1:1 Adducts of 2,2'-[isopropyl­idene­bis(p-phenyl­eneoxy)]diacetic acid with dimethyl­ammonium and 4,4'-bipyridine

The title compounds, dimethyl­ammonium 2-{4-[1-(4-carboxy­methoxy­phenyl)-1-methyl­ethyl]phen­oxy}acetate, C₂H₈N⁺·C₁₉H₁₉O₆^-, (I), and 2,2'-[isopropyl­idenebis(p-phenyl­ene­oxy)]­diacetic acid-4,4'-bipyridine (1/1), C₁₉H₂₀O₆·C₁₀H₈N₂, (II), are 1:1 adducts of 2,2'-[isopropyl­idenebis(p-phenyl­ene­oxy)]diacetic acid (H₂L) with dimethyl­ammonium or 4,4'-bi­pyri­dine. The component ions in (I) are linked by N-H...O, O-H...O and C-H...O hydrogen bonds into continuous two-dimensional layers parallel to the (001) plane. Adjacent layers are stacked via C-H...O hydrogen bonds into a three-dimensional network with an -ABAB- alternation of the two-dimensional layers. In (II), two H₂L molecules, one bipy molecule and two half bipy molecules are linked by O-H...N hydrogen bonds into one-dimensional chains and rectanglar-shaped rings. They are assembled via [pi]-[pi] stacking inter­actions and C-H...O hydrogen bonds into an intriguing zero-dimensional plus one-dimensional poly(pseudo)rotaxane motif.

S1. Comment

Over the past decade, the rational design and synthesis of metal–organic frameworks have received extensive attention in the fields of supramolecular chemistry and crystal engineering (Rosi et al., 2003; Dalgarno et al., 2008). These materials exhibit interesting properties such as catalysis, biological activity, electrical conductivity, magnetism and photochemical activity. In the past five years there has been a growing interest in metal–organic frameworks involving semi-rigid V-shaped dicarboxylate ligands (Tanaka et al., 2008; Zang et al., 2006; Mahata et al., 2008; Furukawa et al., 2008). 4,4'-[Isopropylidenebis(p-phenyleneoxy)]diacetic acid (H₂L) is a typical example of a semi-rigid V-shaped dicarboxylate ligand. To the best of our knowledge there has been no report to date concerning its coordination compounds. Recently, we have focused on preparing metal–organic frameworks containing this organic ligand and metal ions. During this process, two interesting adducts of H₂L with dimethylammonium and 4,4'-bipyridine, compounds (I) and (II), respectively, were obtained, and we report here their synthesis and crystal structures.

Although we failed to formulate coordination polymers at this stage, the present characterization of the crystalline products provids useful information. Thus, when H₂L was reacted with a lanthanum nitrate salt (see Experimental) in the presence of N,N-dimethylformamide (DMF) under hydrothermal conditions, no metal ions were incorporated into the structure. Instead, the 1:1 salt, (I), formed between the monodeprotonated H₂L and a dimethylammonium cation (a product resulting from hydrolysis of DMF). The H atom of one carboxyl group is transferred to the dimethylamine N atom, while the other remains as the acid. The carboxyl and carboxylate groups are almost perpendicular to the benzene ring, with dihedral angles of 80.9 (1) and 86.2 (2)° (Table 1 and Fig. 1), respectively. The arrangement in the carboxylic acid is the less common syn–anti conformation (Kennard et al., 1982; Lynch et al., 2003). The benzene rings of the bent H₂L molecule subtend a dihedral angle of 86.5 (1)°.

The supramolecular structure of (I) can be simply analyzed in terms of three substructures. Firstly, the HL^- anions result in discrete one-dimensional chains via an O5—H5···O2A hydrogen bond [symmetry code: (A) 1 - x, -1/2 + y, 1/2 - z] running parallel to the [010] direction. Secondly, adjacent [010] chains are linked together by dimethylammonium cations through strong N—H···O hydrogen bonds in concert with C—H···O hydrogen bonds (Table 2), forming two-dimensional layers built from R₄⁶(46) hydrogen-bond motifs (Bernstein et al., 1995) which are parallel to the (001) plane (Fig. 2). Finally, neighbouring two-dimensional layers are assembled into a three-dimensional network by means of C—H···O hydrogen bonds with –ABAB– alternation (Fig. 3 and Table 2).

The reaction of H₂L with Pb^II ions in the presence of 4,4'-bipyridyl (bipy) yielded compound (II). As shown in Fig. 4, the asymmetric unit of (II) consists of two H₂L molecules and one bipy molecule, together with two half-bipy molecules, these last both possessing inversion centres. The C—O bond distances support the existence of unionized acid molecules, indicating cocrystal formation (Table 3). H₂L and bipy crystallize to form two different independent networks: a four-member rectangular-shaped ring (Fig. 5a) and a one-dimensional wavelike chain (Fig. 5b). In both networks, the H₂L and bipy molecules are linked together by strong O—H···N hydrogen bonds (Table 4). In the rectangular-shaped ring, the planes of the pyridyl rings of the bipy molecule are twisted by 25.9 (6)° with respect to each other. One of the phenoxyacetic acid groups, that containing atom O11, adopts an antiperiplanar conformation, with a dihedral angle of 44.3 (2)° between the carboxyl group and the benzene ring. The other phenoxyacetic acid group, containing atom O8, adopts a synplanar conformation, with a dihedral angle of 82.2 (1)°. The dihedral angle between the two benzene rings is 88.2 (2)°. In the chain network the bipy molecules, which lie on centres of symmetry, both have planar central portions. The conformation of the H₂L molecule shows some differences from the H₂L molecule in the rectangular ring. One phenoxyacetic acid group (containing atom O3) has an antiperiplanar conformation and the acetic acid arm is almost in the same plane as the benzene ring. The other phenoxyacetic acid group adopts an uncommon syn–anti conformation, like that in (I), and here the dihedral angle between the two benzene rings is 85.9 (2)°.

Interestingly, the rectangular rings and wave-like chains are assembled by π–π stacking interactions and C18—H18B···O12 hydrogen bonds into an intriguing zero-dimensional plus one-dimensional poly(pseudo) rotaxane motif. The π–π interactions occur between the bipy rings, with a ring centroid distance of 3.874 (3) Å, an interplanar spacing of 3.541 (2) Å and an offset angle of 4.20 (1)°. The poly(pseudo) rotaxane motifs are linked into a three-dimensional network by a combination of C—H···O and C—H···π hydrogen bonds (Table 4 and Fig. 6).

In conclusion, the two 1:1 organic compounds formed by H₂L with dimethylammonium and bipy are the first examples of H₂L adducts to be descibed. The phenoxyacetic acid groups in these two adducts show interesting conformations, and an intriguing zero-dimensional plus one-dimensional poly(pseudo) rotaxane structure is found in compound (II).

S2. Experimental

H₂L was synthesized by the literature method (Inouye et al., 1995). Compound (I) was obtained by heating a mixture of La(NO₃)₃.6H₂O (0.130 g, 0.3 mmol), H₂L (0.206 g, 0.6 mmol) and dimethylformamide (DMF; 3 ml) in a sealed 5 ml reactor at 433 K for 48 h, followed by gradual cooling to room temperature. Colourless block-like crystals of (I) were collected by filtration and air-dried. Compound (II) was obtained when a mixture of Pb(NO₃)₃ (0.109 g, 0.33 mmol), bipy (0.019 g, 0.12 mmol) and H₂L (0.042 mg, 0.12 mmol) in H₂O (8 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 443 K for 72 h. A crop of colourless single crystals of compound (II) was obtained after cooling the solution to room temperature. The platelet-shaped crystals were collected and washed with distilled water.

S3. Refinement

All H atoms were placed in idealized positions, with O—H = 0.82, N—H = 0.90 and C—H = 0.93–0.97 Å, and refined as riding atoms, with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O). For structure (II), the R factor is slightly higher than normally expected due to the fact that the crystal diffracted weakly, and only 50% of the data can be considered to be observed [I > 2σ(I)].

Computing details

For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 2. Part of the crystal structure of (I), showing the formation of the two-dimensional layer running parallel to the (001) plane. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted. [Symmetry code: (A) 1 - x, -1/2 + y, 1/2 - z]. Fig. 3. The extended structure of the three-dimensional supramolecular network of (I), viewed along the a axis. H atoms not involved in hydrogen bonding have been omitted for clarity. Fig. 4. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 5. (a) The rectangular-shaped ring formed by the intermolecular O11—H11···N1(-x+1, -y+1, -z+1) and O8—H8···N2(x-1, y, z) hydrogen bonds in (II). (b) The one-dimensional chain formed by the O3—H3···N4(x-1, y, z-1) and O5—H5···N3 hydrogen bonds in (II). H atoms not involved in the interactions have been omitted for clarity. (a) The rectangular-shaped ring formed by the O11—H11···N1 and O8—H8···N2 hydrogen bonds in (II) between the reference molecule and its symmetry equivalents at (1 - x, 1 - y, 1 - z) and (-1 + x, y, z). (b) The one-dimensional chain formed by the O3—H3···N4 and O5—H5···N3 hydrogen bonds in (II) between the reference molecule and its symmetry equivalent at (-1 + x, y, -1 + z). [Please check amended text] Fig. 6. The extended supramolecular hydrogen-bonded network of (II). H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) dimethylammonium 2-{4-[1-(4-carboxymethoxyphenyl)-1-methylethyl]phenoxy}acetate

Crystal data

C2H8N^+·C19H19O6^−	F(000) = 832
Mr = 389.44	Dx = 1.238 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1412 reflections
a = 6.9028 (14) Å	θ = 2.9–21.1°
b = 27.756 (6) Å	µ = 0.09 mm^−1
c = 12.624 (4) Å	T = 295 K
β = 120.21 (2)°	Block, colourless
V = 2090.2 (9) Å^3	0.20 × 0.18 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3693 independent reflections
Radiation source: fine-focus sealed tube	2126 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ϕ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
Tmin = 0.982, Tmax = 0.985	k = −32→24
10877 measured reflections	l = −13→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 0.0341P] where P = (Fo^2 + 2Fc^2)/3
3693 reflections	(Δ/σ)max < 0.001
257 parameters	Δρmax = 0.12 e Å^−3
0 restraints	Δρmin = −0.17 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
O1	0.2193 (3)	0.95382 (7)	0.42290 (16)	0.0730 (6)
O2	0.4092 (2)	0.96870 (6)	0.32783 (15)	0.0559 (5)
O3	0.7206 (2)	0.90150 (6)	0.45967 (14)	0.0555 (5)
O4	0.7744 (3)	0.53223 (7)	0.43833 (16)	0.0725 (5)
O5	0.8680 (3)	0.53345 (6)	0.29336 (15)	0.0601 (5)
H5	0.7748	0.5118	0.2629	0.090*
O6	1.1384 (3)	0.60835 (6)	0.39396 (16)	0.0669 (5)
N1	0.7816 (3)	0.98577 (8)	0.30070 (18)	0.0651 (6)
H1A	0.6973	0.9735	0.3301	0.078*
H1B	0.9231	0.9754	0.3495	0.078*
C1	0.3801 (4)	0.94797 (9)	0.4074 (2)	0.0470 (6)
C2	0.5586 (4)	0.91318 (9)	0.4934 (2)	0.0538 (7)
H2A	0.6349	0.9270	0.5751	0.065*
H2B	0.4865	0.8837	0.4970	0.065*
C3	0.6648 (4)	0.86726 (8)	0.3704 (2)	0.0460 (6)
C4	0.8409 (4)	0.84983 (9)	0.3592 (2)	0.0570 (7)
H4	0.9855	0.8611	0.4108	0.068*
C5	0.8028 (4)	0.81587 (9)	0.2722 (2)	0.0564 (7)
H5A	0.9238	0.8042	0.2668	0.068*
C6	0.5898 (4)	0.79809 (8)	0.1916 (2)	0.0471 (6)
C7	0.4184 (4)	0.81615 (9)	0.2051 (2)	0.0546 (7)
H7	0.2736	0.8050	0.1532	0.066*
C8	0.4521 (4)	0.85036 (9)	0.2931 (2)	0.0538 (6)
H8	0.3318	0.8617	0.2997	0.065*
C9	0.5619 (4)	0.75964 (9)	0.0977 (2)	0.0532 (6)
C10	0.3186 (4)	0.74245 (10)	0.0195 (2)	0.0723 (8)
H10A	0.3105	0.7179	−0.0361	0.109*
H10B	0.2252	0.7691	−0.0262	0.109*
H10C	0.2678	0.7296	0.0719	0.109*
C11	0.6308 (5)	0.78168 (10)	0.0099 (2)	0.0790 (9)
H11A	0.7844	0.7919	0.0556	0.119*
H11B	0.5370	0.8089	−0.0311	0.119*
H11C	0.6139	0.7580	−0.0497	0.119*
C12	0.7102 (4)	0.71674 (8)	0.1689 (2)	0.0472 (6)
C13	0.8967 (4)	0.70208 (9)	0.1646 (2)	0.0572 (7)
H13	0.9317	0.7172	0.1106	0.069*
C14	1.0327 (4)	0.66550 (9)	0.2385 (3)	0.0610 (7)
H14	1.1575	0.6563	0.2336	0.073*
C15	0.9863 (4)	0.64252 (8)	0.3191 (2)	0.0513 (6)
C16	0.7964 (4)	0.65502 (9)	0.3220 (2)	0.0556 (7)
H16	0.7580	0.6387	0.3732	0.067*
C17	0.6637 (4)	0.69186 (9)	0.2484 (2)	0.0537 (6)
H17	0.5371	0.7004	0.2522	0.064*
C18	0.8879 (4)	0.54642 (9)	0.3980 (2)	0.0527 (6)
C19	1.0778 (4)	0.58096 (9)	0.4678 (2)	0.0681 (8)
H19A	1.0367	0.6029	0.5129	0.082*
H19B	1.2079	0.5629	0.5271	0.082*
C20	0.6992 (5)	0.96651 (12)	0.1766 (2)	0.0796 (9)
H20A	0.5526	0.9792	0.1220	0.119*
H20B	0.6916	0.9320	0.1784	0.119*
H20C	0.7997	0.9757	0.1484	0.119*
C21	0.7791 (5)	1.03860 (11)	0.3086 (3)	0.0759 (8)
H21A	0.8740	1.0522	0.2810	0.114*
H21B	0.8330	1.0480	0.3921	0.114*
H21C	0.6287	1.0501	0.2579	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0584 (11)	0.1045 (16)	0.0696 (12)	0.0165 (10)	0.0422 (10)	0.0207 (10)
O2	0.0565 (10)	0.0563 (11)	0.0653 (11)	0.0106 (8)	0.0382 (9)	0.0155 (9)
O3	0.0485 (9)	0.0525 (11)	0.0574 (10)	0.0056 (8)	0.0207 (8)	−0.0056 (8)
O4	0.0794 (13)	0.0832 (14)	0.0656 (12)	0.0006 (11)	0.0443 (11)	0.0043 (10)
O5	0.0638 (11)	0.0568 (11)	0.0639 (11)	−0.0150 (8)	0.0354 (9)	−0.0116 (9)
O6	0.0527 (10)	0.0501 (11)	0.0814 (12)	−0.0010 (9)	0.0214 (9)	−0.0001 (10)
N1	0.0483 (12)	0.0894 (19)	0.0642 (14)	0.0051 (11)	0.0333 (11)	0.0152 (12)
C1	0.0475 (14)	0.0518 (15)	0.0431 (14)	−0.0015 (12)	0.0238 (12)	−0.0026 (11)
C2	0.0626 (16)	0.0556 (16)	0.0465 (14)	0.0043 (13)	0.0299 (12)	0.0006 (12)
C3	0.0504 (14)	0.0365 (13)	0.0444 (13)	0.0041 (11)	0.0189 (11)	0.0025 (11)
C4	0.0406 (13)	0.0543 (16)	0.0639 (16)	0.0031 (12)	0.0172 (12)	−0.0059 (13)
C5	0.0502 (14)	0.0559 (17)	0.0634 (16)	0.0054 (12)	0.0288 (13)	−0.0061 (13)
C6	0.0515 (14)	0.0416 (14)	0.0446 (13)	0.0022 (11)	0.0215 (11)	0.0059 (11)
C7	0.0452 (14)	0.0534 (16)	0.0554 (15)	−0.0010 (12)	0.0180 (12)	−0.0009 (12)
C8	0.0465 (14)	0.0515 (16)	0.0617 (15)	0.0041 (12)	0.0261 (12)	−0.0016 (13)
C9	0.0651 (16)	0.0508 (15)	0.0432 (13)	0.0008 (13)	0.0270 (12)	0.0018 (11)
C10	0.0719 (18)	0.0678 (19)	0.0539 (16)	0.0019 (14)	0.0143 (14)	−0.0093 (14)
C11	0.110 (2)	0.076 (2)	0.0603 (17)	0.0085 (18)	0.0497 (16)	0.0161 (15)
C12	0.0591 (15)	0.0428 (14)	0.0444 (13)	−0.0046 (12)	0.0296 (12)	−0.0081 (11)
C13	0.0699 (17)	0.0524 (16)	0.0669 (17)	−0.0082 (14)	0.0476 (14)	−0.0057 (13)
C14	0.0555 (15)	0.0548 (17)	0.0831 (19)	−0.0043 (13)	0.0426 (14)	−0.0102 (15)
C15	0.0517 (14)	0.0388 (14)	0.0566 (15)	−0.0032 (12)	0.0222 (12)	−0.0103 (12)
C16	0.0733 (17)	0.0485 (16)	0.0557 (15)	0.0047 (14)	0.0405 (13)	0.0044 (12)
C17	0.0604 (15)	0.0519 (16)	0.0608 (16)	0.0079 (13)	0.0395 (13)	0.0034 (13)
C18	0.0574 (16)	0.0472 (16)	0.0464 (15)	0.0121 (12)	0.0209 (13)	0.0062 (12)
C19	0.0659 (17)	0.0530 (17)	0.0583 (16)	0.0043 (14)	0.0111 (14)	0.0039 (14)
C20	0.0732 (19)	0.098 (2)	0.0666 (18)	−0.0084 (17)	0.0344 (15)	−0.0073 (17)
C21	0.0695 (18)	0.084 (2)	0.085 (2)	−0.0080 (16)	0.0471 (16)	−0.0062 (16)

Geometric parameters (Å, º)

O1—C1	1.231 (3)	C9—C10	1.534 (3)
O2—C1	1.258 (3)	C9—C11	1.536 (4)
O3—C3	1.373 (3)	C10—H10A	0.9600
O3—C2	1.420 (3)	C10—H10B	0.9600
O4—C18	1.196 (3)	C10—H10C	0.9600
O5—C18	1.308 (3)	C11—H11A	0.9600
O5—H5	0.8206	C11—H11B	0.9600
O6—C15	1.377 (3)	C11—H11C	0.9600
O6—C19	1.419 (3)	C12—C13	1.377 (3)
N1—C21	1.470 (3)	C12—C17	1.382 (3)
N1—C20	1.472 (3)	C13—C14	1.379 (3)
N1—H1A	0.8997	C13—H13	0.9300
N1—H1B	0.9003	C14—C15	1.368 (3)
C1—C2	1.511 (3)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.374 (3)
C2—H2B	0.9700	C16—C17	1.375 (3)
C3—C8	1.373 (3)	C16—H16	0.9300
C3—C4	1.380 (3)	C17—H17	0.9300
C4—C5	1.369 (3)	C18—C19	1.501 (3)
C4—H4	0.9300	C19—H19A	0.9700
C5—C6	1.391 (3)	C19—H19B	0.9700
C5—H5A	0.9300	C20—H20A	0.9600
C6—C7	1.372 (3)	C20—H20B	0.9600
C6—C9	1.534 (3)	C20—H20C	0.9600
C7—C8	1.389 (3)	C21—H21A	0.9600
C7—H7	0.9300	C21—H21B	0.9600
C8—H8	0.9300	C21—H21C	0.9600
C9—C12	1.533 (3)
C3—O3—C2	117.80 (18)	H10B—C10—H10C	109.5
C18—O5—H5	109.5	C9—C11—H11A	109.5
C15—O6—C19	116.4 (2)	C9—C11—H11B	109.5
C21—N1—C20	115.0 (2)	H11A—C11—H11B	109.5
C21—N1—H1A	108.5	C9—C11—H11C	109.5
C20—N1—H1A	108.5	H11A—C11—H11C	109.5
C21—N1—H1B	108.5	H11B—C11—H11C	109.5
C20—N1—H1B	108.5	C13—C12—C17	116.4 (2)
H1A—N1—H1B	107.5	C13—C12—C9	124.6 (2)
O1—C1—O2	125.8 (2)	C17—C12—C9	119.0 (2)
O1—C1—C2	116.4 (2)	C12—C13—C14	121.5 (2)
O2—C1—C2	117.8 (2)	C12—C13—H13	119.3
O3—C2—C1	114.2 (2)	C14—C13—H13	119.3
O3—C2—H2A	108.7	C15—C14—C13	120.8 (2)
C1—C2—H2A	108.7	C15—C14—H14	119.6
O3—C2—H2B	108.7	C13—C14—H14	119.6
C1—C2—H2B	108.7	C14—C15—C16	119.0 (2)
H2A—C2—H2B	107.6	C14—C15—O6	116.6 (2)
C8—C3—O3	125.3 (2)	C16—C15—O6	124.3 (2)
C8—C3—C4	119.3 (2)	C15—C16—C17	119.3 (2)
O3—C3—C4	115.4 (2)	C15—C16—H16	120.3
C5—C4—C3	120.0 (2)	C17—C16—H16	120.3
C5—C4—H4	120.0	C16—C17—C12	122.9 (2)
C3—C4—H4	120.0	C16—C17—H17	118.6
C4—C5—C6	122.5 (2)	C12—C17—H17	118.6
C4—C5—H5A	118.8	O4—C18—O5	125.5 (2)
C6—C5—H5A	118.8	O4—C18—C19	121.8 (3)
C7—C6—C5	116.1 (2)	O5—C18—C19	112.7 (3)
C7—C6—C9	124.7 (2)	O6—C19—C18	114.6 (2)
C5—C6—C9	119.2 (2)	O6—C19—H19A	108.6
C6—C7—C8	122.8 (2)	C18—C19—H19A	108.6
C6—C7—H7	118.6	O6—C19—H19B	108.6
C8—C7—H7	118.6	C18—C19—H19B	108.6
C3—C8—C7	119.4 (2)	H19A—C19—H19B	107.6
C3—C8—H8	120.3	N1—C20—H20A	109.5
C7—C8—H8	120.3	N1—C20—H20B	109.5
C12—C9—C6	107.44 (17)	H20A—C20—H20B	109.5
C12—C9—C10	109.1 (2)	N1—C20—H20C	109.5
C6—C9—C10	112.6 (2)	H20A—C20—H20C	109.5
C12—C9—C11	112.0 (2)	H20B—C20—H20C	109.5
C6—C9—C11	108.5 (2)	N1—C21—H21A	109.5
C10—C9—C11	107.2 (2)	N1—C21—H21B	109.5
C9—C10—H10A	109.5	H21A—C21—H21B	109.5
C9—C10—H10B	109.5	N1—C21—H21C	109.5
H10A—C10—H10B	109.5	H21A—C21—H21C	109.5
C9—C10—H10C	109.5	H21B—C21—H21C	109.5
H10A—C10—H10C	109.5
C3—O3—C2—C1	−80.7 (2)	C6—C9—C12—C13	−113.2 (3)
O1—C1—C2—O3	170.0 (2)	C10—C9—C12—C13	124.4 (2)
O2—C1—C2—O3	−10.8 (3)	C11—C9—C12—C13	5.8 (3)
C2—O3—C3—C8	14.1 (3)	C6—C9—C12—C17	63.4 (3)
C2—O3—C3—C4	−166.7 (2)	C10—C9—C12—C17	−59.0 (3)
C8—C3—C4—C5	−0.3 (4)	C11—C9—C12—C17	−177.5 (2)
O3—C3—C4—C5	−179.5 (2)	C17—C12—C13—C14	−1.9 (3)
C3—C4—C5—C6	0.8 (4)	C9—C12—C13—C14	174.8 (2)
C4—C5—C6—C7	−0.8 (4)	C12—C13—C14—C15	−0.1 (4)
C4—C5—C6—C9	−179.3 (2)	C13—C14—C15—C16	2.7 (4)
C5—C6—C7—C8	0.3 (4)	C13—C14—C15—O6	−176.4 (2)
C9—C6—C7—C8	178.8 (2)	C19—O6—C15—C14	−173.4 (2)
O3—C3—C8—C7	178.9 (2)	C19—O6—C15—C16	7.6 (3)
C4—C3—C8—C7	−0.2 (4)	C14—C15—C16—C17	−3.2 (3)
C6—C7—C8—C3	0.2 (4)	O6—C15—C16—C17	175.8 (2)
C7—C6—C9—C12	−120.9 (2)	C15—C16—C17—C12	1.2 (4)
C5—C6—C9—C12	57.5 (3)	C13—C12—C17—C16	1.4 (3)
C7—C6—C9—C10	−0.8 (3)	C9—C12—C17—C16	−175.6 (2)
C5—C6—C9—C10	177.7 (2)	C15—O6—C19—C18	69.4 (3)
C7—C6—C9—C11	117.7 (3)	O4—C18—C19—O6	−156.7 (2)
C5—C6—C9—C11	−63.8 (3)	O5—C18—C19—O6	25.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2^i	0.82	1.70	2.507 (2)	167
N1—H1B···O1^ii	0.90	1.87	2.758 (3)	169
N1—H1A···O3	0.90	2.54	3.245 (3)	136
N1—H1A···O2	0.90	1.98	2.800 (3)	151
C20—H20A···O4^iii	0.96	2.47	3.368 (4)	155
C20—H20C···O4^iv	0.96	2.58	3.300 (4)	132
C20—H20C···O5^v	0.96	2.58	3.374 (3)	140
C21—H21A···O5^v	0.96	2.45	3.282 (3)	145
C21—H21B···O1^vi	0.96	2.54	3.390 (4)	148

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

(II) 2,2'-[isopropylidenebis(p-phenyleneoxy)]diacetic acid–4,4'-bipyridine (1/1)

Crystal data

C19H20O6·C10H8N2	Z = 4
Mr = 500.53	F(000) = 1056
Triclinic, P1	Dx = 1.305 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8698 (15) Å	Cell parameters from 1666 reflections
b = 14.673 (2) Å	θ = 2.7–20.7°
c = 20.087 (3) Å	µ = 0.09 mm^−1
α = 96.749 (2)°	T = 295 K
β = 94.180 (3)°	Block, colourless
γ = 99.751 (4)°	0.22 × 0.18 × 0.16 mm
V = 2547.1 (7) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	8949 independent reflections
Radiation source: fine-focus sealed tube	4313 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ϕ and ω scans	θmax = 25.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→10
Tmin = 0.980, Tmax = 0.985	k = −17→15
13525 measured reflections	l = −21→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.070	H-atom parameters constrained
wR(F^2) = 0.235	w = 1/[σ^2(Fo^2) + (0.1089P)^2 + 0.0613P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
8949 reflections	Δρmax = 0.74 e Å^−3
670 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (10)

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
O1	−0.1165 (4)	0.0986 (2)	−0.21956 (14)	0.0670 (9)
O2	−0.3273 (4)	0.0581 (2)	−0.32715 (17)	0.0835 (11)
O3	−0.5169 (4)	0.0527 (3)	−0.25995 (16)	0.0883 (11)
H3	−0.5717	0.0347	−0.2953	0.132*
O4	0.2862 (4)	0.48368 (18)	0.17580 (13)	0.0582 (8)
O5	0.4833 (4)	0.4676 (2)	0.27727 (14)	0.0721 (9)
H5	0.5463	0.4754	0.3103	0.108*
O6	0.3237 (4)	0.4930 (2)	0.35426 (15)	0.0791 (10)
O7	0.6834 (4)	0.7702 (2)	0.60863 (14)	0.0720 (9)
O8	0.3011 (4)	0.7886 (3)	0.56925 (16)	0.0998 (13)
H8	0.2461	0.7820	0.5337	0.150*
O9	0.4771 (4)	0.7688 (3)	0.50218 (15)	0.0938 (10)
O10	1.1784 (3)	0.43722 (18)	0.89018 (14)	0.0562 (8)
O11	0.7802 (4)	0.3336 (2)	0.87660 (15)	0.0654 (9)
H11	0.7140	0.3186	0.8447	0.098*
O12	0.9382 (3)	0.3539 (2)	0.79488 (15)	0.0636 (8)
N1	0.4475 (4)	0.6900 (2)	0.22014 (18)	0.0527 (9)
N2	1.0848 (5)	0.7662 (3)	0.46775 (19)	0.0667 (11)
N3	0.6984 (5)	0.4780 (3)	0.3716 (2)	0.0710 (11)
N4	0.2859 (5)	0.0173 (3)	0.6350 (2)	0.0732 (12)
C1	−0.0066 (5)	0.1165 (3)	−0.1650 (2)	0.0496 (11)
C2	0.1409 (5)	0.1227 (3)	−0.1798 (2)	0.0587 (12)
H2	0.1623	0.1154	−0.2246	0.070*
C3	0.2607 (5)	0.1399 (3)	−0.1289 (2)	0.0573 (12)
H3A	0.3614	0.1449	−0.1400	0.069*
C4	0.2320 (5)	0.1497 (3)	−0.06123 (19)	0.0456 (10)
C5	0.0817 (5)	0.1425 (3)	−0.0483 (2)	0.0545 (11)
H5A	0.0594	0.1495	−0.0037	0.065*
C6	−0.0400 (5)	0.1252 (3)	−0.0988 (2)	0.0543 (11)
H6	−0.1411	0.1198	−0.0881	0.065*
C7	−0.2718 (5)	0.0875 (3)	−0.2066 (2)	0.0626 (13)
H7A	−0.2917	0.1446	−0.1821	0.075*
H7B	−0.2947	0.0378	−0.1790	0.075*
C8	−0.3727 (6)	0.0642 (3)	−0.2722 (3)	0.0595 (13)
C9	0.3594 (5)	0.1647 (3)	−0.0033 (2)	0.0530 (11)
C10	0.3446 (6)	0.0735 (3)	0.0282 (2)	0.0693 (14)
H10A	0.2452	0.0600	0.0445	0.104*
H10B	0.4228	0.0800	0.0650	0.104*
H10C	0.3567	0.0233	−0.0051	0.104*
C11	0.5223 (5)	0.1848 (4)	−0.0274 (2)	0.0774 (15)
H11A	0.5387	0.1319	−0.0570	0.116*
H11B	0.5976	0.1966	0.0109	0.116*
H11C	0.5314	0.2385	−0.0509	0.116*
C12	0.3425 (4)	0.2483 (3)	0.04726 (19)	0.0465 (10)
C13	0.3478 (5)	0.3363 (3)	0.0269 (2)	0.0530 (11)
H13	0.3619	0.3433	−0.0177	0.064*
C14	0.3329 (5)	0.4127 (3)	0.07031 (19)	0.0522 (11)
H14	0.3393	0.4707	0.0553	0.063*
C15	0.3082 (4)	0.4034 (3)	0.13671 (19)	0.0452 (10)
C16	0.3050 (5)	0.3185 (3)	0.1590 (2)	0.0494 (10)
H16	0.2930	0.3124	0.2040	0.059*
C17	0.3198 (4)	0.2408 (3)	0.1139 (2)	0.0478 (10)
H17	0.3143	0.1830	0.1291	0.057*
C18	0.2302 (5)	0.4766 (3)	0.2397 (2)	0.0552 (11)
H18A	0.1576	0.4185	0.2369	0.066*
H18B	0.1748	0.5272	0.2503	0.066*
C19	0.3515 (5)	0.4795 (3)	0.2961 (2)	0.0504 (11)
C20	0.7944 (5)	0.7806 (3)	0.6629 (2)	0.0513 (11)
C21	0.8936 (5)	0.7179 (3)	0.6592 (2)	0.0558 (11)
H21	0.8800	0.6697	0.6237	0.067*
C22	1.0136 (5)	0.7272 (3)	0.7090 (2)	0.0550 (11)
H22	1.0822	0.6858	0.7052	0.066*
C23	1.0357 (5)	0.7961 (3)	0.76432 (19)	0.0449 (10)
C24	0.9327 (5)	0.8565 (3)	0.7664 (2)	0.0550 (11)
H24	0.9438	0.9037	0.8026	0.066*
C25	0.8125 (5)	0.8495 (3)	0.7163 (2)	0.0603 (12)
H25	0.7449	0.8915	0.7192	0.072*
C26	0.5463 (6)	0.7999 (4)	0.6199 (2)	0.0808 (16)
H26A	0.5669	0.8660	0.6366	0.097*
H26B	0.4974	0.7668	0.6539	0.097*
C27	0.4401 (7)	0.7831 (5)	0.5566 (3)	0.0938 (10)
C28	1.1733 (5)	0.8028 (3)	0.8175 (2)	0.0555 (11)
C29	1.1589 (7)	0.8714 (3)	0.8801 (2)	0.0853 (18)
H29A	1.0606	0.8540	0.8966	0.128*
H29B	1.1683	0.9335	0.8681	0.128*
H29C	1.2389	0.8696	0.9145	0.128*
C30	1.3190 (6)	0.8405 (4)	0.7854 (3)	0.098 (2)
H30A	1.4076	0.8426	0.8164	0.146*
H30B	1.3144	0.9022	0.7749	0.146*
H30C	1.3261	0.8004	0.7448	0.146*
C31	1.1775 (4)	0.7066 (3)	0.83881 (19)	0.0440 (10)
C32	1.0711 (5)	0.6680 (3)	0.8788 (2)	0.0511 (11)
H32	1.0003	0.7032	0.8949	0.061*
C33	1.0654 (5)	0.5787 (3)	0.8961 (2)	0.0514 (11)
H33	0.9893	0.5543	0.9219	0.062*
C34	1.1719 (5)	0.5263 (3)	0.87506 (19)	0.0436 (10)
C35	1.2821 (5)	0.5634 (3)	0.8365 (2)	0.0530 (11)
H35	1.3551	0.5289	0.8221	0.064*
C36	1.2850 (5)	0.6522 (3)	0.8190 (2)	0.0535 (11)
H36	1.3613	0.6763	0.7932	0.064*
C37	1.0442 (5)	0.3861 (3)	0.9106 (2)	0.0578 (12)
H37A	1.0084	0.4238	0.9470	0.069*
H37B	1.0692	0.3309	0.9278	0.069*
C38	0.9154 (5)	0.3564 (3)	0.8541 (2)	0.0511 (11)
C39	0.5847 (5)	0.6722 (3)	0.2055 (2)	0.0518 (11)
H39	0.5960	0.6506	0.1610	0.062*
C40	0.7106 (5)	0.6837 (3)	0.2519 (2)	0.0511 (11)
H40	0.8038	0.6705	0.2388	0.061*
C41	0.6964 (5)	0.7153 (3)	0.3188 (2)	0.0470 (10)
C42	0.5519 (5)	0.7301 (3)	0.3347 (2)	0.0574 (12)
H42	0.5355	0.7487	0.3791	0.069*
C43	0.4334 (5)	0.7171 (3)	0.2845 (2)	0.0585 (12)
H43	0.3379	0.7279	0.2963	0.070*
C44	0.8315 (5)	0.7337 (3)	0.37042 (19)	0.0468 (10)
C45	0.9795 (5)	0.7559 (3)	0.3534 (2)	0.0687 (14)
H45	0.9976	0.7602	0.3088	0.082*
C46	1.1021 (6)	0.7720 (4)	0.4032 (2)	0.0761 (15)
H46	1.2010	0.7875	0.3906	0.091*
C47	0.9420 (6)	0.7478 (3)	0.4831 (2)	0.0687 (13)
H47	0.9266	0.7469	0.5284	0.082*
C48	0.8133 (5)	0.7298 (3)	0.4374 (2)	0.0618 (12)
H48	0.7158	0.7153	0.4517	0.074*
C49	0.8451 (6)	0.4955 (3)	0.3585 (2)	0.0679 (13)
H49	0.8672	0.5022	0.3146	0.082*
C50	0.9643 (5)	0.5038 (3)	0.4074 (2)	0.0607 (12)
H50	1.0650	0.5154	0.3962	0.073*
C51	0.9366 (5)	0.4951 (3)	0.4727 (2)	0.0581 (12)
C52	0.7853 (6)	0.4784 (4)	0.4862 (3)	0.0919 (18)
H52	0.7606	0.4725	0.5299	0.110*
C53	0.6698 (6)	0.4703 (4)	0.4343 (3)	0.0946 (18)
H53	0.5680	0.4590	0.4442	0.114*
C54	0.1414 (7)	−0.0080 (4)	0.6425 (3)	0.0881 (18)
H54	0.1147	−0.0220	0.6845	0.106*
C55	0.0244 (6)	−0.0156 (4)	0.5913 (2)	0.0831 (16)
H55	−0.0776	−0.0332	0.5994	0.100*
C56	0.0610 (5)	0.0034 (3)	0.5281 (2)	0.0574 (12)
C57	0.2143 (6)	0.0290 (4)	0.5213 (3)	0.0886 (17)
H57	0.2460	0.0422	0.4798	0.106*
C58	0.3228 (6)	0.0354 (4)	0.5757 (3)	0.0878 (17)
H58	0.4261	0.0532	0.5696	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.063 (2)	0.081 (2)	0.0501 (19)	0.0081 (17)	−0.0143 (17)	0.0025 (15)
O2	0.082 (3)	0.110 (3)	0.056 (2)	0.022 (2)	−0.017 (2)	0.0066 (19)
O3	0.070 (3)	0.116 (3)	0.066 (2)	−0.016 (2)	−0.022 (2)	0.023 (2)
O4	0.082 (2)	0.0487 (16)	0.0411 (16)	0.0096 (15)	−0.0065 (16)	0.0038 (13)
O5	0.050 (2)	0.118 (3)	0.0454 (18)	0.0229 (19)	−0.0070 (16)	−0.0040 (18)
O6	0.074 (2)	0.120 (3)	0.0402 (18)	0.014 (2)	0.0047 (17)	0.0012 (17)
O7	0.063 (2)	0.108 (3)	0.0466 (18)	0.0314 (19)	−0.0089 (17)	0.0011 (16)
O8	0.064 (3)	0.177 (4)	0.056 (2)	0.039 (2)	−0.0118 (19)	−0.011 (2)
O9	0.060 (2)	0.174 (3)	0.0478 (17)	0.0291 (19)	−0.0004 (17)	0.009 (2)
O10	0.0464 (18)	0.0528 (17)	0.0708 (19)	0.0115 (14)	−0.0048 (15)	0.0164 (14)
O11	0.045 (2)	0.078 (2)	0.072 (2)	0.0043 (16)	−0.0025 (17)	0.0221 (17)
O12	0.058 (2)	0.085 (2)	0.0507 (19)	0.0289 (16)	−0.0018 (16)	0.0010 (16)
N1	0.043 (2)	0.050 (2)	0.063 (2)	0.0077 (16)	−0.0051 (19)	0.0045 (17)
N2	0.056 (3)	0.092 (3)	0.050 (2)	0.020 (2)	−0.003 (2)	−0.002 (2)
N3	0.060 (3)	0.094 (3)	0.056 (3)	0.020 (2)	−0.011 (2)	−0.001 (2)
N4	0.069 (3)	0.076 (3)	0.066 (3)	−0.005 (2)	−0.016 (2)	0.015 (2)
C1	0.052 (3)	0.052 (2)	0.042 (2)	0.008 (2)	−0.011 (2)	0.0026 (19)
C2	0.062 (3)	0.071 (3)	0.041 (3)	0.009 (2)	0.001 (2)	0.003 (2)
C3	0.055 (3)	0.062 (3)	0.056 (3)	0.011 (2)	0.006 (2)	0.007 (2)
C4	0.047 (3)	0.046 (2)	0.044 (2)	0.0116 (19)	0.001 (2)	0.0055 (18)
C5	0.053 (3)	0.069 (3)	0.041 (2)	0.013 (2)	0.000 (2)	0.004 (2)
C6	0.045 (3)	0.069 (3)	0.048 (3)	0.012 (2)	−0.001 (2)	0.006 (2)
C7	0.062 (3)	0.060 (3)	0.059 (3)	0.003 (2)	−0.015 (3)	0.008 (2)
C8	0.065 (4)	0.052 (3)	0.058 (3)	0.006 (2)	−0.020 (3)	0.014 (2)
C9	0.047 (3)	0.062 (3)	0.050 (3)	0.016 (2)	−0.005 (2)	0.003 (2)
C10	0.089 (4)	0.061 (3)	0.059 (3)	0.032 (3)	−0.017 (3)	0.004 (2)
C11	0.055 (3)	0.103 (4)	0.075 (3)	0.028 (3)	−0.002 (3)	−0.001 (3)
C12	0.038 (2)	0.052 (2)	0.048 (2)	0.0068 (18)	−0.007 (2)	0.0068 (19)
C13	0.059 (3)	0.062 (3)	0.039 (2)	0.011 (2)	−0.001 (2)	0.013 (2)
C14	0.066 (3)	0.046 (2)	0.044 (2)	0.009 (2)	−0.005 (2)	0.0127 (19)
C15	0.043 (3)	0.043 (2)	0.046 (2)	0.0048 (18)	−0.007 (2)	0.0047 (19)
C16	0.052 (3)	0.052 (3)	0.042 (2)	0.006 (2)	−0.006 (2)	0.0090 (19)
C17	0.043 (3)	0.048 (2)	0.052 (3)	0.0042 (19)	−0.004 (2)	0.014 (2)
C18	0.055 (3)	0.058 (3)	0.051 (3)	0.014 (2)	−0.004 (2)	0.003 (2)
C19	0.051 (3)	0.054 (3)	0.045 (3)	0.008 (2)	−0.003 (2)	0.0062 (19)
C20	0.051 (3)	0.065 (3)	0.038 (2)	0.013 (2)	−0.006 (2)	0.008 (2)
C21	0.072 (3)	0.062 (3)	0.035 (2)	0.021 (2)	0.001 (2)	0.0058 (19)
C22	0.061 (3)	0.060 (3)	0.049 (3)	0.025 (2)	0.000 (2)	0.012 (2)
C23	0.042 (3)	0.042 (2)	0.049 (2)	0.0025 (18)	−0.004 (2)	0.0137 (19)
C24	0.063 (3)	0.052 (2)	0.046 (3)	0.012 (2)	−0.011 (2)	0.0008 (19)
C25	0.063 (3)	0.065 (3)	0.056 (3)	0.028 (2)	−0.004 (2)	0.007 (2)
C26	0.053 (3)	0.130 (5)	0.056 (3)	0.027 (3)	−0.009 (3)	−0.007 (3)
C27	0.060 (2)	0.174 (3)	0.0478 (17)	0.0291 (19)	−0.0004 (17)	0.009 (2)
C28	0.043 (3)	0.054 (3)	0.065 (3)	0.001 (2)	−0.012 (2)	0.014 (2)
C29	0.118 (5)	0.052 (3)	0.076 (3)	0.018 (3)	−0.048 (3)	−0.003 (2)
C30	0.055 (3)	0.088 (4)	0.151 (5)	−0.008 (3)	−0.011 (4)	0.066 (4)
C31	0.035 (2)	0.048 (2)	0.047 (2)	0.0086 (19)	−0.006 (2)	0.0057 (18)
C32	0.041 (3)	0.057 (3)	0.058 (3)	0.019 (2)	0.004 (2)	0.006 (2)
C33	0.041 (3)	0.064 (3)	0.053 (3)	0.011 (2)	0.009 (2)	0.015 (2)
C34	0.037 (2)	0.051 (2)	0.043 (2)	0.0114 (19)	−0.007 (2)	0.0079 (18)
C35	0.039 (3)	0.063 (3)	0.060 (3)	0.016 (2)	0.006 (2)	0.008 (2)
C36	0.044 (3)	0.061 (3)	0.055 (3)	0.003 (2)	0.010 (2)	0.016 (2)
C37	0.055 (3)	0.055 (3)	0.062 (3)	0.003 (2)	−0.007 (2)	0.019 (2)
C38	0.052 (3)	0.041 (2)	0.062 (3)	0.019 (2)	−0.010 (3)	0.007 (2)
C39	0.049 (3)	0.053 (2)	0.051 (3)	0.009 (2)	−0.001 (2)	0.0028 (19)
C40	0.042 (3)	0.059 (3)	0.051 (3)	0.010 (2)	0.003 (2)	−0.001 (2)
C41	0.035 (3)	0.050 (2)	0.054 (3)	0.0081 (18)	0.000 (2)	0.0036 (19)
C42	0.045 (3)	0.066 (3)	0.058 (3)	0.008 (2)	0.003 (2)	−0.002 (2)
C43	0.039 (3)	0.065 (3)	0.072 (3)	0.014 (2)	0.002 (2)	0.003 (2)
C44	0.042 (3)	0.055 (2)	0.042 (2)	0.0092 (19)	0.001 (2)	0.0005 (18)
C45	0.049 (3)	0.107 (4)	0.044 (3)	0.005 (3)	0.004 (2)	0.001 (2)
C46	0.044 (3)	0.118 (4)	0.058 (3)	0.006 (3)	−0.001 (3)	−0.004 (3)
C47	0.065 (4)	0.098 (4)	0.047 (3)	0.024 (3)	0.008 (3)	0.011 (2)
C48	0.052 (3)	0.087 (3)	0.049 (3)	0.021 (2)	0.006 (2)	0.007 (2)
C49	0.067 (4)	0.086 (3)	0.051 (3)	0.026 (3)	−0.004 (3)	−0.004 (2)
C50	0.050 (3)	0.078 (3)	0.051 (3)	0.019 (2)	−0.006 (2)	−0.007 (2)
C51	0.053 (3)	0.069 (3)	0.050 (3)	0.017 (2)	−0.012 (2)	0.000 (2)
C52	0.052 (4)	0.158 (6)	0.061 (3)	0.007 (3)	−0.008 (3)	0.019 (3)
C53	0.053 (4)	0.152 (6)	0.075 (4)	0.009 (3)	−0.010 (3)	0.020 (4)
C54	0.082 (4)	0.116 (4)	0.055 (3)	−0.016 (3)	−0.015 (3)	0.022 (3)
C55	0.066 (4)	0.119 (4)	0.054 (3)	−0.012 (3)	−0.011 (3)	0.020 (3)
C56	0.058 (3)	0.061 (3)	0.046 (3)	−0.002 (2)	−0.010 (2)	0.008 (2)
C57	0.064 (4)	0.131 (5)	0.065 (3)	−0.006 (3)	−0.007 (3)	0.033 (3)
C58	0.051 (4)	0.122 (5)	0.085 (4)	−0.004 (3)	−0.009 (3)	0.027 (3)

Geometric parameters (Å, º)

O1—C1	1.382 (4)	C22—C23	1.390 (5)
O1—C7	1.406 (5)	C22—H22	0.9300
O2—C8	1.201 (5)	C23—C24	1.376 (6)
O3—C8	1.306 (6)	C23—C28	1.544 (6)
O3—H3	0.8200	C24—C25	1.395 (6)
O4—C15	1.388 (4)	C24—H24	0.9300
O4—C18	1.418 (5)	C25—H25	0.9300
O5—C19	1.289 (5)	C26—C27	1.495 (7)
O5—H5	0.8200	C26—H26A	0.9700
O6—C19	1.211 (5)	C26—H26B	0.9700
O7—C26	1.384 (5)	C28—C31	1.528 (5)
O7—C20	1.391 (5)	C28—C30	1.535 (6)
O8—C27	1.291 (6)	C28—C29	1.544 (6)
O8—H8	0.8200	C29—H29A	0.9600
O9—C27	1.169 (5)	C29—H29B	0.9600
O10—C34	1.386 (4)	C29—H29C	0.9600
O10—C37	1.410 (5)	C30—H30A	0.9600
O11—C38	1.316 (5)	C30—H30B	0.9600
O11—H11	0.8200	C30—H30C	0.9600
O12—C38	1.218 (5)	C31—C32	1.376 (5)
N1—C43	1.329 (5)	C31—C36	1.394 (5)
N1—C39	1.333 (5)	C32—C33	1.388 (5)
N2—C47	1.317 (6)	C32—H32	0.9300
N2—C46	1.327 (6)	C33—C34	1.375 (5)
N3—C53	1.318 (6)	C33—H33	0.9300
N3—C49	1.334 (6)	C34—C35	1.371 (5)
N4—C54	1.297 (6)	C35—C36	1.384 (5)
N4—C58	1.303 (6)	C35—H35	0.9300
C1—C2	1.353 (6)	C36—H36	0.9300
C1—C6	1.380 (5)	C37—C38	1.519 (6)
C2—C3	1.389 (6)	C37—H37A	0.9700
C2—H2	0.9300	C37—H37B	0.9700
C3—C4	1.396 (5)	C39—C40	1.376 (5)
C3—H3A	0.9300	C39—H39	0.9300
C4—C5	1.366 (5)	C40—C41	1.391 (5)
C4—C9	1.530 (5)	C40—H40	0.9300
C5—C6	1.394 (5)	C41—C42	1.389 (5)
C5—H5A	0.9300	C41—C44	1.493 (5)
C6—H6	0.9300	C42—C43	1.375 (6)
C7—C8	1.509 (6)	C42—H42	0.9300
C7—H7A	0.9700	C43—H43	0.9300
C7—H7B	0.9700	C44—C48	1.374 (5)
C9—C12	1.534 (5)	C44—C45	1.375 (6)
C9—C10	1.537 (6)	C45—C46	1.392 (6)
C9—C11	1.548 (6)	C45—H45	0.9300
C10—H10A	0.9600	C46—H46	0.9300
C10—H10B	0.9600	C47—C48	1.380 (6)
C10—H10C	0.9600	C47—H47	0.9300
C11—H11A	0.9600	C48—H48	0.9300
C11—H11B	0.9600	C49—C50	1.369 (6)
C11—H11C	0.9600	C49—H49	0.9300
C12—C17	1.382 (5)	C50—C51	1.369 (6)
C12—C13	1.393 (5)	C50—H50	0.9300
C13—C14	1.368 (5)	C51—C52	1.375 (6)
C13—H13	0.9300	C51—C51^i	1.488 (8)
C14—C15	1.386 (5)	C52—C53	1.387 (7)
C14—H14	0.9300	C52—H52	0.9300
C15—C16	1.369 (5)	C53—H53	0.9300
C16—C17	1.400 (5)	C54—C55	1.388 (7)
C16—H16	0.9300	C54—H54	0.9300
C17—H17	0.9300	C55—C56	1.381 (6)
C18—C19	1.496 (6)	C55—H55	0.9300
C18—H18A	0.9700	C56—C57	1.370 (7)
C18—H18B	0.9700	C56—C56^ii	1.487 (8)
C20—C25	1.365 (6)	C57—C58	1.386 (7)
C20—C21	1.376 (6)	C57—H57	0.9300
C21—C22	1.384 (6)	C58—H58	0.9300
C21—H21	0.9300
C1—O1—C7	117.8 (3)	O9—C27—O8	123.6 (5)
C8—O3—H3	109.5	O9—C27—C26	125.0 (5)
C15—O4—C18	119.0 (3)	O8—C27—C26	111.3 (4)
C19—O5—H5	109.5	C31—C28—C30	112.0 (4)
C26—O7—C20	118.1 (3)	C31—C28—C29	109.0 (3)
C27—O8—H8	109.5	C30—C28—C29	108.6 (4)
C34—O10—C37	117.3 (3)	C31—C28—C23	109.5 (3)
C38—O11—H11	109.5	C30—C28—C23	107.2 (4)
C43—N1—C39	116.4 (4)	C29—C28—C23	110.6 (4)
C47—N2—C46	115.8 (4)	C28—C29—H29A	109.5
C53—N3—C49	117.8 (4)	C28—C29—H29B	109.5
C54—N4—C58	117.9 (5)	H29A—C29—H29B	109.5
C2—C1—C6	120.2 (4)	C28—C29—H29C	109.5
C2—C1—O1	115.8 (4)	H29A—C29—H29C	109.5
C6—C1—O1	124.0 (4)	H29B—C29—H29C	109.5
C1—C2—C3	120.7 (4)	C28—C30—H30A	109.5
C1—C2—H2	119.7	C28—C30—H30B	109.5
C3—C2—H2	119.7	H30A—C30—H30B	109.5
C2—C3—C4	121.0 (4)	C28—C30—H30C	109.5
C2—C3—H3A	119.5	H30A—C30—H30C	109.5
C4—C3—H3A	119.5	H30B—C30—H30C	109.5
C5—C4—C3	116.6 (4)	C32—C31—C36	115.9 (4)
C5—C4—C9	120.5 (4)	C32—C31—C28	120.7 (4)
C3—C4—C9	122.9 (4)	C36—C31—C28	123.4 (4)
C4—C5—C6	123.2 (4)	C31—C32—C33	122.5 (4)
C4—C5—H5A	118.4	C31—C32—H32	118.7
C6—C5—H5A	118.4	C33—C32—H32	118.7
C1—C6—C5	118.3 (4)	C34—C33—C32	120.1 (4)
C1—C6—H6	120.8	C34—C33—H33	120.0
C5—C6—H6	120.8	C32—C33—H33	120.0
O1—C7—C8	109.6 (4)	C35—C34—C33	118.9 (4)
O1—C7—H7A	109.8	C35—C34—O10	116.2 (4)
C8—C7—H7A	109.8	C33—C34—O10	124.9 (4)
O1—C7—H7B	109.8	C34—C35—C36	120.3 (4)
C8—C7—H7B	109.8	C34—C35—H35	119.9
H7A—C7—H7B	108.2	C36—C35—H35	119.9
O2—C8—O3	125.4 (4)	C35—C36—C31	122.2 (4)
O2—C8—C7	125.2 (5)	C35—C36—H36	118.9
O3—C8—C7	109.4 (4)	C31—C36—H36	118.9
C4—C9—C12	109.6 (3)	O10—C37—C38	113.2 (3)
C4—C9—C10	106.8 (3)	O10—C37—H37A	108.9
C12—C9—C10	112.5 (3)	C38—C37—H37A	108.9
C4—C9—C11	112.7 (3)	O10—C37—H37B	108.9
C12—C9—C11	107.5 (3)	C38—C37—H37B	108.9
C10—C9—C11	107.8 (4)	H37A—C37—H37B	107.7
C9—C10—H10A	109.5	O12—C38—O11	125.0 (4)
C9—C10—H10B	109.5	O12—C38—C37	122.5 (4)
H10A—C10—H10B	109.5	O11—C38—C37	112.5 (4)
C9—C10—H10C	109.5	N1—C39—C40	124.2 (4)
H10A—C10—H10C	109.5	N1—C39—H39	117.9
H10B—C10—H10C	109.5	C40—C39—H39	117.9
C9—C11—H11A	109.5	C39—C40—C41	119.0 (4)
C9—C11—H11B	109.5	C39—C40—H40	120.5
H11A—C11—H11B	109.5	C41—C40—H40	120.5
C9—C11—H11C	109.5	C42—C41—C40	116.9 (4)
H11A—C11—H11C	109.5	C42—C41—C44	122.0 (4)
H11B—C11—H11C	109.5	C40—C41—C44	121.1 (4)
C17—C12—C13	117.0 (4)	C43—C42—C41	119.6 (4)
C17—C12—C9	122.6 (4)	C43—C42—H42	120.2
C13—C12—C9	120.4 (4)	C41—C42—H42	120.2
C14—C13—C12	122.3 (4)	N1—C43—C42	123.8 (4)
C14—C13—H13	118.8	N1—C43—H43	118.1
C12—C13—H13	118.8	C42—C43—H43	118.1
C13—C14—C15	119.8 (4)	C48—C44—C45	116.9 (4)
C13—C14—H14	120.1	C48—C44—C41	121.3 (4)
C15—C14—H14	120.1	C45—C44—C41	121.8 (4)
C16—C15—C14	119.6 (4)	C44—C45—C46	119.8 (4)
C16—C15—O4	124.9 (4)	C44—C45—H45	120.1
C14—C15—O4	115.5 (3)	C46—C45—H45	120.1
C15—C16—C17	119.8 (4)	N2—C46—C45	123.3 (5)
C15—C16—H16	120.1	N2—C46—H46	118.4
C17—C16—H16	120.1	C45—C46—H46	118.4
C12—C17—C16	121.4 (4)	N2—C47—C48	125.1 (4)
C12—C17—H17	119.3	N2—C47—H47	117.4
C16—C17—H17	119.3	C48—C47—H47	117.4
O4—C18—C19	114.7 (4)	C44—C48—C47	119.0 (4)
O4—C18—H18A	108.6	C44—C48—H48	120.5
C19—C18—H18A	108.6	C47—C48—H48	120.5
O4—C18—H18B	108.6	N3—C49—C50	122.4 (4)
C19—C18—H18B	108.6	N3—C49—H49	118.8
H18A—C18—H18B	107.6	C50—C49—H49	118.8
O6—C19—O5	124.6 (4)	C51—C50—C49	120.6 (5)
O6—C19—C18	120.8 (4)	C51—C50—H50	119.7
O5—C19—C18	114.6 (4)	C49—C50—H50	119.7
C25—C20—C21	119.9 (4)	C50—C51—C52	116.9 (4)
C25—C20—O7	124.3 (4)	C50—C51—C51^i	122.0 (6)
C21—C20—O7	115.7 (4)	C52—C51—C51^i	121.1 (5)
C20—C21—C22	119.4 (4)	C51—C52—C53	119.7 (5)
C20—C21—H21	120.3	C51—C52—H52	120.1
C22—C21—H21	120.3	C53—C52—H52	120.1
C21—C22—C23	122.5 (4)	N3—C53—C52	122.6 (5)
C21—C22—H22	118.8	N3—C53—H53	118.7
C23—C22—H22	118.8	C52—C53—H53	118.7
C24—C23—C22	116.2 (4)	N4—C54—C55	123.7 (5)
C24—C23—C28	124.2 (4)	N4—C54—H54	118.1
C22—C23—C28	119.6 (4)	C55—C54—H54	118.1
C23—C24—C25	122.3 (4)	C56—C55—C54	119.3 (5)
C23—C24—H24	118.8	C56—C55—H55	120.3
C25—C24—H24	118.8	C54—C55—H55	120.3
C20—C25—C24	119.7 (4)	C57—C56—C55	115.8 (4)
C20—C25—H25	120.2	C57—C56—C56^ii	123.2 (5)
C24—C25—H25	120.2	C55—C56—C56^ii	121.0 (6)
O7—C26—C27	111.1 (4)	C56—C57—C58	120.6 (5)
O7—C26—H26A	109.4	C56—C57—H57	119.7
C27—C26—H26A	109.4	C58—C57—H57	119.7
O7—C26—H26B	109.4	N4—C58—C57	122.6 (5)
C27—C26—H26B	109.4	N4—C58—H58	118.7
H26A—C26—H26B	108.0	C57—C58—H58	118.7
C7—O1—C1—C2	177.3 (4)	C22—C23—C28—C30	72.0 (5)
C7—O1—C1—C6	−0.9 (6)	C24—C23—C28—C29	12.4 (6)
C6—C1—C2—C3	−1.3 (6)	C22—C23—C28—C29	−169.7 (4)
O1—C1—C2—C3	−179.6 (3)	C30—C28—C31—C32	168.6 (4)
C1—C2—C3—C4	1.0 (6)	C29—C28—C31—C32	48.5 (5)
C2—C3—C4—C5	−0.7 (6)	C23—C28—C31—C32	−72.6 (5)
C2—C3—C4—C9	177.4 (4)	C30—C28—C31—C36	−12.3 (6)
C3—C4—C5—C6	0.7 (6)	C29—C28—C31—C36	−132.5 (4)
C9—C4—C5—C6	−177.4 (4)	C23—C28—C31—C36	106.5 (4)
C2—C1—C6—C5	1.4 (6)	C36—C31—C32—C33	−3.0 (6)
O1—C1—C6—C5	179.5 (4)	C28—C31—C32—C33	176.1 (4)
C4—C5—C6—C1	−1.1 (6)	C31—C32—C33—C34	2.3 (6)
C1—O1—C7—C8	−177.3 (3)	C32—C33—C34—C35	−0.6 (6)
O1—C7—C8—O2	−1.5 (6)	C32—C33—C34—O10	179.0 (4)
O1—C7—C8—O3	179.2 (4)	C37—O10—C34—C35	−160.6 (3)
C5—C4—C9—C12	−52.2 (5)	C37—O10—C34—C33	19.8 (5)
C3—C4—C9—C12	129.7 (4)	C33—C34—C35—C36	−0.2 (6)
C5—C4—C9—C10	69.9 (5)	O10—C34—C35—C36	−179.8 (4)
C3—C4—C9—C10	−108.2 (4)	C34—C35—C36—C31	−0.6 (6)
C5—C4—C9—C11	−172.0 (4)	C32—C31—C36—C35	2.1 (6)
C3—C4—C9—C11	10.0 (5)	C28—C31—C36—C35	−177.0 (4)
C4—C9—C12—C17	120.0 (4)	C34—O10—C37—C38	69.6 (4)
C10—C9—C12—C17	1.3 (6)	O10—C37—C38—O12	19.1 (6)
C11—C9—C12—C17	−117.2 (4)	O10—C37—C38—O11	−161.5 (3)
C4—C9—C12—C13	−59.3 (5)	C43—N1—C39—C40	−2.6 (6)
C10—C9—C12—C13	−177.9 (4)	N1—C39—C40—C41	0.4 (6)
C11—C9—C12—C13	63.6 (5)	C39—C40—C41—C42	2.3 (6)
C17—C12—C13—C14	0.6 (6)	C39—C40—C41—C44	−176.8 (3)
C9—C12—C13—C14	179.9 (4)	C40—C41—C42—C43	−2.7 (6)
C12—C13—C14—C15	−1.5 (6)	C44—C41—C42—C43	176.3 (4)
C13—C14—C15—C16	2.6 (6)	C39—N1—C43—C42	2.2 (6)
C13—C14—C15—O4	−176.6 (4)	C41—C42—C43—N1	0.5 (6)
C18—O4—C15—C16	−11.6 (6)	C42—C41—C44—C48	26.2 (6)
C18—O4—C15—C14	167.5 (4)	C40—C41—C44—C48	−154.8 (4)
C14—C15—C16—C17	−2.8 (6)	C42—C41—C44—C45	−153.3 (4)
O4—C15—C16—C17	176.2 (4)	C40—C41—C44—C45	25.8 (6)
C13—C12—C17—C16	−0.8 (6)	C48—C44—C45—C46	0.9 (7)
C9—C12—C17—C16	179.9 (4)	C41—C44—C45—C46	−179.7 (4)
C15—C16—C17—C12	2.0 (6)	C47—N2—C46—C45	−2.7 (7)
C15—O4—C18—C19	86.2 (4)	C44—C45—C46—N2	0.6 (8)
O4—C18—C19—O6	164.9 (4)	C46—N2—C47—C48	3.5 (7)
O4—C18—C19—O5	−14.5 (5)	C45—C44—C48—C47	−0.2 (6)
C26—O7—C20—C25	−29.7 (6)	C41—C44—C48—C47	−179.7 (4)
C26—O7—C20—C21	152.7 (5)	N2—C47—C48—C44	−2.1 (7)
C25—C20—C21—C22	−1.9 (6)	C53—N3—C49—C50	1.1 (7)
O7—C20—C21—C22	175.8 (4)	N3—C49—C50—C51	−0.5 (7)
C20—C21—C22—C23	2.3 (6)	C49—C50—C51—C52	−0.4 (7)
C21—C22—C23—C24	−1.4 (6)	C49—C50—C51—C51^i	−179.1 (5)
C21—C22—C23—C28	−179.4 (4)	C50—C51—C52—C53	0.6 (8)
C22—C23—C24—C25	0.2 (6)	C51^i—C51—C52—C53	179.4 (6)
C28—C23—C24—C25	178.1 (4)	C49—N3—C53—C52	−0.8 (8)
C21—C20—C25—C24	0.8 (7)	C51—C52—C53—N3	−0.1 (9)
O7—C20—C25—C24	−176.7 (4)	C58—N4—C54—C55	−1.0 (9)
C23—C24—C25—C20	0.0 (7)	N4—C54—C55—C56	0.9 (9)
C20—O7—C26—C27	−179.6 (4)	C54—C55—C56—C57	−0.1 (8)
O7—C26—C27—O9	−17.6 (9)	C54—C55—C56—C56^ii	−179.7 (5)
O7—C26—C27—O8	164.1 (5)	C55—C56—C57—C58	−0.4 (8)
C24—C23—C28—C31	132.5 (4)	C56^ii—C56—C57—C58	179.2 (5)
C22—C23—C28—C31	−49.7 (5)	C54—N4—C58—C57	0.4 (8)
C24—C23—C28—C30	−105.8 (5)	C56—C57—C58—N4	0.3 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N4^iii	0.82	1.78	2.584 (5)	166
O5—H5···N3	0.82	1.75	2.561 (5)	169
O8—H8···N2^iv	0.82	1.84	2.647 (5)	166
O11—H11···N1^v	0.82	1.84	2.647 (4)	167
C18—H18B···O12^v	0.97	2.39	3.227 (5)	144
C35—H35···O5^i	0.93	2.54	3.245 (5)	133
C40—H40···O12^i	0.93	2.50	3.432 (5)	176
C42—H42···O9	0.93	2.56	3.476 (5)	170
C50—H50···O6^vi	0.93	2.56	3.458 (6)	162
C52—H52···O6^v	0.93	2.52	3.414 (6)	162
C16—H16···Cg1^v	0.93	2.90	3.669 (5)	141
C32—H32···Cg2^v	0.93	2.89	3.625 (5)	137

Symmetry codes: (i) −x+2, −y+1, −z+1; (iii) x−1, y, z−1; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) x+1, y, z.