Cocrystals composed of 4,4′-(fluorene-9,9-di­yl)diphenol and 6-methyl-2H-pyridone

Lavy, T.; Meirovich, N.; Sparkes, H.A.; Howard, J.A.K.; Kaftory, M.

doi:10.1107/S010827010604474X

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 63| Part 2| February 2007| Pages o89-o92

doi:10.1107/S010827010604474X

Cocrystals composed of 4,4′-(fluorene-9,9-diyl)diphenol and 6-methyl-2H-pyridone

T. Lavy,^a N. Meirovich,^a H. A. Sparkes,^b J. A. K. Howard ^b and M. Kaftory ^a ^*

^aSchulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa 32000, Israel, and ^bUniversity of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: kaftory@tx.technion.ac.il

(Received 10 September 2006; accepted 26 October 2006; online 13 January 2007)

The crystal structures of two cocrystals composed of 4,4′-(fluorene-9,9-diyl)diphenol (C₂₅H₁₈O₂) and 6-methyl-2H-pyridone (C₆H₇NO) are reported, namely 4,4′-(fluorene-9,9-diyl)diphenol–6-methyl-2H-pyridone (1/2), C₂₅H₁₈O₂·2C₆H₇NO, (I), and 4,4′-(fluorene-9,9-diyl)diphenol–6-methyl-2H-pyridone–water (1/3/3), C₂₅H₁₈O₂·3C₆H₇NO·3H₂O, (II). In both cocrystals, the mutual orientation between two 6-methyl-2H-pyridone molecules in principle enables photodimerization, yet in both cases no photodimerization occurs. In cocrystal (I) this is probably due to poor orbital overlap, while in the case of cocrystal (II) it is suggested that the lack of reaction is due to the highly complex hydrogen-bonding network that exists in the structure.

Comment

Among the numerous uses of solid inclusion compounds (Tanaka & Toda, 2002 ; Toda et al., 2001 ; Toda, 1995 , 1996 , 1988 ; Toda & Tanaka, 1984 ), those consisting of light-stable host molecules and light-sensitive guest molecules can be used for monitoring photochemical reactions in the solid state provided that the integrity of the single crystal is preserved throughout the reaction. The reaction of the guest molecules takes place in a cavity formed by the host; therefore, in the cases where the volume of the cavity is sufficient to accommodate the product, single-crystal-to-single-crystal transformations can occur (Lavy et al., 2004 ; Tanaka et al., 2000 ; Hosomi et al., 2000 ; Tanaka, Mizutani et al., 1999 ; Tanaka, Toda et al., 1999 ). 4,4′-(Fluorene-9,9-diyl)diphenol (A) was found to be an effective clathrate host and a useful construction element to form rigid macrocyclic host compounds (Apel et al., 2001 ). However, only two cocrystals containing A were found in the Cambridge Structural Database [Allen, 2002 ; refcodes ABUCIJ and ABUCUV (Apel et al., 2001)]. We report here the structures of two new cocrystals containing A and the photosensitive molecule 6-methyl-2H-pyridone (B). These cocrystals were crystallized in an attempt to achieve single-crystal-to-single-crystal photodimerization in inclusion compounds. Cocrystal (I) (Fig. 1) crystallizes in the monoclinic space group C2/c. The asymmetric unit contains one molecule of A and two molecules of B. Cocrystal (II) (Fig. 2) also crystallizes in the monoclinic space group C2/c. In this case, the asymmetric unit contains one molecule of A, three molecules of B (Ba, Bb and Bc) and three water molecules.

In cocrystal (I), pairs of molecules of B form hydrogen-bonded dimers, as in many structures of pyridone derivatives (Lavy & Kaftory, 2006 ; Lavy et al., 2006 ). Each dimer is connected via hydrogen bonding to two molecules of A, creating infinite chains (Fig. 3 and Table 1). The mutual relationship between two adjacent molecules of B in different chains has been examined with respect to their potential to undergo photodimerization in the solid state. The distances between the potentially reactive atoms for a head-to-head photodimerization are 4.160 (3) Å [C30(Ba)⋯C36(Bb)] and 4.735 (3) Å [C27(Ba)⋯C33(Bb)] (Fig. 4); the former separation distance falls just within the literature limit of 4.2 Å for solid-state photodimerization (Schmidt, 1971 ). The angle between the mean planes of the two molecules of B is 39.02 (8)°, which deviates significantly from parallelism. The long distances and large angle result in poor orbital overlap efficiency, according to the definition given by Kearsley (1987 ). Nonetheless, a single crystal of (I) was irradiated for 15 h, after which there was no evidence of photodimerization having occurred.

In cocrystal (II), the three methylpyridone molecules in the asymmetric unit are arranged in an antiparallel manner. The methyl group of molecule Ba faces in the opposite direction to that of Bc but has the same direction as the methyl group of Bb (Fig. 5). The structure consists of a complex hydrogen-bonded network (Fig. 6 and Table 2), with pairs of methylpyridone molecules forming hydrogen-bonded dimers, which are stacked in parallel above one another. Each methylpyridone dimer is hydrogen bonded to two water molecules, one on each side of the dimer. In turn, each water molecule is also hydrogen bonded to the host molecule A and another water molecule in an adjacent layer. For a possible head-to-tail photodimerization, the distances between potentially reacting atoms in the case of reaction between molecules Ba and Bc are 3.773 (3) Å [C27(Ba)⋯C42(Bc)] and 3.780 (3) Å [C30(Ba)⋯C39(Bc)], and the distances between potentially reacting atoms in the case of head-to-tail reaction between molecules Bb and Bc are 3.879 (3) Å [C33(Bb)⋯C42(Bc)] and 3.755 (3) Å [C36(Bb)⋯C39(Bc)]. The distances between potentially reacting atoms in the case of head-to-head reaction between Ba and Bb are 3.752 (3) Å [C30(Ba)⋯C36(Bb)] and 3.677 (3) Å [C27(Ba)⋯C33(Bb)]. In principle, all of these distances enable photodimerization; however, no photodimerization occurred after irradiation of a single crystal of (II) for 17 h.

In the case of (I), we believe that the unfavourable orientation of two 6-methyl-2H-pyridone molecules with respect to each other for photodimerization explains the lack of reaction. However, in the case of (II) the situation is different. The mutual orientation between the potentially reacting molecules in (II) would seem to permit photodimerization in a manner seen previously (Lavy & Kaftory, 2007 ). We suggest that the complex hydrogen bonding described above prevents photodimerization, as any such reaction would require disruption of the hydrogen-bonding network, which is probably energetically unfavourable.

Figure 1
The asymmetric unit of cocrystal (I). Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The asymmetric unit of cocrystal (II). Displacement ellipsoids are drawn at the 50% probability level.

Figure 3
The hydrogen-bond network in (I) (hydrogen bonds are shown as dotted lines).

Figure 4
The mutual relationship between two adjacent dimers of 6-methyl-2H-pyridone in (I) (hydrogen bonds are shown as dotted lines). [Symmetry code: (i) $[-x, y+1, -z+{1\over2}]$ .]

Figure 5
The mutual relationship between B molecules in cocrystal (II). [Symmetry codes: (i) $[x+{1\over2}]$ , $[-y+{3\over2}, z-{1\over2}]$ ; (ii) $[x+1, -y+1, z-{1\over2}]$ ; (iii) -x+2, -y+1, -z.]

Figure 6
The hydrogen-bond network in cocrystal (II) (hydrogen bonds are shown as dotted lines). [Symmetry codes: (i) $[-x+{3\over2}, y+{1\over2}, -z+{1\over2}]$ ; (ii) $[-x+1, y, -z+{1\over2}]$ ; (iii) $[x-{1\over2}, -y+{3\over2}, z+{1\over2}]$ ; (iv) $[x, -y+2, z+{1\over2}]$ ; (v) -x+1, -y+2, -z+1; (vi) $[-x+{1\over2}, -y+{3\over2}, -z+1]$ .]

Experimental

The component substances were purchased from Sigma. The cocrystals were obtained from ethyl acetate solutions of mixtures of the components (typical quantities 0.005 g). The solution was left to evaporate at room temperature and, after a week, crystals were obtained. Two types of crystals were found in the same vial and were selected by their different morphological forms.

Cocrystal (I)

Crystal data

C₂₅H₁₈O₂·2C₆H₇NO
M_r = 568.65
Monoclinic, C 2/c
a = 17.480 (4) Å
b = 11.114 (2) Å
c = 29.698 (6) Å
β = 93.894 (8)°
V = 5756 (2) Å³
Z = 8
D_x = 1.312 Mg m⁻³
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 (2) K
Prism, colourless
0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART 6K CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.975, T_max = 0.992
23891 measured reflections
5129 independent reflections
3823 reflections with I > 2σ(I)
R_int = 0.056
θ_max = 25.1°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.147
S = 1.16
5129 reflections
390 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.064P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3	0.84	1.89	2.672 (2)	155
O2—H2A⋯O4	0.84	1.89	2.646 (2)	149
N1—H1B⋯O3ⁱ	0.88	1.88	2.755 (2)	174
N2—H2B⋯O4ⁱⁱ	0.88	2.18	2.940 (2)	145
Symmetry codes: (i) -x, -y, -z+1; (ii) -x, -y-1, -z.

Cocrystal (II)

Crystal data

C₂₅H₁₈O₂·3C₆H₇NO·3H₂O
M_r = 731.82
Monoclinic, C 2/c
a = 14.432 (4) Å
b = 14.665 (5) Å
c = 35.675 (10) Å
β = 90.133 (14)°
V = 7550 (4) Å³
Z = 8
D_x = 1.288 Mg m⁻³
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 (2) K
Block, colourless
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART 6K CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) T_min = 0.970, T_max = 0.987
24437 measured reflections
6729 independent reflections
5287 reflections with I > 2σ(I)
R_int = 0.048
θ_max = 25.1°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.113
S = 1.28
6729 reflections
515 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0401P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.005
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O7	0.84	1.84	2.680 (2)	174
O2—H2A⋯O8	0.84	1.77	2.605 (2)	178
O6—H6A⋯O5	0.95 (3)	1.80 (3)	2.738 (2)	170 (2)
O6—H6B⋯O1ⁱ	0.88 (3)	2.11 (3)	2.962 (2)	165 (3)
O7—H7A⋯O3	0.92 (3)	1.80 (3)	2.708 (2)	168 (3)
O7—H7B⋯O2ⁱⁱ	0.86 (3)	2.20 (3)	3.020 (3)	161 (3)
O8—H8A⋯O6	0.91 (3)	1.87 (3)	2.778 (3)	175 (2)
O8—H8B⋯O4ⁱⁱⁱ	0.90 (3)	1.79 (3)	2.685 (2)	174 (3)
N1—H1B⋯O4	0.88	1.88	2.755 (2)	179
N2—H2B⋯O3	0.88	1.93	2.805 (2)	176
N3—H3B⋯O5ⁱⁱ	0.88	1.90	2.777 (2)	176
Symmetry codes: (i) $[-x+1, y, z+{1\over2}]$ ; (ii) $[-x+{3\over 2}, y-{1\over2}, -z+{1\over2}]$ ; (iii) $[x-{1\over2}]$ , $[-y+{3\over2}]$ , $[z-{3\over2}]$ .

The water H atoms in (II) were found in a difference Fourier map and then freely refined. All other H atoms were positioned geometrically (aromatic C—H = 0.95 Å, N—H = 0.88 Å, methyl C—H = 0.98 Å and O—H = 0.84 Å) and refined using a riding model [U_iso(H) = 1.2U_eq(aromatic C and N) and 1.5U_eq(methyl C and O)].

For both cocrystals, data collection: SMART-NT (Bruker, 2000 ); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and MERCURY (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b ).

Supporting information

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S010827010604474X/av3045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827010604474X/av3045Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S010827010604474X/av3045IIsup3.hkl

Comment top

Among the numerous uses of solid inclusion compounds (Tanaka & Toda, 2002; Toda et al., 2001; Toda, 1995, 1996, 1988; Toda & Tanaka, 1984), those consisting of light-stable host molecules and light-sensitive guest molecules can be used for monitoring photochemical reactions in the solid state, provided that the integrity of the single-crystal is preserved throughout the reaction. The reaction of the guest molecules takes place in a cavity formed by the host; therefore, in the cases where the volume of the cavity is sufficient to accommodate the product, single-crystal-to-single-crystal transformations can occur (Lavy et al., 2004; Tanaka et al., 2000; Hosomi et al., 2000; Tanaka, Mizutani et al., 1999; Tanaka, Toda et al., 1999). 4,4'-(Fluorene-9,9-diyl)diphenol, (1), was found to be an effective clathrate host and a useful construction element to form rigid macrocyclic host compounds (Apel et al., 2001). However, only two cocrystals containing (1) were found in the Cambridge Structural Database (Allen, 2002; refcodes ABUCIJ and ABUCUV). We report here the structures of two new cocrystals containing the molecule (1) and photosensitive molecule, 6-methyl-2H-pyridone, (2). These cocrystals were crystallized in an attempt to achieve single-crystal-to-single-crystal photodimerization in inclusion compounds. Cocrystal (I) (Fig. 1) crystallizes in the monoclinic space group C2/c. The asymmetric unit contains one molecule of 4,4'-(fluorene-9,9-diyl)diphenol and two molecules of 6-methyl-2H-pyridone. Cocrystal (II) (Fig. 2) also crystallizes in the monoclinic space group C2/c. In this case, the asymmetric unit contains one molecule of (1), three molecules of (2) [(2a), (2b) and (2c)] and three water molecules.

In cocrystal (I), pairs of molecules of (2) form hydrogen-bonded dimers, as in many structures of pyridone derivatives (Lavy & Kaftory, 2006a; Lavy et al., 2006). Each dimer is connected via hydrogen bonding to two molecules of (1), creating infinite chains (Fig. 3 and Table 1). The mutual relationship between two adjacent molecules of (2) in different chains has been examined with respect to their potential to undergo photodimerization in the solid state. The distances between the potentially reactive atoms for a head-to-head photodimerization are 4.160 (3) Å [C30(2a)—C36(2b)] and 4.735 (3) Å [C27(2a)—C33(2b)] (Fig. 4); the former separation distance falls just within the literature limit of 4.2 Å for solid-state photodimerization (Schmidt, 1971). The angle between the mean planes of the two molecules of (2) is 39.02 (8)°, which deviates significantly from parallelism. The long distances and large angle result in poor orbital overlap efficiency, according to the definition given by Kearsley (Kearsley, 1987). Nonetheless, a single-crystal of (I) was irradiated for 15 h, after which there was no evidence of photodimerization having occurred.

In cocrystal (II), the three methylpyridone molecules in the asymmetric unit are arranged in an antiparallel manner. The methyl group of molecule (2a) faces in the opposite direction to that of (2c) but has the same direction as the methyl group of (2b) (Fig. 5). The structure consists of a complex hydrogen-bonded network (Fig. 6 and Table 2), with pairs of methylpyridone molecules forming hydrogen-bonded dimers, which are stacked in parallel above one another. Each methylpyridone dimer is hydrogen bonded to two water molecules, one on each side of the dimer. In turn, each water molecule is also hydrogen bonded to the host molecule (1) and another water molecule in an adjacent layer. For a possible head-to-tail photodimerization, the distances between potentially reacting atoms in the case of reaction between molecules (2a) and (2c) are 3.773 (3) Å [C27(2a)—C42(2c)] and 3.780 (3) Å [C30(2a)—C39(2c)], and the distances between potentially reacting atoms in case of head-to-tail reaction between molecules (2b) and (2c) are 3.879 (3) Å [C33(2b)—C42(2c)] and 3.755 (3) Å [C36(2b)—C39(2c)]. The distances between potentially reacting atoms in the case of head-to-head reaction between (2a) and (2b) are 3.752 (3) Å [C30(2a)—C36(2b)] and 3.677 (3) Å [C27(2a)—C33(2b)]. In principle, all of these distances enable photodimerization; however, no photodimerization occurred after irradiation of a single-crystal of (II) for 17 h.

In the case of (I), we believe that the unfavourable orientation of two 6-methyl-2H-pyridone molecules with respect to each other for photodimerization explains the lack of reaction. However, in the case of (II) the situation is different. The mutual orientation between the potentially reacting molecules in cocrystal (II) would seem to permit photodimerization in a manner seen previously (Lavy & Kaftory, 2006b). We suggest that the complex hydrogen bonding described above prevents the photodimerization, as any such reaction would require disruption of the hydrogen-bonding network, which is probably energetically unfavourable.

Related literature top

For related literature, see: Allen (2002); Apel et al. (2001); Hosomi et al. (2000); Kearsley (1987); Lavy & Kaftory (2006a, 2006b); Lavy et al. (2004, 2006); Schmidt (1971); Tanaka & Toda (2002); Tanaka et al. (2000); Tanaka, Mizutani, Miyahara, Hirotsu & Toda (1999); Tanaka, Toda, Mochizuki, Yasui, Kai, Miyahara & Hirotsu (1999); Toda (1988, 1995, 1996); Toda & Tanaka (1984); Toda et al. (2001).

Experimental top

The component substances were purchased from Sigma. The cocrystals were obtained from an ethylacetate solution of a mixture of the components (quantities of reagents?). The solution was left for evaporation at room temperature and after a week crystals were obtained. In the same vial, two kind of crystals were found. They were selected from the sample vial by their different morphological form.

Computing details top

For both compounds, data collection: SMART-NT (Bruker, 2000); cell refinement: SAINT-NT ?? (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. Assymetric unit of cocrystal (I). Ellipsoids are drawn in 50% probability level.
	Fig. 2. Assymetric unit of cocrystal (II)·Ellipsoids are drawn in 50% probability level.
	Fig. 3. Hydrogen bond network in cocrystal (I) (hydrogen bonds are in doted lines). (i) x, y, z; (ii) -x, 1 + y, 1/2 - z.
	Fig. 4. Mutual relationship between two adjacent dimers of 6-methyl-2H-pyridone in cocrystals (I) (hydrogen bonds are in Blue doted lines).
	Fig. 5. Mutual relationship between molecules of (2) in cocrystal (II). The symmetry codes are: (i) x, y, z; (ii) 1/2 + x, 3/2 - y, -1/2 + z; (iii) 1 + x, 1 - y, -1/2 + z; (iv) 2 - x, 1 - y, -z.
	Fig. 6. Hydrogen bond network in cocrystal (II) (hydrogen bonds are in doted lines). The symmetry codes are: (i) x, y, z; (ii) 3/2 - x, 1/2 + y, 1/2 - z; (iii) 1 - x, y, 1/2 - z; (iv) -1/2 + x, 3/2 - y, 1/2 + z; (v) x, 2 - y, 1/2 + z; (vi) 1 - x, 2 - y, 1 - z; (vii) 1/2 - x, 3/2 - y, 1 - z..

(I) 4,4'-(fluorene-9,9-diyl)diphenol–6-methyl-2H-pyridone (1/2) top

Crystal data top

C₂₅H₁₈O₂·2C₆H₇NO	F(000) = 2400
M_r = 568.65	D_x = 1.312 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4017 reflections
a = 17.480 (4) Å	θ = 2.3–28.7°
b = 11.114 (2) Å	µ = 0.09 mm⁻¹
c = 29.698 (6) Å	T = 120 K
β = 93.894 (8)°	Prism, colourless
V = 5756 (2) Å³	0.30 × 0.10 × 0.10 mm
Z = 8

Data collection top

Bruker SMART 6K CCD diffractometer	5129 independent reflections
Radiation source: fine-focus sealed tube	3823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 8 pixels mm^-1	θ_max = 25.1°, θ_min = 1.4°
ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −13→13
T_min = 0.975, T_max = 0.992	l = −35→35
23891 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.064P)²] where P = (F_o² + 2F_c²)/3
5129 reflections	(Δ/σ)_max < 0.001
390 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₅H₁₈O₂·2C₆H₇NO	V = 5756 (2) Å³
M_r = 568.65	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.480 (4) Å	µ = 0.09 mm⁻¹
b = 11.114 (2) Å	T = 120 K
c = 29.698 (6) Å	0.30 × 0.10 × 0.10 mm
β = 93.894 (8)°

Data collection top

Bruker SMART 6K CCD diffractometer	5129 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	3823 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.992	R_int = 0.056
23891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.16	Δρ_max = 0.32 e Å⁻³
5129 reflections	Δρ_min = −0.23 e Å⁻³
390 parameters

Special details top

Experimental. The irradiation was carried out by using BENTHAM Xenon light source, model IL7 with OSRAM lamp, model XBO 150 W/ CR OFR.

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	0.12775 (8)	0.16495 (13)	0.40423 (4)	0.0351 (4)
H1O1	0.0845	0.1411	0.4111	0.042*
O2	0.04369 (8)	−0.33117 (11)	0.12825 (4)	0.0320 (4)
H2O2	0.0422	−0.3247	0.1000	0.038*
O3	0.01403 (8)	0.07280 (13)	0.44912 (5)	0.0366 (4)
O4	0.03808 (9)	−0.39918 (14)	0.04273 (5)	0.0456 (4)
N1	−0.06682 (9)	0.12544 (15)	0.50253 (5)	0.0295 (4)
H1N1	−0.0480	0.0653	0.5191	0.035*
N2	0.09197 (10)	−0.43701 (15)	−0.02313 (6)	0.0359 (4)
H1N2	0.0461	−0.4566	−0.0349	0.043*
C1	0.16138 (10)	0.09378 (16)	0.26851 (6)	0.0229 (4)
C2	0.21342 (11)	0.15990 (16)	0.29649 (6)	0.0246 (4)
H2	0.2588	0.1894	0.2844	0.030*
C3	0.20124 (11)	0.18368 (17)	0.34087 (6)	0.0276 (4)
H3	0.2375	0.2302	0.3587	0.033*
C4	0.13646 (11)	0.14019 (17)	0.35979 (6)	0.0262 (4)
C5	0.08336 (11)	0.07404 (17)	0.33288 (6)	0.0279 (4)
H5	0.0387	0.0432	0.3453	0.033*
C6	0.09571 (11)	0.05303 (17)	0.28761 (6)	0.0259 (4)
H6	0.0583	0.0098	0.2694	0.031*
C7	0.13606 (10)	−0.02561 (16)	0.19367 (6)	0.0227 (4)
C8	0.12677 (10)	−0.13441 (17)	0.21587 (6)	0.0252 (4)
H8	0.1415	−0.1401	0.2472	0.030*
C9	0.09655 (10)	−0.23465 (17)	0.19333 (6)	0.0254 (4)
H9	0.0907	−0.3077	0.2094	0.030*
C10	0.07482 (10)	−0.22937 (17)	0.14759 (6)	0.0248 (4)
C11	0.08499 (11)	−0.12262 (17)	0.12451 (6)	0.0264 (4)
H11	0.0715	−0.1179	0.0930	0.032*
C12	0.11500 (11)	−0.02275 (17)	0.14762 (6)	0.0263 (4)
H12	0.1214	0.0499	0.1315	0.032*
C13	0.17656 (10)	0.08037 (16)	0.21795 (6)	0.0232 (4)
C14	0.26345 (10)	0.07036 (16)	0.21239 (6)	0.0223 (4)
C15	0.31190 (11)	−0.02301 (17)	0.22542 (6)	0.0254 (4)
H15	0.2927	−0.0934	0.2389	0.030*
C16	0.38942 (11)	−0.01197 (18)	0.21843 (6)	0.0276 (4)
H16	0.4235	−0.0759	0.2269	0.033*
C17	0.41776 (11)	0.09145 (18)	0.19921 (6)	0.0285 (4)
H17	0.4711	0.0982	0.1953	0.034*
C18	0.36896 (11)	0.18469 (17)	0.18578 (6)	0.0264 (4)
H18	0.3884	0.2552	0.1725	0.032*
C19	0.29106 (10)	0.17373 (16)	0.19201 (6)	0.0223 (4)
C20	0.15923 (10)	0.20267 (16)	0.19544 (6)	0.0235 (4)
C21	0.09003 (11)	0.26290 (17)	0.19045 (6)	0.0262 (4)
H21	0.0445	0.2271	0.2000	0.031*
C22	0.08834 (11)	0.37734 (17)	0.17115 (6)	0.0281 (4)
H22	0.0410	0.4192	0.1669	0.034*
C23	0.15508 (12)	0.43069 (17)	0.15814 (6)	0.0294 (5)
H23	0.1529	0.5093	0.1455	0.035*
C24	0.22479 (11)	0.37146 (17)	0.16322 (6)	0.0270 (4)
H24	0.2704	0.4085	0.1543	0.032*
C25	0.22647 (11)	0.25596 (16)	0.18174 (6)	0.0241 (4)
C26	−0.03796 (11)	0.14287 (18)	0.46153 (6)	0.0299 (5)
C27	−0.06994 (12)	0.23983 (19)	0.43560 (7)	0.0359 (5)
H27	−0.0520	0.2572	0.4068	0.043*
C28	−0.12603 (13)	0.30756 (19)	0.45194 (7)	0.0383 (5)
H28	−0.1476	0.3717	0.4341	0.046*
C29	−0.15317 (12)	0.28576 (19)	0.49433 (7)	0.0371 (5)
H29	−0.1926	0.3346	0.5052	0.044*
C30	−0.12257 (12)	0.19391 (18)	0.51987 (7)	0.0324 (5)
C31	−0.14416 (13)	0.1618 (2)	0.56605 (7)	0.0434 (6)
H31A	−0.0991	0.1689	0.5874	0.065*
H31B	−0.1632	0.0789	0.5661	0.065*
H31C	−0.1844	0.2165	0.5750	0.065*
C32	0.09792 (13)	−0.40152 (19)	0.02122 (7)	0.0390 (5)
C33	0.17391 (14)	−0.3748 (2)	0.03879 (7)	0.0432 (6)
H33	0.1826	−0.3495	0.0693	0.052*
C34	0.23378 (14)	−0.3849 (2)	0.01256 (8)	0.0450 (6)
H34	0.2841	−0.3688	0.0252	0.054*
C35	0.22320 (13)	−0.4189 (2)	−0.03311 (8)	0.0430 (6)
H35	0.2657	−0.4238	−0.0514	0.052*
C36	0.15141 (13)	−0.44439 (18)	−0.05059 (7)	0.0377 (5)
C37	0.13046 (14)	−0.4803 (2)	−0.09828 (8)	0.0468 (6)
H37A	0.0971	−0.5513	−0.0987	0.056*
H37B	0.1771	−0.4994	−0.1134	0.056*
H37C	0.1034	−0.4139	−0.1141	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0401 (8)	0.0426 (9)	0.0230 (8)	−0.0009 (7)	0.0062 (6)	−0.0039 (6)
O2	0.0413 (8)	0.0287 (8)	0.0257 (8)	−0.0076 (6)	0.0006 (6)	−0.0036 (6)
O3	0.0434 (9)	0.0375 (8)	0.0303 (8)	0.0072 (7)	0.0120 (7)	0.0039 (6)
O4	0.0531 (10)	0.0521 (10)	0.0317 (9)	−0.0120 (8)	0.0027 (7)	−0.0112 (7)
N1	0.0353 (10)	0.0285 (9)	0.0248 (9)	0.0044 (7)	0.0020 (7)	0.0031 (7)
N2	0.0414 (11)	0.0374 (10)	0.0283 (10)	−0.0037 (8)	−0.0027 (8)	−0.0053 (8)
C1	0.0234 (10)	0.0220 (9)	0.0232 (10)	0.0025 (8)	−0.0002 (7)	0.0020 (8)
C2	0.0242 (10)	0.0223 (10)	0.0275 (11)	−0.0001 (8)	0.0034 (8)	0.0014 (8)
C3	0.0297 (11)	0.0265 (10)	0.0263 (11)	0.0011 (8)	−0.0012 (8)	−0.0022 (8)
C4	0.0299 (11)	0.0268 (10)	0.0221 (10)	0.0055 (8)	0.0034 (8)	0.0010 (8)
C5	0.0245 (10)	0.0327 (11)	0.0267 (11)	0.0003 (8)	0.0042 (8)	0.0044 (8)
C6	0.0216 (10)	0.0311 (11)	0.0244 (10)	0.0012 (8)	−0.0015 (8)	−0.0009 (8)
C7	0.0206 (10)	0.0246 (10)	0.0230 (10)	0.0018 (8)	0.0019 (7)	−0.0003 (8)
C8	0.0237 (10)	0.0293 (10)	0.0223 (10)	−0.0004 (8)	−0.0001 (7)	0.0015 (8)
C9	0.0264 (10)	0.0232 (10)	0.0268 (10)	−0.0009 (8)	0.0029 (8)	0.0036 (8)
C10	0.0230 (10)	0.0260 (10)	0.0256 (10)	−0.0004 (8)	0.0029 (8)	−0.0045 (8)
C11	0.0322 (11)	0.0280 (11)	0.0190 (10)	0.0018 (8)	0.0007 (8)	−0.0006 (8)
C12	0.0293 (10)	0.0240 (10)	0.0259 (11)	0.0012 (8)	0.0049 (8)	0.0031 (8)
C13	0.0226 (10)	0.0237 (10)	0.0233 (10)	0.0010 (8)	0.0018 (7)	0.0024 (8)
C14	0.0239 (10)	0.0249 (10)	0.0181 (9)	−0.0024 (8)	0.0007 (7)	−0.0021 (7)
C15	0.0294 (11)	0.0267 (10)	0.0203 (10)	0.0003 (8)	0.0033 (8)	−0.0013 (8)
C16	0.0279 (11)	0.0310 (11)	0.0240 (10)	0.0039 (8)	0.0028 (8)	−0.0015 (8)
C17	0.0243 (10)	0.0359 (11)	0.0255 (10)	−0.0022 (9)	0.0031 (8)	−0.0036 (8)
C18	0.0292 (11)	0.0293 (11)	0.0213 (10)	−0.0034 (8)	0.0057 (8)	−0.0029 (8)
C19	0.0280 (10)	0.0227 (10)	0.0161 (9)	−0.0018 (8)	0.0014 (7)	−0.0037 (7)
C20	0.0298 (11)	0.0228 (10)	0.0177 (9)	0.0003 (8)	0.0001 (8)	−0.0023 (7)
C21	0.0262 (10)	0.0282 (11)	0.0239 (10)	0.0000 (8)	0.0000 (8)	−0.0038 (8)
C22	0.0331 (11)	0.0265 (11)	0.0242 (10)	0.0056 (9)	−0.0016 (8)	−0.0037 (8)
C23	0.0418 (12)	0.0223 (10)	0.0238 (10)	0.0014 (9)	−0.0006 (9)	0.0003 (8)
C24	0.0338 (11)	0.0253 (10)	0.0222 (10)	−0.0019 (9)	0.0036 (8)	−0.0004 (8)
C25	0.0302 (10)	0.0254 (10)	0.0168 (9)	−0.0018 (8)	0.0012 (7)	−0.0026 (7)
C26	0.0352 (11)	0.0324 (11)	0.0223 (10)	−0.0015 (9)	0.0031 (8)	−0.0025 (8)
C27	0.0468 (13)	0.0366 (12)	0.0239 (11)	0.0029 (10)	−0.0008 (9)	0.0023 (9)
C28	0.0472 (13)	0.0318 (12)	0.0347 (12)	0.0042 (10)	−0.0061 (10)	−0.0008 (9)
C29	0.0367 (12)	0.0339 (11)	0.0404 (13)	0.0066 (10)	0.0010 (9)	−0.0034 (10)
C30	0.0323 (11)	0.0338 (12)	0.0311 (11)	−0.0002 (9)	0.0024 (9)	−0.0064 (9)
C31	0.0465 (14)	0.0473 (14)	0.0378 (13)	0.0077 (11)	0.0138 (10)	−0.0006 (11)
C32	0.0483 (14)	0.0369 (12)	0.0310 (12)	−0.0081 (10)	−0.0027 (10)	−0.0022 (9)
C33	0.0591 (16)	0.0395 (13)	0.0296 (12)	−0.0171 (11)	−0.0087 (11)	0.0022 (10)
C34	0.0454 (14)	0.0398 (13)	0.0485 (15)	−0.0131 (11)	−0.0070 (11)	0.0056 (11)
C35	0.0462 (14)	0.0361 (13)	0.0466 (14)	−0.0086 (10)	0.0030 (11)	0.0006 (10)
C36	0.0476 (14)	0.0294 (12)	0.0362 (12)	−0.0031 (10)	0.0034 (10)	−0.0009 (9)
C37	0.0568 (16)	0.0465 (14)	0.0377 (14)	−0.0076 (12)	0.0080 (11)	−0.0110 (11)

Geometric parameters (Å, º) top

O1—C4	1.367 (2)	C16—C17	1.389 (3)
O1—H1O1	0.8400	C16—H16	0.9500
O2—C10	1.365 (2)	C17—C18	1.384 (3)
O2—H2O2	0.8400	C17—H17	0.9500
O3—C26	1.270 (2)	C18—C19	1.392 (3)
O4—C32	1.262 (3)	C18—H18	0.9500
N1—C26	1.363 (2)	C19—C25	1.468 (3)
N1—C30	1.365 (2)	C20—C21	1.382 (3)
N1—H1N1	0.8800	C20—C25	1.401 (3)
N2—C36	1.366 (3)	C21—C22	1.395 (3)
N2—C32	1.372 (3)	C21—H21	0.9500
N2—H1N2	0.8800	C22—C23	1.387 (3)
C1—C6	1.390 (3)	C22—H22	0.9500
C1—C2	1.398 (3)	C23—C24	1.384 (3)
C1—C13	1.549 (2)	C23—H23	0.9500
C2—C3	1.375 (3)	C24—C25	1.396 (3)
C2—H2	0.9500	C24—H24	0.9500
C3—C4	1.385 (3)	C26—C27	1.417 (3)
C3—H3	0.9500	C27—C28	1.352 (3)
C4—C5	1.393 (3)	C27—H27	0.9500
C5—C6	1.396 (3)	C28—C29	1.396 (3)
C5—H5	0.9500	C28—H28	0.9500
C6—H6	0.9500	C29—C30	1.360 (3)
C7—C12	1.392 (3)	C29—H29	0.9500
C7—C8	1.392 (3)	C30—C31	1.490 (3)
C7—C13	1.530 (3)	C31—H31A	0.9800
C8—C9	1.386 (3)	C31—H31B	0.9800
C8—H8	0.9500	C31—H31C	0.9800
C9—C10	1.387 (3)	C32—C33	1.425 (3)
C9—H9	0.9500	C33—C34	1.351 (3)
C10—C11	1.388 (3)	C33—H33	0.9500
C11—C12	1.389 (3)	C34—C35	1.408 (3)
C11—H11	0.9500	C34—H34	0.9500
C12—H12	0.9500	C35—C36	1.355 (3)
C13—C20	1.536 (3)	C35—H35	0.9500
C13—C14	1.543 (2)	C36—C37	1.493 (3)
C14—C15	1.378 (3)	C37—H37A	0.9800
C14—C19	1.400 (2)	C37—H37B	0.9800
C15—C16	1.390 (3)	C37—H37C	0.9800
C15—H15	0.9500

C4—O1—H1O1	109.5	C19—C18—H18	120.5
C10—O2—H2O2	109.5	C18—C19—C14	119.90 (17)
C26—N1—C30	125.10 (17)	C18—C19—C25	131.55 (17)
C26—N1—H1N1	117.4	C14—C19—C25	108.54 (16)
C30—N1—H1N1	117.4	C21—C20—C25	120.65 (17)
C36—N2—C32	125.38 (19)	C21—C20—C13	128.37 (17)
C36—N2—H1N2	117.3	C25—C20—C13	110.86 (15)
C32—N2—H1N2	117.3	C20—C21—C22	118.68 (18)
C6—C1—C2	116.77 (17)	C20—C21—H21	120.7
C6—C1—C13	124.37 (16)	C22—C21—H21	120.7
C2—C1—C13	118.62 (16)	C23—C22—C21	120.64 (18)
C3—C2—C1	122.27 (17)	C23—C22—H22	119.7
C3—C2—H2	118.9	C21—C22—H22	119.7
C1—C2—H2	118.9	C24—C23—C22	121.16 (18)
C2—C3—C4	120.39 (18)	C24—C23—H23	119.4
C2—C3—H3	119.8	C22—C23—H23	119.4
C4—C3—H3	119.8	C23—C24—C25	118.36 (18)
O1—C4—C3	117.99 (17)	C23—C24—H24	120.8
O1—C4—C5	123.13 (17)	C25—C24—H24	120.8
C3—C4—C5	118.88 (17)	C24—C25—C20	120.50 (17)
C4—C5—C6	120.02 (18)	C24—C25—C19	130.49 (17)
C4—C5—H5	120.0	C20—C25—C19	108.96 (15)
C6—C5—H5	120.0	O3—C26—N1	119.18 (18)
C1—C6—C5	121.65 (18)	O3—C26—C27	124.89 (18)
C1—C6—H6	119.2	N1—C26—C27	115.93 (18)
C5—C6—H6	119.2	C28—C27—C26	119.81 (19)
C12—C7—C8	116.97 (17)	C28—C27—H27	120.1
C12—C7—C13	121.91 (16)	C26—C27—H27	120.1
C8—C7—C13	120.71 (16)	C27—C28—C29	121.7 (2)
C9—C8—C7	121.49 (17)	C27—C28—H28	119.1
C9—C8—H8	119.3	C29—C28—H28	119.1
C7—C8—H8	119.3	C30—C29—C28	119.2 (2)
C8—C9—C10	120.61 (17)	C30—C29—H29	120.4
C8—C9—H9	119.7	C28—C29—H29	120.4
C10—C9—H9	119.7	C29—C30—N1	118.17 (19)
O2—C10—C9	116.86 (16)	C29—C30—C31	125.36 (19)
O2—C10—C11	124.17 (17)	N1—C30—C31	116.47 (18)
C9—C10—C11	118.97 (17)	C30—C31—H31A	109.5
C10—C11—C12	119.73 (17)	C30—C31—H31B	109.5
C10—C11—H11	120.1	H31A—C31—H31B	109.5
C12—C11—H11	120.1	C30—C31—H31C	109.5
C11—C12—C7	122.20 (17)	H31A—C31—H31C	109.5
C11—C12—H12	118.9	H31B—C31—H31C	109.5
C7—C12—H12	118.9	O4—C32—N2	118.70 (19)
C7—C13—C20	113.89 (15)	O4—C32—C33	126.4 (2)
C7—C13—C14	108.76 (14)	N2—C32—C33	114.8 (2)
C20—C13—C14	100.58 (14)	C34—C33—C32	120.7 (2)
C7—C13—C1	115.26 (14)	C34—C33—H33	119.6
C20—C13—C1	107.16 (14)	C32—C33—H33	119.6
C14—C13—C1	110.20 (14)	C33—C34—C35	121.4 (2)
C15—C14—C19	121.08 (17)	C33—C34—H34	119.3
C15—C14—C13	127.94 (16)	C35—C34—H34	119.3
C19—C14—C13	110.97 (15)	C36—C35—C34	118.9 (2)
C14—C15—C16	118.57 (17)	C36—C35—H35	120.6
C14—C15—H15	120.7	C34—C35—H35	120.6
C16—C15—H15	120.7	C35—C36—N2	118.8 (2)
C17—C16—C15	120.85 (18)	C35—C36—C37	125.5 (2)
C17—C16—H16	119.6	N2—C36—C37	115.8 (2)
C15—C16—H16	119.6	C36—C37—H37A	109.5
C18—C17—C16	120.53 (18)	C36—C37—H37B	109.5
C18—C17—H17	119.7	H37A—C37—H37B	109.5
C16—C17—H17	119.7	C36—C37—H37C	109.5
C17—C18—C19	119.05 (18)	H37A—C37—H37C	109.5
C17—C18—H18	120.5	H37B—C37—H37C	109.5

C6—C1—C2—C3	0.3 (3)	C15—C14—C19—C18	−1.8 (3)
C13—C1—C2—C3	175.03 (16)	C13—C14—C19—C18	177.20 (15)
C1—C2—C3—C4	1.2 (3)	C15—C14—C19—C25	179.55 (16)
C2—C3—C4—O1	179.04 (16)	C13—C14—C19—C25	−1.5 (2)
C2—C3—C4—C5	−1.2 (3)	C7—C13—C20—C21	65.0 (2)
O1—C4—C5—C6	179.49 (17)	C14—C13—C20—C21	−178.85 (18)
C3—C4—C5—C6	−0.3 (3)	C1—C13—C20—C21	−63.7 (2)
C2—C1—C6—C5	−1.8 (3)	C7—C13—C20—C25	−119.06 (16)
C13—C1—C6—C5	−176.18 (16)	C14—C13—C20—C25	−2.93 (18)
C4—C5—C6—C1	1.8 (3)	C1—C13—C20—C25	112.24 (16)
C12—C7—C8—C9	−1.2 (3)	C25—C20—C21—C22	0.5 (3)
C13—C7—C8—C9	−174.05 (16)	C13—C20—C21—C22	176.11 (17)
C7—C8—C9—C10	0.3 (3)	C20—C21—C22—C23	−1.4 (3)
C8—C9—C10—O2	−178.30 (16)	C21—C22—C23—C24	1.1 (3)
C8—C9—C10—C11	1.1 (3)	C22—C23—C24—C25	0.2 (3)
O2—C10—C11—C12	177.94 (16)	C23—C24—C25—C20	−1.0 (3)
C9—C10—C11—C12	−1.4 (3)	C23—C24—C25—C19	−178.40 (17)
C10—C11—C12—C7	0.4 (3)	C21—C20—C25—C24	0.7 (3)
C8—C7—C12—C11	0.9 (3)	C13—C20—C25—C24	−175.62 (16)
C13—C7—C12—C11	173.64 (17)	C21—C20—C25—C19	178.56 (16)
C12—C7—C13—C20	26.8 (2)	C13—C20—C25—C19	2.3 (2)
C8—C7—C13—C20	−160.77 (16)	C18—C19—C25—C24	−1.3 (3)
C12—C7—C13—C14	−84.5 (2)	C14—C19—C25—C24	177.12 (18)
C8—C7—C13—C14	88.0 (2)	C18—C19—C25—C20	−178.95 (18)
C12—C7—C13—C1	151.21 (17)	C14—C19—C25—C20	−0.5 (2)
C8—C7—C13—C1	−36.3 (2)	C30—N1—C26—O3	180.00 (18)
C6—C1—C13—C7	−26.5 (2)	C30—N1—C26—C27	−0.5 (3)
C2—C1—C13—C7	159.20 (16)	O3—C26—C27—C28	179.0 (2)
C6—C1—C13—C20	101.37 (19)	N1—C26—C27—C28	−0.5 (3)
C2—C1—C13—C20	−72.9 (2)	C26—C27—C28—C29	0.8 (3)
C6—C1—C13—C14	−150.06 (17)	C27—C28—C29—C30	−0.1 (3)
C2—C1—C13—C14	35.7 (2)	C28—C29—C30—N1	−0.8 (3)
C7—C13—C14—C15	−58.6 (2)	C28—C29—C30—C31	178.4 (2)
C20—C13—C14—C15	−178.49 (17)	C26—N1—C30—C29	1.2 (3)
C1—C13—C14—C15	68.7 (2)	C26—N1—C30—C31	−178.10 (18)
C7—C13—C14—C19	122.52 (16)	C36—N2—C32—O4	−179.8 (2)
C20—C13—C14—C19	2.62 (18)	C36—N2—C32—C33	−2.0 (3)
C1—C13—C14—C19	−110.25 (16)	O4—C32—C33—C34	177.5 (2)
C19—C14—C15—C16	0.8 (3)	N2—C32—C33—C34	0.0 (3)
C13—C14—C15—C16	−177.98 (17)	C32—C33—C34—C35	1.8 (4)
C14—C15—C16—C17	0.7 (3)	C33—C34—C35—C36	−1.5 (3)
C15—C16—C17—C18	−1.3 (3)	C34—C35—C36—N2	−0.4 (3)
C16—C17—C18—C19	0.4 (3)	C34—C35—C36—C37	179.3 (2)
C17—C18—C19—C14	1.2 (3)	C32—N2—C36—C35	2.3 (3)
C17—C18—C19—C25	179.48 (18)	C32—N2—C36—C37	−177.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.84	1.89	2.672 (2)	156
O2—H2A···O4	0.84	1.89	2.646 (2)	149
N1—H1B···O3ⁱ	0.88	1.88	2.755 (2)	174
N2—H2B···O4ⁱⁱ	0.88	2.18	2.940 (2)	145

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y−1, −z.

(II) 4,4'-(fluorene-9,9-diyl)diphenol–6-methyl-2H-pyridone–water (1/3/3) top

Crystal data top

C₂₅H₁₈O₂·3C₆H₇NO·3H₂O	F(000) = 3104
M_r = 731.82	D_x = 1.288 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4069 reflections
a = 14.432 (4) Å	θ = 2.3–2.6°
b = 14.665 (5) Å	µ = 0.09 mm⁻¹
c = 35.675 (10) Å	T = 120 K
β = 90.133 (14)°	Block, colourless
V = 7550 (4) Å³	0.35 × 0.25 × 0.15 mm
Z = 8

Data collection top

Bruker SMART 6K CCD diffractometer	6729 independent reflections
Radiation source: 60W microfocus Bede Microsource with glass polycapillary optics	5287 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 8 pixels mm^-1	θ_max = 25.1°, θ_min = 2.1°
ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −17→17
T_min = 0.970, T_max = 0.987	l = −42→42
24437 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ²(F_o²) + (0.0401P)²] where P = (F_o² + 2F_c²)/3
6729 reflections	(Δ/σ)_max = 0.007
515 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₅H₁₈O₂·3C₆H₇NO·3H₂O	V = 7550 (4) Å³
M_r = 731.82	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.432 (4) Å	µ = 0.09 mm⁻¹
b = 14.665 (5) Å	T = 120 K
c = 35.675 (10) Å	0.35 × 0.25 × 0.15 mm
β = 90.133 (14)°

Data collection top

Bruker SMART 6K CCD diffractometer	6729 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	5287 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.987	R_int = 0.048
24437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	Δρ_max = 0.25 e Å⁻³
6729 reflections	Δρ_min = −0.21 e Å⁻³
515 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.66355 (10)	0.48528 (10)	0.12373 (4)	0.0238 (4)
H1A	0.7085	0.4627	0.1120	0.029*
O2	0.63584 (10)	0.74053 (9)	0.37947 (4)	0.0255 (4)
H2A	0.6183	0.7211	0.4004	0.031*
O3	0.92982 (10)	0.54667 (10)	0.05593 (4)	0.0241 (4)
O4	1.00587 (10)	0.67102 (10)	−0.02179 (4)	0.0266 (4)
O5	0.33089 (10)	0.66228 (10)	0.48859 (4)	0.0242 (4)
O6	0.43857 (12)	0.55996 (12)	0.44151 (5)	0.0321 (4)
H6A	0.3952 (19)	0.5908 (19)	0.4571 (8)	0.061 (9)*
H6B	0.407 (2)	0.549 (2)	0.4209 (9)	0.089 (13)*
O7	0.81393 (12)	0.42388 (13)	0.08770 (4)	0.0284 (4)
H7A	0.859 (2)	0.463 (2)	0.0793 (8)	0.081 (11)*
H7B	0.840 (2)	0.374 (2)	0.0940 (8)	0.063 (10)*
O8	0.58419 (12)	0.68348 (13)	0.44535 (5)	0.0302 (4)
H8A	0.5384 (18)	0.6411 (18)	0.4450 (7)	0.042 (8)*
H8B	0.560 (2)	0.731 (2)	0.4577 (8)	0.071 (10)*
N1	1.04067 (11)	0.65611 (11)	0.05393 (5)	0.0196 (4)
H1B	1.0296	0.6614	0.0298	0.036 (7)*
N2	0.88690 (11)	0.57024 (12)	−0.02018 (5)	0.0208 (4)
H2B	0.8977	0.5637	0.0040	0.025*
N3	0.30908 (12)	0.73455 (11)	0.54404 (5)	0.0193 (4)
H3B	0.2669	0.7684	0.5329	0.023*
C1	0.70639 (14)	0.46336 (13)	0.23927 (5)	0.0156 (5)
C2	0.77044 (14)	0.42929 (14)	0.21405 (6)	0.0185 (5)
H2	0.8244	0.3998	0.2233	0.022*
C3	0.75798 (15)	0.43708 (14)	0.17562 (6)	0.0210 (5)
H3	0.8035	0.4137	0.1590	0.025*
C4	0.67959 (15)	0.47876 (14)	0.16148 (6)	0.0180 (5)
C5	0.61451 (14)	0.51406 (14)	0.18600 (6)	0.0186 (5)
H5	0.5605	0.5432	0.1766	0.022*
C6	0.62861 (14)	0.50659 (13)	0.22437 (6)	0.0183 (5)
H6	0.5840	0.5317	0.2410	0.022*
C7	0.68671 (13)	0.52388 (13)	0.30631 (5)	0.0153 (5)
C8	0.71068 (14)	0.61347 (14)	0.29720 (6)	0.0187 (5)
H8	0.7394	0.6257	0.2738	0.022*
C9	0.69335 (14)	0.68472 (14)	0.32161 (6)	0.0205 (5)
H9	0.7107	0.7451	0.3149	0.025*
C10	0.65066 (14)	0.66841 (14)	0.35586 (6)	0.0181 (5)
C11	0.62426 (14)	0.58061 (14)	0.36470 (6)	0.0192 (5)
H11	0.5931	0.5689	0.3876	0.023*
C12	0.64290 (14)	0.50959 (14)	0.34040 (6)	0.0193 (5)
H12	0.6253	0.4494	0.3472	0.023*
C13	0.71580 (14)	0.44374 (13)	0.28160 (5)	0.0162 (5)
C14	0.66345 (14)	0.35470 (13)	0.28928 (5)	0.0157 (5)
C15	0.56957 (15)	0.33875 (14)	0.28804 (5)	0.0204 (5)
H15	0.5275	0.3873	0.2835	0.025*
C16	0.53711 (16)	0.25026 (15)	0.29355 (6)	0.0244 (5)
H16	0.4724	0.2385	0.2930	0.029*
C17	0.59880 (16)	0.17912 (15)	0.29983 (6)	0.0253 (5)
H17	0.5759	0.1188	0.3029	0.030*
C18	0.69313 (16)	0.19513 (14)	0.30169 (6)	0.0233 (5)
H18	0.7351	0.1462	0.3059	0.028*
C19	0.72579 (14)	0.28375 (14)	0.29734 (5)	0.0175 (5)
C20	0.81529 (14)	0.41507 (14)	0.29143 (5)	0.0162 (5)
C21	0.89483 (14)	0.46789 (14)	0.29252 (5)	0.0194 (5)
H21	0.8926	0.5309	0.2865	0.023*
C22	0.97778 (15)	0.42698 (15)	0.30260 (6)	0.0256 (5)
H22	1.0327	0.4626	0.3035	0.031*
C23	0.98182 (15)	0.33533 (16)	0.31132 (6)	0.0288 (6)
H23	1.0393	0.3089	0.3185	0.035*
C24	0.90315 (16)	0.28140 (15)	0.30981 (6)	0.0260 (5)
H24	0.9062	0.2181	0.3154	0.031*
C25	0.81950 (14)	0.32202 (14)	0.29996 (5)	0.0185 (5)
C26	0.98975 (15)	0.59361 (14)	0.07339 (6)	0.0211 (5)
C27	1.01095 (15)	0.58564 (15)	0.11203 (6)	0.0245 (5)
H27	0.9783	0.5431	0.1271	0.029*
C28	1.07803 (16)	0.63892 (15)	0.12759 (6)	0.0281 (6)
H28	1.0921	0.6325	0.1535	0.034*
C29	1.12676 (15)	0.70306 (15)	0.10623 (6)	0.0263 (5)
H29	1.1727	0.7404	0.1176	0.032*
C30	1.10777 (15)	0.71138 (14)	0.06906 (6)	0.0222 (5)
C31	1.15537 (16)	0.77549 (16)	0.04272 (6)	0.0303 (6)
H31A	1.1089	0.8081	0.0278	0.045*
H31B	1.1962	0.7409	0.0260	0.045*
H31C	1.1921	0.8195	0.0571	0.045*
C32	0.94106 (15)	0.63000 (14)	−0.03927 (6)	0.0221 (5)
C33	0.92005 (15)	0.64095 (15)	−0.07793 (6)	0.0243 (5)
H33	0.9546	0.6827	−0.0927	0.029*
C34	0.85052 (16)	0.59164 (15)	−0.09375 (6)	0.0271 (6)
H34	0.8372	0.5993	−0.1197	0.033*
C35	0.79794 (15)	0.52967 (15)	−0.07266 (6)	0.0244 (5)
H35	0.7498	0.4954	−0.0842	0.029*
C36	0.81682 (14)	0.51941 (14)	−0.03555 (6)	0.0215 (5)
C37	0.76685 (16)	0.45653 (15)	−0.00951 (6)	0.0283 (6)
H37A	0.8117	0.4171	0.0032	0.043*
H37B	0.7232	0.4189	−0.0238	0.043*
H37C	0.7328	0.4924	0.0091	0.043*
C38	0.35367 (14)	0.67070 (14)	0.52283 (6)	0.0204 (5)
C39	0.42248 (15)	0.61882 (14)	0.54171 (6)	0.0221 (5)
H39	0.4564	0.5736	0.5285	0.027*
C40	0.44008 (15)	0.63351 (14)	0.57865 (6)	0.0228 (5)
H40	0.4866	0.5986	0.5909	0.027*
C41	0.39062 (15)	0.69957 (14)	0.59911 (6)	0.0218 (5)
H41	0.4030	0.7089	0.6250	0.026*
C42	0.32483 (15)	0.74987 (14)	0.58118 (6)	0.0205 (5)
C43	0.26696 (15)	0.82270 (15)	0.59880 (6)	0.0259 (5)
H43A	0.2704	0.8783	0.5836	0.039*
H43B	0.2901	0.8354	0.6241	0.039*
H43C	0.2025	0.8021	0.6002	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0249 (9)	0.0316 (9)	0.0149 (8)	0.0006 (7)	−0.0018 (6)	0.0033 (7)
O2	0.0343 (9)	0.0186 (8)	0.0237 (8)	0.0018 (7)	0.0034 (7)	−0.0051 (7)
O3	0.0248 (9)	0.0252 (9)	0.0222 (8)	−0.0054 (7)	−0.0003 (7)	0.0015 (7)
O4	0.0305 (9)	0.0277 (9)	0.0215 (8)	−0.0105 (7)	−0.0040 (7)	0.0042 (7)
O5	0.0262 (9)	0.0278 (9)	0.0185 (9)	0.0064 (7)	−0.0024 (7)	−0.0033 (7)
O6	0.0272 (10)	0.0389 (11)	0.0300 (10)	0.0076 (8)	−0.0026 (8)	−0.0117 (8)
O7	0.0325 (10)	0.0261 (10)	0.0267 (9)	−0.0007 (9)	0.0048 (8)	0.0040 (8)
O8	0.0335 (10)	0.0290 (10)	0.0281 (10)	0.0047 (9)	0.0026 (8)	−0.0093 (8)
N1	0.0214 (10)	0.0224 (10)	0.0151 (10)	−0.0007 (8)	−0.0022 (8)	0.0000 (8)
N2	0.0224 (10)	0.0239 (10)	0.0160 (10)	−0.0023 (8)	−0.0018 (8)	0.0004 (8)
N3	0.0216 (10)	0.0185 (10)	0.0179 (10)	0.0042 (8)	−0.0017 (8)	0.0007 (8)
C1	0.0190 (12)	0.0111 (11)	0.0168 (11)	−0.0031 (9)	−0.0013 (9)	0.0019 (9)
C2	0.0185 (12)	0.0174 (11)	0.0195 (12)	0.0026 (9)	−0.0026 (9)	0.0005 (9)
C3	0.0240 (12)	0.0233 (12)	0.0157 (11)	0.0007 (10)	0.0023 (9)	0.0008 (9)
C4	0.0244 (12)	0.0154 (11)	0.0143 (11)	−0.0055 (9)	−0.0030 (9)	0.0033 (9)
C5	0.0138 (11)	0.0175 (11)	0.0244 (12)	−0.0022 (9)	−0.0038 (9)	0.0049 (9)
C6	0.0183 (12)	0.0165 (11)	0.0200 (12)	−0.0013 (9)	0.0024 (9)	0.0014 (9)
C7	0.0127 (11)	0.0178 (11)	0.0155 (11)	0.0018 (9)	−0.0038 (9)	0.0003 (9)
C8	0.0194 (12)	0.0198 (11)	0.0167 (11)	0.0012 (9)	0.0008 (9)	0.0034 (9)
C9	0.0220 (12)	0.0135 (11)	0.0259 (12)	0.0006 (9)	−0.0020 (10)	0.0015 (9)
C10	0.0169 (11)	0.0166 (11)	0.0208 (12)	0.0042 (9)	−0.0026 (9)	−0.0034 (9)
C11	0.0202 (12)	0.0228 (12)	0.0145 (11)	0.0023 (10)	0.0019 (9)	0.0008 (9)
C12	0.0229 (12)	0.0143 (11)	0.0207 (12)	−0.0001 (9)	−0.0016 (9)	0.0014 (9)
C13	0.0167 (11)	0.0164 (11)	0.0154 (11)	0.0008 (9)	0.0000 (9)	0.0004 (9)
C14	0.0224 (12)	0.0141 (11)	0.0107 (10)	0.0004 (9)	0.0007 (9)	−0.0012 (8)
C15	0.0271 (13)	0.0192 (12)	0.0150 (11)	−0.0007 (10)	−0.0006 (9)	0.0023 (9)
C16	0.0250 (13)	0.0278 (13)	0.0204 (12)	−0.0066 (10)	0.0011 (10)	0.0011 (10)
C17	0.0360 (14)	0.0160 (12)	0.0238 (13)	−0.0058 (11)	0.0011 (11)	0.0003 (10)
C18	0.0346 (14)	0.0172 (12)	0.0181 (12)	0.0033 (10)	0.0041 (10)	−0.0004 (9)
C19	0.0251 (12)	0.0166 (11)	0.0109 (11)	0.0019 (9)	0.0006 (9)	0.0002 (9)
C20	0.0206 (12)	0.0171 (11)	0.0110 (11)	0.0044 (9)	−0.0008 (9)	−0.0016 (9)
C21	0.0207 (12)	0.0186 (12)	0.0188 (12)	0.0012 (10)	−0.0004 (9)	−0.0017 (9)
C22	0.0195 (12)	0.0283 (13)	0.0290 (13)	0.0006 (10)	−0.0031 (10)	−0.0064 (11)
C23	0.0209 (13)	0.0317 (14)	0.0339 (14)	0.0127 (11)	−0.0051 (10)	0.0004 (11)
C24	0.0297 (14)	0.0202 (12)	0.0283 (13)	0.0095 (11)	−0.0006 (10)	0.0024 (10)
C25	0.0220 (12)	0.0195 (11)	0.0140 (11)	0.0029 (9)	−0.0010 (9)	−0.0007 (9)
C26	0.0205 (12)	0.0195 (12)	0.0234 (12)	0.0033 (10)	0.0021 (10)	−0.0001 (10)
C27	0.0275 (13)	0.0261 (13)	0.0199 (12)	0.0045 (11)	0.0012 (10)	0.0044 (10)
C28	0.0337 (14)	0.0302 (14)	0.0203 (12)	0.0056 (11)	−0.0031 (11)	−0.0005 (10)
C29	0.0246 (13)	0.0286 (13)	0.0257 (13)	0.0026 (10)	−0.0063 (10)	−0.0051 (11)
C30	0.0194 (12)	0.0224 (12)	0.0249 (13)	0.0012 (10)	0.0000 (10)	−0.0023 (10)
C31	0.0269 (14)	0.0300 (14)	0.0339 (14)	−0.0050 (11)	−0.0006 (11)	−0.0004 (11)
C32	0.0251 (13)	0.0191 (12)	0.0221 (12)	0.0015 (10)	0.0007 (10)	−0.0003 (10)
C33	0.0258 (13)	0.0252 (13)	0.0220 (12)	−0.0002 (10)	−0.0006 (10)	0.0034 (10)
C34	0.0323 (14)	0.0308 (14)	0.0184 (12)	0.0072 (11)	−0.0035 (10)	−0.0013 (10)
C35	0.0221 (13)	0.0264 (13)	0.0248 (13)	0.0023 (10)	−0.0050 (10)	−0.0057 (10)
C36	0.0179 (12)	0.0194 (12)	0.0273 (13)	0.0021 (10)	0.0011 (10)	−0.0030 (10)
C37	0.0293 (14)	0.0247 (13)	0.0311 (14)	−0.0032 (11)	0.0020 (11)	−0.0023 (10)
C38	0.0213 (12)	0.0189 (12)	0.0209 (13)	−0.0027 (10)	0.0030 (10)	−0.0018 (10)
C39	0.0229 (12)	0.0186 (12)	0.0249 (13)	0.0027 (10)	0.0002 (10)	0.0003 (10)
C40	0.0224 (12)	0.0187 (12)	0.0273 (13)	−0.0008 (10)	−0.0041 (10)	0.0057 (10)
C41	0.0262 (13)	0.0197 (12)	0.0193 (12)	−0.0031 (10)	−0.0024 (10)	0.0035 (10)
C42	0.0244 (13)	0.0186 (11)	0.0186 (12)	−0.0044 (10)	0.0003 (9)	0.0009 (9)
C43	0.0299 (13)	0.0281 (13)	0.0196 (12)	0.0024 (11)	−0.0003 (10)	−0.0019 (10)

Geometric parameters (Å, º) top

O1—C4	1.369 (2)	C16—C17	1.389 (3)
O1—H1A	0.8400	C16—H16	0.9500
O2—C10	1.369 (2)	C17—C18	1.383 (3)
O2—H2A	0.8400	C17—H17	0.9500
O3—C26	1.268 (3)	C18—C19	1.391 (3)
O4—C32	1.274 (3)	C18—H18	0.9500
O5—C38	1.270 (2)	C19—C25	1.467 (3)
O6—H6A	0.95 (3)	C20—C21	1.385 (3)
O6—H6B	0.88 (3)	C20—C25	1.399 (3)
O7—H7A	0.92 (3)	C21—C22	1.386 (3)
O7—H7B	0.86 (3)	C21—H21	0.9500
O8—H8A	0.91 (3)	C22—C23	1.381 (3)
O8—H8B	0.90 (3)	C22—H22	0.9500
N1—C26	1.365 (3)	C23—C24	1.385 (3)
N1—C30	1.372 (3)	C23—H23	0.9500
N1—H1B	0.8800	C24—C25	1.390 (3)
N2—C32	1.358 (3)	C24—H24	0.9500
N2—C36	1.370 (3)	C26—C27	1.416 (3)
N2—H2B	0.8800	C27—C28	1.361 (3)
N3—C42	1.362 (3)	C27—H27	0.9500
N3—C38	1.366 (2)	C28—C29	1.401 (3)
N3—H3B	0.8800	C28—H28	0.9500
C1—C2	1.385 (3)	C29—C30	1.359 (3)
C1—C6	1.393 (3)	C29—H29	0.9500
C1—C13	1.543 (3)	C30—C31	1.497 (3)
C2—C3	1.387 (3)	C31—H31A	0.9800
C2—H2	0.9500	C31—H31B	0.9800
C3—C4	1.380 (3)	C31—H31C	0.9800
C3—H3	0.9500	C32—C33	1.421 (3)
C4—C5	1.385 (3)	C33—C34	1.359 (3)
C5—C6	1.388 (3)	C33—H33	0.9500
C5—H5	0.9500	C34—C35	1.404 (3)
C6—H6	0.9500	C34—H34	0.9500
C7—C12	1.388 (3)	C35—C36	1.359 (3)
C7—C8	1.397 (3)	C35—H35	0.9500
C7—C13	1.528 (3)	C36—C37	1.495 (3)
C8—C9	1.383 (3)	C37—H37A	0.9800
C8—H8	0.9500	C37—H37B	0.9800
C9—C10	1.391 (3)	C37—H37C	0.9800
C9—H9	0.9500	C38—C39	1.420 (3)
C10—C11	1.379 (3)	C39—C40	1.359 (3)
C11—C12	1.382 (3)	C39—H39	0.9500
C11—H11	0.9500	C40—C41	1.408 (3)
C12—H12	0.9500	C40—H40	0.9500
C13—C14	1.534 (3)	C41—C42	1.361 (3)
C13—C20	1.536 (3)	C41—H41	0.9500
C14—C15	1.375 (3)	C42—C43	1.495 (3)
C14—C19	1.405 (3)	C43—H43A	0.9800
C15—C16	1.394 (3)	C43—H43B	0.9800
C15—H15	0.9500	C43—H43C	0.9800

C4—O1—H1A	109.5	C20—C21—H21	120.6
C10—O2—H2A	109.5	C22—C21—H21	120.6
H6A—O6—H6B	104 (3)	C23—C22—C21	121.1 (2)
H7A—O7—H7B	108 (3)	C23—C22—H22	119.5
H8A—O8—H8B	105 (2)	C21—C22—H22	119.5
C26—N1—C30	125.21 (19)	C22—C23—C24	120.9 (2)
C26—N1—H1B	117.4	C22—C23—H23	119.6
C30—N1—H1B	117.4	C24—C23—H23	119.6
C32—N2—C36	125.13 (18)	C23—C24—C25	118.5 (2)
C32—N2—H2B	117.4	C23—C24—H24	120.8
C36—N2—H2B	117.4	C25—C24—H24	120.8
C42—N3—C38	125.03 (18)	C24—C25—C20	120.7 (2)
C42—N3—H3B	117.5	C24—C25—C19	130.7 (2)
C38—N3—H3B	117.5	C20—C25—C19	108.64 (18)
C2—C1—C6	117.05 (18)	O3—C26—N1	118.81 (19)
C2—C1—C13	120.75 (18)	O3—C26—C27	125.4 (2)
C6—C1—C13	121.81 (17)	N1—C26—C27	115.8 (2)
C1—C2—C3	121.8 (2)	C28—C27—C26	120.1 (2)
C1—C2—H2	119.1	C28—C27—H27	120.0
C3—C2—H2	119.1	C26—C27—H27	120.0
C4—C3—C2	120.13 (19)	C27—C28—C29	121.4 (2)
C4—C3—H3	119.9	C27—C28—H28	119.3
C2—C3—H3	119.9	C29—C28—H28	119.3
O1—C4—C3	121.80 (18)	C30—C29—C28	119.4 (2)
O1—C4—C5	118.78 (19)	C30—C29—H29	120.3
C3—C4—C5	119.41 (19)	C28—C29—H29	120.3
C4—C5—C6	119.7 (2)	C29—C30—N1	118.1 (2)
C4—C5—H5	120.2	C29—C30—C31	125.2 (2)
C6—C5—H5	120.2	N1—C30—C31	116.64 (19)
C5—C6—C1	121.90 (19)	C30—C31—H31A	109.5
C5—C6—H6	119.1	C30—C31—H31B	109.5
C1—C6—H6	119.1	H31A—C31—H31B	109.5
C12—C7—C8	117.34 (18)	C30—C31—H31C	109.5
C12—C7—C13	121.04 (18)	H31A—C31—H31C	109.5
C8—C7—C13	121.36 (17)	H31B—C31—H31C	109.5
C9—C8—C7	121.24 (19)	O4—C32—N2	118.81 (19)
C9—C8—H8	119.4	O4—C32—C33	125.2 (2)
C7—C8—H8	119.4	N2—C32—C33	116.0 (2)
C8—C9—C10	120.29 (19)	C34—C33—C32	119.9 (2)
C8—C9—H9	119.9	C34—C33—H33	120.0
C10—C9—H9	119.9	C32—C33—H33	120.0
O2—C10—C11	122.47 (18)	C33—C34—C35	121.4 (2)
O2—C10—C9	118.55 (18)	C33—C34—H34	119.3
C11—C10—C9	118.98 (18)	C35—C34—H34	119.3
C10—C11—C12	120.38 (19)	C36—C35—C34	119.1 (2)
C10—C11—H11	119.8	C36—C35—H35	120.5
C12—C11—H11	119.8	C34—C35—H35	120.5
C11—C12—C7	121.72 (19)	C35—C36—N2	118.4 (2)
C11—C12—H12	119.1	C35—C36—C37	125.3 (2)
C7—C12—H12	119.1	N2—C36—C37	116.33 (19)
C7—C13—C14	114.55 (16)	C36—C37—H37A	109.5
C7—C13—C20	109.68 (16)	C36—C37—H37B	109.5
C14—C13—C20	100.77 (16)	H37A—C37—H37B	109.5
C7—C13—C1	113.41 (16)	C36—C37—H37C	109.5
C14—C13—C1	106.94 (16)	H37A—C37—H37C	109.5
C20—C13—C1	110.77 (16)	H37B—C37—H37C	109.5
C15—C14—C19	120.74 (19)	O5—C38—N3	118.57 (19)
C15—C14—C13	128.65 (18)	O5—C38—C39	125.68 (19)
C19—C14—C13	110.58 (18)	N3—C38—C39	115.75 (19)
C14—C15—C16	119.0 (2)	C40—C39—C38	120.3 (2)
C14—C15—H15	120.5	C40—C39—H39	119.9
C16—C15—H15	120.5	C38—C39—H39	119.9
C17—C16—C15	120.4 (2)	C39—C40—C41	121.2 (2)
C17—C16—H16	119.8	C39—C40—H40	119.4
C15—C16—H16	119.8	C41—C40—H40	119.4
C18—C17—C16	120.7 (2)	C42—C41—C40	118.9 (2)
C18—C17—H17	119.6	C42—C41—H41	120.6
C16—C17—H17	119.6	C40—C41—H41	120.6
C17—C18—C19	119.1 (2)	C41—C42—N3	118.85 (19)
C17—C18—H18	120.4	C41—C42—C43	125.4 (2)
C19—C18—H18	120.4	N3—C42—C43	115.76 (19)
C18—C19—C14	119.8 (2)	C42—C43—H43A	109.5
C18—C19—C25	131.5 (2)	C42—C43—H43B	109.5
C14—C19—C25	108.64 (18)	H43A—C43—H43B	109.5
C21—C20—C25	120.23 (19)	C42—C43—H43C	109.5
C21—C20—C13	128.87 (18)	H43A—C43—H43C	109.5
C25—C20—C13	110.90 (17)	H43B—C43—H43C	109.5
C20—C21—C22	118.7 (2)

C6—C1—C2—C3	−0.4 (3)	C14—C13—C20—C21	−175.36 (19)
C13—C1—C2—C3	172.55 (19)	C1—C13—C20—C21	71.7 (2)
C1—C2—C3—C4	−0.8 (3)	C7—C13—C20—C25	125.93 (17)
C2—C3—C4—O1	−178.01 (18)	C14—C13—C20—C25	4.8 (2)
C2—C3—C4—C5	1.1 (3)	C1—C13—C20—C25	−108.14 (18)
O1—C4—C5—C6	178.77 (18)	C25—C20—C21—C22	−0.7 (3)
C3—C4—C5—C6	−0.4 (3)	C13—C20—C21—C22	179.42 (19)
C4—C5—C6—C1	−0.8 (3)	C20—C21—C22—C23	0.2 (3)
C2—C1—C6—C5	1.1 (3)	C21—C22—C23—C24	0.8 (3)
C13—C1—C6—C5	−171.71 (18)	C22—C23—C24—C25	−1.2 (3)
C12—C7—C8—C9	1.5 (3)	C23—C24—C25—C20	0.6 (3)
C13—C7—C8—C9	−172.72 (19)	C23—C24—C25—C19	−177.6 (2)
C7—C8—C9—C10	−0.5 (3)	C21—C20—C25—C24	0.3 (3)
C8—C9—C10—O2	179.11 (18)	C13—C20—C25—C24	−179.80 (18)
C8—C9—C10—C11	−1.3 (3)	C21—C20—C25—C19	178.89 (17)
O2—C10—C11—C12	−178.27 (19)	C13—C20—C25—C19	−1.2 (2)
C9—C10—C11—C12	2.2 (3)	C18—C19—C25—C24	−4.3 (4)
C10—C11—C12—C7	−1.2 (3)	C14—C19—C25—C24	175.0 (2)
C8—C7—C12—C11	−0.6 (3)	C18—C19—C25—C20	177.3 (2)
C13—C7—C12—C11	173.61 (19)	C14—C19—C25—C20	−3.3 (2)
C12—C7—C13—C14	21.5 (3)	C30—N1—C26—O3	−179.89 (19)
C8—C7—C13—C14	−164.47 (18)	C30—N1—C26—C27	−1.4 (3)
C12—C7—C13—C20	−90.9 (2)	O3—C26—C27—C28	178.9 (2)
C8—C7—C13—C20	83.1 (2)	N1—C26—C27—C28	0.5 (3)
C12—C7—C13—C1	144.69 (19)	C26—C27—C28—C29	0.7 (3)
C8—C7—C13—C1	−41.3 (3)	C27—C28—C29—C30	−1.0 (3)
C2—C1—C13—C7	143.47 (19)	C28—C29—C30—N1	0.2 (3)
C6—C1—C13—C7	−44.0 (3)	C28—C29—C30—C31	−178.8 (2)
C2—C1—C13—C14	−89.3 (2)	C26—N1—C30—C29	1.0 (3)
C6—C1—C13—C14	83.3 (2)	C26—N1—C30—C31	−179.88 (19)
C2—C1—C13—C20	19.6 (3)	C36—N2—C32—O4	−177.89 (19)
C6—C1—C13—C20	−167.78 (18)	C36—N2—C32—C33	1.8 (3)
C7—C13—C14—C15	57.5 (3)	O4—C32—C33—C34	178.3 (2)
C20—C13—C14—C15	175.1 (2)	N2—C32—C33—C34	−1.3 (3)
C1—C13—C14—C15	−69.1 (2)	C32—C33—C34—C35	0.3 (3)
C7—C13—C14—C19	−124.48 (18)	C33—C34—C35—C36	0.4 (3)
C20—C13—C14—C19	−6.8 (2)	C34—C35—C36—N2	−0.1 (3)
C1—C13—C14—C19	108.95 (18)	C34—C35—C36—C37	179.8 (2)
C19—C14—C15—C16	−2.3 (3)	C32—N2—C36—C35	−1.1 (3)
C13—C14—C15—C16	175.58 (19)	C32—N2—C36—C37	179.00 (19)
C14—C15—C16—C17	−0.7 (3)	C42—N3—C38—O5	178.59 (18)
C15—C16—C17—C18	1.7 (3)	C42—N3—C38—C39	−1.3 (3)
C16—C17—C18—C19	0.3 (3)	O5—C38—C39—C40	−179.3 (2)
C17—C18—C19—C14	−3.2 (3)	N3—C38—C39—C40	0.5 (3)
C17—C18—C19—C25	176.1 (2)	C38—C39—C40—C41	0.4 (3)
C15—C14—C19—C18	4.3 (3)	C39—C40—C41—C42	−0.7 (3)
C13—C14—C19—C18	−173.97 (17)	C40—C41—C42—N3	0.0 (3)
C15—C14—C19—C25	−175.18 (18)	C40—C41—C42—C43	−179.63 (19)
C13—C14—C19—C25	6.6 (2)	C38—N3—C42—C41	1.0 (3)
C7—C13—C20—C21	−54.2 (3)	C38—N3—C42—C43	−179.31 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.84	1.84	2.680 (2)	174
O2—H2A···O8	0.84	1.77	2.605 (2)	178
O6—H6A···O5	0.95 (3)	1.80 (3)	2.738 (2)	170 (2)
O6—H6B···O1ⁱ	0.88 (3)	2.11 (3)	2.962 (2)	165 (3)
O7—H7A···O3	0.92 (3)	1.80 (3)	2.708 (2)	168 (3)
O7—H7B···O2ⁱⁱ	0.86 (3)	2.20 (3)	3.020 (3)	161 (3)
O8—H8A···O6	0.91 (3)	1.87 (3)	2.778 (3)	175 (2)
O8—H8B···O4ⁱⁱⁱ	0.90 (3)	1.79 (3)	2.685 (2)	174 (3)
N1—H1B···O4	0.88	1.88	2.755 (2)	179
N2—H2B···O3	0.88	1.93	2.805 (2)	176
N3—H3B···O5ⁱⁱ	0.88	1.90	2.777 (2)	176

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

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₂₅H₁₈O₂·2C₆H₇NO	C₂₅H₁₈O₂·3C₆H₇NO·3H₂O
M_r	568.65	731.82
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	120	120
a, b, c (Å)	17.480 (4), 11.114 (2), 29.698 (6)	14.432 (4), 14.665 (5), 35.675 (10)
β (°)	93.894 (8)	90.133 (14)
V (Å³)	5756 (2)	7550 (4)
Z	8	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.09	0.09
Crystal size (mm)	0.30 × 0.10 × 0.10	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART 6K CCD diffractometer	Bruker SMART 6K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.975, 0.992	0.970, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	23891, 5129, 3823	24437, 6729, 5287
R_int	0.056	0.048
(sin θ/λ)_max (Å⁻¹)	0.597	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.147, 1.16	0.055, 0.113, 1.28
No. of reflections	5129	6729
No. of parameters	390	515
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.23	0.25, −0.21

Computer programs: SMART-NT (Bruker, 2000), SAINT-NT ?? (Bruker, 2000), SAINT-NT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), ORTEP (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.84	1.89	2.672 (2)	155.5
O2—H2A···O4	0.84	1.89	2.646 (2)	149.1
N1—H1B···O3ⁱ	0.88	1.88	2.755 (2)	174.4
N2—H2B···O4ⁱⁱ	0.88	2.18	2.940 (2)	144.7

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y−1, −z.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.84	1.84	2.680 (2)	174.0
O2—H2A···O8	0.84	1.77	2.605 (2)	177.7
O6—H6A···O5	0.95 (3)	1.80 (3)	2.738 (2)	170 (2)
O6—H6B···O1ⁱ	0.88 (3)	2.11 (3)	2.962 (2)	165 (3)
O7—H7A···O3	0.92 (3)	1.80 (3)	2.708 (2)	168 (3)
O7—H7B···O2ⁱⁱ	0.86 (3)	2.20 (3)	3.020 (3)	161 (3)
O8—H8A···O6	0.91 (3)	1.87 (3)	2.778 (3)	175 (2)
O8—H8B···O4ⁱⁱⁱ	0.90 (3)	1.79 (3)	2.685 (2)	174 (3)
N1—H1B···O4	0.88	1.88	2.755 (2)	179.3
N2—H2B···O3	0.88	1.93	2.805 (2)	176.1
N3—H3B···O5ⁱⁱ	0.88	1.90	2.777 (2)	175.5

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

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STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 63| Part 2| February 2007| Pages o89-o92

doi:10.1107/S010827010604474X

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Cocrystals composed of 4,4′-(fluorene-9,9-di­yl)diphenol and 6-methyl-2H-pyridone

Comment

Experimental

Cocrystal (I)

Crystal data

Data collection

Refinement

Cocrystal (II)

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

Cocrystals composed of 4,4′-(fluorene-9,9-diyl)diphenol and 6-methyl-2H-pyridone