π stacking interactions, with a ring–centroid separation of less than 4.0 Å, are listed in Table 3. The relatively large value of Δ in each case suggests that these interactions are weak.

The structure shown in Fig. 1 is dissymmetric, but crystal symmetry generates a racemic mixture that is consistent with the lack of optical activity shown by (I) in solution (Lillie et al., 1976). The interconversion of the two enantiomeric forms would be expected to occur readily in solution by analogy with the behaviour of trisubstituted biphenyls such as (II) (Adams & Teeter, 1940), which undergo rapid racemization in solution. The unit-cell packing of (I) is shown in Fig. 3.

Experimental top

Diospyrin was isolated from Diospyros montana (cf. Lillie et al., 1976) and recrystallized from chloroform as an intense orange powder accompanied by one or two well faceted orange plates.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The asymmetric unit of (I) (50% probability displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are indicated by dashed lines.
	Fig. 2. A detail of (I), showing the [010] stacking resulting from O—H···O bydrogen bonds (50% probability displacement ellipsoids). [Symmetry codes: (i) 1/2 − x, 1/2 + y, 1/2 − z; (ii) x, 1 + y, z.]
	Fig. 3. The crystal packing of (I), projected on to (010) (H atoms have been omitted for clarity).

1',5-dihydroxy-3',7-dimethyl-2,2'-binaphthalene-1,4,5',8'-tetrone top

Crystal data top

C₂₂H₁₄O₆	F(000) = 776
M_r = 374.33	D_x = 1.504 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2069 reflections
a = 13.5603 (10) Å	θ = 2.6–25.5°
b = 7.8549 (6) Å	µ = 0.11 mm⁻¹
c = 15.8121 (11) Å	T = 293 K
β = 101.063 (2)°	Plate, orange
V = 1652.9 (2) Å³	0.36 × 0.29 × 0.05 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	3091 independent reflections
Radiation source: fine-focus sealed tube	1739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 25.6°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −16→14
T_min = 0.920, T_max = 0.995	k = −9→8
10116 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (C-H)
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.069P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
3091 reflections	Δρ_max = 0.22 e Å⁻³
255 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

Crystal data top

C₂₂H₁₄O₆	V = 1652.9 (2) Å³
M_r = 374.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.5603 (10) Å	µ = 0.11 mm⁻¹
b = 7.8549 (6) Å	T = 293 K
c = 15.8121 (11) Å	0.36 × 0.29 × 0.05 mm
β = 101.063 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	3091 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1739 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.995	R_int = 0.039
10116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 0.92	Δρ_max = 0.22 e Å⁻³
3091 reflections	Δρ_min = −0.19 e Å⁻³
255 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.67119 (14)	0.3929 (3)	−0.06871 (11)	0.0706 (6)
O2	0.33522 (12)	0.0988 (3)	−0.01421 (10)	0.0661 (6)
O3	0.37668 (11)	0.1809 (2)	0.14853 (9)	0.0505 (5)
H1	0.3427	0.1212	0.0983	0.061*
O4	0.62949 (13)	0.1313 (2)	0.33927 (10)	0.0634 (5)
O5	0.30530 (11)	0.4599 (2)	0.39318 (9)	0.0496 (5)
O6	0.34246 (11)	0.3695 (2)	0.55636 (9)	0.0510 (5)
H2	0.3024	0.4207	0.5036	0.061*
C1	0.59863 (18)	0.3184 (3)	−0.05253 (14)	0.0449 (6)
C2	0.53119 (19)	0.2234 (3)	−0.12023 (15)	0.0563 (7)
H3	0.5485	0.2126	−0.1741	0.068*
C3	0.44699 (19)	0.1528 (3)	−0.10728 (15)	0.0560 (7)
H4	0.4064	0.0953	−0.1524	0.067*
C4	0.41564 (17)	0.1630 (3)	−0.02276 (14)	0.0449 (6)
C5	0.48317 (15)	0.2454 (3)	0.04771 (12)	0.0369 (5)
C6	0.57353 (16)	0.3201 (3)	0.03472 (13)	0.0373 (5)
C7	0.63802 (15)	0.3939 (3)	0.10202 (13)	0.0416 (6)
H5	0.6974	0.4424	0.0923	0.050*
C8	0.61665 (15)	0.3981 (3)	0.18499 (13)	0.0388 (5)
C9	0.52763 (15)	0.3260 (3)	0.19949 (13)	0.0346 (5)
C10	0.46086 (15)	0.2503 (3)	0.13101 (13)	0.0364 (5)
C11	0.68818 (17)	0.4857 (4)	0.25561 (14)	0.0591 (8)
H6	0.7400	0.5406	0.2319	0.089*
H7	0.7178	0.4034	0.2978	0.089*
H8	0.6525	0.5692	0.2824	0.089*
C12	0.50020 (14)	0.3249 (3)	0.28660 (13)	0.0346 (5)
C13	0.41787 (15)	0.4030 (3)	0.30217 (13)	0.0367 (5)
H9	0.3792	0.4660	0.2581	0.044*
C14	0.38558 (15)	0.3939 (3)	0.38549 (13)	0.0353 (5)
C15	0.45032 (14)	0.3069 (3)	0.45627 (12)	0.0326 (5)
C16	0.53997 (14)	0.2289 (3)	0.44382 (13)	0.0345 (5)
C17	0.56283 (15)	0.2224 (3)	0.35557 (13)	0.0383 (5)
C18	0.42673 (15)	0.3008 (3)	0.53877 (13)	0.0358 (5)
C19	0.49258 (15)	0.2243 (3)	0.60535 (14)	0.0395 (5)
H10	0.4759	0.2204	0.6597	0.047*
C20	0.58219 (15)	0.1535 (3)	0.59406 (13)	0.0374 (5)
C21	0.60467 (15)	0.1542 (3)	0.51152 (13)	0.0378 (5)
H11	0.6637	0.1039	0.5022	0.045*
C22	0.65535 (16)	0.0810 (3)	0.66902 (13)	0.0513 (6)
H12	0.6970	−0.0022	0.6485	0.077*
H13	0.6191	0.0281	0.7085	0.077*
H14	0.6967	0.1707	0.6979	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0842 (13)	0.0900 (15)	0.0464 (11)	−0.0220 (11)	0.0350 (10)	−0.0037 (10)
O2	0.0535 (11)	0.0962 (16)	0.0487 (11)	−0.0201 (10)	0.0100 (8)	−0.0171 (10)
O3	0.0442 (9)	0.0720 (13)	0.0388 (9)	−0.0181 (8)	0.0166 (7)	−0.0120 (8)
O4	0.0697 (11)	0.0819 (14)	0.0463 (10)	0.0361 (10)	0.0307 (9)	0.0157 (9)
O5	0.0422 (9)	0.0669 (12)	0.0430 (9)	0.0149 (8)	0.0162 (7)	0.0027 (8)
O6	0.0476 (9)	0.0729 (13)	0.0364 (9)	0.0147 (8)	0.0178 (7)	0.0019 (8)
C1	0.0545 (15)	0.0507 (16)	0.0342 (13)	0.0013 (11)	0.0200 (11)	0.0055 (11)
C2	0.0701 (17)	0.075 (2)	0.0270 (12)	0.0019 (14)	0.0172 (12)	−0.0051 (12)
C3	0.0610 (17)	0.074 (2)	0.0311 (13)	−0.0001 (13)	0.0051 (12)	−0.0075 (12)
C4	0.0448 (14)	0.0547 (17)	0.0346 (13)	0.0006 (11)	0.0064 (11)	−0.0037 (11)
C5	0.0406 (12)	0.0417 (15)	0.0293 (12)	0.0011 (10)	0.0091 (10)	−0.0004 (10)
C6	0.0446 (13)	0.0395 (14)	0.0295 (12)	0.0031 (10)	0.0118 (10)	0.0033 (10)
C7	0.0395 (13)	0.0507 (16)	0.0382 (13)	−0.0068 (10)	0.0169 (10)	−0.0001 (11)
C8	0.0383 (12)	0.0472 (15)	0.0325 (12)	−0.0038 (10)	0.0111 (10)	0.0002 (10)
C9	0.0369 (12)	0.0413 (15)	0.0271 (11)	0.0010 (9)	0.0095 (9)	0.0013 (9)
C10	0.0359 (12)	0.0417 (15)	0.0336 (12)	0.0001 (9)	0.0119 (9)	0.0005 (10)
C11	0.0502 (15)	0.090 (2)	0.0382 (13)	−0.0199 (13)	0.0119 (11)	−0.0076 (14)
C12	0.0362 (12)	0.0401 (14)	0.0298 (11)	−0.0040 (9)	0.0122 (9)	−0.0014 (10)
C13	0.0392 (12)	0.0421 (14)	0.0291 (11)	0.0011 (10)	0.0075 (9)	0.0029 (10)
C14	0.0339 (12)	0.0397 (14)	0.0340 (12)	−0.0016 (10)	0.0104 (9)	−0.0035 (10)
C15	0.0353 (12)	0.0349 (13)	0.0289 (11)	−0.0008 (9)	0.0092 (9)	−0.0026 (9)
C16	0.0373 (12)	0.0363 (14)	0.0325 (12)	−0.0021 (9)	0.0137 (9)	−0.0018 (10)
C17	0.0403 (12)	0.0429 (14)	0.0353 (12)	0.0043 (10)	0.0161 (10)	0.0019 (10)
C18	0.0366 (12)	0.0399 (14)	0.0336 (12)	−0.0013 (9)	0.0132 (10)	−0.0050 (10)
C19	0.0488 (14)	0.0436 (15)	0.0291 (11)	−0.0026 (11)	0.0148 (10)	−0.0014 (10)
C20	0.0419 (13)	0.0400 (14)	0.0306 (12)	−0.0035 (9)	0.0077 (10)	0.0004 (10)
C21	0.0363 (12)	0.0443 (15)	0.0344 (12)	0.0029 (9)	0.0107 (10)	0.0010 (10)
C22	0.0545 (15)	0.0632 (18)	0.0362 (13)	0.0066 (12)	0.0087 (11)	0.0075 (12)

Geometric parameters (Å, º) top

O1—C1	1.214 (3)	C9—C12	1.494 (3)
O2—C4	1.232 (3)	C11—H6	0.9600
O3—C10	1.341 (2)	C11—H7	0.9600
O3—H1	0.9612	C11—H8	0.9600
O4—C17	1.218 (2)	C12—C13	1.337 (3)
O5—C14	1.233 (2)	C12—C17	1.485 (3)
O6—C18	1.340 (2)	C13—C14	1.468 (3)
O6—H2	0.9899	C13—H9	0.9300
C1—C2	1.471 (3)	C14—C15	1.454 (3)
C1—C6	1.483 (3)	C15—C18	1.402 (3)
C2—C3	1.320 (3)	C15—C16	1.408 (3)
C2—H3	0.9300	C16—C21	1.378 (3)
C3—C4	1.480 (3)	C16—C17	1.487 (3)
C3—H4	0.9300	C18—C19	1.381 (3)
C4—C5	1.452 (3)	C19—C20	1.379 (3)
C5—C10	1.407 (3)	C19—H10	0.9300
C5—C6	1.409 (3)	C20—C21	1.396 (3)
C6—C7	1.370 (3)	C20—C22	1.504 (3)
C7—C8	1.397 (3)	C21—H11	0.9300
C7—H5	0.9300	C22—H12	0.9600
C8—C9	1.391 (3)	C22—H13	0.9600
C8—C11	1.499 (3)	C22—H14	0.9600
C9—C10	1.404 (3)

C10—O3—H1	108.7	H7—C11—H8	109.5
C18—O6—H2	109.9	C13—C12—C17	119.58 (18)
O1—C1—C2	120.5 (2)	C13—C12—C9	122.10 (19)
O1—C1—C6	122.1 (2)	C17—C12—C9	118.15 (17)
C2—C1—C6	117.4 (2)	C12—C13—C14	123.1 (2)
C3—C2—C1	122.4 (2)	C12—C13—H9	118.4
C3—C2—H3	118.8	C14—C13—H9	118.4
C1—C2—H3	118.8	O5—C14—C15	122.43 (19)
C2—C3—C4	121.6 (2)	O5—C14—C13	119.29 (19)
C2—C3—H4	119.2	C15—C14—C13	118.28 (18)
C4—C3—H4	119.2	C18—C15—C16	118.19 (19)
O2—C4—C5	122.6 (2)	C18—C15—C14	121.35 (18)
O2—C4—C3	119.4 (2)	C16—C15—C14	120.44 (18)
C5—C4—C3	118.0 (2)	C21—C16—C15	120.96 (19)
C10—C5—C6	118.31 (19)	C21—C16—C17	119.85 (18)
C10—C5—C4	120.88 (19)	C15—C16—C17	119.16 (19)
C6—C5—C4	120.80 (19)	O4—C17—C12	120.42 (19)
C7—C6—C5	120.44 (19)	O4—C17—C16	121.0 (2)
C7—C6—C1	120.0 (2)	C12—C17—C16	118.52 (18)
C5—C6—C1	119.5 (2)	O6—C18—C19	117.99 (18)
C6—C7—C8	121.53 (19)	O6—C18—C15	122.37 (19)
C6—C7—H5	119.2	C19—C18—C15	119.63 (18)
C8—C7—H5	119.2	C20—C19—C18	122.28 (19)
C9—C8—C7	119.21 (19)	C20—C19—H10	118.9
C9—C8—C11	121.46 (19)	C18—C19—H10	118.9
C7—C8—C11	119.29 (19)	C19—C20—C21	118.39 (19)
C8—C9—C10	119.79 (18)	C19—C20—C22	121.02 (19)
C8—C9—C12	122.12 (19)	C21—C20—C22	120.58 (19)
C10—C9—C12	118.09 (17)	C16—C21—C20	120.47 (19)
O3—C10—C9	117.48 (18)	C16—C21—H11	119.8
O3—C10—C5	121.79 (18)	C20—C21—H11	119.8
C9—C10—C5	120.72 (18)	C20—C22—H12	109.5
C8—C11—H6	109.5	C20—C22—H13	109.5
C8—C11—H7	109.5	H12—C22—H13	109.5
H6—C11—H7	109.5	C20—C22—H14	109.5
C8—C11—H8	109.5	H12—C22—H14	109.5
H6—C11—H8	109.5	H13—C22—H14	109.5

C8—C9—C12—C17	−66.2 (3)	C10—C9—C12—C17	113.3 (2)
C8—C9—C12—C13	118.5 (2)	C10—C9—C12—C13	−61.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O2	0.96	1.77	2.607 (2)	144
O3—H1···O5ⁱ	0.96	2.40	2.986 (2)	119
O6—H2···O5	0.99	1.78	2.630 (2)	142
O6—H2···O2ⁱⁱ	0.99	2.36	2.980 (2)	120
C11—H6···O4ⁱⁱⁱ	0.96	2.38	3.331 (3)	170
C22—H12···O1^iv	0.96	2.52	3.415 (3)	156

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

Experimental details

Crystal data
Chemical formula	C₂₂H₁₄O₆
M_r	374.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.5603 (10), 7.8549 (6), 15.8121 (11)
β (°)	101.063 (2)
V (Å³)	1652.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.36 × 0.29 × 0.05

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.920, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	10116, 3091, 1739
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 0.92
No. of reflections	3091
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected bond lengths (Å) top

O1—C1	1.214 (3)	C8—C11	1.499 (3)
O2—C4	1.232 (3)	C9—C10	1.404 (3)
O3—C10	1.341 (2)	C9—C12	1.494 (3)
O4—C17	1.218 (2)	C12—C13	1.337 (3)
O5—C14	1.233 (2)	C12—C17	1.485 (3)
O6—C18	1.340 (2)	C13—C14	1.468 (3)
C1—C2	1.471 (3)	C14—C15	1.454 (3)
C1—C6	1.483 (3)	C15—C18	1.402 (3)
C2—C3	1.320 (3)	C15—C16	1.408 (3)
C3—C4	1.480 (3)	C16—C21	1.378 (3)
C4—C5	1.452 (3)	C16—C17	1.487 (3)
C5—C10	1.407 (3)	C18—C19	1.381 (3)
C5—C6	1.409 (3)	C19—C20	1.379 (3)
C6—C7	1.370 (3)	C20—C21	1.396 (3)
C7—C8	1.397 (3)	C20—C22	1.504 (3)
C8—C9	1.391 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O2	0.96	1.77	2.607 (2)	144
O3—H1···O5ⁱ	0.96	2.40	2.986 (2)	119
O6—H2···O5	0.99	1.78	2.630 (2)	142
O6—H2···O2ⁱⁱ	0.99	2.36	2.980 (2)	120
C11—H6···O4ⁱⁱⁱ	0.96	2.38	3.331 (3)	170
C22—H12···O1^iv	0.96	2.52	3.415 (3)	156

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

π-π stacking Interactions in (I) top

Ring1	Ring2	ϕ	d	Δ
π1	π2ⁱ	0.0	3.9219 (14)	2.15
π1	π2ⁱⁱ	2.9	3.7161 (14)	1.17
π3	π4ⁱⁱⁱ	4.5	3.9486 (14)	2.02
π4	π4^iv	0.0	3.6772 (14)	1.36

Notes: π1 = centroid of atoms C1-C6; π2 = centroid of atoms C5-C10; π3 = centroid of atoms C12-C17; π4 = centroid of atoms C15, C16, C18-C21. ϕ = dihedral angle (°) between ring best planes; d = distance between ring centroids (Å); and Δ = displacement (Å) of the centroid of ring 2 relative to the intersection point of the normal to the centroid of ring 1 and the best least-squares plane of ring 2. Symmetry codes: (i) 1 − x, −y, −z; (ii) 1 − x, 1 − y, −z; (iii) 1 − x, 1 − y, 1 − z; (iv) 1 − x, −y, 1 − z.

References

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ISSN: 2053-2296

Volume 60| Part 6| June 2004| Pages o399-o401

doi:10.1107/S0108270104007826

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Diospyrin

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

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