Supramolecular inter­actions in the 2,6-bis­(benzimidazol-2-yl)pyridine–terephthalic acid–water (2/1/4) cocrystal

In the title compound, 2C₁₉H₁₃N₅·C₈H₆O₄·4H₂O, the terephthalic acid mol­ecule lies on a crystallographic inversion centre and the H atoms of one water mol­ecule exhibit disorder. The maximum deviation of any atom from the mean plane through the C and N atoms of the 2,6-bis(benzimidazol-2-yl)pyridine molecule is only 0.161 (4) Å. In the crystal structure, the water mol­ecules play an important role in linking the other mol­ecules via hydrogen bonding. The structure forms a three-dimensional framework via strong inter­molecular hydrogen bonding. In addition, there are π–π stacking inter­actions between the imidazole, pyridine and benzene rings.

S1. Comment

Supramolecular interactions such as hydrogen bonding, C—H···π interactions, π–π stacking interactions and metal–ligand coordination interactions have all been utilized in recent years to manipulate the way in which molecules are arranged in crystal structures (Desiraju, 2005; Burrows, 2004; Stephenson & Hardie, 2007). In contrast with utilizing potentially active metal centres when creating supramolecular materials, the prediction of the solid-state packing of simple organic co-crystals still remains an ongoing challenge (Dunitz, 2003; Dale et al., 2004). Organic molecules bearing hydrogen-bond donor and/or acceptor functionalities capable of participating in supramolecular synthons (Desiraju, 1995) have probably received the most interest, many using a combination of both strong and weak hydrogen-bond interactions (Steiner, 2002). Complexes of 2,6-bis(benzimidazol-2-yl)pyridine and its derivatives have been studied for more than 30 years because of their unusual coordination and magnetic properties (Boča et al., 2000). However, the structures of supramolecular complexes consisting of this ligand and other organic molecules have been reported only occasionally. Chetia & Iyer (2006) demonstrated that 2,6-bis(benzimidazol-2-yl)pyridine is an efficient receptor for binding urea with high affinity, and it forms hydrogen-bonded complexes with various metabolites of benzene, even in the presence of a competitive solvent environment, which is proof of its potential application in chemical and biological sensing (Chetia & Iyer, 2007). In order to research the superamolecular chemistry of this compound, we synthesized the title co-crystal, (I), and report its crystal structure here. This forms part of a wider study of the supramolecular structures and properties of this compound being undertaken in our research group.

The asymmetric unit of (I) consists of one 2,6-bis(benzimidazol-2-yl)pyridine molecule, half a terephthalic acid molecule on a centre of symmetry [symmetry code (-x + 1, -y + 1, -z + 1)] and two water molecules. The aromatic C—C and C—N distances in both the benzimidazole and pyridine rings are within the usual ranges, and this confirms the aromatic character of the pyridine and benzimidazole moieties. All C and N atoms of the 2,6-bis(benzimidazol-2-yl)pyridine moiety lie in a plane, with a mean deviation of 0.075 Å, and the largest deviation is 0.347 Å for atom C4. This is similar to other compounds containing 2,6-bis(benzimidazol-2-yl)pyridine and organic molecules, for example 2-[6-(1H-benzimidazol-2-yl)-2-pyridyl]-1H-benzimidazol-3-ium perchlorate monohydrate (Boča et al., 2000), 2,6-bis(benzimidazol-2-yl)pyridine urea (Chetia & Iyer, 2006) and 2,6-bis(benzimidazol-2-yl)pyridine hydroquinone (Chetia & Iyer, 2007). In contrast, the corresponding moiety in 2-(1-methyl-3-benzimidazolinium-2-yl)-6(1-methylbenzimidazol-2-yl)pyridine perchlorate is quite bent, with the planes of the benzimidazole forming dihedral angles of 30.5 and 45.3° with the pyridine ring (Petoud et al., 1997).

In the crystal structure of (I), there are many intermolecular interactions (Table 2 and Fig. 2). Each 2,6-bis(benzimidazol-2-yl)pyridine molecule traps a water molecule via a pair of N—H···O hydrogen bonds (involving atoms N1, N5 and O2W) in an R₂¹(10) motif (Bernstein et al., 1995). Two 2,6-bis(benzimidazol-2-yl)pyridine molecules are linked face-to-face by four water molecules in an R₄²(8) diamond motif via the two interactions mentioned above plus pairs of O2W—H4W···O1W and O2W—H5W···O1W hydrogen bonds via symmetry code (-x + 1, -y + 1, -z). It should be noted that the H atoms in this diamond are subject to some disorder (see Refinement). The 2,6-bis(benzimidazol-2-yl)pyridine molecules are also linked back-to-back by one terephthalic acid molecule via strong intermolecular O2—H2···N2ⁱ and C9—H9···O1ⁱ [O1···H9 = 2.23 Å and angle at H9 = 169°; symmetry code: (i) x + 1, y - 1, z] hydrogen bonds in an R₂²(9) motif, closely related to the carboxylic acid–pyridine motif, Y, described by Dale et al. (2004), but here using the closest available CH group rather than the CH adjacent to the pyridyl N atom. The diamonds of water molecules not only link to the 2,6-bis(benzimidazol-2-yl)pyridine molecules, but also to the terephthalic acid molecules via O1W—H2W···O1 hydrogen bonds. The remaining strong hydrogen-bond donors and acceptors also act as a bridge between the planes via an O1W—H1W···N4ⁱⁱ hydrogen bond [symmetry code: (ii) -x, -y + 1, -z]. The overall packing has the 2,6-bis(benzimidazol-2-yl)pyridine, the terephthalic acid and the O2W water molecules in a layer, with these layers linked via the diamonds of water molecules to give a three-dimensional hydrogen-bonded supramolecular network (Figs. 2 and 3).

In addition, there are some fairly long π–π stacking interactions between the layers at separations in the range 3.6–3.8 Å. These are between overlapping rings in the 2,6-bis(benzimidazol-2-yl)pyridine molecules, suggesting that the hydrogen bonds, via the diamonds of water molecules, predominantly dictate the interlayer separations. The centroid-to-centroid distances are Cg1···Cg2 = 3.816 (2), Cg3···Cg3 = 3.602 (2) and Cg2···Cg4 = 3.736 (2) Å, where Cg1, Cg2, Cg3 and Cg4 refer to imidazole ring N1/C1/C6/N2/C7, pyridine ring N3/C8–C12, imidazole ring N4/C13/N5/C19/C14 and phenyl ring C14–C19, respectively. The combination of hydrogen bonding and π–π stacking interactions stabilizes the whole strucutre.

Related literature

For related literature, see: Bernstein et al. (1995); Boča et al. (2000); Burrows (2004); Chetia & Iyer (2006, 2007); Dale et al. (2004); Desiraju (1995, 2005); Dunitz (2003); Petoud et al. (1997); Steiner (2002); Stephenson & Hardie (2007).

S2. Experimental

Single crystals of the title compound suitable for X-ray analysis were obtained from a mixture of 2,6-bis(benzimidazol-2-yl)pyridine (0.031 g, 0.10 mmol) in ethanol (10 ml) and terephthalic acid (0.017 g, 0.10 mmol) in ethanol (20 ml) after one week at room temperature. [Source of water in structure?]

S3. Refinement

The positions of all H atoms bonded to N or O atoms were intitially found in a difference Fourier map. The H atoms on water molecule O2W were refined, with atom H3W fully occupied and the other (H4W/H5W) disordered over two positions, with a major component of 0.55 (6). Geometric restraints were applied to both water molecules, with O—H and H···H distances restrained to 0.83 (2) and 1.35 (2) Å, respectively. All other H atoms were fixed geometrically and treated as riding on the parent C, O or N atom, with C—H = 0.93, O—H = 0.82 and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O).

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) 1 - x, 1 - y, 1 - z.]
	Fig. 2. Hydrogen-bond interactions in (I) (dashed lines). The black bonds indicate atom H5W, the minor disorder component. Terephthalic acid molecules lie on centres of symmetry at (1/2, 1/2, 1/2) for the molecule involving atom O1 [Not shown], at (1/2, 1/2, -1/2) for the unlabelled molecule at the bottom, and (?, ?, ?) [Please complete] for the molecule involving atom O1^i [Not shown]. There is also a centre of symmetry at (1/2, 1/2, 0) at the heart of the diamond of water molecules. [Symmetry code: (i) x + 1, y - 1, z. Not shown] [Most of this caption appears not to relate to this figure - please check and amend as necessary]
	Fig. 3. The three-dimensional network in the structure of (I).

2,6-bis(benzimidazol-2-yl)pyridine–terephthalic acid–water (2/1/4)

Crystal data

C19H13N5·0.5C8H6O4·2H2O	Z = 2
Mr = 430.44	F(000) = 450
Triclinic, P1	Dx = 1.374 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5040 (19) Å	Cell parameters from 25 reflections
b = 9.888 (2) Å	θ = 4–14°
c = 11.713 (2) Å	µ = 0.10 mm^−1
α = 80.19 (3)°	T = 295 K
β = 81.13 (3)°	Block, yellow
γ = 74.88 (3)°	0.25 × 0.22 × 0.18 mm
V = 1040.1 (3) Å^3

Data collection

Enraf–Nonius CAD-4 diffractometer	1926 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 25.0°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.976, Tmax = 0.983	l = 0→13
3660 measured reflections	3 standard reflections every 100 reflections
3660 independent reflections	intensity decay: none

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0819P)^2] where P = (Fo^2 + 2Fc^2)/3
3660 reflections	(Δ/σ)max < 0.001
305 parameters	Δρmax = 0.29 e Å^−3
9 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	Occ. (<1)
N1	0.1641 (2)	0.8680 (3)	0.1945 (2)	0.0591 (7)
H1	0.2028	0.8023	0.1516	0.071*
N2	−0.0078 (2)	1.0315 (3)	0.2810 (2)	0.0585 (7)
N3	−0.0278 (2)	0.8192 (3)	0.0638 (2)	0.0528 (7)
N4	−0.1258 (2)	0.6490 (3)	−0.1512 (2)	0.0592 (7)
N5	0.0903 (2)	0.6236 (3)	−0.0879 (2)	0.0558 (7)
H5	0.1540	0.6361	−0.0485	0.067*
C1	0.2364 (3)	0.9215 (4)	0.2658 (3)	0.0577 (8)
C2	0.3815 (3)	0.8940 (4)	0.2815 (3)	0.0699 (10)
H2A	0.4524	0.8256	0.2451	0.084*
C3	0.4170 (4)	0.9729 (5)	0.3540 (3)	0.0861 (13)
H3	0.5144	0.9582	0.3666	0.103*
C4	0.3089 (4)	1.0754 (5)	0.4095 (3)	0.0842 (12)
H4	0.3358	1.1278	0.4576	0.101*
C5	0.1648 (3)	1.0987 (4)	0.3933 (3)	0.0709 (10)
H5A	0.0929	1.1648	0.4313	0.085*
C6	0.1284 (3)	1.0220 (4)	0.3191 (3)	0.0594 (9)
C7	0.0218 (3)	0.9389 (3)	0.2065 (2)	0.0540 (8)
C8	−0.0829 (3)	0.9177 (4)	0.1366 (2)	0.0534 (8)
C9	−0.2281 (3)	0.9958 (3)	0.1418 (3)	0.0599 (9)
H9	−0.2634	1.0634	0.1923	0.072*
C10	−0.3174 (3)	0.9708 (4)	0.0708 (3)	0.0679 (10)
H10	−0.4147	1.0218	0.0726	0.081*
C11	−0.2645 (3)	0.8716 (4)	−0.0024 (3)	0.0602 (9)
H11	−0.3247	0.8541	−0.0509	0.072*
C12	−0.1198 (3)	0.7975 (3)	−0.0035 (2)	0.0506 (8)
C13	−0.0546 (3)	0.6907 (3)	−0.0812 (2)	0.0517 (8)
C14	−0.0198 (3)	0.5495 (3)	−0.2093 (2)	0.0549 (8)
C15	−0.0325 (3)	0.4745 (4)	−0.2952 (3)	0.0691 (10)
H15	−0.1223	0.4863	−0.3225	0.083*
C16	0.0900 (4)	0.3825 (4)	−0.3388 (3)	0.0756 (11)
H16	0.0836	0.3317	−0.3969	0.091*
C17	0.2262 (3)	0.3638 (4)	−0.2967 (3)	0.0746 (10)
H17	0.3080	0.2998	−0.3270	0.090*
C18	0.2402 (3)	0.4384 (4)	−0.2115 (3)	0.0650 (9)
H18	0.3298	0.4261	−0.1836	0.078*
C19	0.1163 (3)	0.5318 (3)	−0.1696 (2)	0.0550 (8)
O1	0.6153 (2)	0.2410 (3)	0.2946 (2)	0.0892 (9)
O2	0.7970 (2)	0.2170 (3)	0.40003 (18)	0.0715 (7)
H2	0.8460	0.1739	0.3476	0.107*
C20	0.4424 (3)	0.4649 (4)	0.4124 (3)	0.0666 (10)
H20	0.4035	0.4414	0.3523	0.080*
C21	0.5803 (3)	0.3894 (3)	0.4407 (2)	0.0538 (8)
C22	0.6370 (3)	0.4268 (4)	0.5284 (3)	0.0636 (9)
H22	0.7300	0.3782	0.5476	0.076*
C23	0.6644 (3)	0.2755 (4)	0.3714 (3)	0.0595 (9)
O1W	0.4218 (2)	0.3516 (3)	0.1293 (2)	0.0794 (8)
H1W	0.337 (2)	0.341 (5)	0.145 (3)	0.119*
H2W	0.468 (3)	0.319 (5)	0.187 (2)	0.119*
O2W	0.3381 (2)	0.6469 (4)	0.0495 (3)	0.0884 (8)
H3W	0.410 (4)	0.658 (5)	0.087 (3)	0.133*
H4W	0.392 (5)	0.645 (8)	−0.019 (2)	0.133*	0.55 (6)
H5W	0.350 (8)	0.556 (3)	0.074 (6)	0.133*	0.45 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0440 (12)	0.0550 (19)	0.0753 (16)	−0.0032 (12)	−0.0028 (12)	−0.0177 (14)
N2	0.0478 (13)	0.0590 (19)	0.0678 (16)	−0.0038 (12)	−0.0062 (12)	−0.0205 (14)
N3	0.0435 (12)	0.0507 (18)	0.0623 (14)	−0.0071 (11)	−0.0046 (11)	−0.0105 (13)
N4	0.0497 (13)	0.0615 (19)	0.0671 (15)	−0.0072 (12)	−0.0123 (12)	−0.0155 (14)
N5	0.0431 (12)	0.0577 (19)	0.0660 (15)	−0.0061 (12)	−0.0072 (11)	−0.0157 (14)
C1	0.0503 (16)	0.056 (2)	0.0692 (19)	−0.0127 (15)	−0.0151 (15)	−0.0089 (17)
C2	0.0534 (17)	0.073 (3)	0.082 (2)	−0.0043 (17)	−0.0129 (16)	−0.017 (2)
C3	0.0548 (19)	0.104 (4)	0.101 (3)	−0.016 (2)	−0.0293 (19)	−0.006 (3)
C4	0.080 (2)	0.093 (3)	0.093 (3)	−0.023 (2)	−0.036 (2)	−0.021 (2)
C5	0.0680 (19)	0.075 (3)	0.073 (2)	−0.0069 (18)	−0.0187 (17)	−0.0251 (19)
C6	0.0507 (16)	0.064 (2)	0.0632 (18)	−0.0096 (16)	−0.0099 (14)	−0.0119 (17)
C7	0.0442 (14)	0.054 (2)	0.0623 (18)	−0.0071 (14)	−0.0023 (13)	−0.0135 (16)
C8	0.0436 (14)	0.052 (2)	0.0657 (18)	−0.0107 (14)	−0.0087 (13)	−0.0101 (16)
C9	0.0481 (15)	0.055 (2)	0.075 (2)	−0.0017 (15)	−0.0016 (15)	−0.0251 (17)
C10	0.0453 (15)	0.066 (3)	0.090 (2)	0.0016 (16)	−0.0121 (16)	−0.023 (2)
C11	0.0447 (14)	0.060 (2)	0.075 (2)	−0.0013 (15)	−0.0128 (14)	−0.0180 (18)
C12	0.0471 (14)	0.045 (2)	0.0594 (17)	−0.0099 (14)	−0.0049 (13)	−0.0101 (15)
C13	0.0432 (14)	0.052 (2)	0.0583 (17)	−0.0050 (14)	−0.0078 (13)	−0.0111 (15)
C14	0.0527 (16)	0.051 (2)	0.0604 (18)	−0.0070 (14)	−0.0057 (14)	−0.0155 (16)
C15	0.0674 (19)	0.071 (3)	0.073 (2)	−0.0091 (18)	−0.0136 (17)	−0.0260 (19)
C16	0.087 (2)	0.069 (3)	0.072 (2)	−0.013 (2)	−0.0024 (19)	−0.028 (2)
C17	0.0646 (19)	0.064 (3)	0.083 (2)	0.0013 (18)	0.0101 (18)	−0.019 (2)
C18	0.0549 (17)	0.068 (3)	0.068 (2)	−0.0086 (16)	0.0016 (15)	−0.0168 (18)
C19	0.0539 (16)	0.052 (2)	0.0581 (17)	−0.0095 (15)	−0.0007 (14)	−0.0143 (16)
O1	0.0613 (13)	0.096 (2)	0.1162 (19)	0.0104 (13)	−0.0251 (13)	−0.0640 (17)
O2	0.0517 (11)	0.0745 (18)	0.0839 (15)	0.0068 (11)	−0.0104 (10)	−0.0305 (13)
C20	0.0498 (15)	0.074 (3)	0.078 (2)	0.0001 (16)	−0.0136 (15)	−0.0342 (19)
C21	0.0456 (14)	0.052 (2)	0.0621 (17)	−0.0057 (14)	0.0010 (13)	−0.0204 (16)
C22	0.0500 (16)	0.067 (3)	0.0720 (19)	0.0009 (16)	−0.0113 (15)	−0.0238 (18)
C23	0.0465 (16)	0.058 (2)	0.074 (2)	−0.0079 (15)	−0.0048 (15)	−0.0164 (18)
O1W	0.0541 (12)	0.098 (2)	0.0891 (17)	−0.0168 (13)	−0.0082 (11)	−0.0234 (15)
O2W	0.0681 (14)	0.081 (2)	0.107 (2)	−0.0019 (14)	0.0075 (13)	−0.0285 (16)

Geometric parameters (Å, º)

N1—C7	1.349 (3)	C11—C12	1.378 (4)
N1—C1	1.402 (4)	C11—H11	0.9300
N1—H1	0.8599	C12—C13	1.463 (4)
N2—C7	1.320 (4)	C14—C15	1.384 (4)
N2—C6	1.408 (3)	C14—C19	1.399 (4)
N3—C12	1.342 (3)	C15—C16	1.366 (4)
N3—C8	1.352 (4)	C15—H15	0.9300
N4—C13	1.316 (4)	C16—C17	1.411 (4)
N4—C14	1.395 (4)	C16—H16	0.9300
N5—C13	1.361 (3)	C17—C18	1.379 (5)
N5—C19	1.381 (4)	C17—H17	0.9300
N5—H5	0.8599	C18—C19	1.375 (4)
C1—C2	1.370 (4)	C18—H18	0.9300
C1—C6	1.383 (4)	O1—C23	1.209 (3)
C2—C3	1.376 (5)	O2—C23	1.311 (3)
C2—H2A	0.9300	O2—H2	0.8202
C3—C4	1.407 (5)	C20—C22^i	1.367 (4)
C3—H3	0.9300	C20—C21	1.387 (4)
C4—C5	1.366 (4)	C20—H20	0.9300
C4—H4	0.9300	C21—C22	1.374 (4)
C5—C6	1.380 (4)	C21—C23	1.486 (4)
C5—H5A	0.9300	C22—C20^i	1.367 (4)
C7—C8	1.457 (4)	C22—H22	0.9300
C8—C9	1.392 (4)	O1W—H1W	0.824 (18)
C9—C10	1.368 (4)	O1W—H2W	0.838 (18)
C9—H9	0.9300	O2W—H3W	0.911 (18)
C10—C11	1.359 (4)	O2W—H4W	0.88 (2)
C10—H10	0.9300	O2W—H5W	0.87 (2)
C7—N1—C1	106.9 (2)	N3—C12—C11	123.2 (3)
C7—N1—H1	126.5	N3—C12—C13	115.0 (2)
C1—N1—H1	126.6	C11—C12—C13	121.8 (3)
C7—N2—C6	104.5 (2)	N4—C13—N5	112.8 (3)
C12—N3—C8	117.2 (2)	N4—C13—C12	125.2 (2)
C13—N4—C14	105.0 (2)	N5—C13—C12	122.0 (2)
C13—N5—C19	107.4 (2)	C15—C14—N4	129.9 (3)
C13—N5—H5	126.3	C15—C14—C19	120.3 (3)
C19—N5—H5	126.3	N4—C14—C19	109.8 (3)
C2—C1—C6	123.1 (3)	C16—C15—C14	118.5 (3)
C2—C1—N1	131.6 (3)	C16—C15—H15	120.8
C6—C1—N1	105.2 (2)	C14—C15—H15	120.8
C1—C2—C3	116.5 (3)	C15—C16—C17	120.8 (3)
C1—C2—H2A	121.7	C15—C16—H16	119.6
C3—C2—H2A	121.7	C17—C16—H16	119.6
C2—C3—C4	121.4 (3)	C18—C17—C16	121.3 (3)
C2—C3—H3	119.3	C18—C17—H17	119.4
C4—C3—H3	119.3	C16—C17—H17	119.4
C5—C4—C3	120.6 (3)	C19—C18—C17	117.2 (3)
C5—C4—H4	119.7	C19—C18—H18	121.4
C3—C4—H4	119.7	C17—C18—H18	121.4
C4—C5—C6	118.5 (3)	C18—C19—N5	133.0 (3)
C4—C5—H5A	120.8	C18—C19—C14	122.0 (3)
C6—C5—H5A	120.8	N5—C19—C14	105.0 (2)
C5—C6—C1	119.9 (3)	C23—O2—H2	109.5
C5—C6—N2	130.1 (3)	C22^i—C20—C21	120.8 (3)
C1—C6—N2	109.9 (3)	C22^i—C20—H20	119.6
N2—C7—N1	113.4 (2)	C21—C20—H20	119.6
N2—C7—C8	125.1 (2)	C22—C21—C20	118.8 (3)
N1—C7—C8	121.3 (3)	C22—C21—C23	122.2 (2)
N3—C8—C9	122.4 (3)	C20—C21—C23	118.9 (3)
N3—C8—C7	115.1 (2)	C20^i—C22—C21	120.4 (3)
C9—C8—C7	122.5 (3)	C20^i—C22—H22	119.8
C10—C9—C8	118.3 (3)	C21—C22—H22	119.8
C10—C9—H9	120.8	O1—C23—O2	123.0 (3)
C8—C9—H9	120.8	O1—C23—C21	122.9 (3)
C11—C10—C9	120.3 (3)	O2—C23—C21	114.1 (3)
C11—C10—H10	119.9	H1W—O1W—H2W	110 (3)
C9—C10—H10	119.9	H3W—O2W—H4W	94 (2)
C10—C11—C12	118.7 (3)	H3W—O2W—H5W	95 (2)
C10—C11—H11	120.7	H4W—O2W—H5W	100 (3)
C12—C11—H11	120.7
C7—N1—C1—C2	−175.6 (4)	C10—C11—C12—C13	−179.1 (3)
C7—N1—C1—C6	1.2 (3)	C14—N4—C13—N5	−1.1 (4)
C6—C1—C2—C3	−0.3 (5)	C14—N4—C13—C12	178.8 (3)
N1—C1—C2—C3	176.0 (3)	C19—N5—C13—N4	0.7 (4)
C1—C2—C3—C4	0.5 (6)	C19—N5—C13—C12	−179.2 (3)
C2—C3—C4—C5	0.4 (6)	N3—C12—C13—N4	177.3 (3)
C3—C4—C5—C6	−1.6 (6)	C11—C12—C13—N4	−4.0 (5)
C4—C5—C6—C1	1.8 (5)	N3—C12—C13—N5	−2.8 (4)
C4—C5—C6—N2	−175.2 (3)	C11—C12—C13—N5	175.8 (3)
C2—C1—C6—C5	−0.8 (5)	C13—N4—C14—C15	−178.0 (4)
N1—C1—C6—C5	−178.0 (3)	C13—N4—C14—C19	1.1 (4)
C2—C1—C6—N2	176.7 (3)	N4—C14—C15—C16	179.7 (3)
N1—C1—C6—N2	−0.5 (4)	C19—C14—C15—C16	0.6 (5)
C7—N2—C6—C5	176.7 (4)	C14—C15—C16—C17	0.4 (6)
C7—N2—C6—C1	−0.4 (4)	C15—C16—C17—C18	−0.7 (6)
C6—N2—C7—N1	1.3 (4)	C16—C17—C18—C19	−0.1 (5)
C6—N2—C7—C8	−175.0 (3)	C17—C18—C19—N5	−178.8 (4)
C1—N1—C7—N2	−1.6 (4)	C17—C18—C19—C14	1.2 (5)
C1—N1—C7—C8	174.8 (3)	C13—N5—C19—C18	−180.0 (4)
C12—N3—C8—C9	−0.9 (5)	C13—N5—C19—C14	0.1 (3)
C12—N3—C8—C7	−179.1 (3)	C15—C14—C19—C18	−1.5 (5)
N2—C7—C8—N3	178.4 (3)	N4—C14—C19—C18	179.3 (3)
N1—C7—C8—N3	2.4 (4)	C15—C14—C19—N5	178.5 (3)
N2—C7—C8—C9	0.2 (5)	N4—C14—C19—N5	−0.7 (4)
N1—C7—C8—C9	−175.8 (3)	C22^i—C20—C21—C22	−1.0 (6)
N3—C8—C9—C10	0.4 (5)	C22^i—C20—C21—C23	−178.1 (3)
C7—C8—C9—C10	178.5 (3)	C20—C21—C22—C20^i	1.0 (6)
C8—C9—C10—C11	0.1 (5)	C23—C21—C22—C20^i	178.0 (3)
C9—C10—C11—C12	0.0 (5)	C22—C21—C23—O1	179.5 (4)
C8—N3—C12—C11	1.0 (5)	C20—C21—C23—O1	−3.5 (5)
C8—N3—C12—C13	179.6 (3)	C22—C21—C23—O2	−1.3 (5)
C10—C11—C12—N3	−0.5 (5)	C20—C21—C23—O2	175.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2W	0.86	2.14	2.985 (4)	169
N5—H5···O2W	0.86	2.27	3.125 (4)	174
O2—H2···N2^ii	0.82	1.88	2.655 (3)	157
O1W—H1W···N4^iii	0.82 (2)	1.98 (2)	2.787 (3)	167 (4)
O1W—H2W···O1	0.84 (2)	1.94 (2)	2.766 (3)	167 (4)
O2W—H5W···O1W	0.87 (2)	1.99 (3)	2.849 (5)	168 (6)
O2W—H4W···O1W^iv	0.88 (2)	2.03 (3)	2.850 (4)	155 (5)

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