Borylated porphyrins: 5,10,15,20-tetra­kis(5,5-dimethyl-1,3,2-dioxa­borinan-2-yl)porphyrin nitro­benzene disolvate

The title compound, C₆₄H₆₆B₄N₄O₈·2C₆H₅NO₂, is a nitro­benzene solvate of a meso-tetra­phenyl­porphyrin species with unconventional peripheral boronic ester substituents. The porphyrin units reside in the crystal on centers of inversion and exhibit a channel clathrate-type structure, wherein mol­ecules of nitro­benzene are accommodated in tunnels of width 7-8 Å that propagate through the crystal parallel to the b axis between layers of tightly offset-stacked porphyrins. The scientific significance of the reported results is twofold. They describe the synthetic route to newly functionalized building blocks for the formulation of porphyrin-based supra­molecular assemblies, namely the corresponding tetra­boronic acid derivative; the title compound represents an essential inter­mediate in this process. They reveal also that channel-type clathrates can be formed not only with the parent tetra­phenyl­porphyrins but also with their laterally extended derivatives.

S1. Comment

This study is part of our ongoing effort to formulate framework solids with suitably functionalized porphyrin building blocks. We and others have shown to this end that meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) is a uniquely versatile building block for the construction of molecular sieve-type architectures (Goldberg, 2005, and references therein; Suslick et al., 2005; Lipstman et al., 2007). The peripheral COOH functional groups provide multiple active sites for co-operative intermolecular hydrogen bonding and for effective inter-coordination through external metal ion bridges. At the next stage we attempted the synthesis of the boronic tetraacid porphyrin analog (TBPP). The boronic acid represents an alternative BOOH₂ molecular recognition function for supramolecular assembly. However, due to its high reactivity and sensitivity to experimental conditions, the synthesis of the TBPP porphyrin from the corresponding 4-formylphenylboronic acid and pyrrole starting materials (see Experimental) required initial protection of the BOOH₂ residue by esterification with an appropriate alcohol reagent. This led to the title porphyrin as an intermediate product. The crystallographic characterization of its nitrobenzene disolvate, (I), is described in this report, revealing an interesting intermolecular organization. Only a very small number of porphyrins appended with one or two boronic ester groups has been structurally characterized previously (Hyslop et al., 1998; Hata et al., 2005).

The porphyrin macrocycle is essentially planar (Fig. 1), with minimal distorsions of its atoms from the mean plane of the 24-atom ring (within sc/Desktop/publcif/symbols/plusmn.png" height="12" />0.05 Å). The compound resides on a crystallographic center of inversion at (0, 1/2, 1/2). The dioxaborinane residues diverge in the four equatorial directions, adopting an envelope-type conformation. The molecular structure of (I) is characterized by common geometric features. Yet, its supramolecular organization is of particular interest and deserves further attention. As shown in Fig. 2, the molecules are arranged in open layers, sustained by van der Waals interactions between the diverging boronic ester appended aryl arms. These layers are perpendicular to the b axis of the crystal. There are no short intermolecular contacts within the layers that may indicate a possible significance of specific interactions other than dispersion. Yet, the open-layer organization prevails (Fig. 2) even in the absence of any direct π–π or T-shape phenyl–phenyl attractions observed previously in common clathrates of the unsubstituted tetraphenylporphyrins (Byrn et al., 1993, and references therein). By measuring the shortest interatomic distances between molecules located accross the interporphyrin voids, and considering the van der Waals radii of the corresponding fragments that line these voids, their effective width is estimated within 7–8 Å. Consecutive layers are tightly stacked along the b axis in an offset manner, with a c/2 shift along the c axis. Fig. 3 illustrates the crystal packing in (I), along with the inclusion of the nitrobenzene solvent molecules in the channel voids created in the porphyrin-stacked lattice. The resulting structure resembles the channel clathrates observed in many solvates of the unsubstituted tetraphenylporphyrins (Byrn et al., 1993), as well as their tetrakis(4-cyanophenyl) analogs (Krishna Kumar et al., 1998).

The formation of channel-type clathrates by laterally extended tetraphenylporphyrins is not very common, as such open-structure formation is associated with large interporphyrin voids. Usually, this represents a thermodynamically unfavorable molecular organization versus a more tightly packed alternative arrangements. In the absence of specific directional intermolecular synthons, it is affected mostly by dispersion forces, shape features of the porphyrin scaffold, and the presence of suitable templates in the crystallization mixture. It the latter context, nitrobenzene was found to be an excellent template for an open-porphyrin assembly to organize porphyrin molecules around it (Goldberg, 2005, and references therein). Indeed, only a small number of similar channel-type clathrates has been observed with alkyl/aryl-extended porphyrin scaffolds. An interesting example is illustrated in Fig. 4. It relates to the open assembly of copper(II)-metalated TCPP, in which the four carboxylic functions associate by hydrogen bonds to 4-acetylpyridine groups at the four corners of TCPP. The laterally extended 1:4 porphyrin–4-acetylpyridine aggregates assemble into open-channel voids with very wide channels (Fig. 4) filled with uncoordinated solvent (Lipstman et al., 2006). In spite of the large interporphyrin pores, characterized by van der Waals width of about 17 Å, these layers do not interweave in this structure. Rather, they are stacked one on top of the other in a partly offset manner giving rise to about 14Å wide tunnels (accessible to the solvent) that propagate through the crystal perpendicular to the layers.

In summary, we have described the synthetic route to the title compound, (I), and to the tetraboric acid porphyrin analog that represents a new scaffold for the contruction of porphyrin-based supramolecular assemblies. Another focus is on the interesting clathrate-type organization observed in tetraphenylporphyrin compounds, extended in the four lateral directions by additional substituents without coordination or hydrogen bonding functions. Such interporphyrin layered arrangements sustain large voids primarily by dispersion forces, and are rarely observed with such expanded tetraphenylporphyrin scaffolds.

Related literature

For related literature, see: Byrn et al. (1993); Goldberg (2005); Hata et al. (2005); Hyslop et al. (1998); Krishna Kumar, Balasubramanian & Goldberg (1998); Lindsey & Wagner (1989); Lipstman et al. (2006, 2007); Suslick et al. (2005).

S2. Experimental

The synthesis of the title compound proceeded in two steps, using commercially available reagents, following the procedures reported by Lindsey & Wagner (1989) and Hyslop et al. (1998). First, a mixture of 4-formylphenylboronic acid (2.35 g) and 2,2-dimethylpropane-1,3-diol (1.80 g) in dry tetrahydrofuran (THF; 25 ml) was stirred for 3 h. After evaporation of the solvent under reduced pressure, the resulting residue was dissolved in CH₂Cl₂ (20 ml), washed several times with water, dried with anhydrous sodium sulfate and concentrated in a vaccum. The residue was added to hexane with shaking (50 ml) and the resulting suspension was concentrated under vacuum to give the desired white solid product 2-(4-formylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane (yield 3.54 g, 90%). In the next step, the title compound was synthesized by condensing the product (2.51 g) from the first step dissolved in CH₂Cl₂ (1000 ml) with pyrrole (0.8 ml) (purged with nitrogen gas). To this, 0.9M BF₃ etherate (10 ml) was added under nitrogen, followed by addition of p-chloranil (2.12 g). After the common work-up procedure (Lindsey & Wagner, 1989), the raw product was run through a silica-gel column with a 4% acetone-in-chloroform eluent. Recrystallization from a 1:3 chloroform–methanol mixture, with a few drops of nitrobenzene added, afforded pure (I) (yield 0.59 g, 16%).¹H NMR (CDCl₃): δ 8.82 (s, 8H), 8.18 (s, 16H), 3.93 (s, 16H), 1.16 (s, 24H), -2.85 (s, 2H). FAB mass spectrum (m/z) for C₆₄H₆₆B₄N₄O₈: found 1058, calculated 1058.3. Conversion of (I) to the corresponding tetraboronic acid (deprotection of the tetra ester) was made by treatment with a solution of KOH in a mixture of THF and methanol at 363 K for 2 d. The crude product was washed with 10% HCl, filtered and neutralized by 10% solution of Et₃N in methanol and pyridine. The final product was washed with water and dried. ¹H NMR (DMSO-d₆): δ 8.77 (s, 8H), 8.32 (s, 8H), 8.15 (q, 16H, J = 8.2 Hz, J = 2.1 Hz), -2.98 (s, 2H). MALDI–TOF mass spectrum (m/z) for C₄₄H₃₄B₄N₄O₈: found 791.3, calculated 790.02. Compound (I) crystallized as long thin red needles which exhibited relatively weak diffraction. Repeated attempts to crystallize TBPP has resulted thus far in solids of very poor crystallinity.

S3. Refinement

H atoms bound to C atoms were located in calculated positions and constrained to ride on their parent atoms, with C—H = 0.95 (aryl), 0.98 (methyl) or 0.99 Å (methylene) and with U_iso(H) = 1.2U_eq(aryl and methylene) and 1.5U_eq(methyl). The two N-pyrrole bound H atoms are disordered between the four N-atom sites. Some of the small B atoms exhibit minor conformational disorder. Large-amplitude anisotropic displacement parameters characterize the nitrobenzene solvent species.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, showing the atom-labeling scheme. Ellipsoids are drawn at the 50% probability level at ca 110 K. Compound (I) is located on center of inversion at (0, 1/2, 1/2) and only atoms of the asymmetric unit are labeled. H atoms have been omitted.
	Fig. 2. The intermolecular organization in a single layered porphyrin array projected down the b axis of the crystal. Note the large interporphyrin voids within such an ensemble. The nitrobenzene solvent molecules and the H atoms have been omitted.
	Fig. 3. The crystal packing of (I) projected down the b axis, showing occlusion of the solvent molecules in the channel voids. H atoms have been omitted. The four porphyrin units in the upper layer are shown by darker wireframe, while the six units of the lower layer by all-gray wireframe. Adjacent layers along b are related to each other by the screw/glide symmetry. The nitrobenzene solvent molecules are depicted as dotted atoms.
	Fig. 4. The open layered porphyrin assembly of hydrogen-bonded 1:4 adduct of Cu–TCPP with 4-acetylpyridine (Lipstman et al., 2006). Hydrogen bonds are indicated by dotted lines and H atoms have been omitted.

5,10,15,20-tetrakis(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)porphyrin nitrobenzene clathrate

Crystal data

C64H66B4N4O8·2C6H5NO2	F(000) = 1380
Mr = 1308.67	Dx = 1.286 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.6511 (7) Å	Cell parameters from 6670 reflections
b = 9.2969 (3) Å	θ = 2.1–25.6°
c = 20.7606 (9) Å	µ = 0.09 mm^−1
β = 110.1016 (13)°	T = 110 K
V = 3380.5 (2) Å^3	Needle, red
Z = 2	0.55 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	3223 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.089
Graphite monochromator	θmax = 25.6°, θmin = 2.1°
Detector resolution: 12.8 pixels mm^-1	h = 0→22
1° ϕ and ω scans	k = 0→11
23064 measured reflections	l = −25→23
6333 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.179	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0857P)^2] where P = (Fo^2 + 2Fc^2)/3
6333 reflections	(Δ/σ)max < 0.001
446 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.24 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	Occ. (<1)
C1	0.10510 (17)	0.5143 (3)	0.65093 (16)	0.0312 (8)
C2	0.18541 (17)	0.5290 (4)	0.69390 (17)	0.0342 (8)
H2	0.2057	0.5270	0.7426	0.041*
C3	0.22466 (17)	0.5456 (4)	0.65163 (16)	0.0335 (8)
H3	0.2783	0.5588	0.6646	0.040*
C4	0.17045 (17)	0.5400 (3)	0.58224 (16)	0.0309 (8)
C5	0.19049 (17)	0.5500 (3)	0.52301 (16)	0.0288 (7)
C6	0.14025 (17)	0.5423 (3)	0.45521 (16)	0.0287 (7)
C7	0.15951 (18)	0.5447 (3)	0.39453 (16)	0.0337 (8)
H7	0.2097	0.5520	0.3929	0.040*
C8	0.09429 (17)	0.5348 (3)	0.33938 (16)	0.0332 (8)
H8	0.0909	0.5337	0.2927	0.040*
C9	0.03186 (17)	0.5263 (3)	0.36369 (16)	0.0302 (7)
C10	−0.04624 (17)	0.5101 (3)	0.32335 (16)	0.0304 (8)
N11	0.09793 (13)	0.5214 (3)	0.58305 (13)	0.0303 (6)
H11	0.0555	0.5152	0.5474	0.036*	0.50
N12	0.06145 (13)	0.5309 (3)	0.43427 (12)	0.0297 (6)
H12	0.0346	0.5272	0.4617	0.036*	0.50
C13	0.27299 (17)	0.5745 (4)	0.53271 (16)	0.0310 (8)
C14	0.29634 (18)	0.7053 (4)	0.51442 (17)	0.0364 (8)
H14	0.2599	0.7788	0.4952	0.044*
C15	0.37279 (17)	0.7289 (4)	0.52416 (16)	0.0371 (8)
H15	0.3873	0.8184	0.5103	0.045*
C16	0.42939 (17)	0.6260 (4)	0.55364 (16)	0.0348 (8)
C17	0.40478 (18)	0.4951 (4)	0.57136 (16)	0.0368 (8)
H17	0.4414	0.4219	0.5908	0.044*
C18	0.32822 (17)	0.4682 (4)	0.56145 (16)	0.0349 (8)
H18	0.3134	0.3778	0.5742	0.042*
B19	0.5161 (2)	0.6565 (4)	0.56741 (18)	0.0302 (9)
O20	0.53311 (12)	0.7843 (3)	0.54225 (11)	0.0427 (6)
O21	0.56859 (12)	0.5640 (2)	0.60577 (12)	0.0421 (6)
C22	0.61162 (17)	0.8256 (4)	0.55784 (18)	0.0427 (9)
H22A	0.6158	0.9316	0.5617	0.051*
H22B	0.6288	0.7956	0.5197	0.051*
C23	0.66384 (18)	0.7579 (4)	0.62469 (18)	0.0420 (9)
C24	0.64878 (18)	0.5974 (4)	0.61875 (19)	0.0432 (9)
H24A	0.6639	0.5584	0.5809	0.052*
H24B	0.6805	0.5498	0.6618	0.052*
C25	0.6479 (2)	0.8194 (4)	0.68656 (18)	0.0498 (10)
H25A	0.5943	0.8028	0.6813	0.075*
H25B	0.6583	0.9230	0.6897	0.075*
H25C	0.6809	0.7719	0.7284	0.075*
C26	0.74636 (18)	0.7868 (4)	0.6306 (2)	0.0501 (10)
H26A	0.7809	0.7401	0.6719	0.075*
H26B	0.7558	0.8908	0.6335	0.075*
H26C	0.7554	0.7483	0.5901	0.075*
C27	−0.06432 (17)	0.5189 (4)	0.24746 (16)	0.0322 (8)
C28	−0.09710 (17)	0.4022 (4)	0.20476 (16)	0.0351 (8)
H28	−0.1109	0.3181	0.2238	0.042*
C29	−0.10962 (18)	0.4085 (4)	0.13475 (17)	0.0360 (8)
H29	−0.1312	0.3276	0.1068	0.043*
C30	−0.09133 (17)	0.5305 (4)	0.10473 (16)	0.0340 (8)
C31	−0.06084 (17)	0.6474 (4)	0.14730 (16)	0.0341 (8)
H31	−0.0484	0.7325	0.1281	0.041*
C32	−0.04825 (17)	0.6420 (4)	0.21740 (16)	0.0319 (8)
H32	−0.0283	0.7241	0.2450	0.038*
B33	−0.1020 (2)	0.5335 (4)	0.0267 (2)	0.0345 (9)
O34	−0.13593 (13)	0.4181 (3)	−0.01263 (11)	0.0431 (6)
O35	−0.07314 (13)	0.6469 (3)	0.00261 (11)	0.0432 (6)
C36	−0.1408 (2)	0.4138 (4)	−0.08389 (16)	0.0437 (9)
H36A	−0.1862	0.3571	−0.1107	0.052*
H36B	−0.0950	0.3652	−0.0872	0.052*
C37	−0.14665 (19)	0.5634 (4)	−0.11408 (17)	0.0405 (9)
C38	−0.07898 (19)	0.6507 (4)	−0.06852 (17)	0.0414 (9)
H38A	−0.0313	0.6122	−0.0728	0.050*
H38B	−0.0845	0.7518	−0.0845	0.050*
C39	−0.1406 (2)	0.5538 (4)	−0.18535 (18)	0.0528 (11)
H39A	−0.0924	0.5069	−0.1822	0.079*
H39B	−0.1420	0.6508	−0.2042	0.079*
H39C	−0.1835	0.4975	−0.2154	0.079*
C40	−0.22227 (19)	0.6344 (4)	−0.11809 (19)	0.0497 (10)
H40A	−0.2256	0.6396	−0.0720	0.075*
H40B	−0.2649	0.5772	−0.1479	0.075*
H40C	−0.2246	0.7316	−0.1369	0.075*
C41	0.5819 (2)	0.2984 (4)	0.20101 (19)	0.0449 (9)
C42	0.5573 (2)	0.3314 (4)	0.2545 (2)	0.0525 (10)
H42	0.5848	0.2991	0.2997	0.063*
C43	0.4916 (2)	0.4124 (5)	0.2412 (2)	0.0608 (11)
H43	0.4738	0.4383	0.2773	0.073*
C44	0.4521 (2)	0.4556 (4)	0.1743 (2)	0.0636 (12)
H44	0.4068	0.5108	0.1648	0.076*
C45	0.4774 (3)	0.4199 (5)	0.1220 (2)	0.0667 (13)
H45	0.4498	0.4506	0.0766	0.080*
C46	0.5433 (2)	0.3390 (4)	0.1349 (2)	0.0538 (11)
H46	0.5611	0.3126	0.0988	0.065*
N47	0.6536 (2)	0.2180 (4)	0.2153 (2)	0.0611 (10)
O48	0.67506 (17)	0.1430 (4)	0.26750 (19)	0.0809 (10)
O49	0.68842 (18)	0.2308 (4)	0.17540 (18)	0.0820 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0246 (16)	0.0380 (19)	0.0303 (18)	0.0001 (14)	0.0084 (15)	−0.0005 (15)
C2	0.0262 (17)	0.046 (2)	0.0283 (18)	−0.0025 (15)	0.0062 (15)	−0.0025 (16)
C3	0.0233 (16)	0.044 (2)	0.0318 (19)	0.0011 (15)	0.0074 (15)	−0.0044 (16)
C4	0.0264 (17)	0.0340 (19)	0.0330 (19)	0.0012 (14)	0.0108 (15)	−0.0008 (15)
C5	0.0257 (16)	0.0304 (18)	0.0296 (18)	0.0065 (14)	0.0084 (14)	0.0035 (14)
C6	0.0254 (16)	0.0310 (18)	0.0301 (18)	−0.0002 (14)	0.0101 (15)	−0.0018 (14)
C7	0.0257 (17)	0.039 (2)	0.038 (2)	−0.0007 (15)	0.0134 (16)	0.0008 (16)
C8	0.0307 (17)	0.041 (2)	0.0292 (18)	0.0009 (15)	0.0114 (15)	−0.0003 (15)
C9	0.0289 (17)	0.0340 (19)	0.0296 (18)	0.0013 (14)	0.0126 (15)	−0.0010 (15)
C10	0.0293 (17)	0.0314 (18)	0.0321 (18)	0.0026 (14)	0.0123 (15)	−0.0011 (15)
N11	0.0229 (14)	0.0393 (16)	0.0268 (15)	−0.0013 (12)	0.0060 (12)	0.0002 (12)
N12	0.0226 (13)	0.0388 (16)	0.0271 (15)	0.0011 (12)	0.0079 (12)	0.0015 (12)
C13	0.0258 (17)	0.042 (2)	0.0281 (18)	−0.0024 (15)	0.0125 (15)	−0.0046 (15)
C14	0.0300 (18)	0.043 (2)	0.038 (2)	0.0041 (16)	0.0139 (16)	0.0086 (16)
C15	0.0323 (18)	0.044 (2)	0.0357 (19)	−0.0023 (16)	0.0121 (15)	0.0030 (16)
C16	0.0284 (17)	0.046 (2)	0.0304 (18)	−0.0008 (16)	0.0109 (15)	−0.0008 (16)
C17	0.0295 (18)	0.047 (2)	0.035 (2)	0.0061 (16)	0.0129 (16)	0.0010 (16)
C18	0.0295 (17)	0.040 (2)	0.0361 (19)	−0.0037 (15)	0.0120 (15)	0.0016 (16)
B19	0.032 (2)	0.038 (2)	0.024 (2)	−0.0063 (18)	0.0139 (17)	−0.0035 (17)
O20	0.0281 (12)	0.0577 (16)	0.0422 (14)	−0.0021 (11)	0.0120 (11)	0.0030 (12)
O21	0.0281 (12)	0.0478 (15)	0.0515 (15)	−0.0018 (11)	0.0152 (11)	0.0022 (12)
C22	0.0276 (18)	0.053 (2)	0.047 (2)	−0.0061 (16)	0.0123 (16)	0.0030 (18)
C23	0.0302 (18)	0.050 (2)	0.044 (2)	−0.0040 (17)	0.0101 (17)	−0.0009 (18)
C24	0.0242 (18)	0.057 (2)	0.048 (2)	−0.0057 (16)	0.0117 (16)	0.0020 (19)
C25	0.042 (2)	0.058 (3)	0.045 (2)	−0.0009 (18)	0.0096 (18)	−0.0052 (19)
C26	0.0312 (19)	0.061 (3)	0.056 (2)	−0.0066 (18)	0.0126 (18)	0.001 (2)
C27	0.0252 (16)	0.042 (2)	0.0298 (18)	0.0049 (15)	0.0095 (14)	−0.0015 (16)
C28	0.0318 (18)	0.040 (2)	0.0333 (19)	−0.0005 (15)	0.0110 (15)	0.0006 (16)
C29	0.0321 (18)	0.0372 (19)	0.037 (2)	−0.0026 (15)	0.0099 (16)	−0.0074 (17)
C30	0.0283 (17)	0.040 (2)	0.0324 (19)	0.0018 (15)	0.0093 (15)	0.0001 (16)
C31	0.0292 (17)	0.0370 (19)	0.036 (2)	0.0001 (15)	0.0111 (15)	0.0052 (16)
C32	0.0282 (17)	0.0367 (19)	0.0312 (19)	0.0024 (15)	0.0107 (15)	−0.0031 (15)
B33	0.0270 (19)	0.039 (2)	0.038 (2)	−0.0034 (18)	0.0118 (18)	−0.0035 (19)
O34	0.0519 (15)	0.0440 (14)	0.0334 (13)	−0.0053 (12)	0.0146 (12)	0.0001 (11)
O35	0.0486 (15)	0.0479 (15)	0.0360 (14)	−0.0083 (12)	0.0183 (12)	−0.0014 (12)
C36	0.049 (2)	0.049 (2)	0.032 (2)	0.0012 (18)	0.0126 (17)	−0.0014 (17)
C37	0.042 (2)	0.046 (2)	0.0326 (19)	0.0022 (17)	0.0118 (17)	0.0036 (16)
C38	0.045 (2)	0.043 (2)	0.036 (2)	−0.0041 (17)	0.0137 (17)	0.0027 (17)
C39	0.055 (2)	0.070 (3)	0.037 (2)	0.006 (2)	0.0196 (19)	0.0030 (19)
C40	0.043 (2)	0.062 (3)	0.044 (2)	0.0073 (19)	0.0147 (18)	0.005 (2)
C41	0.046 (2)	0.041 (2)	0.047 (2)	−0.0036 (18)	0.0166 (19)	−0.0056 (18)
C42	0.057 (3)	0.052 (2)	0.048 (2)	−0.002 (2)	0.018 (2)	0.0055 (19)
C43	0.063 (3)	0.065 (3)	0.062 (3)	−0.006 (2)	0.031 (2)	−0.003 (2)
C44	0.048 (2)	0.059 (3)	0.078 (3)	0.000 (2)	0.013 (2)	−0.007 (3)
C45	0.074 (3)	0.058 (3)	0.050 (3)	−0.002 (2)	−0.001 (2)	0.002 (2)
C46	0.070 (3)	0.049 (2)	0.043 (2)	−0.018 (2)	0.020 (2)	−0.011 (2)
N47	0.058 (2)	0.049 (2)	0.078 (3)	−0.0079 (18)	0.025 (2)	−0.014 (2)
O48	0.072 (2)	0.070 (2)	0.090 (2)	0.0108 (17)	0.0151 (19)	0.008 (2)
O49	0.073 (2)	0.083 (2)	0.110 (3)	−0.0108 (18)	0.057 (2)	−0.024 (2)

Geometric parameters (Å, º)

C1—N11	1.371 (4)	C25—H25C	0.9800
C1—C10^i	1.395 (4)	C26—H26A	0.9800
C1—C2	1.463 (4)	C26—H26B	0.9800
C2—C3	1.331 (4)	C26—H26C	0.9800
C2—H2	0.9500	C27—C32	1.385 (4)
C3—C4	1.449 (4)	C27—C28	1.401 (4)
C3—H3	0.9500	C28—C29	1.392 (4)
C4—N11	1.369 (4)	C28—H28	0.9500
C4—C5	1.406 (4)	C29—C30	1.392 (4)
C5—C6	1.399 (4)	C29—H29	0.9500
C5—C13	1.499 (4)	C30—C31	1.393 (4)
C6—N12	1.386 (4)	C30—B33	1.563 (5)
C6—C7	1.424 (4)	C31—C32	1.393 (4)
C7—C8	1.357 (4)	C31—H31	0.9500
C7—H7	0.9500	C32—H32	0.9500
C8—C9	1.421 (4)	B33—O35	1.355 (4)
C8—H8	0.9500	B33—O34	1.364 (4)
C9—N12	1.378 (4)	O34—C36	1.451 (4)
C9—C10	1.417 (4)	O35—C38	1.443 (4)
C10—C1^i	1.395 (4)	C36—C37	1.514 (5)
C10—C27	1.496 (4)	C36—H36A	0.9900
N11—H11	0.8800	C36—H36B	0.9900
N12—H12	0.8800	C37—C39	1.525 (5)
C13—C14	1.387 (4)	C37—C38	1.525 (5)
C13—C18	1.404 (4)	C37—C40	1.533 (5)
C14—C15	1.387 (4)	C38—H38A	0.9900
C14—H14	0.9500	C38—H38B	0.9900
C15—C16	1.400 (4)	C39—H39A	0.9800
C15—H15	0.9500	C39—H39B	0.9800
C16—C17	1.395 (5)	C39—H39C	0.9800
C16—B19	1.568 (5)	C40—H40A	0.9800
C17—C18	1.394 (4)	C40—H40B	0.9800
C17—H17	0.9500	C40—H40C	0.9800
C18—H18	0.9500	C41—C46	1.366 (5)
B19—O21	1.340 (4)	C41—C42	1.375 (5)
B19—O20	1.378 (4)	C41—N47	1.470 (5)
O20—C22	1.439 (4)	C42—C43	1.383 (5)
O21—C24	1.459 (4)	C42—H42	0.9500
C22—C23	1.530 (5)	C43—C44	1.389 (6)
C22—H22A	0.9900	C43—H43	0.9500
C22—H22B	0.9900	C44—C45	1.366 (6)
C23—C24	1.515 (5)	C44—H44	0.9500
C23—C25	1.526 (5)	C45—C46	1.386 (6)
C23—C26	1.526 (5)	C45—H45	0.9500
C24—H24A	0.9900	C46—H46	0.9500
C24—H24B	0.9900	N47—O49	1.221 (4)
C25—H25A	0.9800	N47—O48	1.234 (4)
C25—H25B	0.9800
N11—C1—C10^i	126.2 (3)	H25B—C25—H25C	109.5
N11—C1—C2	109.9 (3)	C23—C26—H26A	109.5
C10^i—C1—C2	123.9 (3)	C23—C26—H26B	109.5
C3—C2—C1	106.8 (3)	H26A—C26—H26B	109.5
C3—C2—H2	126.6	C23—C26—H26C	109.5
C1—C2—H2	126.6	H26A—C26—H26C	109.5
C2—C3—C4	107.3 (3)	H26B—C26—H26C	109.5
C2—C3—H3	126.3	C32—C27—C28	118.0 (3)
C4—C3—H3	126.3	C32—C27—C10	121.0 (3)
N11—C4—C5	125.4 (3)	C28—C27—C10	121.0 (3)
N11—C4—C3	110.3 (3)	C29—C28—C27	120.6 (3)
C5—C4—C3	124.3 (3)	C29—C28—H28	119.7
C6—C5—C4	126.1 (3)	C27—C28—H28	119.7
C6—C5—C13	116.4 (3)	C28—C29—C30	121.5 (3)
C4—C5—C13	117.5 (3)	C28—C29—H29	119.2
N12—C6—C5	126.2 (3)	C30—C29—H29	119.2
N12—C6—C7	106.7 (3)	C29—C30—C31	117.5 (3)
C5—C6—C7	127.1 (3)	C29—C30—B33	121.0 (3)
C8—C7—C6	108.6 (3)	C31—C30—B33	121.5 (3)
C8—C7—H7	125.7	C30—C31—C32	121.4 (3)
C6—C7—H7	125.7	C30—C31—H31	119.3
C7—C8—C9	108.1 (3)	C32—C31—H31	119.3
C7—C8—H8	126.0	C27—C32—C31	121.1 (3)
C9—C8—H8	126.0	C27—C32—H32	119.5
N12—C9—C10	125.9 (3)	C31—C32—H32	119.5
N12—C9—C8	107.4 (2)	O35—B33—O34	123.5 (3)
C10—C9—C8	126.7 (3)	O35—B33—C30	118.1 (3)
C1^i—C10—C9	125.1 (3)	O34—B33—C30	118.3 (3)
C1^i—C10—C27	119.3 (3)	B33—O34—C36	119.0 (3)
C9—C10—C27	115.5 (3)	B33—O35—C38	119.8 (3)
C4—N11—C1	105.7 (2)	O34—C36—C37	111.5 (3)
C4—N11—H11	127.1	O34—C36—H36A	109.3
C1—N11—H11	127.1	C37—C36—H36A	109.3
C9—N12—C6	109.3 (2)	O34—C36—H36B	109.3
C9—N12—H12	125.4	C37—C36—H36B	109.3
C6—N12—H12	125.4	H36A—C36—H36B	108.0
C14—C13—C18	118.7 (3)	C36—C37—C39	109.2 (3)
C14—C13—C5	120.0 (3)	C36—C37—C38	107.8 (3)
C18—C13—C5	121.3 (3)	C39—C37—C38	108.2 (3)
C13—C14—C15	120.2 (3)	C36—C37—C40	110.6 (3)
C13—C14—H14	119.9	C39—C37—C40	110.3 (3)
C15—C14—H14	119.9	C38—C37—C40	110.8 (3)
C14—C15—C16	122.6 (3)	O35—C38—C37	112.1 (3)
C14—C15—H15	118.7	O35—C38—H38A	109.2
C16—C15—H15	118.7	C37—C38—H38A	109.2
C17—C16—C15	116.4 (3)	O35—C38—H38B	109.2
C17—C16—B19	121.5 (3)	C37—C38—H38B	109.2
C15—C16—B19	122.1 (3)	H38A—C38—H38B	107.9
C18—C17—C16	122.1 (3)	C37—C39—H39A	109.5
C18—C17—H17	119.0	C37—C39—H39B	109.5
C16—C17—H17	119.0	H39A—C39—H39B	109.5
C17—C18—C13	120.1 (3)	C37—C39—H39C	109.5
C17—C18—H18	120.0	H39A—C39—H39C	109.5
C13—C18—H18	120.0	H39B—C39—H39C	109.5
O21—B19—O20	124.2 (3)	C37—C40—H40A	109.5
O21—B19—C16	119.3 (3)	C37—C40—H40B	109.5
O20—B19—C16	116.4 (3)	H40A—C40—H40B	109.5
B19—O20—C22	119.6 (3)	C37—C40—H40C	109.5
B19—O21—C24	117.8 (3)	H40A—C40—H40C	109.5
O20—C22—C23	112.1 (3)	H40B—C40—H40C	109.5
O20—C22—H22A	109.2	C46—C41—C42	122.9 (4)
C23—C22—H22A	109.2	C46—C41—N47	118.2 (4)
O20—C22—H22B	109.2	C42—C41—N47	118.9 (4)
C23—C22—H22B	109.2	C41—C42—C43	118.6 (4)
H22A—C22—H22B	107.9	C41—C42—H42	120.7
C24—C23—C25	110.7 (3)	C43—C42—H42	120.7
C24—C23—C26	109.5 (3)	C42—C43—C44	119.2 (4)
C25—C23—C26	110.4 (3)	C42—C43—H43	120.4
C24—C23—C22	106.8 (3)	C44—C43—H43	120.4
C25—C23—C22	111.2 (3)	C45—C44—C43	121.0 (4)
C26—C23—C22	108.1 (3)	C45—C44—H44	119.5
O21—C24—C23	112.0 (3)	C43—C44—H44	119.5
O21—C24—H24A	109.2	C44—C45—C46	120.3 (4)
C23—C24—H24A	109.2	C44—C45—H45	119.9
O21—C24—H24B	109.2	C46—C45—H45	119.9
C23—C24—H24B	109.2	C41—C46—C45	118.1 (4)
H24A—C24—H24B	107.9	C41—C46—H46	121.0
C23—C25—H25A	109.5	C45—C46—H46	121.0
C23—C25—H25B	109.5	O49—N47—O48	124.3 (4)
H25A—C25—H25B	109.5	O49—N47—C41	118.2 (4)
C23—C25—H25C	109.5	O48—N47—C41	117.6 (4)
H25A—C25—H25C	109.5
N11—C1—C2—C3	0.5 (4)	C16—B19—O21—C24	−178.7 (3)
C10^i—C1—C2—C3	177.7 (3)	B19—O20—C22—C23	−25.7 (4)
C1—C2—C3—C4	−0.7 (4)	O20—C22—C23—C24	52.9 (4)
C2—C3—C4—N11	0.7 (4)	O20—C22—C23—C25	−68.0 (4)
C2—C3—C4—C5	−178.4 (3)	O20—C22—C23—C26	170.6 (3)
N11—C4—C5—C6	−0.2 (5)	B19—O21—C24—C23	33.9 (4)
C3—C4—C5—C6	178.7 (3)	C25—C23—C24—O21	64.0 (4)
N11—C4—C5—C13	178.3 (3)	C26—C23—C24—O21	−174.0 (3)
C3—C4—C5—C13	−2.8 (5)	C22—C23—C24—O21	−57.2 (4)
C4—C5—C6—N12	3.6 (5)	C1^i—C10—C27—C32	120.2 (3)
C13—C5—C6—N12	−175.0 (3)	C9—C10—C27—C32	−60.6 (4)
C4—C5—C6—C7	−176.5 (3)	C1^i—C10—C27—C28	−60.6 (4)
C13—C5—C6—C7	5.0 (5)	C9—C10—C27—C28	118.6 (3)
N12—C6—C7—C8	−0.1 (4)	C32—C27—C28—C29	2.9 (4)
C5—C6—C7—C8	179.9 (3)	C10—C27—C28—C29	−176.3 (3)
C6—C7—C8—C9	0.2 (4)	C27—C28—C29—C30	−1.0 (5)
C7—C8—C9—N12	−0.2 (4)	C28—C29—C30—C31	−0.8 (5)
C7—C8—C9—C10	−177.8 (3)	C28—C29—C30—B33	177.0 (3)
N12—C9—C10—C1^i	−5.0 (5)	C29—C30—C31—C32	0.7 (5)
C8—C9—C10—C1^i	172.2 (3)	B33—C30—C31—C32	−177.1 (3)
N12—C9—C10—C27	175.8 (3)	C28—C27—C32—C31	−3.0 (4)
C8—C9—C10—C27	−7.0 (5)	C10—C27—C32—C31	176.1 (3)
C5—C4—N11—C1	178.7 (3)	C30—C31—C32—C27	1.2 (5)
C3—C4—N11—C1	−0.3 (3)	C29—C30—B33—O35	−170.7 (3)
C10^i—C1—N11—C4	−177.2 (3)	C31—C30—B33—O35	7.1 (5)
C2—C1—N11—C4	−0.1 (3)	C29—C30—B33—O34	5.6 (5)
C10—C9—N12—C6	177.8 (3)	C31—C30—B33—O34	−176.6 (3)
C8—C9—N12—C6	0.1 (3)	O35—B33—O34—C36	1.0 (5)
C5—C6—N12—C9	179.9 (3)	C30—B33—O34—C36	−175.1 (3)
C7—C6—N12—C9	0.0 (3)	O34—B33—O35—C38	1.3 (5)
C6—C5—C13—C14	68.2 (4)	C30—B33—O35—C38	177.4 (3)
C4—C5—C13—C14	−110.5 (4)	B33—O34—C36—C37	−30.6 (4)
C6—C5—C13—C18	−113.1 (3)	O34—C36—C37—C39	172.3 (3)
C4—C5—C13—C18	68.2 (4)	O34—C36—C37—C38	55.0 (4)
C18—C13—C14—C15	0.4 (5)	O34—C36—C37—C40	−66.2 (4)
C5—C13—C14—C15	179.2 (3)	B33—O35—C38—C37	26.2 (4)
C13—C14—C15—C16	−1.5 (5)	C36—C37—C38—O35	−53.0 (4)
C14—C15—C16—C17	1.7 (5)	C39—C37—C38—O35	−171.0 (3)
C14—C15—C16—B19	−177.2 (3)	C40—C37—C38—O35	68.1 (4)
C15—C16—C17—C18	−1.0 (5)	C46—C41—C42—C43	−1.7 (6)
B19—C16—C17—C18	177.9 (3)	N47—C41—C42—C43	177.2 (3)
C16—C17—C18—C13	0.1 (5)	C41—C42—C43—C44	1.1 (6)
C14—C13—C18—C17	0.2 (5)	C42—C43—C44—C45	−0.4 (6)
C5—C13—C18—C17	−178.5 (3)	C43—C44—C45—C46	0.2 (7)
C17—C16—B19—O21	−9.8 (5)	C42—C41—C46—C45	1.5 (6)
C15—C16—B19—O21	169.0 (3)	N47—C41—C46—C45	−177.4 (3)
C17—C16—B19—O20	174.4 (3)	C44—C45—C46—C41	−0.7 (6)
C15—C16—B19—O20	−6.8 (5)	C46—C41—N47—O49	23.6 (5)
O21—B19—O20—C22	−0.9 (5)	C42—C41—N47—O49	−155.4 (4)
C16—B19—O20—C22	174.7 (3)	C46—C41—N47—O48	−157.2 (4)
O20—B19—O21—C24	−3.3 (5)	C42—C41—N47—O48	23.9 (5)

Symmetry code: (i) −x, −y+1, −z+1.