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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010800468X/sf3072sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010800468X/sf3072Isup2.hkl
Contains datablock I

CCDC reference: 682838

Comment top

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 ππ 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 top

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).

Experimental top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(aryl and methylene) and 1.5Ueq(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 top

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 top
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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 top
Crystal data top
C64H66B4N4O8·2C6H5NO2F(000) = 1380
Mr = 1308.67Dx = 1.286 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 18.6511 (7) ÅCell parameters from 6670 reflections
b = 9.2969 (3) Åθ = 2.1–25.6°
c = 20.7606 (9) ŵ = 0.09 mm1
β = 110.1016 (13)°T = 110 K
V = 3380.5 (2) Å3Needle, red
Z = 20.55 × 0.20 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer
3223 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.089
Graphite monochromatorθmax = 25.6°, θmin = 2.1°
Detector resolution: 12.8 pixels mm-1h = 022
ϕ and ω scansk = 011
23064 measured reflectionsl = 2523
6333 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0857P)2]
where P = (Fo2 + 2Fc2)/3
6333 reflections(Δ/σ)max < 0.001
446 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C64H66B4N4O8·2C6H5NO2V = 3380.5 (2) Å3
Mr = 1308.67Z = 2
Monoclinic, P21/cMo Kα radiation
a = 18.6511 (7) ŵ = 0.09 mm1
b = 9.2969 (3) ÅT = 110 K
c = 20.7606 (9) Å0.55 × 0.20 × 0.15 mm
β = 110.1016 (13)°
Data collection top
Nonius KappaCCD
diffractometer
3223 reflections with I > 2σ(I)
23064 measured reflectionsRint = 0.089
6333 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.179H-atom parameters constrained
S = 0.97Δρmax = 0.33 e Å3
6333 reflectionsΔρmin = 0.24 e Å3
446 parameters
Special details top

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
xyzUiso*/UeqOcc. (<1)
C10.10510 (17)0.5143 (3)0.65093 (16)0.0312 (8)
C20.18541 (17)0.5290 (4)0.69390 (17)0.0342 (8)
H20.20570.52700.74260.041*
C30.22466 (17)0.5456 (4)0.65163 (16)0.0335 (8)
H30.27830.55880.66460.040*
C40.17045 (17)0.5400 (3)0.58224 (16)0.0309 (8)
C50.19049 (17)0.5500 (3)0.52301 (16)0.0288 (7)
C60.14025 (17)0.5423 (3)0.45521 (16)0.0287 (7)
C70.15951 (18)0.5447 (3)0.39453 (16)0.0337 (8)
H70.20970.55200.39290.040*
C80.09429 (17)0.5348 (3)0.33938 (16)0.0332 (8)
H80.09090.53370.29270.040*
C90.03186 (17)0.5263 (3)0.36369 (16)0.0302 (7)
C100.04624 (17)0.5101 (3)0.32335 (16)0.0304 (8)
N110.09793 (13)0.5214 (3)0.58305 (13)0.0303 (6)
H110.05550.51520.54740.036*0.50
N120.06145 (13)0.5309 (3)0.43427 (12)0.0297 (6)
H120.03460.52720.46170.036*0.50
C130.27299 (17)0.5745 (4)0.53271 (16)0.0310 (8)
C140.29634 (18)0.7053 (4)0.51442 (17)0.0364 (8)
H140.25990.77880.49520.044*
C150.37279 (17)0.7289 (4)0.52416 (16)0.0371 (8)
H150.38730.81840.51030.045*
C160.42939 (17)0.6260 (4)0.55364 (16)0.0348 (8)
C170.40478 (18)0.4951 (4)0.57136 (16)0.0368 (8)
H170.44140.42190.59080.044*
C180.32822 (17)0.4682 (4)0.56145 (16)0.0349 (8)
H180.31340.37780.57420.042*
B190.5161 (2)0.6565 (4)0.56741 (18)0.0302 (9)
O200.53311 (12)0.7843 (3)0.54225 (11)0.0427 (6)
O210.56859 (12)0.5640 (2)0.60577 (12)0.0421 (6)
C220.61162 (17)0.8256 (4)0.55784 (18)0.0427 (9)
H22A0.61580.93160.56170.051*
H22B0.62880.79560.51970.051*
C230.66384 (18)0.7579 (4)0.62469 (18)0.0420 (9)
C240.64878 (18)0.5974 (4)0.61875 (19)0.0432 (9)
H24A0.66390.55840.58090.052*
H24B0.68050.54980.66180.052*
C250.6479 (2)0.8194 (4)0.68656 (18)0.0498 (10)
H25A0.59430.80280.68130.075*
H25B0.65830.92300.68970.075*
H25C0.68090.77190.72840.075*
C260.74636 (18)0.7868 (4)0.6306 (2)0.0501 (10)
H26A0.78090.74010.67190.075*
H26B0.75580.89080.63350.075*
H26C0.75540.74830.59010.075*
C270.06432 (17)0.5189 (4)0.24746 (16)0.0322 (8)
C280.09710 (17)0.4022 (4)0.20476 (16)0.0351 (8)
H280.11090.31810.22380.042*
C290.10962 (18)0.4085 (4)0.13475 (17)0.0360 (8)
H290.13120.32760.10680.043*
C300.09133 (17)0.5305 (4)0.10473 (16)0.0340 (8)
C310.06084 (17)0.6474 (4)0.14730 (16)0.0341 (8)
H310.04840.73250.12810.041*
C320.04825 (17)0.6420 (4)0.21740 (16)0.0319 (8)
H320.02830.72410.24500.038*
B330.1020 (2)0.5335 (4)0.0267 (2)0.0345 (9)
O340.13593 (13)0.4181 (3)0.01263 (11)0.0431 (6)
O350.07314 (13)0.6469 (3)0.00261 (11)0.0432 (6)
C360.1408 (2)0.4138 (4)0.08389 (16)0.0437 (9)
H36A0.18620.35710.11070.052*
H36B0.09500.36520.08720.052*
C370.14665 (19)0.5634 (4)0.11408 (17)0.0405 (9)
C380.07898 (19)0.6507 (4)0.06852 (17)0.0414 (9)
H38A0.03130.61220.07280.050*
H38B0.08450.75180.08450.050*
C390.1406 (2)0.5538 (4)0.18535 (18)0.0528 (11)
H39A0.09240.50690.18220.079*
H39B0.14200.65080.20420.079*
H39C0.18350.49750.21540.079*
C400.22227 (19)0.6344 (4)0.11809 (19)0.0497 (10)
H40A0.22560.63960.07200.075*
H40B0.26490.57720.14790.075*
H40C0.22460.73160.13690.075*
C410.5819 (2)0.2984 (4)0.20101 (19)0.0449 (9)
C420.5573 (2)0.3314 (4)0.2545 (2)0.0525 (10)
H420.58480.29910.29970.063*
C430.4916 (2)0.4124 (5)0.2412 (2)0.0608 (11)
H430.47380.43830.27730.073*
C440.4521 (2)0.4556 (4)0.1743 (2)0.0636 (12)
H440.40680.51080.16480.076*
C450.4774 (3)0.4199 (5)0.1220 (2)0.0667 (13)
H450.44980.45060.07660.080*
C460.5433 (2)0.3390 (4)0.1349 (2)0.0538 (11)
H460.56110.31260.09880.065*
N470.6536 (2)0.2180 (4)0.2153 (2)0.0611 (10)
O480.67506 (17)0.1430 (4)0.26750 (19)0.0809 (10)
O490.68842 (18)0.2308 (4)0.17540 (18)0.0820 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0246 (16)0.0380 (19)0.0303 (18)0.0001 (14)0.0084 (15)0.0005 (15)
C20.0262 (17)0.046 (2)0.0283 (18)0.0025 (15)0.0062 (15)0.0025 (16)
C30.0233 (16)0.044 (2)0.0318 (19)0.0011 (15)0.0074 (15)0.0044 (16)
C40.0264 (17)0.0340 (19)0.0330 (19)0.0012 (14)0.0108 (15)0.0008 (15)
C50.0257 (16)0.0304 (18)0.0296 (18)0.0065 (14)0.0084 (14)0.0035 (14)
C60.0254 (16)0.0310 (18)0.0301 (18)0.0002 (14)0.0101 (15)0.0018 (14)
C70.0257 (17)0.039 (2)0.038 (2)0.0007 (15)0.0134 (16)0.0008 (16)
C80.0307 (17)0.041 (2)0.0292 (18)0.0009 (15)0.0114 (15)0.0003 (15)
C90.0289 (17)0.0340 (19)0.0296 (18)0.0013 (14)0.0126 (15)0.0010 (15)
C100.0293 (17)0.0314 (18)0.0321 (18)0.0026 (14)0.0123 (15)0.0011 (15)
N110.0229 (14)0.0393 (16)0.0268 (15)0.0013 (12)0.0060 (12)0.0002 (12)
N120.0226 (13)0.0388 (16)0.0271 (15)0.0011 (12)0.0079 (12)0.0015 (12)
C130.0258 (17)0.042 (2)0.0281 (18)0.0024 (15)0.0125 (15)0.0046 (15)
C140.0300 (18)0.043 (2)0.038 (2)0.0041 (16)0.0139 (16)0.0086 (16)
C150.0323 (18)0.044 (2)0.0357 (19)0.0023 (16)0.0121 (15)0.0030 (16)
C160.0284 (17)0.046 (2)0.0304 (18)0.0008 (16)0.0109 (15)0.0008 (16)
C170.0295 (18)0.047 (2)0.035 (2)0.0061 (16)0.0129 (16)0.0010 (16)
C180.0295 (17)0.040 (2)0.0361 (19)0.0037 (15)0.0120 (15)0.0016 (16)
B190.032 (2)0.038 (2)0.024 (2)0.0063 (18)0.0139 (17)0.0035 (17)
O200.0281 (12)0.0577 (16)0.0422 (14)0.0021 (11)0.0120 (11)0.0030 (12)
O210.0281 (12)0.0478 (15)0.0515 (15)0.0018 (11)0.0152 (11)0.0022 (12)
C220.0276 (18)0.053 (2)0.047 (2)0.0061 (16)0.0123 (16)0.0030 (18)
C230.0302 (18)0.050 (2)0.044 (2)0.0040 (17)0.0101 (17)0.0009 (18)
C240.0242 (18)0.057 (2)0.048 (2)0.0057 (16)0.0117 (16)0.0020 (19)
C250.042 (2)0.058 (3)0.045 (2)0.0009 (18)0.0096 (18)0.0052 (19)
C260.0312 (19)0.061 (3)0.056 (2)0.0066 (18)0.0126 (18)0.001 (2)
C270.0252 (16)0.042 (2)0.0298 (18)0.0049 (15)0.0095 (14)0.0015 (16)
C280.0318 (18)0.040 (2)0.0333 (19)0.0005 (15)0.0110 (15)0.0006 (16)
C290.0321 (18)0.0372 (19)0.037 (2)0.0026 (15)0.0099 (16)0.0074 (17)
C300.0283 (17)0.040 (2)0.0324 (19)0.0018 (15)0.0093 (15)0.0001 (16)
C310.0292 (17)0.0370 (19)0.036 (2)0.0001 (15)0.0111 (15)0.0052 (16)
C320.0282 (17)0.0367 (19)0.0312 (19)0.0024 (15)0.0107 (15)0.0031 (15)
B330.0270 (19)0.039 (2)0.038 (2)0.0034 (18)0.0118 (18)0.0035 (19)
O340.0519 (15)0.0440 (14)0.0334 (13)0.0053 (12)0.0146 (12)0.0001 (11)
O350.0486 (15)0.0479 (15)0.0360 (14)0.0083 (12)0.0183 (12)0.0014 (12)
C360.049 (2)0.049 (2)0.032 (2)0.0012 (18)0.0126 (17)0.0014 (17)
C370.042 (2)0.046 (2)0.0326 (19)0.0022 (17)0.0118 (17)0.0036 (16)
C380.045 (2)0.043 (2)0.036 (2)0.0041 (17)0.0137 (17)0.0027 (17)
C390.055 (2)0.070 (3)0.037 (2)0.006 (2)0.0196 (19)0.0030 (19)
C400.043 (2)0.062 (3)0.044 (2)0.0073 (19)0.0147 (18)0.005 (2)
C410.046 (2)0.041 (2)0.047 (2)0.0036 (18)0.0166 (19)0.0056 (18)
C420.057 (3)0.052 (2)0.048 (2)0.002 (2)0.018 (2)0.0055 (19)
C430.063 (3)0.065 (3)0.062 (3)0.006 (2)0.031 (2)0.003 (2)
C440.048 (2)0.059 (3)0.078 (3)0.000 (2)0.013 (2)0.007 (3)
C450.074 (3)0.058 (3)0.050 (3)0.002 (2)0.001 (2)0.002 (2)
C460.070 (3)0.049 (2)0.043 (2)0.018 (2)0.020 (2)0.011 (2)
N470.058 (2)0.049 (2)0.078 (3)0.0079 (18)0.025 (2)0.014 (2)
O480.072 (2)0.070 (2)0.090 (2)0.0108 (17)0.0151 (19)0.008 (2)
O490.073 (2)0.083 (2)0.110 (3)0.0108 (18)0.057 (2)0.024 (2)
Geometric parameters (Å, º) top
C1—N111.371 (4)C25—H25C0.9800
C1—C10i1.395 (4)C26—H26A0.9800
C1—C21.463 (4)C26—H26B0.9800
C2—C31.331 (4)C26—H26C0.9800
C2—H20.9500C27—C321.385 (4)
C3—C41.449 (4)C27—C281.401 (4)
C3—H30.9500C28—C291.392 (4)
C4—N111.369 (4)C28—H280.9500
C4—C51.406 (4)C29—C301.392 (4)
C5—C61.399 (4)C29—H290.9500
C5—C131.499 (4)C30—C311.393 (4)
C6—N121.386 (4)C30—B331.563 (5)
C6—C71.424 (4)C31—C321.393 (4)
C7—C81.357 (4)C31—H310.9500
C7—H70.9500C32—H320.9500
C8—C91.421 (4)B33—O351.355 (4)
C8—H80.9500B33—O341.364 (4)
C9—N121.378 (4)O34—C361.451 (4)
C9—C101.417 (4)O35—C381.443 (4)
C10—C1i1.395 (4)C36—C371.514 (5)
C10—C271.496 (4)C36—H36A0.9900
N11—H110.8800C36—H36B0.9900
N12—H120.8800C37—C391.525 (5)
C13—C141.387 (4)C37—C381.525 (5)
C13—C181.404 (4)C37—C401.533 (5)
C14—C151.387 (4)C38—H38A0.9900
C14—H140.9500C38—H38B0.9900
C15—C161.400 (4)C39—H39A0.9800
C15—H150.9500C39—H39B0.9800
C16—C171.395 (5)C39—H39C0.9800
C16—B191.568 (5)C40—H40A0.9800
C17—C181.394 (4)C40—H40B0.9800
C17—H170.9500C40—H40C0.9800
C18—H180.9500C41—C461.366 (5)
B19—O211.340 (4)C41—C421.375 (5)
B19—O201.378 (4)C41—N471.470 (5)
O20—C221.439 (4)C42—C431.383 (5)
O21—C241.459 (4)C42—H420.9500
C22—C231.530 (5)C43—C441.389 (6)
C22—H22A0.9900C43—H430.9500
C22—H22B0.9900C44—C451.366 (6)
C23—C241.515 (5)C44—H440.9500
C23—C251.526 (5)C45—C461.386 (6)
C23—C261.526 (5)C45—H450.9500
C24—H24A0.9900C46—H460.9500
C24—H24B0.9900N47—O491.221 (4)
C25—H25A0.9800N47—O481.234 (4)
C25—H25B0.9800
N11—C1—C10i126.2 (3)H25B—C25—H25C109.5
N11—C1—C2109.9 (3)C23—C26—H26A109.5
C10i—C1—C2123.9 (3)C23—C26—H26B109.5
C3—C2—C1106.8 (3)H26A—C26—H26B109.5
C3—C2—H2126.6C23—C26—H26C109.5
C1—C2—H2126.6H26A—C26—H26C109.5
C2—C3—C4107.3 (3)H26B—C26—H26C109.5
C2—C3—H3126.3C32—C27—C28118.0 (3)
C4—C3—H3126.3C32—C27—C10121.0 (3)
N11—C4—C5125.4 (3)C28—C27—C10121.0 (3)
N11—C4—C3110.3 (3)C29—C28—C27120.6 (3)
C5—C4—C3124.3 (3)C29—C28—H28119.7
C6—C5—C4126.1 (3)C27—C28—H28119.7
C6—C5—C13116.4 (3)C28—C29—C30121.5 (3)
C4—C5—C13117.5 (3)C28—C29—H29119.2
N12—C6—C5126.2 (3)C30—C29—H29119.2
N12—C6—C7106.7 (3)C29—C30—C31117.5 (3)
C5—C6—C7127.1 (3)C29—C30—B33121.0 (3)
C8—C7—C6108.6 (3)C31—C30—B33121.5 (3)
C8—C7—H7125.7C30—C31—C32121.4 (3)
C6—C7—H7125.7C30—C31—H31119.3
C7—C8—C9108.1 (3)C32—C31—H31119.3
C7—C8—H8126.0C27—C32—C31121.1 (3)
C9—C8—H8126.0C27—C32—H32119.5
N12—C9—C10125.9 (3)C31—C32—H32119.5
N12—C9—C8107.4 (2)O35—B33—O34123.5 (3)
C10—C9—C8126.7 (3)O35—B33—C30118.1 (3)
C1i—C10—C9125.1 (3)O34—B33—C30118.3 (3)
C1i—C10—C27119.3 (3)B33—O34—C36119.0 (3)
C9—C10—C27115.5 (3)B33—O35—C38119.8 (3)
C4—N11—C1105.7 (2)O34—C36—C37111.5 (3)
C4—N11—H11127.1O34—C36—H36A109.3
C1—N11—H11127.1C37—C36—H36A109.3
C9—N12—C6109.3 (2)O34—C36—H36B109.3
C9—N12—H12125.4C37—C36—H36B109.3
C6—N12—H12125.4H36A—C36—H36B108.0
C14—C13—C18118.7 (3)C36—C37—C39109.2 (3)
C14—C13—C5120.0 (3)C36—C37—C38107.8 (3)
C18—C13—C5121.3 (3)C39—C37—C38108.2 (3)
C13—C14—C15120.2 (3)C36—C37—C40110.6 (3)
C13—C14—H14119.9C39—C37—C40110.3 (3)
C15—C14—H14119.9C38—C37—C40110.8 (3)
C14—C15—C16122.6 (3)O35—C38—C37112.1 (3)
C14—C15—H15118.7O35—C38—H38A109.2
C16—C15—H15118.7C37—C38—H38A109.2
C17—C16—C15116.4 (3)O35—C38—H38B109.2
C17—C16—B19121.5 (3)C37—C38—H38B109.2
C15—C16—B19122.1 (3)H38A—C38—H38B107.9
C18—C17—C16122.1 (3)C37—C39—H39A109.5
C18—C17—H17119.0C37—C39—H39B109.5
C16—C17—H17119.0H39A—C39—H39B109.5
C17—C18—C13120.1 (3)C37—C39—H39C109.5
C17—C18—H18120.0H39A—C39—H39C109.5
C13—C18—H18120.0H39B—C39—H39C109.5
O21—B19—O20124.2 (3)C37—C40—H40A109.5
O21—B19—C16119.3 (3)C37—C40—H40B109.5
O20—B19—C16116.4 (3)H40A—C40—H40B109.5
B19—O20—C22119.6 (3)C37—C40—H40C109.5
B19—O21—C24117.8 (3)H40A—C40—H40C109.5
O20—C22—C23112.1 (3)H40B—C40—H40C109.5
O20—C22—H22A109.2C46—C41—C42122.9 (4)
C23—C22—H22A109.2C46—C41—N47118.2 (4)
O20—C22—H22B109.2C42—C41—N47118.9 (4)
C23—C22—H22B109.2C41—C42—C43118.6 (4)
H22A—C22—H22B107.9C41—C42—H42120.7
C24—C23—C25110.7 (3)C43—C42—H42120.7
C24—C23—C26109.5 (3)C42—C43—C44119.2 (4)
C25—C23—C26110.4 (3)C42—C43—H43120.4
C24—C23—C22106.8 (3)C44—C43—H43120.4
C25—C23—C22111.2 (3)C45—C44—C43121.0 (4)
C26—C23—C22108.1 (3)C45—C44—H44119.5
O21—C24—C23112.0 (3)C43—C44—H44119.5
O21—C24—H24A109.2C44—C45—C46120.3 (4)
C23—C24—H24A109.2C44—C45—H45119.9
O21—C24—H24B109.2C46—C45—H45119.9
C23—C24—H24B109.2C41—C46—C45118.1 (4)
H24A—C24—H24B107.9C41—C46—H46121.0
C23—C25—H25A109.5C45—C46—H46121.0
C23—C25—H25B109.5O49—N47—O48124.3 (4)
H25A—C25—H25B109.5O49—N47—C41118.2 (4)
C23—C25—H25C109.5O48—N47—C41117.6 (4)
H25A—C25—H25C109.5
N11—C1—C2—C30.5 (4)C16—B19—O21—C24178.7 (3)
C10i—C1—C2—C3177.7 (3)B19—O20—C22—C2325.7 (4)
C1—C2—C3—C40.7 (4)O20—C22—C23—C2452.9 (4)
C2—C3—C4—N110.7 (4)O20—C22—C23—C2568.0 (4)
C2—C3—C4—C5178.4 (3)O20—C22—C23—C26170.6 (3)
N11—C4—C5—C60.2 (5)B19—O21—C24—C2333.9 (4)
C3—C4—C5—C6178.7 (3)C25—C23—C24—O2164.0 (4)
N11—C4—C5—C13178.3 (3)C26—C23—C24—O21174.0 (3)
C3—C4—C5—C132.8 (5)C22—C23—C24—O2157.2 (4)
C4—C5—C6—N123.6 (5)C1i—C10—C27—C32120.2 (3)
C13—C5—C6—N12175.0 (3)C9—C10—C27—C3260.6 (4)
C4—C5—C6—C7176.5 (3)C1i—C10—C27—C2860.6 (4)
C13—C5—C6—C75.0 (5)C9—C10—C27—C28118.6 (3)
N12—C6—C7—C80.1 (4)C32—C27—C28—C292.9 (4)
C5—C6—C7—C8179.9 (3)C10—C27—C28—C29176.3 (3)
C6—C7—C8—C90.2 (4)C27—C28—C29—C301.0 (5)
C7—C8—C9—N120.2 (4)C28—C29—C30—C310.8 (5)
C7—C8—C9—C10177.8 (3)C28—C29—C30—B33177.0 (3)
N12—C9—C10—C1i5.0 (5)C29—C30—C31—C320.7 (5)
C8—C9—C10—C1i172.2 (3)B33—C30—C31—C32177.1 (3)
N12—C9—C10—C27175.8 (3)C28—C27—C32—C313.0 (4)
C8—C9—C10—C277.0 (5)C10—C27—C32—C31176.1 (3)
C5—C4—N11—C1178.7 (3)C30—C31—C32—C271.2 (5)
C3—C4—N11—C10.3 (3)C29—C30—B33—O35170.7 (3)
C10i—C1—N11—C4177.2 (3)C31—C30—B33—O357.1 (5)
C2—C1—N11—C40.1 (3)C29—C30—B33—O345.6 (5)
C10—C9—N12—C6177.8 (3)C31—C30—B33—O34176.6 (3)
C8—C9—N12—C60.1 (3)O35—B33—O34—C361.0 (5)
C5—C6—N12—C9179.9 (3)C30—B33—O34—C36175.1 (3)
C7—C6—N12—C90.0 (3)O34—B33—O35—C381.3 (5)
C6—C5—C13—C1468.2 (4)C30—B33—O35—C38177.4 (3)
C4—C5—C13—C14110.5 (4)B33—O34—C36—C3730.6 (4)
C6—C5—C13—C18113.1 (3)O34—C36—C37—C39172.3 (3)
C4—C5—C13—C1868.2 (4)O34—C36—C37—C3855.0 (4)
C18—C13—C14—C150.4 (5)O34—C36—C37—C4066.2 (4)
C5—C13—C14—C15179.2 (3)B33—O35—C38—C3726.2 (4)
C13—C14—C15—C161.5 (5)C36—C37—C38—O3553.0 (4)
C14—C15—C16—C171.7 (5)C39—C37—C38—O35171.0 (3)
C14—C15—C16—B19177.2 (3)C40—C37—C38—O3568.1 (4)
C15—C16—C17—C181.0 (5)C46—C41—C42—C431.7 (6)
B19—C16—C17—C18177.9 (3)N47—C41—C42—C43177.2 (3)
C16—C17—C18—C130.1 (5)C41—C42—C43—C441.1 (6)
C14—C13—C18—C170.2 (5)C42—C43—C44—C450.4 (6)
C5—C13—C18—C17178.5 (3)C43—C44—C45—C460.2 (7)
C17—C16—B19—O219.8 (5)C42—C41—C46—C451.5 (6)
C15—C16—B19—O21169.0 (3)N47—C41—C46—C45177.4 (3)
C17—C16—B19—O20174.4 (3)C44—C45—C46—C410.7 (6)
C15—C16—B19—O206.8 (5)C46—C41—N47—O4923.6 (5)
O21—B19—O20—C220.9 (5)C42—C41—N47—O49155.4 (4)
C16—B19—O20—C22174.7 (3)C46—C41—N47—O48157.2 (4)
O20—B19—O21—C243.3 (5)C42—C41—N47—O4823.9 (5)
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC64H66B4N4O8·2C6H5NO2
Mr1308.67
Crystal system, space groupMonoclinic, P21/c
Temperature (K)110
a, b, c (Å)18.6511 (7), 9.2969 (3), 20.7606 (9)
β (°) 110.1016 (13)
V3)3380.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.55 × 0.20 × 0.15
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
23064, 6333, 3223
Rint0.089
(sin θ/λ)max1)0.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.179, 0.97
No. of reflections6333
No. of parameters446
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.24

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).

 

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