Synthesis and physical properties of ferrocene derivatives. XXI. Crystal structure of a liquid crystalline ferrocene derivative, 1,1'-bis­[3-[4-(4-methoxyphenoxycarbonyl)phen­oxy]propyloxycarbonyl]ferrocene

The crystal structure of the title 1,1′-disubstituted ferrocene derivative was determined by X-ray diffraction using a single crystal. This compound exhibits a nematic phase only. The X-ray structure analysis revealed that the two substituents lie in the same direction (`U' shape) and the flexible spacer adopts a gauche conformation. These conformations are strongly related to the formation of a rod-like shape, which favors liquid crystalline behavior. In the crystal structure, C—H⋯π, π–π and T-stacking interactions were observed. It is considered that these interactions play a major role in stabilizing the molecular packing arrangement and the mesomorphism.

1. Introduction

Ferrocene is a metallocene that shows a remarkable aromaticity combined with thermal stability. It is well known that ferrocene derivatives have the potential to be liquid crystalline materials with unique properties, such as electrochemical (Carano et al., 2002) and photoinduced electron transfer (Even et al., 2001) properties. As substitution reactions occur easily at the cyclopentadienyl rings in the ferrocene molecule, just like in benzene, many different types of liquid crystalline ferrocene derivative have been synthesized and investigated. A number of papers concerned with ferrocene-containing liquid crystals have been published already. These papers deal with the thermal and mesomorphic properties of monosubstituted ferrocenes (Malthête & Billard, 1976; Imrie et al., 2001, 2003; Nakamura, Hanasaki & Onoi, 1993; Nakamura, Hanasaki, Onoi & Oida, 1993; Hanasaki et al., 1993; Nakamura et al., 1994, 1995; Nakamura & Takayama, 1997; Nakamura & Setodoi, 1998a,b, 1999a,b; Nakamura & Oida, 1999; Nakamura, Maekawahara et al., 2000; Nakamura, Setodoi & Hanasaki, 2000; Nakamura, Setodoi & Takayama, 2000; Nakamura et al., 2002; Nakamura et al., 2006a,b; Zhao et al., 2001; Deschenaux, Marendaz et al., 1995; Loubser et al., 1993; Loubser & Imrie, 1997), 1,1′-, 1,3- and 1,2-disubstituted ferrocenes (see next paragraph), 1,1′,3-trisubstituted ferrocene derivatives (Deschenaux, Kosztics & Nocolet, 1995), polycatenar ferrocenes (Deschenaux, Monnet et al., 1998), and ferrocene-containing liquid crystalline dendromers (Carano et al., 2002; Even et al., 2001; Chuard & Deschenaux, 2003; Deschenaux et al., 1997; Dardel et al., 1999; Deschenaux, Even & Guillon, 1998; Campidelli et al., 2004) [see also the reviews by Donnio et al. (2003) and Bruce et al. (2007a)].

From the structural viewpoint, disubstituted ferrocene derivatives can be classified into three families according to the positions of the substituent: 1,1′-, 1,2- and 1,3-disubstituted ferrocene derivatives. It is well known that the 1,1′-disubstituted ferrocene derivatives can adopt an `S' (Nakamura et al., 2005), a `U' (Nakamura & Okabe, 2004; Nakamura et al., 2007) or a `Z' (Nakamura & Nishikawa, 2005) shaped conformation. On the other hand, the 1,3-disubstituted ferrocene derivatives give a `T' (Deschenaux et al., 1993) shaped conformation. In the `S', the `T' and the `Z' shaped conformations, the two substituents lie in opposite directions with respect to the ferrocenyl group, but the `U' shape means that the two substituents lie in the same direction. In general, it is advantageous for the appearance of liquid crystallinity that the aspect ratio of molecular length to breadth should be relatively large. Therefore, it is considered that the `S' and the `T' shaped conformations are typical for liquid crystals of 1,1′-disubstituted ferrocene derivatives. In addition, it has been reported that 1,2-disubstituted ferrocene derivatives do not show liquid crystalline properties because of their unique hairpin structures (Bruce et al., 2007b).

A series of disubstituted ferrocene derivatives, 1,1′-bis[ω-[4-(4-methoxyphenoxycarbonyl)phenoxy]alkyl­oxy­carbonyl]ferrocene (abbreviated hereafter as bMAF-n, n = 2–12, where n is the number of C atoms in the methylene chain), have been prepared in our laboratory. The general structure of bMAF-n is shown in Fig. 1. In the homologous series, bMAF-3 and bMAF-5–bMAF-12 show liquid crystallinity, with nematic and smectic (except n = 3) phases. In contrast, bMAF-2 and bMAF-4 do not exhibit any liquid crystallinity (Hanasaki et al., 1994; Nakamura et al., 1998). The crystal structures of bMAF-2 (Nakamura & Nishikawa, 2005), bMAF-5 (Nakamura et al., 2005), bMAF-9 (Nakamura et al., 2007) and bMAF-10 (Nakamura & Okabe, 2004) have already been determined. In the crystal of bMAF-2 (Nakamura & Nishikawa, 2005), the molecule adopts the `Z' shaped conformation, and bMAF-5 (Nakamura et al., 2005) adopts the `S' shaped one, whereas in the crystals of bMAF-9 (Nakamura et al., 2007) and bMAF-10 (Nakamura & Okabe, 2004), the molecules exhibit the `U' shaped conformation.

Figure 1 General structure of bMAF-n (n = 2–12).

Correlations between the crystal structure and some physical properties can be deduced from the structure analyses.

In this study, the crystal and molecular structures of bMAF-3 were determined by X-ray diffraction methods using single crystals. Some interesting interactions will be discussed.

2. Experimental

Single crystals of the title compound were obtained from a mixed solvent solution of ethylacetate and heptane (1:1) by slow evaporation. The single crystals obtained are orange in color and plate-like. The sample, which had approximate dimensions of 0.75 × 0.10 × 0.05 mm, was mounted on a goniometer.

Data collection was carried out at 294 K, using a Rigaku AFC5R four-circle diffractometer with graphite-monochoromated Cu Kα (λ = 1.54178 Å) radiation, operated at 50 kV and 200 mA.

The unit-cell parameters were obtained from a least-squares refinement using the setting angle of 22 reflections in the range 18.27 < 2θ < 26.62°. The data were collected using the ω–2θ scan technique to a maximum 2θ value of 140.3°.

6153 reflections were measured, of which 4059 were unique. The intensities of three standard reflections were measured after every 150 reflections. Over the course of the data collection, the intensity of the standards decreased by 0.88%. The data were also corrected for Lorentz and polarization effects and for absorption [numerical (Coppens et al., 1965); the minimum and maximum transmission factors were 0.60091 and 0.83876, respectively].

All calculations were performed using the WinGX crystallographic software package (Farrugia, 1999). The atomic scattering factors were taken from Cromer & Waber (1974). The structure was solved by direct methods (SIR92; Altomare et al., 1994) and expanded using the Fourier technique. All non-H atoms were refined anisotropically, and all H atoms were refined isotropically. The H atoms were introduced at their theoretical positions and allowed to ride with the C atoms to which they are attached. The final refinement was made by full-matrix least-squares analysis based on 4059 observed reflections. The refinement cycles converged to R = 0.038, wR(F²) = 0.098, w = 1/[σ²(F_o²) + (0.0211P)² + 1.2943P], where P = [Max(F_o², 0) + 2F_c²]/3, and S = 1.052. The maximum shift s.u. ratio for all atoms in the final cycle is less than 0.001. The final cycles of the refinement resulted in a residual electron density in the range −0.369–0.346 eÅ⁻³.

Experimental details are summarized in Table 1.¹

Table 1
Summarized crystallographic data and results of final refinement

Empirical formula	C46H42O12Fe
Formula weight	842.68
Crystal system	Monoclinic
Space group	P21
a (Å)	5.857 (4)
b (Å)	24.105 (3)
c (Å)	14.069 (4)
β (°)	93.15 (4)
Volume (Å^3)	1983.5 (14)
Z	2
Dcalc (g cm^−3)	1.411
Measured reflections	6153
Independent reflections	4059
Observed reflections	4059
R	0.038
wR(F^2)	0.098
Goodness of fit (S)	1.052
Flack parameter	−0.005(5)

3. Results and discussion

3.1. Molecular structure

An ORTEPIII (Johnson & Burnett, 1996) drawing showing the molecular structure with the numbering for each atom is presented in Fig. 2, where the H atoms have been omitted for simplification.

Figure 2 ORTEPIII (Johnson & Burnett, 1996) views of the molecular structure excluding H atoms in bMAF-3. Displacement ellipsoids are drawn at the 50% probability level. Showing (a) the crystallographic numbering scheme, (b) a side view onto the cyclopentadienyl rings, (c) a view from above, onto the cyclopentadienyl rings, and (d) a projection along the long axis of the molecule. C atoms: black; O atoms: red; Fe atoms: brown.

In the ferrocenyl group, the two cyclopentadienyl rings are almost parallel; the dihedral angle is 1.0 (2)° (Table 2). The average values of the Fe—C and C—C bond distances in the ferrocenyl unit of bMAF-3 are 2.050 (5) and 1.421 (7) Å, respectively. The C—C—C bond angles in the cyclopentadienyl rings are 108.0 (4)°. These values agree with those of ferrocene reported elsewhere (Nakamura & Setodoi, 1998a,b, 1999a,b; Nakamura et al., 2002, 2005, 2006a,b, 2007; Nakamura, Setodoi & Takayama, 2000; Nakamura & Okabe, 2004; Nakamura & Nishikawa, 2005; Dunitz et al., 1956) within experimental error.

Table 2
Dihedral angles between least-squares planes of bMAF-3

Plane No.	Least-squares plane
Plane 1	Cp ring C1–C5
Plane 2	Phenyl ring C10–C15
Plane 3	Phenyl ring C17–C22
Plane 4	Cp ring C24–C28
Plane 5	Phenyl ring C33–C38
Plane 6	Phenyl ring C40–C45

Planes	Dihedral angle (°)
Plane 1–Plane 2	51.6 (2)
Plane 1–Plane 3	14.9 (2)
Plane 1–Plane 4	1.0 (2)
Plane 1–Plane 5	14.8 (2)
Plane 1–Plane 6	46.3 (2)
Plane 2–Plane 3	63.1 (2)
Plane 2–Plane 4	50.8 (2)
Plane 2–Plane 5	65.8 (2)
Plane 2–Plane 6	6.4 (2)
Plane 3–Plane 4	15.3 (2)
Plane 3–Plane 5	6.3 (2)
Plane 3–Plane 6	58.6 (2)
Plane 4–Plane 5	15.6 (2)
Plane 4–Plane 6	45.5 (2)
Plane 5–Plane 6	60.8 (2)

In the flexible spacers (C7–C9 and C30–C32), the C—C—C bond angles are 111.3 (4) and 113.1 (5)°, the average values of the C—C bond length are 1.509 (7) and 1.496 (8) Å, and the lengths of the chains are 2.488 (7) and 2.497 (7) Å, respectively. These values are nearly equal to the values determined for n-paraffin [e.g. the average C—C bond distance is approximately 1.54 Å and the length of the –CH₂—CH₂—CH₂– unit is 2.54 Å (Bunn, 1939)].

The molecular structure of bMAF-3 is somewhat different from that of the previously analyzed `U' shaped homologues bMAF-9 (Nakamura et al., 2007) and bMAF-10 (Nakamura & Okabe, 2004). The dihedral angles of the two phenyl rings (Plane 2–Plane 5 and Plane 3–Plane 6) in the mesogenic group are estimated to be 65.8 (2) and 58.6 (2)°, respectively, as shown in Table 2. In contrast, the dihedral angles between the two phenyl rings of bMAF-9 (Nakamura et al., 2007) and bMAF-10 (Nakamura & Okabe, 2004) are 3.5–11.2°, indicating that these phenyl rings are almost parallel.

The two substituents of bMAF-3 lie in the same direction (`U' shape), and the molecular length of bMAF-3 (C4–C23) is estimated to be 20.856 (16) Å. As the C6—O1—C7—C8, C7—C8—C9—O3, C29—O7—C30—C31 and C30—C31—C32—O9 fragments adopt a gauche conformation in the flexible spacer, the molecules can be considered as rod-like molecules, as shown in Table 3. A new shape of bMAF-n molecule was found by Nakamura & Nishikawa (2005), who reported a novel molecular structure for bMAF-2, the name of which was associated with a `Z' shape. The aspect ratio of bMAF-2 (Nakamura & Nishikawa, 2005) is rather low, which is not advantageous for the appearance of liquid crystallinity. Therefore, the rod-like shape obtained with the molecules analyzed in this paper is an important factor for obtaining a mesomorphic behavior.

Table 3
Selected torsion angles (°) of bMAF-3

C24—Fe1—C1—C6	1.8 (4)
O2—C6—O1—C7	0.3 (7)
C6—O1—C7—C8	78.0 (5)
O1—C7—C8—C9	176.5 (4)
C7—C8—C9—O3	59.4 (6)
C8—C9—O3—C10	176.6 (4)
C13—C16—O4—C17	−174.8 (4)
O5—C16—O4—C17	4.1 (7)
C1—Fe1—C24—C29	2.7 (5)
O8—C29—O7—C30	−3.7 (7)
C29—O7—C30—C31	145.9 (5)
O7—C30—C31—C32	178.1 (5)
C30—C31—C32—O9	63.2 (7)
C31—C32—O9—C33	−178.9 (5)
C36—C39—O10—C40	−179.3 (4)
O11—C39—O10—C40	0.2 (8)

3.2. Crystal structure

Projections of the ab and bc planes of bMAF-3 are shown in Figs. 3(a) and 3(b), respectively. In both projections, herringbone layer structures were observed. Among the other homologues of bMAF-n for which the molecular and crystal structures have been analyzed, only bMAF-3 exhibits such a structure.

Figure 3 Crystal structure of bMAF-3. (a) Projection onto the ab plane and (b) projection onto the bc plane.

The following intermolecular interactions were identified in bMAF-3:

(i) Two C—H⋯π interactions. One is between the H atoms on C8 and C9 of the methylene chains and the C40–C45 benzene ring of the mesogenic group (Fig. 4a). The other is between the H atom on C32 and the C10–C15 benzene ring (Fig. 4b).

Figure 4 Illustration of intermolecular interactions of bMAF-3.

(ii) One T-stacking π–π interaction, between the H atom on C4 of the Cp ring and the C17–C22 benzene ring in a neighboring layer (Fig. 4c).

(iii) A π–π interaction between the C1–C5 Cp ring and the C33–C38 benzene ring (Fig. 4d).

In addition, two intramolecular interactions are identified between the two substituents of the molecule. As shown in Fig. 5, they are two T-stacking interactions between H atoms (on C18, C19 and C37, C38) of the phenyl groups of the mesogenic units and the benzene rings C40–C45 and C10–C15, respectively. Therefore, bMAF-3 has four intermolecular interactions and two intramolecular interactions.

Figure 5 Illustration of intramolecular interactions of bMAF-3.

bMAF-3 exhibits only a monotropic nematic phase. On the other hand, bMAF-9 (Nakamura et al., 2007), for example, possesses a monotropic nematic phase and a smectic one. The difference between the occurrences of these liquid crystal phases is attributed to the different features of the inter- and intramolecular interactions in bMAF-3 and bMAF-9 (Nakamura et al., 2007). In the cooling process from the isotropic liquid phase, bMAF-3 gradually aggregates through the above-mentioned intramolecular interactions between the two substituents of bMAF-3 and the intermolecular interactions between neighboring molecules, while bMAF-9 (Nakamura et al., 2007) aggregates through the only intermolecular interactions between the two substituents of bMAF-9. Consequently, the presence of the different interactions may play an important role in giving rise to the mesomorphism.

Supporting information

S1. Comment

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Computing details

Program(s) used to solve structure: SIR92; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

(bMAF-3)

Crystal data

C46H42FeO12	F(000) = 880
Mr = 842.65	Dx = 1.411 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 22 reflections
a = 5.857 (4) Å	θ = 9.1–13.3°
b = 24.105 (3) Å	µ = 3.61 mm^−1
c = 14.069 (4) Å	T = 294 K
β = 93.15 (4)°	Plate, orange
V = 1983.5 (14) Å^3	0.75 × 0.10 × 0.05 mm
Z = 2

Data collection

Rigaku AFC5R diffractometer	Rint = 0.051
ω–2θ scans	θmax = 70.2°, θmin = 3.2°
Absorption correction: numerical Coppens numerical	h = −2→7
Tmin = 0.601, Tmax = 0.839	k = −2→29
6153 measured reflections	l = −17→17
4059 independent reflections	3 standard reflections every 150 reflections
3409 reflections with I > 2σ(I)	intensity decay: 0.9%

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 1.2943P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max < 0.001
R[F^2 > 2σ(F^2)] = 0.038	Δρmax = 0.35 e Å^−3
wR(F^2) = 0.098	Δρmin = −0.37 e Å^−3
S = 1.05	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
4059 reflections	Extinction coefficient: 0.00185 (16)
533 parameters	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
1 restraint	Absolute structure parameter: −0.005 (5)
All H-atom parameters refined

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.36555 (11)	0.09290 (3)	0.77259 (5)	0.03429 (17)
O1	0.7952 (5)	0.19366 (14)	0.6861 (2)	0.0405 (8)
O2	0.4474 (6)	0.23080 (16)	0.6539 (3)	0.0506 (9)
O3	0.8731 (7)	0.30617 (18)	0.4651 (3)	0.0594 (11)
O4	1.1620 (6)	0.44284 (16)	0.1083 (2)	0.0463 (9)
O5	0.8655 (8)	0.3937 (2)	0.0433 (3)	0.0747 (14)
O6	1.2161 (8)	0.56414 (18)	−0.2226 (3)	0.0646 (11)
O7	0.2608 (6)	0.13152 (17)	0.5087 (2)	0.0502 (9)
O8	0.6241 (5)	0.1026 (2)	0.5283 (2)	0.0606 (11)
O9	0.3436 (7)	0.18467 (17)	0.2281 (3)	0.0623 (11)
O10	0.5471 (7)	0.33786 (16)	−0.1202 (3)	0.0553 (10)
O11	0.8438 (8)	0.27876 (19)	−0.1262 (3)	0.0700 (13)
O12	0.7716 (10)	0.4582 (2)	−0.4357 (4)	0.0979 (18)
C1	0.5083 (7)	0.1697 (2)	0.7853 (3)	0.0361 (10)
C2	0.2857 (8)	0.1705 (2)	0.8218 (3)	0.0397 (11)
H2	0.1634	0.1925	0.8	0.048*
C3	0.2849 (9)	0.1316 (2)	0.8970 (3)	0.0452 (12)
H3	0.1614	0.1236	0.9335	0.054*
C4	0.5058 (8)	0.1070 (2)	0.9074 (3)	0.0457 (13)
H4	0.5517	0.0802	0.952	0.055*
C5	0.6440 (8)	0.1305 (2)	0.8380 (3)	0.0397 (11)
H5	0.7958	0.1217	0.8288	0.048*
C6	0.5757 (8)	0.2019 (2)	0.7021 (3)	0.0353 (10)
C7	0.8831 (9)	0.2222 (2)	0.6044 (3)	0.0405 (11)
H7A	0.7726	0.2195	0.5507	0.049*
H7B	1.0233	0.2044	0.5869	0.049*
C8	0.9294 (9)	0.2822 (2)	0.6271 (3)	0.0421 (11)
H8A	1.0324	0.2848	0.6833	0.051*
H8B	0.7874	0.3004	0.6409	0.051*
C9	1.0345 (9)	0.3114 (2)	0.5450 (3)	0.0460 (12)
H9A	1.0617	0.3502	0.5601	0.055*
H9B	1.1789	0.2943	0.5312	0.055*
C10	0.9208 (9)	0.3316 (2)	0.3826 (4)	0.0449 (12)
C11	0.7601 (10)	0.3232 (3)	0.3075 (4)	0.0558 (15)
H11	0.6319	0.3015	0.3168	0.067*
C12	0.7881 (9)	0.3462 (2)	0.2208 (4)	0.0530 (14)
H12	0.6805	0.3396	0.171	0.064*
C13	0.9773 (8)	0.3796 (2)	0.2061 (3)	0.0375 (10)
C14	1.1339 (9)	0.3882 (2)	0.2799 (3)	0.0442 (12)
H14	1.2599	0.4107	0.2706	0.053*
C15	1.1096 (9)	0.3642 (2)	0.3688 (3)	0.0481 (13)
H15	1.2192	0.3701	0.4181	0.058*
C16	0.9922 (9)	0.4048 (2)	0.1111 (3)	0.0446 (12)
C17	1.1743 (9)	0.4723 (2)	0.0216 (3)	0.0409 (11)
C18	1.3590 (9)	0.4635 (2)	−0.0315 (4)	0.0475 (13)
H18	1.469	0.4372	−0.0129	0.057*
C19	1.3795 (10)	0.4947 (2)	−0.1142 (4)	0.0482 (13)
H19	1.5044	0.4893	−0.1512	0.058*
C20	1.2166 (9)	0.5330 (2)	−0.1411 (3)	0.0443 (11)
C21	1.0319 (9)	0.5415 (2)	−0.0855 (4)	0.0499 (13)
H21	0.9214	0.5677	−0.1034	0.06*
C22	1.0117 (9)	0.5111 (2)	−0.0038 (4)	0.0471 (12)
H22	0.8884	0.5168	0.034	0.057*
C23	1.4000 (13)	0.5555 (3)	−0.2841 (4)	0.084 (2)
H23A	1.3805	0.5795	−0.3385	0.126*
H23B	1.4001	0.5176	−0.3048	0.126*
H23C	1.5427	0.5638	−0.2502	0.126*
C24	0.3464 (8)	0.0703 (2)	0.6321 (3)	0.0395 (10)
C25	0.1221 (7)	0.0711 (2)	0.6687 (3)	0.0378 (10)
H25	−0.0012	0.0928	0.647	0.045*
C26	0.1257 (9)	0.0323 (2)	0.7444 (4)	0.0461 (12)
H26	0.0024	0.0239	0.7808	0.055*
C27	0.3455 (9)	0.0083 (2)	0.7560 (4)	0.0471 (12)
H27	0.3908	−0.0182	0.8012	0.057*
C28	0.4833 (8)	0.0313 (2)	0.6881 (4)	0.0437 (11)
H28	0.6362	0.0229	0.6804	0.052*
C29	0.4314 (8)	0.1026 (2)	0.5522 (3)	0.0403 (11)
C30	0.3165 (9)	0.1675 (2)	0.4313 (4)	0.0493 (13)
H30A	0.4526	0.1542	0.4023	0.059*
H30B	0.3457	0.2048	0.4546	0.059*
C31	0.1195 (10)	0.1675 (3)	0.3604 (4)	0.0595 (15)
H31A	−0.0165	0.179	0.3914	0.071*
H31B	0.0943	0.13	0.3372	0.071*
C32	0.1536 (10)	0.2052 (3)	0.2768 (4)	0.0631 (16)
H32A	0.0173	0.2056	0.2344	0.076*
H32B	0.1837	0.2428	0.2988	0.076*
C33	0.4093 (9)	0.2131 (2)	0.1500 (3)	0.0469 (12)
C34	0.6066 (11)	0.1948 (3)	0.1117 (4)	0.0529 (15)
H34	0.6849	0.1646	0.1388	0.064*
C35	0.6892 (10)	0.2208 (3)	0.0334 (4)	0.0498 (14)
H35	0.8218	0.208	0.0074	0.06*
C36	0.5739 (9)	0.2664 (2)	−0.0066 (4)	0.0460 (12)
C37	0.3739 (10)	0.2834 (2)	0.0302 (4)	0.0521 (13)
H37	0.2931	0.3127	0.0016	0.062*
C38	0.2894 (10)	0.2579 (3)	0.1090 (4)	0.0542 (14)
H38	0.1552	0.2704	0.1342	0.065*
C39	0.6755 (10)	0.2934 (2)	−0.0898 (4)	0.0488 (13)
C40	0.6171 (9)	0.3676 (2)	−0.1985 (4)	0.0466 (12)
C41	0.4730 (10)	0.3699 (2)	−0.2775 (4)	0.0542 (13)
H41	0.3357	0.3505	−0.2793	0.065*
C42	0.5295 (11)	0.4008 (3)	−0.3543 (4)	0.0608 (16)
H42	0.4297	0.4024	−0.408	0.073*
C43	0.7321 (11)	0.4295 (2)	−0.3530 (4)	0.0551 (14)
C44	0.8769 (11)	0.4278 (3)	−0.2745 (4)	0.0584 (15)
H44	1.0132	0.4477	−0.2728	0.07*
C45	0.8203 (10)	0.3960 (2)	−0.1956 (4)	0.0537 (14)
H45	0.9198	0.3941	−0.1419	0.064*
C46	0.960 (2)	0.4893 (5)	−0.4419 (8)	0.137 (4)
H46A	0.9592	0.5062	−0.5037	0.206*
H46B	1.093	0.4662	−0.4325	0.206*
H46C	0.9627	0.5176	−0.3939	0.206*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0345 (4)	0.0346 (3)	0.0338 (3)	−0.0033 (4)	0.0016 (2)	0.0035 (4)
O1	0.0391 (18)	0.0422 (18)	0.0410 (17)	−0.0005 (15)	0.0097 (14)	0.0097 (15)
O2	0.0392 (19)	0.054 (2)	0.058 (2)	0.0044 (18)	−0.0008 (16)	0.0193 (19)
O3	0.066 (2)	0.070 (3)	0.0418 (19)	−0.023 (2)	−0.0051 (17)	0.024 (2)
O4	0.054 (2)	0.049 (2)	0.0347 (16)	−0.0147 (18)	0.0006 (15)	0.0069 (16)
O5	0.094 (3)	0.084 (3)	0.043 (2)	−0.036 (3)	−0.016 (2)	0.014 (2)
O6	0.096 (3)	0.052 (2)	0.047 (2)	0.000 (2)	0.015 (2)	0.012 (2)
O7	0.048 (2)	0.062 (2)	0.0420 (18)	0.0029 (19)	0.0125 (15)	0.0117 (18)
O8	0.0466 (18)	0.085 (3)	0.0512 (18)	0.000 (2)	0.0138 (15)	0.006 (2)
O9	0.083 (3)	0.061 (3)	0.045 (2)	0.007 (2)	0.0212 (19)	0.0107 (19)
O10	0.061 (2)	0.055 (2)	0.051 (2)	0.005 (2)	0.0120 (18)	0.0078 (19)
O11	0.079 (3)	0.064 (3)	0.071 (3)	0.018 (2)	0.031 (2)	0.009 (2)
O12	0.112 (4)	0.086 (4)	0.098 (4)	−0.025 (4)	0.025 (3)	0.029 (3)
C1	0.031 (2)	0.040 (2)	0.037 (2)	0.004 (2)	0.0021 (18)	0.007 (2)
C2	0.040 (3)	0.040 (3)	0.039 (2)	0.001 (2)	0.005 (2)	−0.001 (2)
C3	0.049 (3)	0.049 (3)	0.038 (2)	−0.013 (2)	0.007 (2)	0.003 (2)
C4	0.053 (3)	0.048 (3)	0.035 (2)	−0.006 (2)	−0.0062 (19)	0.010 (2)
C5	0.039 (3)	0.045 (3)	0.035 (2)	0.002 (2)	0.0010 (19)	0.002 (2)
C6	0.033 (2)	0.032 (2)	0.041 (2)	−0.003 (2)	0.0039 (19)	0.001 (2)
C7	0.045 (3)	0.039 (3)	0.038 (2)	−0.004 (2)	0.014 (2)	0.004 (2)
C8	0.047 (3)	0.041 (3)	0.039 (2)	−0.005 (2)	0.008 (2)	0.003 (2)
C9	0.047 (3)	0.051 (3)	0.040 (2)	−0.012 (3)	−0.001 (2)	0.006 (2)
C10	0.049 (3)	0.045 (3)	0.041 (3)	−0.007 (2)	0.004 (2)	0.011 (2)
C11	0.048 (3)	0.065 (4)	0.054 (3)	−0.017 (3)	−0.002 (3)	0.011 (3)
C12	0.051 (3)	0.063 (4)	0.044 (3)	−0.008 (3)	−0.005 (2)	0.006 (3)
C13	0.041 (3)	0.035 (2)	0.036 (2)	−0.006 (2)	0.0027 (19)	0.003 (2)
C14	0.046 (3)	0.044 (3)	0.042 (3)	−0.007 (2)	0.004 (2)	0.004 (2)
C15	0.055 (3)	0.050 (3)	0.038 (3)	−0.013 (3)	−0.002 (2)	0.010 (2)
C16	0.054 (3)	0.045 (3)	0.034 (2)	0.002 (3)	0.001 (2)	0.004 (2)
C17	0.051 (3)	0.038 (3)	0.034 (2)	−0.003 (2)	0.003 (2)	0.004 (2)
C18	0.051 (3)	0.042 (3)	0.050 (3)	0.006 (3)	0.009 (2)	0.001 (2)
C19	0.056 (3)	0.045 (3)	0.045 (3)	0.000 (3)	0.012 (3)	−0.006 (3)
C20	0.059 (3)	0.035 (2)	0.038 (2)	−0.006 (2)	0.001 (2)	0.001 (2)
C21	0.059 (3)	0.044 (3)	0.048 (3)	0.002 (3)	0.005 (2)	0.005 (2)
C22	0.055 (3)	0.048 (3)	0.039 (2)	0.007 (3)	0.010 (2)	0.005 (2)
C23	0.122 (6)	0.081 (5)	0.054 (4)	−0.009 (5)	0.040 (4)	0.017 (4)
C24	0.044 (3)	0.036 (2)	0.038 (2)	0.002 (2)	−0.001 (2)	−0.002 (2)
C25	0.033 (2)	0.042 (2)	0.038 (2)	−0.003 (2)	−0.0025 (19)	−0.002 (2)
C26	0.045 (3)	0.043 (3)	0.050 (3)	−0.018 (2)	0.001 (2)	0.000 (2)
C27	0.055 (3)	0.027 (2)	0.059 (3)	−0.004 (2)	0.000 (2)	0.005 (2)
C28	0.038 (3)	0.042 (3)	0.051 (3)	0.000 (2)	0.003 (2)	−0.009 (2)
C29	0.045 (2)	0.045 (3)	0.0307 (19)	0.000 (3)	0.0055 (17)	−0.006 (2)
C30	0.062 (3)	0.049 (3)	0.038 (3)	0.002 (3)	0.014 (2)	0.005 (2)
C31	0.061 (3)	0.077 (4)	0.040 (3)	−0.007 (3)	0.005 (2)	0.008 (3)
C32	0.061 (4)	0.081 (4)	0.048 (3)	0.010 (4)	0.008 (3)	0.014 (3)
C33	0.057 (3)	0.050 (3)	0.034 (2)	−0.007 (3)	0.004 (2)	0.002 (2)
C34	0.062 (4)	0.047 (3)	0.051 (3)	0.003 (3)	0.011 (3)	0.000 (3)
C35	0.055 (3)	0.048 (3)	0.047 (3)	0.002 (3)	0.006 (2)	−0.007 (3)
C36	0.052 (3)	0.045 (3)	0.041 (3)	−0.002 (2)	0.002 (2)	−0.003 (2)
C37	0.058 (3)	0.052 (3)	0.047 (3)	0.003 (3)	0.007 (2)	0.002 (3)
C38	0.052 (3)	0.058 (3)	0.054 (3)	0.008 (3)	0.012 (3)	0.006 (3)
C39	0.054 (3)	0.051 (3)	0.043 (3)	−0.003 (3)	0.010 (2)	−0.005 (2)
C40	0.053 (3)	0.043 (3)	0.045 (3)	−0.007 (2)	0.012 (2)	−0.003 (2)
C41	0.053 (3)	0.047 (3)	0.061 (3)	−0.004 (3)	−0.005 (3)	0.001 (3)
C42	0.071 (4)	0.056 (3)	0.054 (3)	0.004 (3)	−0.014 (3)	0.006 (3)
C43	0.062 (4)	0.048 (3)	0.055 (3)	−0.008 (3)	0.007 (3)	0.002 (3)
C44	0.058 (4)	0.058 (4)	0.060 (3)	−0.014 (3)	0.008 (3)	−0.006 (3)
C45	0.059 (3)	0.060 (3)	0.042 (3)	−0.005 (3)	0.002 (2)	−0.010 (3)
C46	0.150 (9)	0.123 (9)	0.140 (9)	0.011 (8)	0.019 (8)	0.054 (8)

Geometric parameters (Å, º)

O1—C6	1.332 (5)	C21—H21	0.93
O1—C7	1.457 (5)	C22—H22	0.93
O2—C6	1.206 (6)	C23—H23A	0.96
O3—C10	1.356 (6)	C23—H23B	0.96
O3—C9	1.433 (6)	C23—H23C	0.96
O4—C16	1.354 (6)	C24—C25	1.437 (6)
O4—C17	1.417 (6)	C24—C28	1.441 (7)
O5—C16	1.206 (6)	C24—C29	1.477 (6)
O6—C20	1.370 (6)	C25—C26	1.416 (7)
O6—C23	1.433 (7)	C25—H25	0.93
O7—C29	1.338 (6)	C26—C27	1.412 (7)
O7—C30	1.444 (6)	C26—H26	0.93
O8—C29	1.195 (5)	C27—C28	1.399 (7)
O9—C33	1.367 (6)	C27—H27	0.93
O9—C32	1.428 (6)	C28—H28	0.93
O10—C39	1.364 (7)	C30—C31	1.483 (7)
O10—C40	1.395 (6)	C30—H30A	0.97
O11—C39	1.189 (6)	C30—H30B	0.97
O12—C46	1.340 (11)	C31—C32	1.509 (8)
O12—C43	1.384 (7)	C31—H31A	0.97
C1—C5	1.418 (6)	C31—H31B	0.97
C1—C2	1.427 (6)	C32—H32A	0.97
C1—C6	1.476 (6)	C32—H32B	0.97
C2—C3	1.414 (7)	C33—C34	1.375 (8)
C2—H2	0.93	C33—C38	1.396 (8)
C3—C4	1.424 (7)	C34—C35	1.378 (8)
C3—H3	0.93	C34—H34	0.93
C4—C5	1.419 (6)	C35—C36	1.392 (8)
C4—H4	0.93	C35—H35	0.93
C5—H5	0.93	C36—C37	1.369 (7)
C7—C8	1.504 (7)	C36—C39	1.492 (7)
C7—H7A	0.97	C37—C38	1.382 (7)
C7—H7B	0.97	C37—H37	0.93
C8—C9	1.513 (6)	C38—H38	0.93
C8—H8A	0.97	C40—C41	1.359 (8)
C8—H8B	0.97	C40—C45	1.371 (7)
C9—H9A	0.97	C41—C42	1.369 (8)
C9—H9B	0.97	C41—H41	0.93
C10—C15	1.379 (7)	C42—C43	1.373 (8)
C10—C11	1.391 (7)	C42—H42	0.93
C11—C12	1.358 (7)	C43—C44	1.356 (8)
C11—H11	0.93	C44—C45	1.404 (8)
C12—C13	1.395 (7)	C44—H44	0.93
C12—H12	0.93	C45—H45	0.93
C13—C14	1.362 (7)	C46—H46A	0.96
C13—C16	1.476 (6)	C46—H46B	0.96
C14—C15	1.393 (7)	C46—H46C	0.96
C14—H14	0.93	Fe1—C1	2.035 (5)
C15—H15	0.93	Fe1—C2	2.057 (5)
C17—C18	1.365 (7)	Fe1—C3	2.061 (5)
C17—C22	1.368 (7)	Fe1—C4	2.053 (5)
C18—C19	1.396 (8)	Fe1—C5	2.040 (5)
C18—H18	0.93	Fe1—C24	2.047 (5)
C19—C20	1.367 (8)	Fe1—C25	2.053 (4)
C19—H19	0.93	Fe1—C26	2.050 (5)
C20—C21	1.385 (7)	Fe1—C27	2.055 (5)
C21—C22	1.373 (7)	Fe1—C28	2.045 (5)
C6—O1—C7	116.7 (4)	H23A—C23—H23B	109.5
C10—O3—C9	118.2 (4)	O6—C23—H23C	109.5
C16—O4—C17	115.9 (4)	H23A—C23—H23C	109.5
C20—O6—C23	117.3 (5)	H23B—C23—H23C	109.5
C29—O7—C30	117.6 (4)	C25—C24—C28	107.8 (4)
C33—O9—C32	118.2 (5)	C25—C24—C29	128.2 (4)
C39—O10—C40	118.1 (4)	C28—C24—C29	124.0 (4)
C46—O12—C43	120.7 (7)	C26—C25—C24	106.5 (4)
C5—C1—C2	108.5 (4)	C26—C25—H25	126.7
C5—C1—C6	126.7 (4)	C24—C25—H25	126.7
C2—C1—C6	124.6 (4)	C27—C26—C25	109.4 (4)
C3—C2—C1	107.5 (4)	C27—C26—H26	125.3
C3—C2—H2	126.2	C25—C26—H26	125.3
C1—C2—H2	126.2	C28—C27—C26	108.4 (5)
C2—C3—C4	108.2 (4)	C28—C27—H27	125.8
C2—C3—H3	125.9	C26—C27—H27	125.8
C4—C3—H3	125.9	C27—C28—C24	107.9 (4)
C5—C4—C3	108.2 (4)	C27—C28—H28	126.1
C5—C4—H4	125.9	C24—C28—H28	126.1
C3—C4—H4	125.9	O8—C29—O7	124.4 (5)
C1—C5—C4	107.5 (4)	O8—C29—C24	125.2 (5)
C1—C5—H5	126.2	O7—C29—C24	110.4 (4)
C4—C5—H5	126.2	O7—C30—C31	107.9 (5)
O2—C6—O1	124.7 (4)	O7—C30—H30A	110.1
O2—C6—C1	124.3 (4)	C31—C30—H30A	110.1
O1—C6—C1	111.0 (4)	O7—C30—H30B	110.1
O1—C7—C8	110.8 (4)	C31—C30—H30B	110.1
O1—C7—H7A	109.5	H30A—C30—H30B	108.4
C8—C7—H7A	109.5	C30—C31—C32	113.1 (5)
O1—C7—H7B	109.5	C30—C31—H31A	109
C8—C7—H7B	109.5	C32—C31—H31A	109
H7A—C7—H7B	108.1	C30—C31—H31B	109
C7—C8—C9	111.3 (4)	C32—C31—H31B	109
C7—C8—H8A	109.4	H31A—C31—H31B	107.8
C9—C8—H8A	109.4	O9—C32—C31	107.7 (5)
C7—C8—H8B	109.4	O9—C32—H32A	110.2
C9—C8—H8B	109.4	C31—C32—H32A	110.2
H8A—C8—H8B	108	O9—C32—H32B	110.2
O3—C9—C8	106.2 (4)	C31—C32—H32B	110.2
O3—C9—H9A	110.5	H32A—C32—H32B	108.5
C8—C9—H9A	110.5	O9—C33—C34	115.8 (5)
O3—C9—H9B	110.5	O9—C33—C38	124.2 (5)
C8—C9—H9B	110.5	C34—C33—C38	120.0 (5)
H9A—C9—H9B	108.7	C33—C34—C35	120.5 (6)
O3—C10—C15	125.7 (5)	C33—C34—H34	119.7
O3—C10—C11	114.9 (4)	C35—C34—H34	119.7
C15—C10—C11	119.4 (5)	C34—C35—C36	119.9 (6)
C12—C11—C10	120.8 (5)	C34—C35—H35	120.1
C12—C11—H11	119.6	C36—C35—H35	120.1
C10—C11—H11	119.6	C37—C36—C35	119.3 (5)
C11—C12—C13	120.4 (5)	C37—C36—C39	123.5 (5)
C11—C12—H12	119.8	C35—C36—C39	117.2 (5)
C13—C12—H12	119.8	C36—C37—C38	121.5 (5)
C14—C13—C12	118.8 (4)	C36—C37—H37	119.3
C14—C13—C16	123.8 (4)	C38—C37—H37	119.3
C12—C13—C16	117.4 (4)	C37—C38—C33	118.8 (5)
C13—C14—C15	121.5 (5)	C37—C38—H38	120.6
C13—C14—H14	119.2	C33—C38—H38	120.6
C15—C14—H14	119.2	O11—C39—O10	123.7 (5)
C10—C15—C14	119.0 (5)	O11—C39—C36	125.7 (6)
C10—C15—H15	120.5	O10—C39—C36	110.6 (4)
C14—C15—H15	120.5	C41—C40—C45	120.2 (5)
O5—C16—O4	123.3 (5)	C41—C40—O10	118.1 (5)
O5—C16—C13	124.1 (5)	C45—C40—O10	121.7 (5)
O4—C16—C13	112.7 (4)	C40—C41—C42	120.1 (5)
C18—C17—C22	121.7 (5)	C40—C41—H41	119.9
C18—C17—O4	118.2 (5)	C42—C41—H41	119.9
C22—C17—O4	120.0 (4)	C41—C42—C43	120.6 (6)
C17—C18—C19	118.6 (5)	C41—C42—H42	119.7
C17—C18—H18	120.7	C43—C42—H42	119.7
C19—C18—H18	120.7	C44—C43—C42	119.8 (6)
C20—C19—C18	120.3 (5)	C44—C43—O12	125.0 (6)
C20—C19—H19	119.9	C42—C43—O12	115.1 (6)
C18—C19—H19	119.9	C43—C44—C45	119.7 (6)
C19—C20—O6	124.8 (5)	C43—C44—H44	120.1
C19—C20—C21	119.9 (5)	C45—C44—H44	120.1
O6—C20—C21	115.3 (5)	C40—C45—C44	119.5 (5)
C22—C21—C20	120.0 (5)	C40—C45—H45	120.3
C22—C21—H21	120	C44—C45—H45	120.3
C20—C21—H21	120	O12—C46—H46A	109.5
C17—C22—C21	119.5 (5)	O12—C46—H46B	109.5
C17—C22—H22	120.2	H46A—C46—H46B	109.5
C21—C22—H22	120.2	O12—C46—H46C	109.5
O6—C23—H23A	109.5	H46A—C46—H46C	109.5
O6—C23—H23B	109.5	H46B—C46—H46C	109.5
C5—C1—C2—C3	0.0 (6)	C25—C24—C28—C27	0.9 (6)
C6—C1—C2—C3	176.0 (5)	C29—C24—C28—C27	−179.3 (5)
C1—C2—C3—C4	0.1 (6)	C30—O7—C29—O8	−3.7 (8)
C2—C3—C4—C5	−0.3 (6)	C30—O7—C29—C24	177.3 (4)
C2—C1—C5—C4	−0.2 (5)	C25—C24—C29—O8	175.5 (5)
C6—C1—C5—C4	−176.0 (5)	C28—C24—C29—O8	−4.3 (8)
C3—C4—C5—C1	0.3 (6)	C25—C24—C29—O7	−5.6 (7)
C7—O1—C6—O2	0.2 (7)	C28—C24—C29—O7	174.6 (5)
C7—O1—C6—C1	178.8 (4)	C29—O7—C30—C31	145.9 (5)
C5—C1—C6—O2	172.5 (5)	O7—C30—C31—C32	178.1 (5)
C2—C1—C6—O2	−2.6 (8)	C33—O9—C32—C31	−178.9 (5)
C5—C1—C6—O1	−6.1 (7)	C30—C31—C32—O9	63.2 (7)
C2—C1—C6—O1	178.8 (4)	C32—O9—C33—C34	173.7 (5)
C6—O1—C7—C8	78.0 (5)	C32—O9—C33—C38	−6.6 (8)
O1—C7—C8—C9	176.5 (4)	O9—C33—C34—C35	−179.4 (5)
C10—O3—C9—C8	176.5 (5)	C38—C33—C34—C35	0.8 (9)
C7—C8—C9—O3	59.4 (6)	C33—C34—C35—C36	0.7 (9)
C9—O3—C10—C15	−2.3 (9)	C34—C35—C36—C37	−2.6 (8)
C9—O3—C10—C11	178.0 (5)	C34—C35—C36—C39	178.6 (5)
O3—C10—C11—C12	−179.7 (6)	C35—C36—C37—C38	3.0 (8)
C15—C10—C11—C12	0.6 (9)	C39—C36—C37—C38	−178.3 (5)
C10—C11—C12—C13	−1.1 (10)	C36—C37—C38—C33	−1.5 (9)
C11—C12—C13—C14	0.6 (8)	O9—C33—C38—C37	179.8 (5)
C11—C12—C13—C16	−177.8 (6)	C34—C33—C38—C37	−0.5 (9)
C12—C13—C14—C15	0.4 (8)	C40—O10—C39—O11	0.1 (8)
C16—C13—C14—C15	178.7 (5)	C40—O10—C39—C36	−179.3 (4)
O3—C10—C15—C14	−179.3 (5)	C37—C36—C39—O11	−177.0 (6)
C11—C10—C15—C14	0.4 (9)	C35—C36—C39—O11	1.8 (9)
C13—C14—C15—C10	−0.9 (9)	C37—C36—C39—O10	2.4 (7)
C17—O4—C16—O5	4.2 (8)	C35—C36—C39—O10	−178.9 (5)
C17—O4—C16—C13	−174.7 (4)	C39—O10—C40—C41	118.7 (6)
C14—C13—C16—O5	173.4 (6)	C39—O10—C40—C45	−64.1 (7)
C12—C13—C16—O5	−8.3 (8)	C45—C40—C41—C42	−0.4 (9)
C14—C13—C16—O4	−7.7 (7)	O10—C40—C41—C42	176.9 (5)
C12—C13—C16—O4	170.7 (5)	C40—C41—C42—C43	0.4 (9)
C16—O4—C17—C18	−113.0 (5)	C41—C42—C43—C44	−0.7 (10)
C16—O4—C17—C22	71.2 (6)	C41—C42—C43—O12	178.7 (6)
C22—C17—C18—C19	−0.6 (8)	C46—O12—C43—C44	−2.7 (11)
O4—C17—C18—C19	−176.4 (5)	C46—O12—C43—C42	177.8 (8)
C17—C18—C19—C20	−0.2 (9)	C42—C43—C44—C45	1.1 (10)
C18—C19—C20—O6	−177.4 (5)	O12—C43—C44—C45	−178.3 (6)
C18—C19—C20—C21	0.7 (8)	C41—C40—C45—C44	0.7 (9)
C23—O6—C20—C19	0.1 (8)	O10—C40—C45—C44	−176.4 (5)
C23—O6—C20—C21	−178.0 (5)	C43—C44—C45—C40	−1.1 (9)
C19—C20—C21—C22	−0.4 (8)	C24—Fe1—C1—C6	1.8 (4)
O6—C20—C21—C22	177.9 (5)	C8—C9—O3—C10	176.6 (4)
C18—C17—C22—C21	1.0 (8)	C13—C16—O4—C17	−174.8 (4)
O4—C17—C22—C21	176.6 (5)	O5—C16—O4—C17	4.1 (7)
C20—C21—C22—C17	−0.4 (8)	C1—Fe1—C24—C29	2.7 (5)
C28—C24—C25—C26	−1.0 (5)	O8—C29—O7—C30	−3.7 (7)
C29—C24—C25—C26	179.2 (5)	C31—C32—O9—C33	−178.9 (5)
C24—C25—C26—C27	0.7 (5)	C36—C39—O10—C40	−179.3 (4)
C25—C26—C27—C28	−0.2 (6)	O11—C39—O10—C40	0.2 (8)
C26—C27—C28—C24	−0.4 (6)

 

Footnotes

‡Present address: Film Customer Solution Department, Films Division, Unitika Ltd, 31-3 Uji-Hinojiri, Uji-City, Kyoto 611-0021, Japan.

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: DD5042 ). Services for accessing these data are described at the back of the journal.