N-(1-Naphthyl­acetyl)­glycine phen­acyl ester and phen­acyl (1-naphthyl­acetoxy)­acetate

The structures of the bichromophoric compounds N-(1-naphthyl­acetyl)­gly­cine phen­acyl ester, C₂₂H₁₉NO₄, (I), and its oxy­gen analogue, phen­acyl (1-naphthyl­acetoxy)­acetate, C₂₂H₁₈O₅, (II), have been determined. The mol­ecules of (I) are held together by intermolecular N-H...O hydrogen bonds between the carbonyl and N-H groups, while compound (II) does not show any hydrogen bonding in the crystal.

S1. Comment

In recent years, research in the area of intramolecular charge and energy transfer (ET) in polychromophoric molecules has become increasingly important in connection with understanding the effects of molecular conformation, interchromophore distance, and the bridging architecture on the mechanisms of transfer process (Chattoraj et al., 1991; Morrison et al., 1986; Borkent et al., 1978).

In case of the title compounds, (I) and (II), in solution, ET between an electronically excited triplet donor (phenacyl) and an acceptor (naphthyl) moiety proceeds by an electron-exchange mechanism, which requires a close contact between the chromophores (Zabadal et al., 2002). ET in the bichromophore (II) was found to be faster than that in (I), which should be closely related to a higher flexibility of (II), i.e. conformations with an easier contact of the terminal chromophores.

Contrary to the remarkable difference in the molecular conformations (and corresponding ET rates) in solution, the molecular structures in the solid phase are very similar. In the crystal structure of (I), the C7—C22 distance is 9.009 (3) Å, while the same distance in (II) is 8.818 (2) Å. The mutual distance of chromophores is obviously controlled mainly by the length and shape of the central chain. Replacing the –NH– group in (I) by –O– in (II) does not significantly affect the spatial arrangement of the bridging atoms; the r.m.s. deviations of the superimposed atomic chains (based on C12, N14/O14, C15, C16, O17 and C18) being 0.1425 Å (Fig. 5). This is also reflected in the dihedral angles throughout the chain, where the most different pairs are C15—O14—C12—C11/C15—N14—C12—C11 of −166.28 (10)/-179.18 (12)° and O17—C16—C15—N14/O17—C16—C15—O14 of −161.14 (11)/172.92 (10)°.

Compound (I) forms a hydrogen-bonded polymer (see Fig. 3 and Table 1). Compared to (II), the C12═O13 double bond in (I) is elongated due to the hydrogen bonding, viz. 1.230 (2) versus 1.192 (2) Å. This is similar to what was found for the analogous bond in 1-naphthaleneacetic acid [1.211 (10) Å; Rajan, 1978], which forms hydrogen-bonded dimers. The shortest contact in (II) is between atom O14 and one of the C11 H atoms in two neighboring molecules [2.551 (16) Å], both molecules thus forming a dimer, with atoms O14, C12, C11, and H11A and their symmetry equivalents in another molecule forming an eight-membered ring (Fig. 4).

In spite of an exact crystallographical description of their conformations in the solid phase, the study of polychromophores in solution is of great importance, especially in flexible systems, in which two chromophores are connected by long bridges. The conformations, due to different driving forces in both the solid and liquid phases, differ significantly, and so the crystal structure/ET properties relationships are not directly obvious.

S2. Experimental

Compound (I) was synthesized by the coupling of commercially available N-t-Boc-L-Gly-OH (Fluka, Buchs, Switzerland) and phenacyl bromide (Banerjee & Falvey, 1997) brought about by stirring the mixture for 3 h under argon. The bichromophoric compound (I) was prepared by using DCC (N,N'-dicyclohexylcarbodiimide) and HOBt (1-hydroxybenzotriazole) as coupling reagents after cleavage of N-tert-butyloxycarbonyl protecting group by 3 M HCl in ethyl acetate (Narita et al., 1986). The single crystals of bichromophore (I) were recrystallized from ethanol.

Compound (II) was prepared by coupling of an appropriate carboxylic acid and phenacyl bromide. The acid was obtained by prolonging the 1-naphthaleneacetic acid by the acetyl fragment. In this procedure, the tert-butyl ester of bromoacetic acid was employed in addition to naphthylacetic acid (Ringshaw & Smith, 1964). The intermediate tert-butyl ester was then cleaved to the carboxylic acid using concentrated formic acid (Harada et al., 1997). The crude product (II) was recrystallized from a mixture of methanol and water (8:2).

Computing details

For both compounds, data collection: Xcalibur (Oxford Diffraction Ltd, 2001); cell refinement: Xcalibur; data reduction: Xcalibur; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Packing diagram of compound (I), showing the hydrogen-bonding scheme.
	Fig. 4. The van der Waals interactions in the crystal structure of (II).
	Fig. 5. Superimpositions of the molecular structures of (I) and (II) based on chromophores bridging atoms.

(I)

Crystal data

C22H19NO4	F(000) = 1520
Mr = 361.38	Dx = 1.340 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 500 reflections
a = 9.1467 (18) Å	θ = 4.8–25.5°
b = 16.102 (3) Å	µ = 0.09 mm^−1
c = 24.318 (5) Å	T = 120 K
V = 3581.5 (12) Å^3	Prism, colourless
Z = 8	0.50 × 0.30 × 0.20 mm

Data collection

Kuma KM-4 CCD diffractometer	3034 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 3.4°
Detector resolution: 0.06 mm pixels mm^-1	h = −10→10
ω scans	k = −19→17
19123 measured reflections	l = −28→26
3141 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0322P)^2 + 1.2751P] where P = (Fo^2 + 2Fc^2)/3
3141 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O17	0.65998 (10)	0.23473 (6)	0.59035 (4)	0.0228 (2)
O20	0.78277 (11)	0.31508 (7)	0.50635 (4)	0.0306 (3)
O13	0.66381 (10)	0.24377 (6)	0.74350 (4)	0.0228 (2)
O21	0.72744 (11)	0.34776 (6)	0.63762 (4)	0.0258 (2)
C16	0.73858 (15)	0.27543 (9)	0.62853 (5)	0.0186 (3)
N14	0.88919 (12)	0.24889 (7)	0.70874 (4)	0.0187 (3)
H14A	0.9823	0.2606	0.7136	0.022*
C7	0.74024 (14)	0.33868 (9)	0.83701 (5)	0.0196 (3)
C19	0.65279 (15)	0.32702 (9)	0.51156 (6)	0.0212 (3)
C12	0.79381 (14)	0.26151 (8)	0.74904 (6)	0.0181 (3)
C18	0.56832 (15)	0.28602 (9)	0.55754 (5)	0.0220 (3)
H18A	0.5234	0.3293	0.5810	0.026*
H18B	0.4886	0.2520	0.5417	0.026*
C1	0.67051 (14)	0.41319 (9)	0.81970 (6)	0.0201 (3)
C15	0.83971 (15)	0.21602 (9)	0.65720 (5)	0.0200 (3)
H15A	0.7882	0.1628	0.6636	0.024*
H15B	0.9251	0.2047	0.6333	0.024*
C11	0.85410 (15)	0.29747 (9)	0.80180 (6)	0.0221 (3)
H11A	0.9008	0.2524	0.8232	0.027*
H11B	0.9307	0.3387	0.7926	0.027*
C22	0.56871 (16)	0.38023 (8)	0.47326 (6)	0.0215 (3)
C3	0.50006 (16)	0.52625 (9)	0.83853 (6)	0.0282 (3)
H3A	0.4316	0.5523	0.8623	0.034*
C8	0.70434 (15)	0.30540 (9)	0.88684 (6)	0.0239 (3)
H8A	0.7499	0.2553	0.8983	0.029*
C9	0.60184 (16)	0.34348 (10)	0.92144 (6)	0.0285 (3)
H9A	0.5787	0.3189	0.9559	0.034*
C27	0.42101 (16)	0.39601 (9)	0.48145 (6)	0.0258 (3)
H27A	0.3714	0.3714	0.5117	0.031*
C2	0.56809 (15)	0.45190 (9)	0.85518 (6)	0.0220 (3)
C6	0.70002 (16)	0.45115 (9)	0.76843 (6)	0.0259 (3)
H6A	0.7678	0.4263	0.7438	0.031*
C4	0.53067 (18)	0.56118 (10)	0.78910 (7)	0.0327 (4)
H4A	0.4837	0.6112	0.7783	0.039*
C10	0.53578 (16)	0.41478 (10)	0.90626 (6)	0.0273 (3)
H10A	0.4669	0.4402	0.9302	0.033*
C23	0.63935 (18)	0.41582 (10)	0.42866 (6)	0.0306 (4)
H23A	0.7405	0.4057	0.4228	0.037*
C25	0.4167 (2)	0.48175 (9)	0.40174 (7)	0.0374 (4)
H25A	0.3645	0.5168	0.3772	0.045*
C24	0.5628 (2)	0.46586 (10)	0.39290 (7)	0.0389 (4)
H24A	0.6109	0.4895	0.3620	0.047*
C26	0.34662 (19)	0.44715 (10)	0.44588 (7)	0.0330 (4)
H26A	0.2460	0.4585	0.4520	0.040*
C5	0.63172 (18)	0.52312 (10)	0.75413 (7)	0.0321 (4)
H5A	0.6532	0.5480	0.7196	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O17	0.0252 (5)	0.0217 (5)	0.0214 (5)	0.0024 (4)	−0.0077 (4)	−0.0017 (4)
O20	0.0198 (6)	0.0427 (7)	0.0294 (6)	0.0034 (5)	0.0004 (4)	−0.0017 (5)
O13	0.0129 (5)	0.0302 (5)	0.0254 (5)	−0.0014 (4)	0.0001 (4)	−0.0038 (4)
O21	0.0300 (6)	0.0200 (5)	0.0275 (5)	0.0032 (4)	−0.0075 (4)	−0.0010 (4)
C16	0.0172 (7)	0.0220 (8)	0.0166 (6)	−0.0002 (6)	0.0017 (5)	0.0003 (5)
N14	0.0116 (5)	0.0255 (6)	0.0189 (6)	0.0004 (5)	−0.0013 (4)	0.0007 (5)
C7	0.0150 (6)	0.0233 (7)	0.0205 (7)	−0.0019 (6)	−0.0047 (5)	−0.0023 (6)
C19	0.0208 (7)	0.0222 (7)	0.0207 (7)	−0.0006 (6)	−0.0019 (6)	−0.0060 (6)
C12	0.0143 (6)	0.0179 (6)	0.0220 (7)	0.0018 (5)	−0.0012 (5)	0.0026 (6)
C18	0.0200 (7)	0.0268 (7)	0.0192 (7)	0.0032 (6)	−0.0056 (6)	0.0001 (6)
C1	0.0172 (7)	0.0221 (7)	0.0210 (7)	−0.0050 (6)	−0.0026 (6)	−0.0001 (6)
C15	0.0181 (7)	0.0219 (7)	0.0198 (7)	0.0036 (6)	0.0004 (6)	−0.0006 (6)
C11	0.0159 (7)	0.0278 (8)	0.0226 (7)	0.0003 (6)	−0.0027 (6)	−0.0024 (6)
C22	0.0267 (7)	0.0183 (7)	0.0195 (7)	−0.0023 (6)	−0.0038 (6)	−0.0040 (5)
C3	0.0249 (8)	0.0245 (8)	0.0351 (9)	0.0025 (6)	0.0001 (6)	−0.0016 (7)
C8	0.0226 (7)	0.0253 (8)	0.0239 (7)	0.0019 (6)	−0.0038 (6)	0.0029 (6)
C9	0.0287 (8)	0.0355 (9)	0.0212 (8)	0.0003 (7)	0.0025 (6)	0.0053 (6)
C27	0.0283 (8)	0.0275 (8)	0.0215 (7)	0.0033 (6)	−0.0046 (6)	−0.0035 (6)
C2	0.0176 (7)	0.0237 (7)	0.0247 (7)	−0.0015 (6)	−0.0016 (6)	−0.0013 (6)
C6	0.0279 (7)	0.0264 (8)	0.0234 (7)	−0.0047 (6)	0.0009 (6)	0.0014 (6)
C4	0.0342 (9)	0.0227 (8)	0.0412 (9)	0.0014 (7)	−0.0045 (7)	0.0054 (7)
C10	0.0250 (8)	0.0317 (8)	0.0253 (8)	0.0019 (7)	0.0053 (6)	−0.0017 (6)
C23	0.0345 (9)	0.0279 (8)	0.0293 (8)	−0.0091 (7)	−0.0007 (7)	0.0000 (7)
C25	0.0607 (12)	0.0174 (8)	0.0340 (9)	0.0025 (8)	−0.0205 (8)	−0.0008 (7)
C24	0.0615 (12)	0.0269 (8)	0.0284 (8)	−0.0152 (8)	−0.0059 (8)	0.0069 (7)
C26	0.0390 (9)	0.0287 (8)	0.0313 (9)	0.0103 (7)	−0.0132 (7)	−0.0076 (7)
C5	0.0411 (9)	0.0279 (8)	0.0272 (8)	−0.0053 (7)	−0.0013 (7)	0.0098 (7)

Geometric parameters (Å, º)

O17—C16	1.3448 (16)	C22—C27	1.389 (2)
O17—C18	1.4216 (16)	C3—C4	1.356 (2)
O20—C19	1.2109 (17)	C3—C2	1.409 (2)
O13—C12	1.2303 (16)	C3—H3A	0.9500
O21—C16	1.1897 (17)	C8—C9	1.401 (2)
C16—C15	1.5023 (19)	C8—H8A	0.9500
N14—C12	1.3278 (18)	C9—C10	1.349 (2)
N14—C15	1.4338 (17)	C9—H9A	0.9500
N14—H14A	0.8800	C27—C26	1.375 (2)
C7—C8	1.365 (2)	C27—H27A	0.9500
C7—C1	1.422 (2)	C2—C10	1.410 (2)
C7—C11	1.5026 (19)	C6—C5	1.362 (2)
C19—C22	1.481 (2)	C6—H6A	0.9500
C19—C18	1.5111 (19)	C4—C5	1.397 (2)
C12—C11	1.5119 (19)	C4—H4A	0.9500
C18—H18A	0.9900	C10—H10A	0.9500
C18—H18B	0.9900	C23—C24	1.377 (2)
C1—C6	1.415 (2)	C23—H23A	0.9500
C1—C2	1.418 (2)	C25—C26	1.369 (2)
C15—H15A	0.9900	C25—C24	1.378 (3)
C15—H15B	0.9900	C25—H25A	0.9500
C11—H11A	0.9900	C24—H24A	0.9500
C11—H11B	0.9900	C26—H26A	0.9500
C22—C23	1.387 (2)	C5—H5A	0.9500
C16—O17—C18	114.81 (11)	C27—C22—C19	121.38 (13)
O21—C16—O17	124.02 (13)	C23—C22—C7	135.87 (9)
O21—C16—C15	126.14 (13)	C27—C22—C7	92.42 (8)
O17—C16—C15	109.84 (11)	C4—C3—C2	121.06 (15)
C12—N14—C15	119.62 (11)	C4—C3—H3A	119.5
C12—N14—H14A	120.2	C2—C3—H3A	119.5
C15—N14—H14A	120.2	C7—C8—C9	121.49 (14)
C8—C7—C1	119.07 (13)	C7—C8—H8A	119.3
C8—C7—C11	119.95 (13)	C9—C8—H8A	119.3
C1—C7—C11	120.97 (12)	C10—C9—C8	120.52 (14)
C8—C7—C22	149.20 (9)	C10—C9—H9A	119.7
C1—C7—C22	64.45 (8)	C8—C9—H9A	119.7
C11—C7—C22	66.05 (7)	C26—C27—C22	120.05 (15)
O20—C19—C22	122.41 (13)	C26—C27—H27A	120.0
O20—C19—C18	120.66 (13)	C22—C27—H27A	120.0
C22—C19—C18	116.92 (12)	C3—C2—C10	121.40 (13)
O13—C12—N14	121.24 (13)	C3—C2—C1	119.37 (13)
O13—C12—C11	122.31 (12)	C10—C2—C1	119.23 (13)
N14—C12—C11	116.45 (11)	C5—C6—C1	120.35 (14)
O17—C18—C19	111.56 (11)	C5—C6—H6A	119.8
O17—C18—H18A	109.3	C1—C6—H6A	119.8
C19—C18—H18A	109.3	C3—C4—C5	119.60 (15)
O17—C18—H18B	109.3	C3—C4—H4A	120.2
C19—C18—H18B	109.3	C5—C4—H4A	120.2
H18A—C18—H18B	108.0	C9—C10—C2	120.54 (14)
C6—C1—C2	118.19 (13)	C9—C10—H10A	119.7
C6—C1—C7	122.67 (13)	C2—C10—H10A	119.7
C2—C1—C7	119.14 (13)	C24—C23—C22	119.94 (16)
N14—C15—C16	111.41 (11)	C24—C23—H23A	120.0
N14—C15—H15A	109.3	C22—C23—H23A	120.0
C16—C15—H15A	109.3	C26—C25—C24	120.06 (15)
N14—C15—H15B	109.3	C26—C25—H25A	120.0
C16—C15—H15B	109.3	C24—C25—H25A	120.0
H15A—C15—H15B	108.0	C23—C24—C25	120.23 (16)
C7—C11—C12	113.57 (11)	C23—C24—H24A	119.9
C7—C11—H11A	108.9	C25—C24—H24A	119.9
C12—C11—H11A	108.9	C25—C26—C27	120.38 (16)
C7—C11—H11B	108.9	C25—C26—H26A	119.8
C12—C11—H11B	108.9	C27—C26—H26A	119.8
H11A—C11—H11B	107.7	C6—C5—C4	121.42 (15)
C23—C22—C27	119.33 (14)	C6—C5—H5A	119.3
C23—C22—C19	119.28 (14)	C4—C5—H5A	119.3
C18—O17—C16—O21	4.87 (19)	C11—C7—C22—C27	159.23 (12)
C18—O17—C16—C15	−175.33 (11)	C8—C7—C22—C19	−87.4 (2)
C15—N14—C12—O13	1.66 (19)	C1—C7—C22—C19	168.15 (14)
C15—N14—C12—C11	−179.13 (12)	C11—C7—C22—C19	21.39 (13)
C16—O17—C18—C19	81.18 (14)	C1—C7—C8—C9	−0.7 (2)
O20—C19—C18—O17	−0.62 (19)	C11—C7—C8—C9	178.10 (13)
C22—C19—C18—O17	178.19 (11)	C22—C7—C8—C9	−89.0 (2)
C8—C7—C1—C6	−179.18 (13)	C7—C8—C9—C10	−0.2 (2)
C11—C7—C1—C6	2.0 (2)	C23—C22—C27—C26	−0.7 (2)
C22—C7—C1—C6	−33.75 (11)	C19—C22—C27—C26	178.56 (13)
C8—C7—C1—C2	1.42 (19)	C7—C22—C27—C26	147.28 (12)
C11—C7—C1—C2	−177.40 (12)	C4—C3—C2—C10	−179.37 (15)
C22—C7—C1—C2	146.85 (14)	C4—C3—C2—C1	0.2 (2)
C12—N14—C15—C16	65.17 (16)	C6—C1—C2—C3	−0.2 (2)
O21—C16—C15—N14	18.7 (2)	C7—C1—C2—C3	179.22 (13)
O17—C16—C15—N14	−161.06 (11)	C6—C1—C2—C10	179.36 (13)
C8—C7—C11—C12	113.42 (14)	C7—C1—C2—C10	−1.2 (2)
C1—C7—C11—C12	−67.77 (17)	C2—C1—C6—C5	0.3 (2)
C22—C7—C11—C12	−32.55 (9)	C7—C1—C6—C5	−179.10 (14)
O13—C12—C11—C7	−21.93 (19)	C2—C3—C4—C5	−0.3 (2)
N14—C12—C11—C7	158.87 (12)	C8—C9—C10—C2	0.4 (2)
O20—C19—C22—C23	2.2 (2)	C3—C2—C10—C9	179.87 (14)
C18—C19—C22—C23	−176.63 (12)	C1—C2—C10—C9	0.3 (2)
O20—C19—C22—C27	−177.09 (14)	C27—C22—C23—C24	−0.3 (2)
C18—C19—C22—C27	4.12 (19)	C19—C22—C23—C24	−179.59 (13)
O20—C19—C22—C7	−125.32 (18)	C7—C22—C23—C24	−130.77 (13)
C18—C19—C22—C7	55.90 (10)	C22—C23—C24—C25	1.0 (2)
C8—C7—C22—C23	−171.2 (2)	C26—C25—C24—C23	−0.6 (2)
C1—C7—C22—C23	84.37 (16)	C24—C25—C26—C27	−0.4 (2)
C11—C7—C22—C23	−62.39 (16)	C22—C27—C26—C25	1.1 (2)
C8—C7—C22—C27	50.5 (2)	C1—C6—C5—C4	−0.4 (2)
C1—C7—C22—C27	−54.01 (11)	C3—C4—C5—C6	0.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14A···O13^i	0.88	1.98	2.7686 (15)	149

Symmetry code: (i) x+1/2, y, −z+3/2.

(II)

Crystal data

C22H18O5	F(000) = 760
Mr = 362.36	Dx = 1.354 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 500 reflections
a = 8.927 (2) Å	θ = 4.5–27.8°
b = 11.413 (2) Å	µ = 0.10 mm^−1
c = 17.875 (4) Å	T = 120 K
β = 102.50 (3)°	Prism, colourless
V = 1778.0 (7) Å^3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Kuma KM-4 CCD diffractometer	2917 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 3.4°
Detector resolution: 0.06 mm pixels mm^-1	h = −10→6
ω scans	k = −13→13
10881 measured reflections	l = −20→21
3128 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0366P)^2 + 0.6568P] where P = (Fo^2 + 2Fc^2)/3
3128 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O21	0.20177 (10)	0.20181 (8)	0.07671 (6)	0.0294 (2)
O17	0.07631 (10)	0.36114 (7)	0.10469 (5)	0.0249 (2)
O14	−0.03387 (10)	0.06219 (8)	0.09141 (5)	0.0253 (2)
O20	0.07771 (11)	0.37934 (8)	−0.04304 (5)	0.0291 (2)
O13	0.14173 (11)	0.03358 (8)	0.20015 (5)	0.0325 (2)
C19	0.17067 (14)	0.44126 (10)	−0.00189 (7)	0.0212 (3)
C12	0.07612 (15)	−0.00061 (11)	0.13881 (7)	0.0237 (3)
C27	0.36278 (14)	0.60456 (11)	0.01506 (7)	0.0215 (3)
H27A	0.3686	0.6032	0.0687	0.026*
C16	0.09405 (14)	0.24649 (11)	0.09478 (7)	0.0226 (3)
C25	0.44048 (14)	0.68663 (11)	−0.09360 (8)	0.0249 (3)
H25A	0.4988	0.7423	−0.1147	0.030*
C23	0.26109 (14)	0.52814 (11)	−0.11069 (7)	0.0239 (3)
H23A	0.1969	0.4744	−0.1434	0.029*
C22	0.26760 (13)	0.52613 (10)	−0.03241 (7)	0.0203 (3)
C18	0.18937 (14)	0.43551 (11)	0.08400 (7)	0.0229 (3)
H18A	0.2929	0.4054	0.1074	0.027*
H18B	0.1801	0.5153	0.1043	0.027*
C7	0.22398 (15)	−0.18940 (11)	0.14771 (7)	0.0235 (3)
C1	0.38031 (15)	−0.16346 (11)	0.14962 (7)	0.0251 (3)
C9	0.30239 (19)	−0.35660 (12)	0.22930 (8)	0.0351 (3)
H9A	0.2744	−0.4213	0.2568	0.042*
C6	0.42717 (18)	−0.06697 (12)	0.11045 (8)	0.0334 (3)
H6A	0.3525	−0.0146	0.0828	0.040*
C15	−0.04277 (15)	0.18251 (11)	0.11081 (8)	0.0260 (3)
H15A	−0.0450	0.1900	0.1657	0.031*
H15B	−0.1383	0.2172	0.0803	0.031*
C8	0.18822 (17)	−0.28402 (12)	0.18693 (7)	0.0284 (3)
H8A	0.0835	−0.3012	0.1855	0.034*
C2	0.49524 (16)	−0.23851 (13)	0.19178 (8)	0.0318 (3)
C24	0.34744 (15)	0.60796 (11)	−0.14101 (7)	0.0258 (3)
H24A	0.3430	0.6089	−0.1946	0.031*
C11	0.09842 (16)	−0.11547 (11)	0.10185 (7)	0.0274 (3)
H11A	0.0011	−0.1601	0.0934	0.033*
H11B	0.1217	−0.1000	0.0511	0.033*
C26	0.44885 (14)	0.68438 (11)	−0.01556 (8)	0.0243 (3)
H26A	0.5139	0.7378	0.0170	0.029*
C5	0.5789 (2)	−0.04859 (15)	0.11206 (10)	0.0477 (4)
H5A	0.6089	0.0158	0.0850	0.057*
C10	0.45162 (19)	−0.33513 (13)	0.23132 (8)	0.0364 (4)
H10A	0.5280	−0.3855	0.2596	0.044*
C4	0.6906 (2)	−0.12384 (16)	0.15323 (12)	0.0537 (5)
H4A	0.7958	−0.1101	0.1537	0.064*
C3	0.65069 (18)	−0.21575 (16)	0.19223 (10)	0.0460 (4)
H3A	0.7281	−0.2656	0.2203	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O21	0.0269 (5)	0.0227 (5)	0.0416 (6)	0.0036 (4)	0.0137 (4)	0.0035 (4)
O17	0.0254 (5)	0.0194 (4)	0.0322 (5)	−0.0001 (4)	0.0114 (4)	−0.0003 (4)
O14	0.0259 (5)	0.0210 (5)	0.0278 (5)	−0.0003 (4)	0.0034 (4)	0.0033 (4)
O20	0.0308 (5)	0.0235 (5)	0.0302 (5)	−0.0060 (4)	0.0003 (4)	−0.0015 (4)
O13	0.0450 (6)	0.0270 (5)	0.0227 (5)	0.0055 (4)	0.0013 (4)	−0.0016 (4)
C19	0.0207 (6)	0.0156 (6)	0.0261 (6)	0.0040 (5)	0.0026 (5)	−0.0014 (5)
C12	0.0262 (7)	0.0231 (6)	0.0224 (7)	−0.0011 (5)	0.0063 (5)	0.0037 (5)
C27	0.0237 (6)	0.0197 (6)	0.0210 (6)	0.0024 (5)	0.0045 (5)	−0.0015 (5)
C16	0.0253 (7)	0.0210 (6)	0.0214 (6)	0.0024 (5)	0.0046 (5)	0.0037 (5)
C25	0.0219 (6)	0.0225 (6)	0.0313 (7)	0.0035 (5)	0.0078 (5)	0.0055 (5)
C23	0.0241 (6)	0.0230 (6)	0.0230 (6)	0.0022 (5)	0.0012 (5)	−0.0025 (5)
C22	0.0196 (6)	0.0171 (6)	0.0236 (6)	0.0046 (5)	0.0037 (5)	−0.0002 (5)
C18	0.0232 (6)	0.0181 (6)	0.0281 (7)	−0.0027 (5)	0.0072 (5)	−0.0008 (5)
C7	0.0322 (7)	0.0200 (6)	0.0180 (6)	0.0002 (5)	0.0045 (5)	−0.0052 (5)
C1	0.0323 (7)	0.0217 (6)	0.0217 (6)	−0.0005 (5)	0.0070 (5)	−0.0087 (5)
C9	0.0617 (10)	0.0217 (7)	0.0214 (7)	0.0009 (7)	0.0078 (6)	−0.0006 (5)
C6	0.0452 (8)	0.0246 (7)	0.0344 (8)	−0.0048 (6)	0.0170 (7)	−0.0092 (6)
C15	0.0254 (7)	0.0212 (6)	0.0326 (7)	0.0018 (5)	0.0086 (5)	0.0027 (5)
C8	0.0398 (8)	0.0237 (7)	0.0225 (6)	−0.0034 (6)	0.0083 (6)	−0.0047 (5)
C2	0.0341 (8)	0.0304 (7)	0.0286 (7)	0.0048 (6)	0.0016 (6)	−0.0144 (6)
C24	0.0270 (7)	0.0288 (7)	0.0221 (6)	0.0056 (6)	0.0061 (5)	0.0036 (5)
C11	0.0309 (7)	0.0256 (7)	0.0240 (7)	0.0004 (6)	0.0024 (5)	−0.0023 (5)
C26	0.0227 (6)	0.0195 (6)	0.0298 (7)	0.0003 (5)	0.0039 (5)	−0.0014 (5)
C5	0.0556 (10)	0.0358 (9)	0.0615 (11)	−0.0196 (8)	0.0344 (9)	−0.0226 (8)
C10	0.0513 (9)	0.0282 (7)	0.0248 (7)	0.0135 (7)	−0.0027 (6)	−0.0056 (6)
C4	0.0365 (9)	0.0492 (11)	0.0808 (13)	−0.0103 (8)	0.0242 (9)	−0.0328 (10)
C3	0.0335 (8)	0.0449 (10)	0.0561 (10)	0.0056 (7)	0.0023 (7)	−0.0262 (8)

Geometric parameters (Å, º)

O21—C16	1.1930 (16)	C7—C11	1.4975 (18)
O17—C16	1.3345 (16)	C1—C6	1.4159 (19)
O17—C18	1.4274 (15)	C1—C2	1.4211 (19)
O14—C12	1.3548 (16)	C9—C10	1.347 (2)
O14—C15	1.4227 (16)	C9—C8	1.402 (2)
O20—C19	1.2103 (15)	C9—H9A	0.9500
O13—C12	1.1914 (16)	C6—C5	1.365 (2)
C19—C22	1.4795 (18)	C6—H6A	0.9500
C19—C18	1.5095 (18)	C15—H15A	0.9900
C12—C11	1.5005 (18)	C15—H15B	0.9900
C27—C26	1.3790 (18)	C8—H8A	0.9500
C27—C22	1.3896 (17)	C2—C10	1.409 (2)
C27—H27A	0.9500	C2—C3	1.410 (2)
C16—C15	1.5029 (18)	C24—H24A	0.9500
C25—C26	1.3809 (19)	C11—H11A	0.9900
C25—C24	1.3818 (19)	C11—H11B	0.9900
C25—H25A	0.9500	C26—H26A	0.9500
C23—C24	1.3779 (19)	C5—C4	1.399 (3)
C23—C22	1.3880 (18)	C5—H5A	0.9500
C23—H23A	0.9500	C10—H10A	0.9500
C18—H18A	0.9900	C4—C3	1.349 (3)
C18—H18B	0.9900	C4—H4A	0.9500
C7—C8	1.3626 (18)	C3—H3A	0.9500
C7—C1	1.4198 (19)
C16—O17—C18	115.96 (10)	C5—C6—H6A	119.8
C12—O14—C15	115.43 (10)	C1—C6—H6A	119.8
O20—C19—C22	122.48 (11)	O14—C15—C16	109.39 (10)
O20—C19—C18	120.20 (11)	O14—C15—H15A	109.8
C22—C19—C18	117.31 (10)	C16—C15—H15A	109.8
O13—C12—O14	123.21 (12)	O14—C15—H15B	109.8
O13—C12—C11	127.28 (12)	C16—C15—H15B	109.8
O14—C12—C11	109.52 (11)	H15A—C15—H15B	108.2
C26—C27—C22	120.18 (12)	C7—C8—C9	121.50 (14)
C26—C27—H27A	119.9	C7—C8—H8A	119.2
C22—C27—H27A	119.9	C9—C8—H8A	119.2
O21—C16—O17	125.51 (12)	C10—C2—C3	121.31 (15)
O21—C16—C15	125.44 (12)	C10—C2—C1	119.44 (13)
O17—C16—C15	109.05 (10)	C3—C2—C1	119.25 (15)
C26—C25—C24	120.09 (12)	C23—C24—C25	120.10 (12)
C26—C25—H25A	120.0	C23—C24—H24A	119.9
C24—C25—H25A	120.0	C25—C24—H24A	119.9
C24—C23—C22	120.16 (12)	C7—C11—C12	113.96 (11)
C24—C23—H23A	119.9	C7—C11—H11A	108.8
C22—C23—H23A	119.9	C12—C11—H11A	108.8
C23—C22—C27	119.44 (12)	C7—C11—H11B	108.8
C23—C22—C19	118.83 (11)	C12—C11—H11B	108.8
C27—C22—C19	121.72 (11)	H11A—C11—H11B	107.7
O17—C18—C19	111.14 (10)	C27—C26—C25	120.01 (12)
O17—C18—H18A	109.4	C27—C26—H26A	120.0
C19—C18—H18A	109.4	C25—C26—H26A	120.0
O17—C18—H18B	109.4	C6—C5—C4	120.54 (16)
C19—C18—H18B	109.4	C6—C5—H5A	119.7
H18A—C18—H18B	108.0	C4—C5—H5A	119.7
C8—C7—C1	119.43 (12)	C9—C10—C2	120.51 (13)
C8—C7—C11	119.82 (12)	C9—C10—H10A	119.7
C1—C7—C11	120.74 (12)	C2—C10—H10A	119.7
C6—C1—C7	122.98 (13)	C3—C4—C5	120.74 (15)
C6—C1—C2	118.32 (13)	C3—C4—H4A	119.6
C7—C1—C2	118.70 (12)	C5—C4—H4A	119.6
C10—C9—C8	120.41 (14)	C4—C3—C2	120.66 (16)
C10—C9—H9A	119.8	C4—C3—H3A	119.7
C8—C9—H9A	119.8	C2—C3—H3A	119.7
C5—C6—C1	120.48 (15)