Two hydrates of 2,6-bis­(1H-benzimidazol-2-yl)­pyridine

The structures of the mono- and sesquihydrates of 2,6-bis(1H-benz­imi­da­zol-2-yl)­pyridine (bbip) are reported. Phase (I), C₁₉H₁₃N₅·H₂O, has one water and one bbip mol­ecule in the asymmetric unit, while phase (II), C₁₉H₁₃N₅·1.5H₂O, has three water mol­ecules and two bbip mol­ecules in the asymmetric unit. The compounds exhibit very similar molecular geom­etries but different packing organizations, which result from intricate hydrogen-bonding schemes.

S1. Comment

During the past decade we have been performing a systematic study of the crystal structure of metal–thiosulfate compounds. By changing the size and/or the coordination sites of some accompanying N-polydentate organic ligands, it was expected that useful information about the influence they might have in the binding of the anion to the metal would be revealed. Through this strategy, we have been able to investigate a large number of thiosulfate complexes based on the most common N-bidentate ligands, including 2,2'-bipyridine (Freire et al., 1999; Baggio et al., 1997a, Baggio et al., 1997b; Freire et al., 2000a), 1,10-phenanthroline (Freire et al., 1999; Baggio et al., 1998; Freire et al., 2001; Freire et al., 2000a; Baggio et al., 1996a) and 2,9(or 4,7)-dimethyl-1,10-phenanthroline (Baggio et al., 1997c; Baggio et al., 1996b; Freire et al., 2000b).

As a natural extension of the project, we decided to include N-tridentate ligands in the compounds under study, and among other molecules deemed potentially suitable for our purposes we focused our attention and efforts on 2,6-bis(2-benzimidazolyl) pyridine (hereafter bbip), a molecule far less studied than other common N-tridentate species (terpyridine etc.). A search in the November 2002 release of the Cambridge Structural Database (CSD; Allen, 2002) showed twelve entries in which the molecule acts as a tridentate ligand and complexes with different metals, and another two in which the molecule does not coordinate, viz. hydroxy-triphenyl-tin 2,6-bis(1H-benzimidazol-2-yl)pyridine monohydrate (Kong Mun Lo et al., 1999), in which bbip acts as a neutral moiety, and 2-[6-(1H-benzimidazol-2-yl)-2-pyridyl]-1H-benzimidazol-3-ium perchlorate monohydrate (Boca et al., 2000), in which bbip acts as a singly protonated ion.

During the synthesis of a variety of bbip–thiosulfate complexes, we obtained, as unexpected by-products, well shaped crystals that were suspected to be two different hydrated phases of free bbip. The lack of bbip pure hydrates in the CSD, as well as our interest in the free molecule for comparison with those in the complexes synthesized (to be reported elsewhere), prompted us to undertake their structural study, which is reported here.

Both forms crystallize in the monoclinic space group P2₁/c, but while phase (I) contains one bbip and one hydration water molecule in each asymmetric unit (Fig. 1), phase (II) contains three hydration water and two independent bbip molecules (Fig. 2). The molecular structures do not depart from the expected structure, and they exhibit quite similar bond distances and angles (Table 1); with very few exceptions, homologous parameters in the two structures fall within one standard deviation of one another. The main differences in the molecular geometries arise from the slight rotation of the lateral wings around the C7—C8 and C12—C13 single bonds, under the strains imposed by the extensive hydrogen-bonding interactions. In both structures, all the H atoms amenable to hydrogen bonding are involved in these kinds of interactions, leading in both cases to tightly woven networks.

In (I), the only water molecule present in the structure acts as a donor of its two H atoms (accepted by the unprotonated N atoms of two different bbip molecules) and as an acceptor of those provided by the protonated amine N atoms of a third bbip unit. The water molecule thus acts as a central link for the packing interactions, which build broad two-dimensional structures parallel to the (010) plane (Table 2 and Figs. 1 and 3) at y ~0.25 and 0.75. There is, in addition, a π-stacking interaction, which provides a link between layers and which connects the benzimidazolyl group (N1/N2/C1–C7) with its (1 − x,1 − y,1 − z) centrosymmetric image. The two parallel groups are separated by ~3.4 Å, with an estimated overlap of 30% of their areas.

The packing of (II) is more complicated. There are two different types of hydrogen-bonded aggregates, each involving only one of the two independent bbip molecules present (Table 2 and Figs. 2 and 4). One molecule, bbip(A), interacts with all three water molecules to form a two-dimensional network parallel to the (100) plane at x ~0.50. The central knot is a closed loop built around a center of inversion, which involves water molecules O2W and O3W and to which bbip(A) bonds through the acceptance of one H atom from each of the water molecules H2WA and H3WB. Molecule bbip(A) also chelates with hydrogen bonds the remaining water molecule, O1W, which in turn donates one hydrogen bond to the central knot. On the other hand, molecule bbip(B) is involved in a chain structure, which evolves parallel to the [001] direction and is the result of a pure bbip···bbip interaction that is not mediated by water. Finally, the compact two-dimensional structure formed by the bbip(A) molecules and the set of parallel chains containing the bbip(B) molecules link together through water molecule O1W, which is already involved in the two-dimensional bbip(A) network and which donates its remaining hydrogen bond to the basic N4B atom. No stacking interactions could be found for the bbip(B) aggregate. In the bbip(A) aggregate, the N3A/C8A–C12A pyridyl ring exhibits a parallel overlap of ca 90% of its total area with the N1A/N2A/C1A–C7A benzimidazolyl group (x,1.5 − y,-0.5 + z), with a mean distance of ~3.30 Å between planes. In addition, the operation (1 − x,1 − y,1 − z) generates two parallel images of the N3A/N4A/N5A/C8A–C19A pyridylbenzimidazolyl group, which are separated by ~3.45 Å and exhibit a small overlap (~15%).

Comparison of (I) and (II) with other compounds containing bbip shows that the most significant differences occur again in the torsion angles around the C—C single bonds, all other parameters being almost the same. The structures presented here share with the only free neutral bbip example (Kong Mun Lo et al., 1999) a trans–trans disposition of atoms N2 and N4 with respect to atom N3 (N2—C7—C8—N3 and N3—12—C13–N4 ~180°). When chelating to a metal, the ligand reverses the orientation of the benzimidazolyl wings and the relative disposition becomes cis–cis, with the corresponding torsion angles near zero. However, when considering the relative deviations from 0 or 180°, those in the present structures appear among the largest [8.8 (3)° for (1) and 9.4 (3)° for (2a)]. These departures from planarity (probably due to hydrogen-bonding strain, as already discussed) are comparable to those in strained bbip moieties coordinated to large cations [e.g. bis(2,6-bis(Benzimidazol-2-yl)pyridine-N,N',N'')-dinitrato-cerium(iii) (Shuangxi Wang et al., 1994), where bbip exhibits a maximum torsion angle of 8.3 (2)°].

S2. Experimental

Crystals of bbip appeared as a by-product of the synthesis of different metallic bbip–thiosulfate complexes. In these attempts the ligand was dissolved in dimethylformamide, while the thiosulfate and metal salts were incorporated as aqueous solutions. On standing, small but well shaped crystals of the two differently hydrated species appeared, accompanying the main crop of crystals of the corresponding metal bbip–thiosulfate complex.

S3. Refinement

In spite of their good external appearance, the crystals were of poor diffracting power, as can be assessed by the low N_obs/N_uniq ratio, and hence the data sets were chopped at a 2θ angle of 50°. H atoms attached to C atoms were added at expected positions and treated as riding. H atoms attached to the water molecule and to the protonated N atoms in bbip were found in the final? difference Fourier map and refined with restrained N—H (0.85 Å), O—H (0.90 Å) and H···H (1.66 × O—H) distances.

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : An XP (Sheldrick, 1994) view of (I), showing the atom-numbering scheme and hydrogen-bonding interactions. Displacement ellipsoids are shown at the 50% probability level. [Symmetry codes: (i) x − 1,y,z; (ii) x,3/2 − y,1/2 + z.]
	Fig. 2. : An XP (Sheldrick, 1994) view of (II), showing the atom-numbering scheme and hydrogen-bonding interactions. Displacement ellipsoids are shown at the 50% probability level. [Symmetry codes: (i) x,3/2 − y,z − 1/2); (ii) 1 − x,1/2 + y,3/2 − z; (iii) x,3/2 − y,1/2 + z.]
	Fig. 3. : A view of the packing of (I). For clarity, neither the lateral wings of the bbip molecule nor H atoms attached to C atoms are shown.
	Fig. 4. : A view of the packing of (II). For clarity, neither the lateral wings of the bbip molecule nor the H atoms attached to C atoms are shown.

(I) 2,6-bis(2-benzimidazolyl) pyridine, hydrate

Crystal data

C19H13N5·H2O	F(000) = 688
Mr = 329.36	Dx = 1.305 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.522 (2) Å	Cell parameters from 102 reflections
b = 20.367 (3) Å	θ = 2.1–23.7°
c = 11.264 (2) Å	µ = 0.09 mm^−1
β = 103.76 (2)°	T = 293 K
V = 1676.2 (6) Å^3	Prisms, colorless
Z = 4	0.18 × 0.12 × 0.10 mm

Data collection

CCD area detector diffractometer	1660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ϕ and ω scans	h = −8→8
8338 measured reflections	k = −24→21
2924 independent reflections	l = −13→13

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: geom+difmap
wR(F^2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0454P)^2] where P = (Fo^2 + 2Fc^2)/3
2924 reflections	(Δ/σ)max = 0.007
243 parameters	Δρmax = 0.16 e Å^−3
3 restraints	Δρmin = −0.15 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.5126 (3)	0.58651 (9)	0.58909 (17)	0.0520 (5)
H1N	0.405 (2)	0.6036 (10)	0.5951 (18)	0.058 (7)*
N2	0.7812 (2)	0.57789 (9)	0.53676 (16)	0.0541 (5)
N3	0.4350 (2)	0.70397 (9)	0.47026 (16)	0.0510 (5)
N4	0.1553 (3)	0.84866 (9)	0.38475 (17)	0.0609 (6)
N5	0.1393 (3)	0.76701 (10)	0.51517 (18)	0.0541 (5)
H5N	0.154 (3)	0.7254 (10)	0.546 (2)	0.096 (10)*
C1	0.5934 (3)	0.53014 (11)	0.6436 (2)	0.0515 (6)
C2	0.5386 (4)	0.48450 (12)	0.7204 (2)	0.0671 (7)
H2	0.4284	0.4883	0.7435	0.081*
C3	0.6584 (4)	0.43353 (13)	0.7595 (2)	0.0762 (8)
H3	0.6275	0.4018	0.8105	0.091*
C4	0.8224 (4)	0.42770 (13)	0.7260 (2)	0.0774 (8)
H4	0.8979	0.3922	0.7548	0.093*
C5	0.8778 (3)	0.47273 (12)	0.6512 (2)	0.0678 (7)
H5	0.9885	0.4684	0.6288	0.081*
C6	0.7596 (3)	0.52525 (11)	0.6106 (2)	0.0534 (6)
C7	0.6293 (3)	0.61262 (11)	0.5257 (2)	0.0497 (6)
C8	0.5835 (3)	0.67270 (11)	0.45459 (19)	0.0499 (6)
C9	0.6854 (3)	0.69453 (12)	0.3744 (2)	0.0614 (7)
H9	0.7870	0.6712	0.3640	0.074*
C10	0.6314 (4)	0.75160 (13)	0.3108 (2)	0.0694 (8)
H10	0.6982	0.7678	0.2575	0.083*
C11	0.4798 (3)	0.78453 (12)	0.3257 (2)	0.0646 (7)
H11	0.4414	0.8229	0.2824	0.078*
C12	0.3846 (3)	0.75932 (11)	0.4068 (2)	0.0521 (6)
C13	0.2260 (3)	0.79217 (11)	0.4321 (2)	0.0511 (6)
C14	0.0129 (3)	0.86129 (11)	0.4408 (2)	0.0553 (6)
C15	−0.1068 (3)	0.91373 (12)	0.4284 (2)	0.0717 (8)
H15	−0.1000	0.9484	0.3758	0.086*
C16	−0.2359 (4)	0.91293 (14)	0.4962 (3)	0.0788 (8)
H16	−0.3180	0.9477	0.4891	0.095*
C17	−0.2475 (4)	0.86171 (14)	0.5752 (2)	0.0747 (8)
H17	−0.3377	0.8627	0.6191	0.090*
C18	−0.1290 (3)	0.80970 (12)	0.5902 (2)	0.0645 (7)
H18	−0.1360	0.7755	0.6437	0.077*
C19	0.0013 (3)	0.81028 (11)	0.5220 (2)	0.0517 (6)
O1W	0.1483 (2)	0.63257 (9)	0.62654 (17)	0.0635 (5)
H1WA	0.036 (3)	0.6151 (13)	0.586 (2)	0.123 (12)*
H1WB	0.149 (4)	0.6347 (12)	0.7081 (18)	0.104 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0460 (12)	0.0539 (13)	0.0579 (13)	0.0017 (10)	0.0160 (10)	−0.0051 (10)
N2	0.0499 (12)	0.0580 (13)	0.0560 (12)	0.0006 (10)	0.0157 (10)	−0.0039 (10)
N3	0.0498 (12)	0.0539 (12)	0.0519 (12)	0.0018 (9)	0.0174 (9)	−0.0026 (9)
N4	0.0634 (14)	0.0667 (13)	0.0589 (13)	0.0128 (11)	0.0272 (11)	0.0116 (10)
N5	0.0536 (13)	0.0559 (14)	0.0586 (13)	0.0038 (11)	0.0249 (10)	0.0060 (10)
C1	0.0468 (14)	0.0489 (14)	0.0561 (15)	−0.0047 (12)	0.0071 (12)	−0.0081 (12)
C2	0.0613 (17)	0.0726 (18)	0.0674 (17)	−0.0146 (14)	0.0150 (14)	−0.0023 (14)
C3	0.079 (2)	0.0661 (18)	0.078 (2)	−0.0109 (16)	0.0079 (16)	0.0112 (15)
C4	0.070 (2)	0.0676 (19)	0.089 (2)	0.0037 (15)	0.0076 (16)	0.0090 (16)
C5	0.0567 (16)	0.0699 (18)	0.0734 (18)	0.0061 (14)	0.0089 (14)	−0.0038 (15)
C6	0.0495 (15)	0.0534 (15)	0.0542 (15)	−0.0011 (12)	0.0063 (12)	−0.0072 (12)
C7	0.0457 (14)	0.0513 (14)	0.0530 (15)	−0.0014 (12)	0.0133 (12)	−0.0095 (11)
C8	0.0498 (14)	0.0541 (15)	0.0467 (14)	0.0005 (11)	0.0131 (11)	−0.0078 (11)
C9	0.0605 (16)	0.0726 (17)	0.0569 (16)	0.0085 (13)	0.0255 (13)	−0.0030 (13)
C10	0.0722 (18)	0.086 (2)	0.0612 (17)	0.0115 (15)	0.0376 (15)	0.0108 (15)
C11	0.0662 (17)	0.0777 (17)	0.0564 (16)	0.0138 (14)	0.0273 (14)	0.0171 (13)
C12	0.0516 (14)	0.0573 (15)	0.0500 (14)	0.0017 (12)	0.0172 (12)	0.0017 (12)
C13	0.0500 (14)	0.0595 (15)	0.0473 (14)	0.0034 (12)	0.0183 (11)	0.0044 (12)
C14	0.0550 (15)	0.0620 (16)	0.0524 (15)	0.0074 (12)	0.0199 (12)	0.0057 (12)
C15	0.0783 (19)	0.0753 (19)	0.0658 (18)	0.0216 (15)	0.0257 (15)	0.0111 (14)
C16	0.0735 (19)	0.088 (2)	0.080 (2)	0.0273 (15)	0.0287 (16)	0.0045 (17)
C17	0.0623 (18)	0.100 (2)	0.0674 (19)	0.0117 (16)	0.0270 (14)	0.0015 (16)
C18	0.0610 (16)	0.0759 (17)	0.0629 (17)	0.0039 (14)	0.0270 (14)	0.0050 (14)
C19	0.0486 (14)	0.0599 (15)	0.0499 (14)	−0.0008 (12)	0.0184 (11)	−0.0002 (12)
O1W	0.0593 (12)	0.0814 (13)	0.0528 (11)	−0.0129 (9)	0.0195 (9)	−0.0052 (10)

Geometric parameters (Å, º)

N1—C7	1.364 (3)	C7—C8	1.458 (3)
N1—C1	1.374 (3)	C8—C9	1.389 (3)
N1—H1N	0.896 (16)	C9—C10	1.375 (3)
N2—C7	1.325 (3)	C9—H9	0.9300
N2—C6	1.390 (3)	C10—C11	1.367 (3)
N3—C8	1.333 (2)	C10—H10	0.9300
N3—C12	1.340 (3)	C11—C12	1.387 (3)
N4—C13	1.325 (3)	C11—H11	0.9300
N4—C14	1.391 (3)	C12—C13	1.454 (3)
N5—C13	1.361 (3)	C14—C15	1.382 (3)
N5—C19	1.378 (3)	C14—C19	1.400 (3)
N5—H5N	0.912 (19)	C15—C16	1.371 (3)
C1—C6	1.390 (3)	C15—H15	0.9300
C1—C2	1.397 (3)	C16—C17	1.387 (3)
C2—C3	1.376 (3)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.369 (3)
C3—C4	1.378 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.382 (3)
C4—C5	1.375 (3)	C18—H18	0.9300
C4—H4	0.9300	O1W—H1WA	0.93 (2)
C5—C6	1.397 (3)	O1W—H1WB	0.919 (19)
C5—H5	0.9300
C7—N1—C1	106.77 (19)	C10—C9—H9	121.0
C7—N1—H1N	126.3 (13)	C8—C9—H9	121.0
C1—N1—H1N	126.9 (13)	C11—C10—C9	120.1 (2)
C7—N2—C6	104.30 (18)	C11—C10—H10	119.9
C8—N3—C12	118.08 (18)	C9—C10—H10	119.9
C13—N4—C14	104.86 (18)	C10—C11—C12	118.4 (2)
C13—N5—C19	106.73 (19)	C10—C11—H11	120.8
C13—N5—H5N	125.1 (16)	C12—C11—H11	120.8
C19—N5—H5N	126.8 (16)	N3—C12—C11	122.5 (2)
N1—C1—C6	105.7 (2)	N3—C12—C13	115.06 (19)
N1—C1—C2	132.0 (2)	C11—C12—C13	122.4 (2)
C6—C1—C2	122.3 (2)	N4—C13—N5	113.04 (19)
C3—C2—C1	115.7 (2)	N4—C13—C12	126.2 (2)
C3—C2—H2	122.2	N5—C13—C12	120.7 (2)
C1—C2—H2	122.2	C15—C14—N4	130.6 (2)
C2—C3—C4	122.5 (3)	C15—C14—C19	120.0 (2)
C2—C3—H3	118.7	N4—C14—C19	109.47 (19)
C4—C3—H3	118.7	C16—C15—C14	117.7 (2)
C5—C4—C3	122.1 (3)	C16—C15—H15	121.2
C5—C4—H4	118.9	C14—C15—H15	121.2
C3—C4—H4	118.9	C15—C16—C17	121.8 (2)
C4—C5—C6	116.7 (2)	C15—C16—H16	119.1
C4—C5—H5	121.7	C17—C16—H16	119.1
C6—C5—H5	121.7	C18—C17—C16	121.5 (2)
N2—C6—C1	110.2 (2)	C18—C17—H17	119.2
N2—C6—C5	129.1 (2)	C16—C17—H17	119.2
C1—C6—C5	120.7 (2)	C17—C18—C19	116.9 (2)
N2—C7—N1	113.0 (2)	C17—C18—H18	121.6
N2—C7—C8	125.8 (2)	C19—C18—H18	121.6
N1—C7—C8	121.2 (2)	N5—C19—C18	132.0 (2)
N3—C8—C9	122.8 (2)	N5—C19—C14	105.90 (19)
N3—C8—C7	115.06 (19)	C18—C19—C14	122.1 (2)
C9—C8—C7	122.1 (2)	H1WA—O1W—H1WB	106.9 (18)
C10—C9—C8	118.0 (2)
C7—N1—C1—C6	0.6 (2)	C9—C10—C11—C12	0.7 (4)
C7—N1—C1—C2	178.7 (2)	C8—N3—C12—C11	0.5 (3)
N1—C1—C2—C3	−179.1 (2)	C8—N3—C12—C13	−177.63 (19)
C6—C1—C2—C3	−1.2 (3)	C10—C11—C12—N3	−0.4 (4)
C1—C2—C3—C4	0.3 (4)	C10—C11—C12—C13	177.6 (2)
C2—C3—C4—C5	0.2 (4)	C14—N4—C13—N5	0.1 (3)
C3—C4—C5—C6	0.2 (4)	C14—N4—C13—C12	−177.0 (2)
C7—N2—C6—C1	−0.6 (2)	C19—N5—C13—N4	0.2 (3)
C7—N2—C6—C5	179.4 (2)	C19—N5—C13—C12	177.5 (2)
N1—C1—C6—N2	0.0 (2)	N3—C12—C13—N4	177.1 (2)
C2—C1—C6—N2	−178.3 (2)	C11—C12—C13—N4	−1.0 (4)
N1—C1—C6—C5	−180.0 (2)	N3—C12—C13—N5	0.2 (3)
C2—C1—C6—C5	1.7 (3)	C11—C12—C13—N5	−178.0 (2)
C4—C5—C6—N2	178.9 (2)	C13—N4—C14—C15	178.9 (3)
C4—C5—C6—C1	−1.1 (3)	C13—N4—C14—C19	−0.4 (3)
C6—N2—C7—N1	1.0 (2)	N4—C14—C15—C16	179.9 (3)
C6—N2—C7—C8	−178.9 (2)	C19—C14—C15—C16	−1.0 (4)
C1—N1—C7—N2	−1.0 (2)	C14—C15—C16—C17	0.2 (4)
C1—N1—C7—C8	178.87 (19)	C15—C16—C17—C18	0.6 (4)
C12—N3—C8—C9	−1.0 (3)	C16—C17—C18—C19	−0.6 (4)
C12—N3—C8—C7	−179.51 (18)	C13—N5—C19—C18	179.8 (2)
N2—C7—C8—N3	−171.2 (2)	C13—N5—C19—C14	−0.5 (2)
N1—C7—C8—N3	8.9 (3)	C17—C18—C19—N5	179.6 (2)
N2—C7—C8—C9	10.3 (3)	C17—C18—C19—C14	−0.2 (4)
N1—C7—C8—C9	−169.6 (2)	C15—C14—C19—N5	−178.8 (2)
N3—C8—C9—C10	1.3 (4)	N4—C14—C19—N5	0.5 (3)
C7—C8—C9—C10	179.7 (2)	C15—C14—C19—C18	1.0 (4)
C8—C9—C10—C11	−1.1 (4)	N4—C14—C19—C18	−179.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1W	0.90 (2)	2.13 (2)	3.019 (3)	172 (2)
N5—H5N···O1W	0.91 (2)	2.10 (2)	3.006 (3)	170 (2)
O1W—H1WB···N4^i	0.92 (2)	2.01 (2)	2.922 (3)	173 (2)
O1W—H1WA···N2^ii	0.93 (2)	2.01 (2)	2.926 (3)	167 (2)

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

(II) 2,6-bis(2-benzimidazolyl) pyridine, 1.5 hydrate

Crystal data

C19H13N5·1.5H2O	F(000) = 1416
Mr = 338.37	Dx = 1.300 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.813 (2) Å	Cell parameters from 154 reflections
b = 18.417 (2) Å	θ = 3.1–24.5°
c = 10.322 (2) Å	µ = 0.09 mm^−1
β = 104.81 (2)°	T = 293 K
V = 3457.5 (8) Å^3	Prisms, colorless
Z = 8	0.16 × 0.10 × 0.08 mm

Data collection

CCD area detector diffractometer	2514 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 25.0°, θmin = 1.6°
ϕ and ω scans	h = −21→22
17546 measured reflections	k = −21→18
6086 independent reflections	l = −12→12

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)] = 0.046	Hydrogen site location: geom+difmap
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0202P)^2] where P = (Fo^2 + 2Fc^2)/3
6086 reflections	(Δ/σ)max = 0.010
501 parameters	Δρmax = 0.16 e Å^−3
9 restraints	Δρmin = −0.16 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.30995 (14)	0.72072 (15)	0.2107 (3)	0.0474 (7)
H1NA	0.3083 (15)	0.6699 (10)	0.202 (3)	0.069 (11)*
N2A	0.34517 (14)	0.82498 (13)	0.3208 (3)	0.0492 (7)
N3A	0.38671 (13)	0.63784 (13)	0.4176 (2)	0.0458 (7)
N4A	0.42533 (13)	0.46588 (14)	0.5866 (3)	0.0510 (7)
N5A	0.36874 (15)	0.49305 (16)	0.3743 (3)	0.0523 (8)
H5NA	0.3517 (16)	0.5179 (15)	0.300 (2)	0.083 (14)*
C1A	0.27481 (18)	0.77491 (18)	0.1273 (3)	0.0480 (8)
C2A	0.22814 (17)	0.77360 (18)	0.0006 (3)	0.0577 (9)
H2A	0.2138	0.7301	−0.0442	0.069*
C3A	0.20347 (18)	0.8394 (2)	−0.0570 (3)	0.0660 (10)
H3A	0.1720	0.8406	−0.1427	0.079*
C4A	0.22502 (19)	0.90444 (19)	0.0116 (4)	0.0673 (11)
H4A	0.2076	0.9482	−0.0293	0.081*
C5A	0.27151 (18)	0.90497 (17)	0.1383 (4)	0.0617 (10)
H5A	0.2855	0.9484	0.1836	0.074*
C6A	0.29696 (17)	0.83915 (18)	0.1967 (4)	0.0494 (9)
C7A	0.35102 (17)	0.75324 (17)	0.3239 (3)	0.0439 (8)
C8A	0.39467 (16)	0.70999 (17)	0.4347 (3)	0.0439 (8)
C9A	0.43865 (17)	0.74057 (17)	0.5495 (3)	0.0529 (9)
H9A	0.4443	0.7907	0.5573	0.064*
C10A	0.47390 (16)	0.69581 (17)	0.6520 (3)	0.0576 (10)
H10A	0.5040	0.7153	0.7300	0.069*
C11A	0.46443 (16)	0.62138 (17)	0.6384 (3)	0.0508 (9)
H11A	0.4868	0.5899	0.7072	0.061*
C12A	0.42064 (16)	0.59552 (16)	0.5191 (3)	0.0427 (8)
C13A	0.40619 (16)	0.51745 (17)	0.4960 (3)	0.0433 (8)
C14A	0.39762 (18)	0.40288 (17)	0.5167 (4)	0.0522 (9)
C15A	0.40093 (19)	0.33182 (19)	0.5640 (4)	0.0745 (12)
H15A	0.4232	0.3206	0.6529	0.089*
C16A	0.3699 (2)	0.2793 (2)	0.4736 (5)	0.0906 (14)
H16A	0.3712	0.2312	0.5019	0.109*
C17A	0.3367 (2)	0.2957 (2)	0.3416 (5)	0.0910 (15)
H17A	0.3167	0.2583	0.2832	0.109*
C18A	0.33213 (18)	0.3659 (2)	0.2934 (4)	0.0746 (12)
H18A	0.3098	0.3768	0.2043	0.090*
C19A	0.36268 (17)	0.41893 (18)	0.3852 (4)	0.0538 (9)
N1B	−0.10238 (14)	0.76643 (14)	−0.1618 (3)	0.0447 (7)
H1NB	−0.0923 (14)	0.7419 (13)	−0.084 (2)	0.057 (10)*
N2B	−0.08517 (13)	0.80534 (12)	−0.3568 (2)	0.0489 (7)
N3B	0.01568 (12)	0.67573 (12)	−0.1174 (2)	0.0410 (6)
N4B	0.13112 (13)	0.53523 (13)	0.0697 (2)	0.0503 (7)
N5B	0.02814 (15)	0.58651 (14)	0.0956 (3)	0.0459 (7)
H5NB	−0.0071 (13)	0.6203 (11)	0.084 (3)	0.057 (10)*
C1B	−0.15837 (16)	0.81467 (15)	−0.2106 (3)	0.0415 (8)
C2B	−0.21672 (16)	0.83849 (16)	−0.1628 (3)	0.0523 (9)
H2B	−0.2243	0.8215	−0.0826	0.063*
C3B	−0.26274 (18)	0.88858 (16)	−0.2405 (4)	0.0615 (10)
H3B	−0.3023	0.9062	−0.2114	0.074*
C4B	−0.25232 (19)	0.91385 (17)	−0.3608 (4)	0.0708 (11)
H4B	−0.2848	0.9478	−0.4101	0.085*
C5B	−0.19484 (18)	0.88942 (16)	−0.4080 (3)	0.0637 (10)
H5B	−0.1878	0.9064	−0.4886	0.076*
C6B	−0.14752 (17)	0.83865 (15)	−0.3323 (3)	0.0464 (8)
C7B	−0.06129 (16)	0.76286 (15)	−0.2522 (3)	0.0415 (8)
C8B	0.00376 (16)	0.71590 (15)	−0.2282 (3)	0.0411 (8)
C9B	0.04738 (16)	0.71263 (15)	−0.3180 (3)	0.0529 (9)
H9B	0.0378	0.7420	−0.3938	0.063*
C10B	0.10536 (17)	0.66453 (17)	−0.2914 (3)	0.0570 (9)
H10B	0.1361	0.6614	−0.3489	0.068*
C11B	0.11774 (16)	0.62090 (16)	−0.1788 (3)	0.0526 (9)
H11B	0.1558	0.5872	−0.1605	0.063*
C12B	0.07186 (16)	0.62881 (15)	−0.0942 (3)	0.0416 (8)
C13B	0.07954 (17)	0.58350 (15)	0.0238 (3)	0.0428 (8)
C14B	0.11148 (17)	0.50421 (16)	0.1785 (3)	0.0454 (8)
C15B	0.14423 (18)	0.44798 (16)	0.2628 (4)	0.0653 (10)
H15B	0.1866	0.4255	0.2522	0.078*
C16B	0.1121 (2)	0.42672 (18)	0.3620 (4)	0.0736 (11)
H16B	0.1333	0.3895	0.4200	0.088*
C17B	0.0481 (2)	0.46005 (18)	0.3774 (3)	0.0710 (11)
H17B	0.0275	0.4443	0.4453	0.085*
C18B	0.01501 (19)	0.51516 (16)	0.2955 (3)	0.0614 (10)
H18B	−0.0274	0.5375	0.3064	0.074*
C19B	0.04727 (17)	0.53597 (16)	0.1961 (3)	0.0452 (8)
O1W	0.28800 (16)	0.56690 (13)	0.1324 (2)	0.0625 (7)
H1WA	0.3135 (16)	0.5598 (17)	0.071 (3)	0.112 (16)*
H1WB	0.2410 (12)	0.554 (2)	0.097 (4)	0.17 (2)*
O2W	0.38881 (16)	0.94776 (13)	0.4815 (3)	0.0664 (7)
H2WA	0.3774 (17)	0.9079 (13)	0.433 (3)	0.105 (16)*
H2WB	0.4337 (15)	0.949 (2)	0.533 (4)	0.22 (3)*
O3W	0.46666 (18)	0.44497 (16)	0.8636 (3)	0.0970 (9)
H3WA	0.461 (2)	0.4543 (19)	0.778 (2)	0.124 (19)*
H3WB	0.442 (3)	0.474 (2)	0.905 (4)	0.25 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0539 (19)	0.0426 (18)	0.0510 (19)	0.0000 (16)	0.0230 (15)	0.0001 (17)
N2A	0.0549 (19)	0.0400 (17)	0.057 (2)	−0.0045 (15)	0.0222 (16)	−0.0046 (15)
N3A	0.0456 (18)	0.0427 (17)	0.0530 (19)	−0.0004 (14)	0.0196 (15)	−0.0008 (14)
N4A	0.0544 (18)	0.0488 (17)	0.0524 (19)	0.0080 (15)	0.0183 (15)	0.0059 (15)
N5A	0.0512 (19)	0.051 (2)	0.051 (2)	0.0061 (16)	0.0070 (17)	−0.0022 (18)
C1A	0.049 (2)	0.053 (2)	0.048 (2)	0.0049 (19)	0.0231 (19)	0.005 (2)
C2A	0.058 (2)	0.063 (2)	0.057 (3)	0.004 (2)	0.024 (2)	0.003 (2)
C3A	0.057 (2)	0.085 (3)	0.058 (3)	0.017 (2)	0.020 (2)	0.016 (2)
C4A	0.060 (3)	0.068 (3)	0.080 (3)	0.016 (2)	0.030 (2)	0.023 (2)
C5A	0.059 (3)	0.053 (2)	0.079 (3)	0.000 (2)	0.030 (2)	0.007 (2)
C6A	0.046 (2)	0.046 (2)	0.063 (3)	−0.0005 (19)	0.0265 (19)	0.004 (2)
C7A	0.042 (2)	0.049 (2)	0.044 (2)	−0.0041 (18)	0.0188 (17)	−0.0026 (18)
C8A	0.043 (2)	0.052 (2)	0.040 (2)	−0.0026 (18)	0.0161 (17)	−0.0024 (18)
C9A	0.051 (2)	0.049 (2)	0.060 (2)	−0.0032 (18)	0.0169 (19)	−0.0026 (19)
C10A	0.049 (2)	0.063 (2)	0.059 (3)	−0.007 (2)	0.0101 (19)	−0.014 (2)
C11A	0.045 (2)	0.060 (2)	0.047 (2)	0.0034 (18)	0.0112 (18)	−0.0015 (19)
C12A	0.040 (2)	0.049 (2)	0.042 (2)	0.0074 (17)	0.0162 (17)	−0.0016 (18)
C13A	0.040 (2)	0.047 (2)	0.043 (2)	0.0032 (17)	0.0115 (17)	−0.0040 (18)
C14A	0.049 (2)	0.041 (2)	0.072 (3)	0.0036 (18)	0.027 (2)	−0.005 (2)
C15A	0.082 (3)	0.052 (2)	0.099 (3)	0.005 (2)	0.041 (3)	0.004 (2)
C16A	0.086 (4)	0.052 (3)	0.143 (5)	0.004 (3)	0.047 (3)	−0.001 (3)
C17A	0.060 (3)	0.061 (3)	0.147 (5)	−0.010 (2)	0.018 (3)	−0.030 (3)
C18A	0.051 (3)	0.068 (3)	0.094 (3)	0.007 (2)	0.000 (2)	−0.025 (3)
C19A	0.043 (2)	0.049 (2)	0.070 (3)	0.0025 (19)	0.015 (2)	−0.009 (2)
N1B	0.0435 (17)	0.0537 (18)	0.0399 (18)	0.0033 (14)	0.0165 (15)	0.0058 (15)
N2B	0.0468 (17)	0.0524 (17)	0.0514 (18)	0.0016 (14)	0.0199 (15)	0.0113 (14)
N3B	0.0382 (16)	0.0471 (16)	0.0399 (17)	−0.0016 (13)	0.0142 (13)	0.0011 (13)
N4B	0.0454 (18)	0.0560 (17)	0.0497 (19)	0.0121 (15)	0.0126 (15)	0.0028 (14)
N5B	0.0452 (18)	0.0474 (18)	0.0485 (19)	0.0116 (15)	0.0183 (15)	0.0065 (14)
C1B	0.038 (2)	0.0379 (19)	0.050 (2)	−0.0001 (16)	0.0146 (17)	−0.0033 (16)
C2B	0.044 (2)	0.056 (2)	0.060 (2)	−0.0034 (18)	0.0201 (19)	−0.0078 (18)
C3B	0.049 (2)	0.050 (2)	0.088 (3)	0.0077 (19)	0.023 (2)	−0.005 (2)
C4B	0.058 (3)	0.059 (2)	0.100 (3)	0.0172 (19)	0.028 (2)	0.025 (2)
C5B	0.059 (3)	0.063 (2)	0.073 (3)	0.010 (2)	0.023 (2)	0.023 (2)
C6B	0.043 (2)	0.044 (2)	0.053 (2)	0.0026 (17)	0.0145 (18)	0.0105 (17)
C7B	0.039 (2)	0.046 (2)	0.043 (2)	−0.0030 (16)	0.0172 (17)	0.0026 (16)
C8B	0.036 (2)	0.047 (2)	0.043 (2)	−0.0009 (16)	0.0157 (16)	0.0013 (16)
C9B	0.049 (2)	0.064 (2)	0.050 (2)	−0.0006 (19)	0.0198 (19)	0.0090 (18)
C10B	0.046 (2)	0.076 (2)	0.057 (2)	0.002 (2)	0.0271 (19)	0.001 (2)
C11B	0.047 (2)	0.062 (2)	0.053 (2)	0.0128 (18)	0.0211 (19)	0.0038 (18)
C12B	0.040 (2)	0.045 (2)	0.041 (2)	−0.0008 (16)	0.0138 (17)	−0.0020 (16)
C13B	0.044 (2)	0.047 (2)	0.040 (2)	−0.0011 (17)	0.0164 (17)	−0.0062 (17)
C14B	0.046 (2)	0.042 (2)	0.043 (2)	0.0055 (17)	0.0030 (17)	−0.0016 (17)
C15B	0.063 (3)	0.057 (2)	0.070 (3)	0.013 (2)	0.005 (2)	0.005 (2)
C16B	0.095 (3)	0.061 (3)	0.054 (3)	−0.003 (2)	−0.003 (2)	0.013 (2)
C17B	0.090 (3)	0.071 (3)	0.053 (3)	−0.010 (2)	0.021 (2)	0.007 (2)
C18B	0.074 (3)	0.056 (2)	0.056 (3)	0.004 (2)	0.021 (2)	0.0075 (19)
C19B	0.050 (2)	0.048 (2)	0.038 (2)	0.0002 (17)	0.0110 (17)	0.0040 (17)
O1W	0.0543 (17)	0.0759 (17)	0.0548 (17)	−0.0043 (15)	0.0097 (15)	−0.0097 (13)
O2W	0.066 (2)	0.0614 (18)	0.071 (2)	−0.0071 (14)	0.0160 (15)	−0.0119 (15)
O3W	0.111 (3)	0.114 (2)	0.059 (2)	0.0121 (19)	0.0085 (19)	−0.004 (2)

Geometric parameters (Å, º)

N1A—C7A	1.363 (3)	N2B—C7B	1.316 (3)
N1A—C1A	1.372 (4)	N2B—C6B	1.403 (3)
N1A—H1NA	0.939 (18)	N3B—C8B	1.332 (3)
N2A—C7A	1.325 (3)	N3B—C12B	1.339 (3)
N2A—C6A	1.392 (4)	N4B—C13B	1.312 (3)
N3A—C12A	1.331 (3)	N4B—C14B	1.392 (3)
N3A—C8A	1.344 (3)	N5B—C13B	1.361 (3)
N4A—C13A	1.317 (3)	N5B—C19B	1.371 (3)
N4A—C14A	1.395 (3)	N5B—H5NB	0.895 (17)
N5A—C13A	1.351 (4)	C1B—C2B	1.385 (3)
N5A—C19A	1.377 (4)	C1B—C6B	1.395 (3)
N5A—H5NA	0.876 (19)	C2B—C3B	1.374 (4)
C1A—C2A	1.376 (4)	C2B—H2B	0.9300
C1A—C6A	1.391 (4)	C3B—C4B	1.385 (4)
C2A—C3A	1.377 (4)	C3B—H3B	0.9300
C2A—H2A	0.9300	C4B—C5B	1.371 (4)
C3A—C4A	1.397 (4)	C4B—H4B	0.9300
C3A—H3A	0.9300	C5B—C6B	1.386 (4)
C4A—C5A	1.375 (4)	C5B—H5B	0.9300
C4A—H4A	0.9300	C7B—C8B	1.467 (3)
C5A—C6A	1.384 (4)	C8B—C9B	1.387 (3)
C5A—H5A	0.9300	C9B—C10B	1.377 (3)
C7A—C8A	1.462 (4)	C9B—H9B	0.9300
C8A—C9A	1.380 (4)	C10B—C11B	1.382 (3)
C9A—C10A	1.371 (4)	C10B—H10B	0.9300
C9A—H9A	0.9300	C11B—C12B	1.384 (3)
C10A—C11A	1.385 (3)	C11B—H11B	0.9300
C10A—H10A	0.9300	C12B—C13B	1.453 (4)
C11A—C12A	1.379 (4)	C14B—C15B	1.391 (4)
C11A—H11A	0.9300	C14B—C19B	1.395 (3)
C12A—C13A	1.471 (4)	C15B—C16B	1.373 (4)
C14A—C19A	1.380 (4)	C15B—H15B	0.9300
C14A—C15A	1.393 (4)	C16B—C17B	1.396 (4)
C15A—C16A	1.367 (5)	C16B—H16B	0.9300
C15A—H15A	0.9300	C17B—C18B	1.365 (4)
C16A—C17A	1.380 (5)	C17B—H17B	0.9300
C16A—H16A	0.9300	C18B—C19B	1.373 (4)
C17A—C18A	1.379 (4)	C18B—H18B	0.9300
C17A—H17A	0.9300	O1W—H1WA	0.90 (2)
C18A—C19A	1.380 (4)	O1W—H1WB	0.90 (2)
C18A—H18A	0.9300	O2W—H2WA	0.88 (2)
N1B—C7B	1.357 (3)	O2W—H2WB	0.87 (2)
N1B—C1B	1.372 (3)	O3W—H3WA	0.88 (2)
N1B—H1NB	0.901 (17)	O3W—H3WB	0.89 (5)
C7A—N1A—C1A	107.1 (3)	C1B—N1B—H1NB	128.3 (17)
C7A—N1A—H1NA	121.1 (18)	C7B—N2B—C6B	103.8 (2)
C1A—N1A—H1NA	131.7 (18)	C8B—N3B—C12B	117.6 (2)
C7A—N2A—C6A	103.8 (3)	C13B—N4B—C14B	104.2 (2)
C12A—N3A—C8A	117.4 (3)	C13B—N5B—C19B	107.4 (3)
C13A—N4A—C14A	103.6 (3)	C13B—N5B—H5NB	124.1 (17)
C13A—N5A—C19A	106.7 (3)	C19B—N5B—H5NB	128.0 (17)
C13A—N5A—H5NA	129 (2)	N1B—C1B—C2B	132.8 (3)
C19A—N5A—H5NA	125 (2)	N1B—C1B—C6B	105.1 (3)
N1A—C1A—C2A	132.2 (3)	C2B—C1B—C6B	122.1 (3)
N1A—C1A—C6A	105.2 (3)	C3B—C2B—C1B	116.3 (3)
C2A—C1A—C6A	122.6 (3)	C3B—C2B—H2B	121.8
C1A—C2A—C3A	117.2 (3)	C1B—C2B—H2B	121.8
C1A—C2A—H2A	121.4	C2B—C3B—C4B	122.4 (3)
C3A—C2A—H2A	121.4	C2B—C3B—H3B	118.8
C2A—C3A—C4A	120.9 (3)	C4B—C3B—H3B	118.8
C2A—C3A—H3A	119.6	C5B—C4B—C3B	120.9 (3)
C4A—C3A—H3A	119.6	C5B—C4B—H4B	119.6
C5A—C4A—C3A	121.3 (3)	C3B—C4B—H4B	119.6
C5A—C4A—H4A	119.4	C4B—C5B—C6B	118.2 (3)
C3A—C4A—H4A	119.4	C4B—C5B—H5B	120.9
C4A—C5A—C6A	118.2 (3)	C6B—C5B—H5B	120.9
C4A—C5A—H5A	120.9	C5B—C6B—C1B	120.0 (3)
C6A—C5A—H5A	120.9	C5B—C6B—N2B	129.8 (3)
C5A—C6A—C1A	119.7 (3)	C1B—C6B—N2B	110.2 (3)
C5A—C6A—N2A	129.5 (3)	N2B—C7B—N1B	113.6 (3)
C1A—C6A—N2A	110.7 (3)	N2B—C7B—C8B	125.8 (3)
N2A—C7A—N1A	113.1 (3)	N1B—C7B—C8B	120.6 (3)
N2A—C7A—C8A	126.0 (3)	N3B—C8B—C9B	123.4 (3)
N1A—C7A—C8A	120.9 (3)	N3B—C8B—C7B	115.0 (3)
N3A—C8A—C9A	122.6 (3)	C9B—C8B—C7B	121.5 (3)
N3A—C8A—C7A	114.5 (3)	C10B—C9B—C8B	117.9 (3)
C9A—C8A—C7A	122.9 (3)	C10B—C9B—H9B	121.0
C10A—C9A—C8A	118.8 (3)	C8B—C9B—H9B	121.0
C10A—C9A—H9A	120.6	C9B—C10B—C11B	119.8 (3)
C8A—C9A—H9A	120.6	C9B—C10B—H10B	120.1
C9A—C10A—C11A	119.5 (3)	C11B—C10B—H10B	120.1
C9A—C10A—H10A	120.2	C10B—C11B—C12B	118.1 (3)
C11A—C10A—H10A	120.2	C10B—C11B—H11B	121.0
C12A—C11A—C10A	117.7 (3)	C12B—C11B—H11B	121.0
C12A—C11A—H11A	121.2	N3B—C12B—C11B	123.1 (3)
C10A—C11A—H11A	121.2	N3B—C12B—C13B	115.2 (3)
N3A—C12A—C11A	123.9 (3)	C11B—C12B—C13B	121.6 (3)
N3A—C12A—C13A	114.4 (3)	N4B—C13B—N5B	113.2 (3)
C11A—C12A—C13A	121.7 (3)	N4B—C13B—C12B	126.7 (3)
N4A—C13A—N5A	113.8 (3)	N5B—C13B—C12B	120.1 (3)
N4A—C13A—C12A	125.8 (3)	C15B—C14B—N4B	130.1 (3)
N5A—C13A—C12A	120.4 (3)	C15B—C14B—C19B	119.4 (3)
C19A—C14A—C15A	120.9 (4)	N4B—C14B—C19B	110.5 (3)
C19A—C14A—N4A	110.6 (3)	C16B—C15B—C14B	118.0 (3)
C15A—C14A—N4A	128.5 (4)	C16B—C15B—H15B	121.0
C16A—C15A—C14A	116.9 (4)	C14B—C15B—H15B	121.0
C16A—C15A—H15A	121.5	C15B—C16B—C17B	121.1 (3)
C14A—C15A—H15A	121.5	C15B—C16B—H16B	119.5
C15A—C16A—C17A	121.7 (4)	C17B—C16B—H16B	119.5
C15A—C16A—H16A	119.2	C18B—C17B—C16B	121.8 (3)
C17A—C16A—H16A	119.2	C18B—C17B—H17B	119.1
C18A—C17A—C16A	122.2 (4)	C16B—C17B—H17B	119.1
C18A—C17A—H17A	118.9	C17B—C18B—C19B	116.8 (3)
C16A—C17A—H17A	118.9	C17B—C18B—H18B	121.6
C17A—C18A—C19A	116.0 (4)	C19B—C18B—H18B	121.6
C17A—C18A—H18A	122.0	N5B—C19B—C18B	132.3 (3)
C19A—C18A—H18A	122.0	N5B—C19B—C14B	104.8 (3)
N5A—C19A—C18A	132.4 (4)	C18B—C19B—C14B	122.9 (3)
N5A—C19A—C14A	105.3 (3)	H1WA—O1W—H1WB	109 (2)
C18A—C19A—C14A	122.2 (3)	H2WA—O2W—H2WB	114 (3)
C7B—N1B—C1B	107.3 (3)	H3WA—O3W—H3WB	115 (3)
C7B—N1B—H1NB	124.3 (17)
C7A—N1A—C1A—C2A	178.6 (3)	C7B—N1B—C1B—C2B	178.8 (3)
C7A—N1A—C1A—C6A	−0.2 (3)	C7B—N1B—C1B—C6B	−0.2 (3)
N1A—C1A—C2A—C3A	−178.5 (3)	N1B—C1B—C2B—C3B	179.8 (3)
C6A—C1A—C2A—C3A	0.1 (5)	C6B—C1B—C2B—C3B	−1.5 (4)
C1A—C2A—C3A—C4A	−0.3 (5)	C1B—C2B—C3B—C4B	0.5 (5)
C2A—C3A—C4A—C5A	0.1 (5)	C2B—C3B—C4B—C5B	0.1 (5)
C3A—C4A—C5A—C6A	0.3 (5)	C3B—C4B—C5B—C6B	0.1 (5)
C4A—C5A—C6A—C1A	−0.5 (4)	C4B—C5B—C6B—C1B	−1.0 (5)
C4A—C5A—C6A—N2A	178.4 (3)	C4B—C5B—C6B—N2B	−179.8 (3)
N1A—C1A—C6A—C5A	179.2 (3)	N1B—C1B—C6B—C5B	−179.2 (3)
C2A—C1A—C6A—C5A	0.3 (5)	C2B—C1B—C6B—C5B	1.7 (5)
N1A—C1A—C6A—N2A	0.2 (3)	N1B—C1B—C6B—N2B	−0.2 (3)
C2A—C1A—C6A—N2A	−178.8 (3)	C2B—C1B—C6B—N2B	−179.3 (2)
C7A—N2A—C6A—C5A	−179.0 (3)	C7B—N2B—C6B—C5B	179.3 (3)
C7A—N2A—C6A—C1A	−0.1 (3)	C7B—N2B—C6B—C1B	0.5 (3)
C6A—N2A—C7A—N1A	−0.1 (3)	C6B—N2B—C7B—N1B	−0.6 (3)
C6A—N2A—C7A—C8A	−178.8 (3)	C6B—N2B—C7B—C8B	−179.5 (3)
C1A—N1A—C7A—N2A	0.2 (3)	C1B—N1B—C7B—N2B	0.5 (3)
C1A—N1A—C7A—C8A	179.0 (2)	C1B—N1B—C7B—C8B	179.5 (3)
C12A—N3A—C8A—C9A	2.9 (4)	C12B—N3B—C8B—C9B	−1.6 (4)
C12A—N3A—C8A—C7A	−175.1 (2)	C12B—N3B—C8B—C7B	176.3 (2)
N2A—C7A—C8A—N3A	174.8 (3)	N2B—C7B—C8B—N3B	−177.7 (3)
N1A—C7A—C8A—N3A	−3.9 (4)	N1B—C7B—C8B—N3B	3.4 (4)
N2A—C7A—C8A—C9A	−3.2 (5)	N2B—C7B—C8B—C9B	0.2 (5)
N1A—C7A—C8A—C9A	178.1 (3)	N1B—C7B—C8B—C9B	−178.6 (3)
N3A—C8A—C9A—C10A	−2.0 (5)	N3B—C8B—C9B—C10B	0.9 (4)
C7A—C8A—C9A—C10A	175.8 (3)	C7B—C8B—C9B—C10B	−176.9 (3)
C8A—C9A—C10A—C11A	−0.3 (5)	C8B—C9B—C10B—C11B	0.8 (4)
C9A—C10A—C11A—C12A	1.5 (4)	C9B—C10B—C11B—C12B	−1.7 (5)
C8A—N3A—C12A—C11A	−1.6 (4)	C8B—N3B—C12B—C11B	0.6 (4)
C8A—N3A—C12A—C13A	176.8 (2)	C8B—N3B—C12B—C13B	−176.5 (2)
C10A—C11A—C12A—N3A	−0.6 (5)	C10B—C11B—C12B—N3B	1.1 (4)
C10A—C11A—C12A—C13A	−178.9 (3)	C10B—C11B—C12B—C13B	178.0 (3)
C14A—N4A—C13A—N5A	−0.1 (3)	C14B—N4B—C13B—N5B	0.5 (3)
C14A—N4A—C13A—C12A	178.3 (3)	C14B—N4B—C13B—C12B	−176.6 (3)
C19A—N5A—C13A—N4A	−0.1 (4)	C19B—N5B—C13B—N4B	−0.4 (3)
C19A—N5A—C13A—C12A	−178.6 (3)	C19B—N5B—C13B—C12B	177.0 (3)
N3A—C12A—C13A—N4A	−170.6 (3)	N3B—C12B—C13B—N4B	−177.8 (3)
C11A—C12A—C13A—N4A	7.8 (5)	C11B—C12B—C13B—N4B	5.0 (5)
N3A—C12A—C13A—N5A	7.7 (4)	N3B—C12B—C13B—N5B	5.2 (4)
C11A—C12A—C13A—N5A	−173.9 (3)	C11B—C12B—C13B—N5B	−171.9 (3)
C13A—N4A—C14A—C19A	0.2 (3)	C13B—N4B—C14B—C15B	177.2 (3)
C13A—N4A—C14A—C15A	−178.9 (3)	C13B—N4B—C14B—C19B	−0.5 (3)
C19A—C14A—C15A—C16A	1.7 (5)	N4B—C14B—C15B—C16B	−178.5 (3)
N4A—C14A—C15A—C16A	−179.3 (3)	C19B—C14B—C15B—C16B	−1.0 (5)
C14A—C15A—C16A—C17A	−0.1 (6)	C14B—C15B—C16B—C17B	0.5 (5)
C15A—C16A—C17A—C18A	−0.6 (7)	C15B—C16B—C17B—C18B	−0.3 (6)
C16A—C17A—C18A—C19A	−0.2 (6)	C16B—C17B—C18B—C19B	0.6 (5)
C13A—N5A—C19A—C18A	−178.0 (3)	C13B—N5B—C19B—C18B	−178.9 (3)
C13A—N5A—C19A—C14A	0.2 (3)	C13B—N5B—C19B—C14B	0.0 (3)
C17A—C18A—C19A—N5A	179.7 (3)	C17B—C18B—C19B—N5B	177.7 (3)
C17A—C18A—C19A—C14A	1.8 (5)	C17B—C18B—C19B—C14B	−1.1 (5)
C15A—C14A—C19A—N5A	178.9 (3)	C15B—C14B—C19B—N5B	−177.7 (3)
N4A—C14A—C19A—N5A	−0.3 (4)	N4B—C14B—C19B—N5B	0.3 (3)
C15A—C14A—C19A—C18A	−2.6 (5)	C15B—C14B—C19B—C18B	1.3 (5)
N4A—C14A—C19A—C18A	178.2 (3)	N4B—C14B—C19B—C18B	179.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1W	0.94 (2)	2.03 (2)	2.946 (4)	164 (3)
N5A—H5NA···O1W	0.88 (2)	2.05 (2)	2.907 (4)	166 (3)
N1B—H1NB···N2B^i	0.90 (2)	2.47 (2)	3.353 (4)	167 (2)
N5B—H5NB···N2B^i	0.89 (2)	2.21 (2)	3.048 (3)	157 (2)
O1W—H1WA···O2W^ii	0.90 (3)	1.88 (3)	2.758 (4)	164 (3)
O1W—H1WB···N4B	0.90 (3)	2.04 (3)	2.914 (4)	163 (3)
O2W—H2WA···N2A	0.88 (3)	1.92 (3)	2.800 (4)	175 (3)
O2W—H2WB···O3W^iii	0.87 (3)	1.91 (3)	2.780 (4)	176 (4)
O3W—H3WA···N4A	0.88 (2)	1.93 (2)	2.791 (4)	166 (4)
O3W—H3WB···O2W^i	0.89 (5)	2.03 (5)	2.905 (4)	171 (4)

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