Benzene-1,4-diboronic acid–4,4′-bipyridine–water (1/2/2)

In the presence of water, benzene-1,4-diboronic acid (1,4-bdba) and 4,4′-bipyridine (4,4′-bpy) form a cocrystal of composition (1,4-bdba)(4,4′-bpy)₂(H₂O)₂, in which the mol­ecular components are organized in two, so far unknown, cyclo­phane-type hydrogen-bonding patterns. The asymmetric unit of the title compound, C₆H₈B₂O₄·2C₁₀H₈N₂·2H₂O, contains two 4,4′-bpy, two water mol­ecules and two halves of 1,4-bdba mol­ecules arranged around crystallographic inversion centers. The occurrence of O—H...O and O—H...N hydrogen bonds involving the water mol­ecules and all O atoms of boronic acid gives rise to a two-dimensional hydrogen-bonded layer structure that develops parallel to the (01) plane. This supra­molecular organization is reinforced by π–π inter­actions between symmetry-related 4,4′-bpy mol­ecules.

S1. Comment

Boronic acids form dimeric synthons of the composition PhB(OH)₂···(HO)₂BPh, which are structurally related to the well known carboxylic acid and carboxamide homodimeric motifs (Rodríguez-Cuamatzi, Vargas-Díaz & Höpfl, 2004; Rodríguez-Cuamatzi, Vargas-Díaz, Maris et al., 2004). Since the –B(OH)₂ function can also be integrated into neutral and charged heterodimeric motifs, boronic acids have become interesting building blocks for crystal engineering (Filthaus et al., 2008; Fournier et al., 2003; Kara et al., 2006; Maly et al., 2006; Rodríguez-Cuamatzi et al., 2005; Rogowska et al., 2006; SeethaLekshmi et al., 2006, 2007; Shimpi et al., 2007). In contrast to carboxylic acids, pyridine adducts of boronic acids show a larger structural variety of hydrogen-bonding motifs, which have been studied systematically during the last few years by different research groups (Aakeröy et al., 2004, 2005; Braga et al., 2003). It has been shown that the co-crystallization of boric and boronic acids with 4,4'-bpy gives one-dimensional or two-dimensional hydrogen-bonded supramolecular structures, in which frequently water molecules are incorporated to allow for an optimization of π–π interactions between the 4,4'-bpy molecules (Pedireddi et al., 2004; Rodríguez-Cuamatzi et al., 2009). When combining benzene-1,4-diboronic acid (1,4-bdba) with 4,4'-bipyridine (4,4'-bpy) in benzene, co-crystals of the composition [(1,4-bdba)(4,4'-bpy)₂] have been obtained (Rodríguez-Cuamatzi et al., 2009), in which the –B(OH)₂ groups are hydrogen-bonded to two pyridyl fragments of the 4,4'-bpy molecules to give one-dimensional chains containing hydrogen-bonded cyclophane-type macrocycles (motif I in the scheme).

We report herein on the single-crystal X-ray diffraction analysis of the corresponding dihydrate, (1). Co-crystals of the composition [(1,4-bdba)(4,4'-bpy)₂(H₂O)₂], (1), were obtained by a self-assembly reaction of 1,4-bdba and 4,4'-bpy in a 1:2 stoichiometric ratio in methanol containing small quantities of water. The unit cell of the title compound contains four 4,4'-bpy and four water molecules, of which two are independent in each case. Further, there are two independent 1,4-bdba molecules, which are both located at crystallographic inversion centers. In the crystal structure, each –B(OH)₂ group is involved in one (B)O—H···N_pyr and one (B)O—H···O_w hydrogen-bonding interaction, thus showing an asymmetric hydrogen-bonding behaviour. Similarly, each 4,4'-bpy molecule participates in two different types of O—H···N interactions, of which the first is formed with a BOH group and the second with a water molecule, which is further connected to a –B(OH)₂ moiety.

In the hydrogen-bonding pattern (Table 1) a cyclophane-type macrocycle with the graph set R₆⁶(30) (Bernstein et al., 1995) can be distinguished, involving two 4,4'-bpy molecules, two –B(OH)₂ moieties and two water molecules (motif IV in the scheme) (Fig. 1). Although structurally related, this arrangement is different from all motifs observed so far for boric and boronic acid adducts with 4,4'-bpy (see Scheme) (Pedireddi et al., 2004; Rodríguez-Cuamatzi et al., 2009). In contrast, in motif III one –B(OH)₂ group interacts only with one of its two OH groups in the hydrogen-bonding pattern. In motif V each –B(OH)₂ group participates also with both hydroxyl functions; however, at the same time the configuration of the –B(OH)₂ group changes, one has syn–anti and the other one syn–syn orientation. In the present case (Fig. 1) (motif IV), both –B(OH)₂ functions have syn–syn orientation, with the consequence that both water molecules act as simultaneous hydrogen-bonding donor and acceptor within the macrocycle. In the crystal structure, these cyclophane-type macrocycles are connected further through additional O_w—H···O(H)B interactions to give a two-dimensional hydrogen-bonded layer structure (Fig. 2). Interestingly, this association generates an additional, novel hydrogen-bonded macrocyclic motif that can be described by the graph set R₆⁶(26), in which two 4,4'-bpy and two water molecules, but only two BOH hydroxyl groups are involved (Fig. 1, motif II. This motif completes therefore a series of cyclophane-type hydrogen-bonding motifs I–V (Scheme) containing a varying number of BOH hydroxyl groups (n = 2, 3 and 4) and water molecules (n = 0 and 2). Analogous patterns containing only one water molecule have not been described so far. As described previously (Rodríguez-Cuamatzi et al., 2009), it is probable that the differences in the supramolecular structure of motifs I–V result from the optimization of π–π interactions between the 4,4'-bpy molecules within the crystal structure. Indeed, in the two-dimensional layers of the title compound the 4,4'-bpy are stacked along axis a (Fig. 2). Thereby, the pyridine rings of opposite 4,4'-bpy molecules have slightly displaced parallel-sandwich geometries and are almost coplanar to each other, having perpendicular distances varying from 3.26 to 3.40 Å, centroid–centroid distances from 3.59 to 3.65 Å, N···N distances from 3.59 to 3.67 Å and interplanar angles of 2.7 and 4.4 Å. Within the 4,4'-bpy molecules, the pyridine rings are twisted about the central C—C bonds by angles of 14.3 (2) and 21.4 (2) °.

Related literature

For related literature, see: Aakeröy et al. (2004, 2005); Bernstein et al. (1995); Braga et al. (2003); Filthaus et al. (2008); Fournier et al. (2003); Kara et al. (2006); Maly et al. (2006); Pedireddi & SeethaLekshmi (2004); Rodríguez-Cuamatzi, Arillo-Flores, Bernal-Uruchurtu & Höpfl (2005); Rodríguez-Cuamatzi, Luna-García, Torres-Huerta, Bernal-Uruchurtu, Barba & Höpfl (2009); Rodríguez-Cuamatzi, Vargas-Díaz & Höpfl (2004); Rodríguez-Cuamatzi, Vargas-Díaz, Maris, Wuest & Höpfl (2004); Rogowska et al. (2006); SeethaLekshmi & Pedireddi (2006, 2007); Shimpi et al. (2007).

S2. Experimental

A solution of benzene-1,4-diboronic acid (0.250 g, 1.50 mmol) and 4,4'-bipyridine (0.470 g,3.01 mmol) in 20 ml of methanol was refluxed for 1 h. A precipitate formed upon cooling that was recrystallized from 25 ml of a solvent mixture of methanol and water (10:1) to give crystals suitable for X-ray diffraction analysis (m.p. 573 K).

S3. Refinement

H atoms were positioned geometrically and constrained using the riding-model approximation [C—H_aryl= 0.93 Å, U_iso(H_aryl) = 1.2U_eq(C)]. H atoms bonded to O (H1', H2', H3', H4', H5A, H5B, H6A and H6B) were located in difference Fourier maps. Their coordinates were refined with a distance restraint: O—H = 0.84 Å and [U_iso(H) = 1.5U_eq(O)].

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus NT (Bruker, 2001); data reduction: SAINT-Plus NT (Bruker, 2001); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and and publCIF (Westrip, 2010).

Figures

Fig. 1. Cyclophane-type hydrogen-bonding motifs [(II) and (IV)] found in the crystal structure of [(1,4-bdba)(bpy)2(H2O)2]. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 2. Fragment of the two-dimensional hydrogen-bonded layer found in the crystal structure of [(1,4-bdba)(bpy)2(H2O)2], showing the cyclophane-type hydrogen-bonding motifs [(II) and (IV)]. Dashed lines indicate π–π interactions between the 4,4'-bpy molecules along axis a. Displacement ellipsoids are drawn at the 30% probability level and H atoms not involved in hydrogen-bonding have been omitted for clarity. [Symmetry codes: (i) x, 1 + y, z; (ii) 1 + x, y, z; (iii) 1 + x,1 + y, z.] Scheme 1. Different types of hydrogen-bonding motifs found so far experimentally for adducts formed between 4,4···-bipyridine and boric/boronic acids (including this work).

Benzene-1,4-diboronic acid–4,4'-bipyridine–water (1/2/2)

Crystal data

C6H8B2O4·2C10H8N2·2H2O	Z = 2
Mr = 514.14	F(000) = 540
Triclinic, P1	Dx = 1.333 Mg m^−3
Hall symbol: -P 1	Melting point: 573 K
a = 6.8262 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1914 (13) Å	Cell parameters from 3439 reflections
c = 18.834 (2) Å	θ = 2.2–28.2°
α = 98.825 (2)°	µ = 0.09 mm^−1
β = 90.804 (2)°	T = 100 K
γ = 98.000 (2)°	Rectangular prism, light brown
V = 1281.3 (3) Å^3	0.44 × 0.41 × 0.34 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4495 independent reflections
Radiation source: fine-focus sealed tube	3542 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 8.3 pixels mm^-1	θmax = 25.0°, θmin = 1.1°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.960, Tmax = 0.969	l = −22→22
12443 measured 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.356P] where P = (Fo^2 + 2Fc^2)/3
4495 reflections	(Δ/σ)max < 0.001
343 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	1.00366 (17)	0.36258 (11)	0.09145 (7)	0.0243 (3)
H1'	0.9670	0.4355	0.1092	0.036*
O2	0.66707 (17)	0.26441 (11)	0.05601 (6)	0.0210 (3)
H2'	0.6160	0.3320	0.0738	0.031*
C1	0.9372 (2)	0.12387 (16)	0.02925 (9)	0.0161 (4)
C2	1.1378 (2)	0.10909 (17)	0.02768 (9)	0.0163 (4)
H2	1.2344	0.1831	0.0465	0.020*
C3	1.1974 (2)	−0.01181 (17)	−0.00092 (9)	0.0164 (4)
H3	1.3348	−0.0186	−0.0012	0.020*
B1	0.8643 (3)	0.2613 (2)	0.06120 (10)	0.0174 (4)
O3	0.52342 (17)	0.64073 (11)	0.41006 (7)	0.0241 (3)
H3'	0.5620	0.5694	0.3909	0.036*
O4	0.85741 (17)	0.75050 (11)	0.44009 (6)	0.0211 (3)
H4'	0.9070	0.6810	0.4249	0.032*
C14	0.5747 (2)	0.88023 (16)	0.47058 (9)	0.0158 (4)
C15	0.7004 (2)	0.99541 (16)	0.50211 (9)	0.0158 (4)
H15	0.8391	0.9936	0.5040	0.019*
C16	0.6283 (3)	1.11195 (16)	0.53061 (9)	0.0164 (4)
H16	0.7185	1.1882	0.5514	0.020*
B2	0.6583 (3)	0.74744 (19)	0.43810 (10)	0.0157 (4)
N1	0.9408 (2)	0.60492 (14)	0.15777 (8)	0.0205 (4)
N2	1.0640 (2)	1.28044 (14)	0.33608 (8)	0.0209 (4)
C4	0.9229 (3)	0.70721 (17)	0.12212 (10)	0.0204 (4)
H4	0.8899	0.6874	0.0721	0.024*
C5	0.9499 (2)	0.84017 (17)	0.15457 (9)	0.0176 (4)
H5	0.9357	0.9092	0.1270	0.021*
C6	0.9981 (2)	0.87203 (16)	0.22768 (9)	0.0157 (4)
C7	1.0187 (2)	0.76538 (17)	0.26469 (9)	0.0182 (4)
H7	1.0525	0.7820	0.3147	0.022*
C8	0.9894 (3)	0.63609 (17)	0.22799 (10)	0.0206 (4)
H8	1.0044	0.5651	0.2540	0.025*
C9	1.0831 (3)	1.25078 (17)	0.26506 (10)	0.0203 (4)
H9	1.1108	1.3229	0.2385	0.024*
C10	1.0648 (2)	1.12159 (16)	0.22799 (9)	0.0177 (4)
H10	1.0804	1.1066	0.1775	0.021*
C11	1.0233 (2)	1.01304 (16)	0.26529 (9)	0.0154 (4)
C12	1.0045 (2)	1.04365 (17)	0.33932 (9)	0.0182 (4)
H12	0.9775	0.9737	0.3674	0.022*
C13	1.0253 (3)	1.17622 (17)	0.37173 (10)	0.0208 (4)
H13	1.0114	1.1945	0.4223	0.025*
N3	0.5964 (2)	0.40286 (14)	0.34234 (8)	0.0204 (3)
N4	0.4626 (2)	−0.27539 (14)	0.16698 (8)	0.0215 (4)
C17	0.6045 (3)	0.37180 (17)	0.27103 (10)	0.0207 (4)
H17	0.6261	0.4431	0.2437	0.025*
C18	0.5833 (3)	0.24262 (17)	0.23503 (9)	0.0192 (4)
H18	0.5926	0.2264	0.1842	0.023*
C19	0.5481 (2)	0.13497 (16)	0.27332 (9)	0.0158 (4)
C20	0.5374 (3)	0.16714 (17)	0.34747 (9)	0.0190 (4)
H20	0.5128	0.0980	0.3761	0.023*
C21	0.5629 (3)	0.30013 (17)	0.37928 (10)	0.0206 (4)
H21	0.5563	0.3198	0.4301	0.025*
C22	0.4563 (3)	−0.17298 (17)	0.13038 (10)	0.0208 (4)
H22	0.4322	−0.1929	0.0798	0.025*
C23	0.4830 (2)	−0.03972 (17)	0.16235 (9)	0.0190 (4)
H23	0.4765	0.0290	0.1339	0.023*
C24	0.5194 (2)	−0.00657 (16)	0.23635 (9)	0.0159 (4)
C25	0.5261 (2)	−0.11381 (17)	0.27413 (9)	0.0181 (4)
H25	0.5509	−0.0973	0.3247	0.022*
C26	0.4967 (2)	−0.24348 (17)	0.23794 (10)	0.0195 (4)
H26	0.5008	−0.3144	0.2651	0.023*
O5	0.43577 (19)	0.44785 (12)	0.11056 (7)	0.0319 (4)
H5A	0.3139	0.4230	0.1027	0.048*
H5B	0.4470	0.5316	0.1219	0.048*
O6	1.09092 (18)	0.55994 (12)	0.39151 (7)	0.0281 (3)
H6A	1.2139	0.5790	0.3990	0.042*
H6B	1.0770	0.4757	0.3833	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0221 (7)	0.0134 (7)	0.0347 (8)	0.0052 (5)	−0.0003 (6)	−0.0069 (6)
O2	0.0227 (7)	0.0153 (6)	0.0243 (7)	0.0072 (5)	0.0008 (5)	−0.0031 (5)
C1	0.0219 (9)	0.0153 (9)	0.0116 (9)	0.0040 (7)	0.0012 (7)	0.0024 (7)
C2	0.0195 (9)	0.0130 (9)	0.0145 (9)	−0.0006 (7)	−0.0012 (7)	−0.0003 (7)
C3	0.0157 (9)	0.0190 (9)	0.0152 (9)	0.0052 (7)	0.0010 (7)	0.0025 (7)
B1	0.0223 (11)	0.0174 (11)	0.0130 (10)	0.0030 (8)	0.0025 (8)	0.0042 (8)
O3	0.0224 (7)	0.0134 (7)	0.0339 (8)	0.0045 (5)	0.0021 (6)	−0.0061 (6)
O4	0.0212 (7)	0.0134 (6)	0.0275 (7)	0.0058 (5)	0.0026 (5)	−0.0032 (5)
C14	0.0213 (9)	0.0150 (9)	0.0113 (9)	0.0030 (7)	0.0012 (7)	0.0021 (7)
C15	0.0153 (9)	0.0177 (9)	0.0144 (9)	0.0024 (7)	0.0016 (7)	0.0026 (7)
C16	0.0218 (9)	0.0114 (9)	0.0141 (9)	−0.0002 (7)	0.0010 (7)	−0.0015 (7)
B2	0.0205 (10)	0.0151 (10)	0.0122 (10)	0.0032 (8)	0.0012 (8)	0.0040 (8)
N1	0.0168 (8)	0.0165 (8)	0.0269 (9)	0.0026 (6)	0.0036 (6)	−0.0012 (7)
N2	0.0165 (8)	0.0167 (8)	0.0277 (9)	0.0045 (6)	−0.0031 (6)	−0.0036 (7)
C4	0.0198 (9)	0.0198 (10)	0.0206 (10)	0.0021 (7)	0.0022 (7)	0.0006 (8)
C5	0.0173 (9)	0.0148 (9)	0.0205 (10)	0.0012 (7)	0.0024 (7)	0.0031 (7)
C6	0.0102 (8)	0.0154 (9)	0.0205 (9)	0.0019 (7)	0.0030 (7)	−0.0002 (7)
C7	0.0175 (9)	0.0180 (9)	0.0187 (9)	0.0037 (7)	0.0005 (7)	0.0005 (7)
C8	0.0187 (9)	0.0175 (9)	0.0261 (10)	0.0035 (7)	0.0004 (7)	0.0041 (8)
C9	0.0181 (9)	0.0155 (9)	0.0274 (11)	0.0021 (7)	−0.0025 (7)	0.0038 (8)
C10	0.0176 (9)	0.0165 (9)	0.0186 (9)	0.0029 (7)	0.0005 (7)	0.0011 (7)
C11	0.0108 (8)	0.0155 (9)	0.0199 (9)	0.0038 (7)	−0.0009 (7)	0.0011 (7)
C12	0.0170 (9)	0.0163 (9)	0.0211 (10)	0.0015 (7)	0.0000 (7)	0.0027 (7)
C13	0.0203 (10)	0.0196 (10)	0.0205 (10)	0.0036 (7)	−0.0009 (7)	−0.0032 (8)
N3	0.0168 (8)	0.0157 (8)	0.0280 (9)	0.0030 (6)	0.0018 (6)	0.0001 (7)
N4	0.0172 (8)	0.0178 (8)	0.0275 (9)	0.0024 (6)	0.0006 (6)	−0.0031 (7)
C17	0.0208 (9)	0.0152 (9)	0.0264 (10)	0.0015 (7)	0.0032 (7)	0.0046 (8)
C18	0.0203 (9)	0.0185 (9)	0.0187 (10)	0.0023 (7)	0.0025 (7)	0.0027 (8)
C19	0.0112 (8)	0.0159 (9)	0.0202 (10)	0.0038 (7)	0.0013 (7)	0.0010 (7)
C20	0.0199 (9)	0.0158 (9)	0.0209 (10)	0.0023 (7)	0.0008 (7)	0.0022 (7)
C21	0.0245 (10)	0.0177 (10)	0.0188 (10)	0.0053 (7)	0.0024 (7)	−0.0022 (8)
C22	0.0182 (9)	0.0224 (10)	0.0202 (10)	0.0046 (7)	−0.0012 (7)	−0.0035 (8)
C23	0.0186 (9)	0.0181 (9)	0.0203 (10)	0.0044 (7)	−0.0010 (7)	0.0015 (8)
C24	0.0097 (8)	0.0163 (9)	0.0211 (10)	0.0019 (7)	0.0025 (7)	0.0007 (7)
C25	0.0179 (9)	0.0175 (9)	0.0180 (9)	0.0016 (7)	0.0014 (7)	0.0009 (7)
C26	0.0185 (9)	0.0158 (9)	0.0246 (10)	0.0033 (7)	0.0041 (7)	0.0037 (8)
O5	0.0229 (7)	0.0170 (7)	0.0517 (10)	0.0048 (5)	−0.0013 (6)	−0.0084 (6)
O6	0.0219 (7)	0.0146 (7)	0.0452 (9)	0.0044 (5)	−0.0014 (6)	−0.0051 (6)

Geometric parameters (Å, º)

O1—B1	1.351 (2)	C8—H8	0.9500
O1—H1'	0.8393	C9—C10	1.381 (2)
O2—B1	1.354 (2)	C9—H9	0.9500
O2—H2'	0.8412	C10—C11	1.398 (2)
C1—C3^i	1.393 (2)	C10—H10	0.9500
C1—C2	1.398 (2)	C11—C12	1.393 (2)
C1—B1	1.586 (3)	C12—C13	1.382 (2)
C2—C3	1.384 (2)	C12—H12	0.9500
C2—H2	0.9500	C13—H13	0.9500
C3—C1^i	1.393 (2)	N3—C17	1.335 (2)
C3—H3	0.9500	N3—C21	1.339 (2)
O3—B2	1.357 (2)	N4—C26	1.335 (2)
O3—H3'	0.8388	N4—C22	1.341 (2)
O4—B2	1.355 (2)	C17—C18	1.373 (2)
O4—H4'	0.8399	C17—H17	0.9500
C14—C15	1.399 (2)	C18—C19	1.398 (2)
C14—C16^ii	1.399 (2)	C18—H18	0.9500
C14—B2	1.582 (2)	C19—C20	1.390 (2)
C15—C16	1.384 (2)	C19—C24	1.488 (2)
C15—H15	0.9500	C20—C21	1.381 (2)
C16—C14^ii	1.399 (2)	C20—H20	0.9500
C16—H16	0.9500	C21—H21	0.9500
N1—C8	1.338 (2)	C22—C23	1.385 (2)
N1—C4	1.342 (2)	C22—H22	0.9500
N2—C9	1.338 (2)	C23—C24	1.393 (2)
N2—C13	1.340 (2)	C23—H23	0.9500
C4—C5	1.385 (2)	C24—C25	1.398 (2)
C4—H4	0.9500	C25—C26	1.377 (2)
C5—C6	1.389 (2)	C25—H25	0.9500
C5—H5	0.9500	C26—H26	0.9500
C6—C7	1.400 (2)	O5—H5A	0.8396
C6—C11	1.487 (2)	O5—H5B	0.8398
C7—C8	1.377 (2)	O6—H6A	0.8397
C7—H7	0.9500	O6—H6B	0.8401
B1—O1—H1'	118.2	C10—C9—H9	118.0
B1—O2—H2'	122.0	C9—C10—C11	119.55 (16)
C3^i—C1—C2	116.85 (15)	C9—C10—H10	120.2
C3^i—C1—B1	121.04 (16)	C11—C10—H10	120.2
C2—C1—B1	122.11 (15)	C12—C11—C10	116.64 (15)
C3—C2—C1	120.94 (15)	C12—C11—C6	121.70 (15)
C3—C2—H2	119.5	C10—C11—C6	121.66 (16)
C1—C2—H2	119.5	C13—C12—C11	119.66 (16)
C2—C3—C1^i	122.21 (16)	C13—C12—H12	120.2
C2—C3—H3	118.9	C11—C12—H12	120.2
C1^i—C3—H3	118.9	N2—C13—C12	123.84 (17)
O1—B1—O2	126.57 (17)	N2—C13—H13	118.1
O1—B1—C1	117.19 (16)	C12—C13—H13	118.1
O2—B1—C1	116.24 (15)	C17—N3—C21	116.73 (15)
B2—O3—H3'	119.7	C26—N4—C22	116.54 (15)
B2—O4—H4'	120.1	N3—C17—C18	123.68 (16)
C15—C14—C16^ii	116.81 (15)	N3—C17—H17	118.2
C15—C14—B2	121.57 (15)	C18—C17—H17	118.2
C16^ii—C14—B2	121.63 (15)	C17—C18—C19	119.84 (16)
C16—C15—C14	121.88 (16)	C17—C18—H18	120.1
C16—C15—H15	119.1	C19—C18—H18	120.1
C14—C15—H15	119.1	C20—C19—C18	116.55 (16)
C15—C16—C14^ii	121.31 (15)	C20—C19—C24	121.79 (16)
C15—C16—H16	119.3	C18—C19—C24	121.64 (16)
C14^ii—C16—H16	119.3	C21—C20—C19	119.68 (16)
O4—B2—O3	125.82 (16)	C21—C20—H20	120.2
O4—B2—C14	117.38 (15)	C19—C20—H20	120.2
O3—B2—C14	116.80 (15)	N3—C21—C20	123.51 (17)
C8—N1—C4	116.95 (15)	N3—C21—H21	118.2
C9—N2—C13	116.38 (15)	C20—C21—H21	118.2
N1—C4—C5	123.32 (17)	N4—C22—C23	123.53 (17)
N1—C4—H4	118.3	N4—C22—H22	118.2
C5—C4—H4	118.3	C23—C22—H22	118.2
C4—C5—C6	119.56 (16)	C22—C23—C24	119.86 (17)
C4—C5—H5	120.2	C22—C23—H23	120.1
C6—C5—H5	120.2	C24—C23—H23	120.1
C5—C6—C7	117.08 (15)	C23—C24—C25	116.30 (16)
C5—C6—C11	121.50 (16)	C23—C24—C19	121.94 (16)
C7—C6—C11	121.41 (16)	C25—C24—C19	121.76 (16)
C8—C7—C6	119.41 (16)	C26—C25—C24	119.92 (16)
C8—C7—H7	120.3	C26—C25—H25	120.0
C6—C7—H7	120.3	C24—C25—H25	120.0
N1—C8—C7	123.67 (16)	N4—C26—C25	123.86 (17)
N1—C8—H8	118.2	N4—C26—H26	118.1
C7—C8—H8	118.2	C25—C26—H26	118.1
N2—C9—C10	123.92 (16)	H5A—O5—H5B	104.8
N2—C9—H9	118.0	H6A—O6—H6B	101.5
C3^i—C1—C2—C3	0.1 (3)	C7—C6—C11—C12	−21.1 (2)
B1—C1—C2—C3	−179.60 (15)	C5—C6—C11—C10	−21.4 (2)
C1—C2—C3—C1^i	−0.1 (3)	C7—C6—C11—C10	159.62 (16)
C3^i—C1—B1—O1	176.17 (15)	C10—C11—C12—C13	0.6 (2)
C2—C1—B1—O1	−4.2 (2)	C6—C11—C12—C13	−178.72 (16)
C3^i—C1—B1—O2	−3.1 (2)	C9—N2—C13—C12	−0.2 (2)
C2—C1—B1—O2	176.57 (15)	C11—C12—C13—N2	−0.2 (3)
C16^ii—C14—C15—C16	−0.2 (3)	C21—N3—C17—C18	−0.9 (3)
B2—C14—C15—C16	179.98 (15)	N3—C17—C18—C19	1.0 (3)
C14—C15—C16—C14^ii	0.2 (3)	C17—C18—C19—C20	−0.3 (2)
C15—C14—B2—O4	−1.8 (2)	C17—C18—C19—C24	178.51 (15)
C16^ii—C14—B2—O4	178.37 (15)	C18—C19—C20—C21	−0.5 (2)
C15—C14—B2—O3	178.74 (15)	C24—C19—C20—C21	−179.27 (16)
C16^ii—C14—B2—O3	−1.0 (2)	C17—N3—C21—C20	0.1 (3)
C8—N1—C4—C5	−0.7 (2)	C19—C20—C21—N3	0.6 (3)
N1—C4—C5—C6	−0.1 (3)	C26—N4—C22—C23	0.1 (2)
C4—C5—C6—C7	0.6 (2)	N4—C22—C23—C24	0.2 (3)
C4—C5—C6—C11	−178.34 (15)	C22—C23—C24—C25	−0.1 (2)
C5—C6—C7—C8	−0.5 (2)	C22—C23—C24—C19	−179.67 (15)
C11—C6—C7—C8	178.46 (15)	C20—C19—C24—C23	164.43 (16)
C4—N1—C8—C7	0.8 (2)	C18—C19—C24—C23	−14.3 (2)
C6—C7—C8—N1	−0.2 (3)	C20—C19—C24—C25	−15.1 (2)
C13—N2—C9—C10	0.2 (2)	C18—C19—C24—C25	166.21 (16)
N2—C9—C10—C11	0.2 (3)	C23—C24—C25—C26	−0.2 (2)
C9—C10—C11—C12	−0.6 (2)	C19—C24—C25—C26	179.29 (15)
C9—C10—C11—C6	178.71 (15)	C22—N4—C26—C25	−0.5 (2)
C5—C6—C11—C12	157.82 (16)	C24—C25—C26—N4	0.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1′···N1	0.84	1.86	2.6846 (18)	168
O2—H2′···O5	0.84	1.89	2.7058 (17)	164
O3—H3′···N3	0.84	1.85	2.6753 (18)	169
O4—H4′···O6	0.84	1.93	2.7398 (16)	163
O5—H5A···O1^iii	0.84	2.12	2.9574 (18)	176
O5—H5B···N4^iv	0.84	2.01	2.8371 (19)	170
O6—H6A···O3^v	0.84	2.12	2.9533 (17)	174
O6—H6B···N2^vi	0.84	2.04	2.8591 (19)	164

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