Hierarchy of hydrogen bonding in bis­(1,4,7-trioxa-10-azoniacyclo­dodecane) bis­(4-amino­benzoate) trihydrate

In the title compound, 2C₈H₁₈NO₃⁺·2C₇H₆NO₂^-·3H₂O, proton transfer occurs from the carboxylic acid group of the 4-amino­benzoic acid (PABA) mol­ecule to the amine group of the macrocycle, resulting in the formation of a salt-like adduct. The anions are combined into helical chains which are further bound by the water mol­ecules into sheets. The macrocyclic cations are situated between these layers and are bound to the anions both directly and via bridging water mol­ecules. The structure exhibits a diverse system of hydrogen bonding.

S1. Comment

The title compound, (I), was investigated as a part of study on D—H···A hydrogen bonding in systems containing biologically important molecules and macrocyclic ligands. A search of the Cambridge Structural Database (Version?; Allen, 2002) revealed a list of p-aminobenzoic acid (PABA) co-crystals, in neutral (Lynch et al., 1992b; Lynch & McClenaghan, 2001; Moreno-Fuquen et al., 2003), cationic (protonated on the amino group) (Benali-Cherif et al., 2002; Lynch et al., 1992a), and anionic forms (deprotonated on the carboxylic acid group) (Smith et al., 1999). Only three examples are known so far for PABA co-crystals with O-containing crown ethers, namely with 18-crown-6 (Elbasyouny et al., 1983) and with two cis-isomers of dicyclohexyl-18-crown-6 (Fonari et al., 1994), which revealed that both complexes are adducts with 1:2 stoichiometry, with the amino group of PABA responsible for the N—H···O crown hydrogen bonds. A robust dimeric carboxylic R₂²(8) homosynthon (Desiraju, 1995) was responsible for the PABA molecules associating into dimers. Here, we report the first example, (I), of a PABA co-crystal with the mixed N,O-macrocycle 1,4,7-trioxa-10-azacyclododecane.

Compound (I) is a salt-like adduct due to the protonation of the macrocycle by PABA molecules. The asymmetric unit contains two tight cation–anion pairs, designated as A and B, and three water molecules (Fig. 1). Molecular dimensions are unexceptional and are freely available via the archived CIF.

The macrocyclic cations have an exo–endo orientation of the >NH₂⁺ ammonium functionality, with one H atom being involved in the intramolecular bifurcated N—H···O hydrogen bond inside the macrocycle and the second H atom being involved in the intermolecular hydrogen bonding with the PABA anions. The macrocycles have slightly different conformations and shapes, with the heteroatoms being coplanar to within 0.39 Å in macrocycle A and 0.14 Å in macrocycle B. The mutual arrangement in the cation–anion units is described by the dihedral angle between the planes through the planar skeleton of PABA anions and four heteroatoms of the macrocycle, with values of 48.9 (1)° in unit A and 62.9 (1)° in unit B.

In the A and B cation–anion units, the components are held together through a pair of N—H(>NH₂⁺)···O(COO^-) and C—H···O(COO^-) hydrogen bonds (Table 1). These N—H···O hydrogen bonds, with N2···O2 separations of 2.697 (2) and 2.735 (2) Å in units A and B, respectively, are the shortest of all those that sustain the structure. Each carboxylate functionality acts in a chelate mode via an R₂²(8) ring. This heterosynthon substitutes the planar robust centrosymmetric R₂²(8) homosynthon typical for two carboxylic groups. The environments of the macrocyclic cations are different in this structure, and whilst cation A does not have any direct contacts with water molecules, the water molecule O1W interacts with the B cation as a single H-donor and a single H-acceptor.

Although the mode of cation–anion interaction is similar in the A and B units, the structural functions of the A and B PABA anions are quite different in the supramolecular structure organization. PABA A anions are linked via N—H···O hydrogen bonds form a C(8) helical chain running parallel to the [010] direction (Fig. 2). Each PABA B anion, acting as a single H-donor and a single H-acceptor, links a pair of PABA A anions separated by the translation along the same direction, thus formulating the outer surface of the helix. Propagation of these four hydrogen bonds generates a chain of fused R₄⁴(22) rings. Water molecule O3W acts as a double hydrogen-bond donor to atom O1A at (x, y, z + 1) and atom O2B at (-x, y + 1/2, -z + 1), thus generating a second type of ring, R₄²(8), to stabilize the helix further (Fig. 2). Water molecule O2W acts as a single donor towards atom O1B at (-x, y + 1/2, -z + 1) and as a single acceptor towards atom N2B at (-x, y - 1/2, - z + 1), combining two neighbouring helices into a negative sheet via R₆⁶(26) fused rings (Fig. 2).

The negative sheets are linked into a continuous framework by the cations with the water molecules, which play a vital role in the association of the cationic and anionic components into a three-dimensional network. Three water molecules themselves formulate a three-membered water cluster, O3W···O1W···O2W, with O···O separations of 2.736 (3) and 2.846 (3) Å for units A and B, respectively, whose terminal members contact with PABA anions, while the bridging O1W water molecule is associated with the B macrocyclic cation via O1W···O5B and N1B···O1W hydrogen bonds (Table 1). Thus, the incorporation of the macrocyclic cations between the negative sheets occurs via direct cation–anion contacts (for A and B pairs) and via a mediating water molecule for the macrocyclic B cation (Fig. 3).

S2. Experimental

To obtain complex (I), 1,4,7-trioxa-10-azacyclododecane (175 mg, 0.1 mmol) and PABA (137 mg, 1 mmol) were dissolved in a water (1 ml)–methanol (5 ml) mixture at 337 K. The reaction mixture was then allowed to stand until crystals were deposited. These were filtered off and recrystallized from a mixture of methanol (2 ml), butanol (1 ml), ethyl acetate (2 ml) and heptane (2 ml) to give colourless [Yellow below?] crystals of (I) (m.p. 387–388 K). Analysis, calculated for C₃₀H₅₄N₄O₁₃: C 53.08, H 8.02, N 8.25%; found: C 53.02, H 8.09, N 8.30°. Spectroscopic analysis: ¹H NMR (DMSO-d₆, 300 MHz, σ): 3.48 (m, 32H, CH₂N, CH₂O, aza-12-crown-4), 7.11 (m, 8H, CH, Ph).

S3. Refinement

C-bound H atoms were placed in calculated positions, with C—H distances of 0.93 or 0.97 Å, and were treated using a riding-model approximation, with U_iso(H) = 1.2U_eq(C). N– and O(water)-bound H atoms were determined from a difference Fourier map and were then allowed to refine isotropically subject to SADI restraint (SHELXL97; Sheldrick, 1997) for N—H and O—H distances in amino groups, ammonia groups and water molecules, and with an angular H—O—H DFIX restraint for the O2W molecule [H—H = 1.46 Å], as well as a floating origin restraint. In the absence of species of atomic number higher than that of O, no significant anomalous dispersion is observed. Therefore, Friedel pairs were merged using the MERG 4 instruction (SHELXL97); the Flack (1983) parameter is meaningless in this case and the absolute structure is indeterminate.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of (I), with the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown by dashed lines.
	Fig. 2. Part of the crystal structure of (I), showing the linking of the [010] chains by the water molecules. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (-x, y - 1/2, - z + 1), (-x, y - 1/2, - z) and (-x, y + 1/2, - z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing the linking of the sheets by the cations. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

bis(1,4,7-trioxa-10-azoniacyclododecane) bis(4-aminobenzoate) trihydrate

Crystal data

2C8H18NO3^+·2C7H6NO2^−·3H2O	F(000) = 732
Mr = 678.77	Dx = 1.263 Mg m^−3
Monoclinic, P21	Melting point = 114–115 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 12.541 (3) Å	Cell parameters from 40 reflections
b = 9.5315 (19) Å	θ = 5.0–12.5°
c = 15.989 (3) Å	µ = 0.10 mm^−1
β = 110.91 (3)°	T = 293 K
V = 1785.4 (6) Å^3	Prism, yellow
Z = 2	0.29 × 0.23 × 0.21 mm

Data collection

Bruker P4 diffractometer	2856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 26.0°, θmin = 1.4°
ω/2θ scans	h = −15→15
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −11→11
Tmin = 0.745, Tmax = 1.000	l = −19→19
17540 measured reflections	3 standard reflections every 97 reflections
3714 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0314P)^2] where P = (Fo^2 + 2Fc^2)/3
3714 reflections	(Δ/σ)max < 0.001
480 parameters	Δρmax = 0.12 e Å^−3
9 restraints	Δρmin = −0.11 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1A	0.24649 (13)	0.62262 (19)	−0.04897 (10)	0.0667 (5)
O2A	0.35709 (13)	0.65431 (19)	0.09205 (9)	0.0631 (5)
O3A	0.49150 (14)	0.68480 (19)	−0.13857 (10)	0.0661 (4)
O4A	0.70885 (13)	0.69235 (18)	−0.00681 (10)	0.0608 (4)
O5A	0.69762 (12)	0.61932 (16)	0.15883 (10)	0.0547 (4)
N1A	−0.04635 (19)	0.3086 (3)	0.14951 (15)	0.0647 (6)
H1	−0.0233 (19)	0.282 (3)	0.2066 (13)	0.067 (8)*
H2	−0.101 (2)	0.262 (3)	0.1081 (14)	0.077 (9)*
N2A	0.51447 (14)	0.77132 (19)	0.03471 (11)	0.0393 (4)
H3	0.4543 (16)	0.730 (2)	0.0478 (13)	0.059 (7)*
H4	0.5565 (16)	0.705 (2)	0.0187 (12)	0.045 (6)*
C1A	0.18593 (17)	0.5271 (2)	0.06337 (13)	0.0430 (5)
C2A	0.08725 (18)	0.4681 (3)	0.00285 (14)	0.0519 (6)
H2A	0.0719	0.4789	−0.0582	0.062*
C3A	0.01207 (18)	0.3944 (3)	0.03032 (14)	0.0544 (6)
H3A	−0.0534	0.3569	−0.0122	0.065*
C4A	0.03185 (18)	0.3748 (2)	0.12063 (14)	0.0465 (5)
C5A	0.1317 (2)	0.4301 (2)	0.18203 (14)	0.0519 (6)
H5A	0.1482	0.4161	0.2429	0.062*
C6A	0.20653 (18)	0.5054 (2)	0.15388 (14)	0.0487 (5)
H6A	0.2722	0.5425	0.1963	0.058*
C7A	0.26790 (18)	0.6064 (2)	0.03288 (14)	0.0473 (5)
C8A	0.4718 (2)	0.8706 (3)	−0.04112 (14)	0.0548 (6)
H8A	0.5344	0.9284	−0.0434	0.066*
H8B	0.4150	0.9318	−0.0322	0.066*
C9A	0.4198 (2)	0.7928 (3)	−0.12812 (15)	0.0641 (7)
H9A	0.3477	0.7523	−0.1309	0.077*
H9B	0.4043	0.8586	−0.1773	0.077*
C10A	0.5902 (2)	0.7300 (3)	−0.15657 (16)	0.0738 (8)
H10A	0.6003	0.8304	−0.1470	0.089*
H10B	0.5799	0.7106	−0.2185	0.089*
C11A	0.6928 (2)	0.6552 (3)	−0.09648 (17)	0.0745 (8)
H11A	0.6822	0.5546	−0.1045	0.089*
H11B	0.7592	0.6817	−0.1104	0.089*
C12A	0.7995 (2)	0.6191 (3)	0.05786 (18)	0.0689 (7)
H12A	0.8714	0.6432	0.0516	0.083*
H12B	0.7879	0.5188	0.0490	0.083*
C13A	0.80260 (19)	0.6584 (3)	0.14895 (17)	0.0660 (7)
H13A	0.8658	0.6111	0.1939	0.079*
H13B	0.8141	0.7588	0.1576	0.079*
C14A	0.64228 (19)	0.7271 (3)	0.18862 (14)	0.0539 (6)
H14A	0.6970	0.7710	0.2412	0.065*
H14B	0.5827	0.6858	0.2061	0.065*
C15A	0.59051 (19)	0.8376 (2)	0.11905 (13)	0.0495 (5)
H15A	0.5470	0.9030	0.1407	0.059*
H15B	0.6506	0.8894	0.1077	0.059*
O1B	0.17022 (14)	0.2620 (2)	0.43687 (12)	0.0842 (6)
O2B	0.01808 (12)	0.17720 (19)	0.33246 (9)	0.0587 (4)
O3B	−0.02684 (13)	0.15892 (16)	0.59312 (10)	0.0593 (4)
O4B	−0.25975 (13)	0.25188 (18)	0.53294 (10)	0.0609 (4)
O5B	−0.35169 (14)	0.3408 (2)	0.35742 (10)	0.0706 (5)
N1B	0.40986 (19)	−0.1823 (3)	0.26326 (16)	0.0751 (7)
H5	0.385 (2)	−0.234 (3)	0.2128 (14)	0.077 (8)*
H6	0.4834 (17)	−0.190 (3)	0.3000 (15)	0.075 (8)*
N2B	−0.09659 (16)	0.3074 (2)	0.42751 (11)	0.0474 (5)
H7	−0.1380 (17)	0.240 (2)	0.4419 (13)	0.053 (6)*
H8	−0.0490 (19)	0.266 (3)	0.4003 (15)	0.076 (8)*
C1B	0.34067 (19)	−0.0902 (3)	0.28604 (15)	0.0502 (6)
C2B	0.22488 (19)	−0.0774 (3)	0.23523 (14)	0.0524 (6)
H2B	0.1934	−0.1298	0.1831	0.063*
C3B	0.15654 (18)	0.0124 (2)	0.26162 (13)	0.0483 (5)
H3B	0.0793	0.0184	0.2270	0.058*
C4B	0.19965 (17)	0.0943 (2)	0.33857 (13)	0.0428 (5)
C5B	0.31661 (18)	0.0842 (3)	0.38654 (14)	0.0506 (5)
H5B	0.3491	0.1401	0.4369	0.061*
C6B	0.38478 (19)	−0.0057 (3)	0.36138 (15)	0.0540 (6)
H6B	0.4623	−0.0104	0.3954	0.065*
C7B	0.12606 (19)	0.1846 (3)	0.37171 (14)	0.0490 (5)
C8B	−0.0304 (2)	0.3776 (2)	0.51386 (14)	0.0534 (6)
H8C	−0.0825	0.4249	0.5370	0.064*
H8D	0.0198	0.4476	0.5036	0.064*
C9B	0.0394 (2)	0.2727 (3)	0.58150 (16)	0.0585 (6)
H9C	0.0994	0.2367	0.5624	0.070*
H9D	0.0754	0.3196	0.6385	0.070*
C10B	−0.0911 (2)	0.1877 (3)	0.64907 (15)	0.0661 (7)
H10C	−0.0843	0.2863	0.6650	0.079*
H10D	−0.0607	0.1333	0.7038	0.079*
C11B	−0.2130 (2)	0.1518 (3)	0.60230 (17)	0.0671 (7)
H11C	−0.2199	0.0581	0.5773	0.081*
H11D	−0.2534	0.1547	0.6439	0.081*
C12B	−0.3758 (2)	0.2265 (3)	0.48330 (17)	0.0734 (8)
H12C	−0.4194	0.2272	0.5227	0.088*
H12D	−0.3847	0.1353	0.4547	0.088*
C13B	−0.4182 (2)	0.3386 (4)	0.41411 (17)	0.0773 (8)
H13C	−0.4977	0.3214	0.3783	0.093*
H13D	−0.4131	0.4290	0.4432	0.093*
C14B	−0.2726 (2)	0.4539 (3)	0.37296 (17)	0.0687 (7)
H14C	−0.2519	0.4868	0.4341	0.082*
H14D	−0.3072	0.5312	0.3330	0.082*
C15B	−0.1680 (2)	0.4042 (3)	0.35683 (15)	0.0587 (6)
H15C	−0.1911	0.3567	0.2995	0.070*
H15D	−0.1224	0.4849	0.3537	0.070*
O1W	0.2686 (2)	0.5588 (2)	0.66298 (15)	0.0908 (6)
H11W	0.316 (3)	0.633 (4)	0.686 (3)	0.167 (19)*
H12W	0.242 (3)	0.538 (4)	0.709 (2)	0.151 (16)*
O2W	0.35037 (18)	0.3246 (2)	0.59307 (14)	0.0828 (6)
H21W	0.301 (2)	0.309 (3)	0.5402 (15)	0.096 (11)*
H22W	0.319 (3)	0.391 (3)	0.615 (2)	0.116 (14)*
O3W	0.15606 (16)	0.5148 (2)	0.77913 (13)	0.0679 (5)
H31W	0.098 (2)	0.560 (3)	0.7483 (17)	0.095 (11)*
H32W	0.178 (2)	0.550 (4)	0.8300 (15)	0.095 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0556 (9)	0.0998 (14)	0.0457 (9)	−0.0114 (9)	0.0191 (7)	0.0085 (9)
O2A	0.0504 (9)	0.0882 (13)	0.0519 (9)	−0.0235 (9)	0.0195 (8)	−0.0085 (9)
O3A	0.0796 (11)	0.0633 (11)	0.0589 (9)	−0.0202 (10)	0.0291 (9)	−0.0075 (8)
O4A	0.0617 (10)	0.0651 (11)	0.0637 (10)	0.0072 (9)	0.0323 (8)	−0.0027 (9)
O5A	0.0488 (9)	0.0517 (9)	0.0604 (9)	0.0012 (7)	0.0158 (7)	0.0020 (8)
N1A	0.0604 (14)	0.0726 (16)	0.0608 (14)	−0.0123 (12)	0.0214 (12)	0.0132 (12)
N2A	0.0385 (10)	0.0372 (10)	0.0416 (10)	0.0010 (8)	0.0135 (8)	0.0014 (8)
C1A	0.0385 (11)	0.0487 (13)	0.0432 (12)	0.0037 (10)	0.0162 (9)	−0.0016 (9)
C2A	0.0445 (13)	0.0690 (16)	0.0400 (11)	−0.0015 (12)	0.0125 (10)	0.0025 (11)
C3A	0.0404 (13)	0.0653 (16)	0.0524 (14)	−0.0073 (12)	0.0104 (11)	−0.0010 (11)
C4A	0.0453 (13)	0.0448 (13)	0.0526 (13)	0.0008 (11)	0.0215 (11)	0.0034 (10)
C5A	0.0614 (15)	0.0551 (14)	0.0421 (11)	−0.0046 (12)	0.0219 (11)	−0.0013 (11)
C6A	0.0458 (12)	0.0537 (13)	0.0436 (12)	−0.0076 (11)	0.0123 (10)	−0.0059 (11)
C7A	0.0411 (12)	0.0543 (14)	0.0486 (13)	0.0043 (11)	0.0187 (10)	−0.0012 (11)
C8A	0.0596 (15)	0.0490 (14)	0.0528 (13)	0.0044 (12)	0.0166 (12)	0.0106 (11)
C9A	0.0623 (15)	0.0729 (18)	0.0522 (14)	−0.0029 (14)	0.0144 (12)	0.0129 (13)
C10A	0.092 (2)	0.084 (2)	0.0574 (15)	−0.0132 (17)	0.0413 (15)	−0.0022 (14)
C11A	0.090 (2)	0.0756 (19)	0.0807 (18)	−0.0063 (17)	0.0591 (17)	−0.0097 (16)
C12A	0.0489 (14)	0.0665 (17)	0.098 (2)	0.0086 (13)	0.0342 (14)	0.0011 (16)
C13A	0.0427 (13)	0.0688 (17)	0.0782 (17)	0.0039 (13)	0.0116 (12)	0.0015 (14)
C14A	0.0552 (14)	0.0595 (15)	0.0426 (12)	0.0028 (12)	0.0119 (11)	−0.0029 (11)
C15A	0.0503 (13)	0.0448 (13)	0.0503 (12)	−0.0025 (11)	0.0139 (10)	−0.0093 (11)
O1B	0.0578 (10)	0.1074 (15)	0.0801 (12)	−0.0014 (11)	0.0157 (9)	−0.0492 (12)
O2B	0.0424 (9)	0.0768 (11)	0.0551 (9)	0.0001 (9)	0.0150 (7)	−0.0093 (9)
O3B	0.0668 (10)	0.0518 (10)	0.0691 (10)	0.0083 (8)	0.0361 (8)	0.0057 (8)
O4B	0.0494 (9)	0.0690 (11)	0.0611 (9)	−0.0053 (8)	0.0160 (8)	−0.0012 (9)
O5B	0.0596 (10)	0.0924 (14)	0.0556 (10)	−0.0092 (10)	0.0153 (9)	−0.0140 (9)
N1B	0.0509 (14)	0.0978 (19)	0.0741 (15)	0.0049 (13)	0.0192 (13)	−0.0320 (14)
N2B	0.0549 (12)	0.0435 (11)	0.0477 (11)	−0.0048 (10)	0.0230 (10)	−0.0020 (9)
C1B	0.0474 (13)	0.0584 (15)	0.0498 (12)	−0.0055 (11)	0.0234 (11)	−0.0059 (11)
C2B	0.0514 (14)	0.0627 (15)	0.0421 (11)	−0.0064 (11)	0.0154 (10)	−0.0097 (11)
C3B	0.0395 (11)	0.0619 (14)	0.0395 (11)	−0.0023 (11)	0.0091 (9)	−0.0024 (11)
C4B	0.0428 (12)	0.0475 (12)	0.0392 (11)	−0.0048 (10)	0.0158 (9)	0.0016 (10)
C5B	0.0471 (13)	0.0594 (15)	0.0453 (12)	−0.0089 (12)	0.0166 (10)	−0.0096 (11)
C6B	0.0379 (12)	0.0689 (16)	0.0538 (13)	−0.0066 (12)	0.0146 (10)	−0.0078 (12)
C7B	0.0504 (14)	0.0545 (14)	0.0428 (12)	−0.0014 (12)	0.0174 (10)	0.0005 (11)
C8B	0.0598 (15)	0.0455 (13)	0.0507 (13)	−0.0074 (12)	0.0145 (11)	−0.0057 (11)
C9B	0.0546 (14)	0.0603 (16)	0.0595 (14)	0.0002 (13)	0.0190 (12)	0.0038 (12)
C10B	0.0650 (16)	0.0857 (19)	0.0521 (13)	0.0091 (15)	0.0264 (12)	0.0106 (14)
C11B	0.0736 (18)	0.0707 (18)	0.0667 (15)	0.0020 (15)	0.0367 (14)	0.0115 (14)
C12B	0.0479 (14)	0.103 (2)	0.0685 (16)	−0.0140 (15)	0.0202 (13)	−0.0105 (17)
C13B	0.0478 (14)	0.118 (3)	0.0636 (15)	0.0032 (16)	0.0173 (13)	−0.0120 (18)
C14B	0.0712 (18)	0.0622 (17)	0.0634 (16)	0.0146 (15)	0.0128 (14)	0.0081 (13)
C15B	0.0649 (15)	0.0587 (15)	0.0496 (13)	−0.0075 (13)	0.0169 (12)	0.0068 (11)
O1W	0.1130 (18)	0.0765 (15)	0.1050 (17)	−0.0087 (13)	0.0659 (15)	−0.0115 (13)
O2W	0.0640 (13)	0.0933 (17)	0.0759 (14)	0.0060 (12)	0.0064 (11)	−0.0143 (12)
O3W	0.0649 (12)	0.0750 (13)	0.0591 (12)	0.0208 (10)	0.0166 (10)	0.0011 (10)

Geometric parameters (Å, º)

O1A—C7A	1.248 (2)	O3B—C10B	1.428 (3)
O2A—C7A	1.265 (2)	O4B—C12B	1.407 (3)
O3A—C9A	1.415 (3)	O4B—C11B	1.421 (3)
O3A—C10A	1.434 (3)	O5B—C14B	1.425 (3)
O4A—C12A	1.418 (3)	O5B—C13B	1.434 (3)
O4A—C11A	1.420 (3)	N1B—C1B	1.372 (3)
O5A—C14A	1.414 (3)	N1B—H5	0.90 (2)
O5A—C13A	1.430 (3)	N1B—H6	0.902 (19)
N1A—C4A	1.377 (3)	N2B—C15B	1.486 (3)
N1A—H1	0.891 (19)	N2B—C8B	1.492 (3)
N1A—H2	0.881 (19)	N2B—H7	0.907 (18)
N2A—C8A	1.479 (3)	N2B—H8	0.943 (18)
N2A—C15A	1.486 (3)	C1B—C6B	1.389 (3)
N2A—H3	0.940 (18)	C1B—C2B	1.393 (3)
N2A—H4	0.916 (17)	C2B—C3B	1.379 (3)
C1A—C2A	1.389 (3)	C2B—H2B	0.9300
C1A—C6A	1.392 (3)	C3B—C4B	1.393 (3)
C1A—C7A	1.491 (3)	C3B—H3B	0.9300
C2A—C3A	1.368 (3)	C4B—C5B	1.395 (3)
C2A—H2A	0.9300	C4B—C7B	1.490 (3)
C3A—C4A	1.388 (3)	C5B—C6B	1.369 (3)
C3A—H3A	0.9300	C5B—H5B	0.9300
C4A—C5A	1.390 (3)	C6B—H6B	0.9300
C5A—C6A	1.379 (3)	C8B—C9B	1.503 (3)
C5A—H5A	0.9300	C8B—H8C	0.9700
C6A—H6A	0.9300	C8B—H8D	0.9700
C8A—C9A	1.504 (3)	C9B—H9C	0.9700
C8A—H8A	0.9700	C9B—H9D	0.9700
C8A—H8B	0.9700	C10B—C11B	1.482 (3)
C9A—H9A	0.9700	C10B—H10C	0.9700
C9A—H9B	0.9700	C10B—H10D	0.9700
C10A—C11A	1.485 (4)	C11B—H11C	0.9700
C10A—H10A	0.9700	C11B—H11D	0.9700
C10A—H10B	0.9700	C12B—C13B	1.493 (4)
C11A—H11A	0.9700	C12B—H12C	0.9700
C11A—H11B	0.9700	C12B—H12D	0.9700
C12A—C13A	1.491 (3)	C13B—H13C	0.9700
C12A—H12A	0.9700	C13B—H13D	0.9700
C12A—H12B	0.9700	C14B—C15B	1.501 (3)
C13A—H13A	0.9700	C14B—H14C	0.9700
C13A—H13B	0.9700	C14B—H14D	0.9700
C14A—C15A	1.501 (3)	C15B—H15C	0.9700
C14A—H14A	0.9700	C15B—H15D	0.9700
C14A—H14B	0.9700	O1W—H11W	0.92 (2)
C15A—H15A	0.9700	O1W—H12W	0.93 (2)
C15A—H15B	0.9700	O2W—H21W	0.86 (2)
O1B—C7B	1.235 (3)	O2W—H22W	0.88 (2)
O2B—C7B	1.275 (2)	O3W—H31W	0.84 (2)
O3B—C9B	1.418 (3)	O3W—H32W	0.83 (2)
C9A—O3A—C10A	115.8 (2)	C14B—O5B—C13B	115.2 (2)
C12A—O4A—C11A	113.68 (19)	C1B—N1B—H5	122.4 (17)
C14A—O5A—C13A	115.46 (18)	C1B—N1B—H6	118.3 (17)
C4A—N1A—H1	117.7 (16)	H5—N1B—H6	119 (3)
C4A—N1A—H2	115.5 (17)	C15B—N2B—C8B	114.27 (19)
H1—N1A—H2	120 (3)	C15B—N2B—H7	112.9 (13)
C8A—N2A—C15A	113.53 (17)	C8B—N2B—H7	105.3 (13)
C8A—N2A—H3	111.6 (13)	C15B—N2B—H8	102.8 (15)
C15A—N2A—H3	106.4 (13)	C8B—N2B—H8	112.4 (15)
C8A—N2A—H4	106.7 (12)	H7—N2B—H8	109 (2)
C15A—N2A—H4	107.5 (12)	N1B—C1B—C6B	120.5 (2)
H3—N2A—H4	111.1 (19)	N1B—C1B—C2B	121.8 (2)
C2A—C1A—C6A	116.93 (19)	C6B—C1B—C2B	117.7 (2)
C2A—C1A—C7A	121.62 (18)	C3B—C2B—C1B	120.5 (2)
C6A—C1A—C7A	121.43 (19)	C3B—C2B—H2B	119.7
C3A—C2A—C1A	121.94 (19)	C1B—C2B—H2B	119.7
C3A—C2A—H2A	119.0	C2B—C3B—C4B	122.0 (2)
C1A—C2A—H2A	119.0	C2B—C3B—H3B	119.0
C2A—C3A—C4A	121.1 (2)	C4B—C3B—H3B	119.0
C2A—C3A—H3A	119.5	C3B—C4B—C5B	116.6 (2)
C4A—C3A—H3A	119.5	C3B—C4B—C7B	122.90 (19)
N1A—C4A—C3A	121.8 (2)	C5B—C4B—C7B	120.48 (19)
N1A—C4A—C5A	120.4 (2)	C6B—C5B—C4B	121.7 (2)
C3A—C4A—C5A	117.7 (2)	C6B—C5B—H5B	119.1
C6A—C5A—C4A	120.90 (19)	C4B—C5B—H5B	119.1
C6A—C5A—H5A	119.6	C5B—C6B—C1B	121.4 (2)
C4A—C5A—H5A	119.6	C5B—C6B—H6B	119.3
C5A—C6A—C1A	121.4 (2)	C1B—C6B—H6B	119.3
C5A—C6A—H6A	119.3	O1B—C7B—O2B	121.7 (2)
C1A—C6A—H6A	119.3	O1B—C7B—C4B	119.79 (19)
O1A—C7A—O2A	122.8 (2)	O2B—C7B—C4B	118.5 (2)
O1A—C7A—C1A	119.34 (19)	N2B—C8B—C9B	110.90 (19)
O2A—C7A—C1A	117.85 (18)	N2B—C8B—H8C	109.5
N2A—C8A—C9A	110.70 (19)	C9B—C8B—H8C	109.5
N2A—C8A—H8A	109.5	N2B—C8B—H8D	109.5
C9A—C8A—H8A	109.5	C9B—C8B—H8D	109.5
N2A—C8A—H8B	109.5	H8C—C8B—H8D	108.0
C9A—C8A—H8B	109.5	O3B—C9B—C8B	112.64 (19)
H8A—C8A—H8B	108.1	O3B—C9B—H9C	109.1
O3A—C9A—C8A	112.57 (19)	C8B—C9B—H9C	109.1
O3A—C9A—H9A	109.1	O3B—C9B—H9D	109.1
C8A—C9A—H9A	109.1	C8B—C9B—H9D	109.1
O3A—C9A—H9B	109.1	H9C—C9B—H9D	107.8
C8A—C9A—H9B	109.1	O3B—C10B—C11B	110.53 (19)
H9A—C9A—H9B	107.8	O3B—C10B—H10C	109.5
O3A—C10A—C11A	109.7 (2)	C11B—C10B—H10C	109.5
O3A—C10A—H10A	109.7	O3B—C10B—H10D	109.5
C11A—C10A—H10A	109.7	C11B—C10B—H10D	109.5
O3A—C10A—H10B	109.7	H10C—C10B—H10D	108.1
C11A—C10A—H10B	109.7	O4B—C11B—C10B	107.6 (2)
H10A—C10A—H10B	108.2	O4B—C11B—H11C	110.2
O4A—C11A—C10A	108.1 (2)	C10B—C11B—H11C	110.2
O4A—C11A—H11A	110.1	O4B—C11B—H11D	110.2
C10A—C11A—H11A	110.1	C10B—C11B—H11D	110.2
O4A—C11A—H11B	110.1	H11C—C11B—H11D	108.5
C10A—C11A—H11B	110.1	O4B—C12B—C13B	108.6 (2)
H11A—C11A—H11B	108.4	O4B—C12B—H12C	110.0
O4A—C12A—C13A	108.88 (19)	C13B—C12B—H12C	110.0
O4A—C12A—H12A	109.9	O4B—C12B—H12D	110.0
C13A—C12A—H12A	109.9	C13B—C12B—H12D	110.0
O4A—C12A—H12B	109.9	H12C—C12B—H12D	108.4
C13A—C12A—H12B	109.9	O5B—C13B—C12B	110.2 (2)
H12A—C12A—H12B	108.3	O5B—C13B—H13C	109.6
O5A—C13A—C12A	109.7 (2)	C12B—C13B—H13C	109.6
O5A—C13A—H13A	109.7	O5B—C13B—H13D	109.6
C12A—C13A—H13A	109.7	C12B—C13B—H13D	109.6
O5A—C13A—H13B	109.7	H13C—C13B—H13D	108.1
C12A—C13A—H13B	109.7	O5B—C14B—C15B	109.1 (2)
H13A—C13A—H13B	108.2	O5B—C14B—H14C	109.9
O5A—C14A—C15A	113.24 (17)	C15B—C14B—H14C	109.9
O5A—C14A—H14A	108.9	O5B—C14B—H14D	109.9
C15A—C14A—H14A	108.9	C15B—C14B—H14D	109.9
O5A—C14A—H14B	108.9	H14C—C14B—H14D	108.3
C15A—C14A—H14B	108.9	N2B—C15B—C14B	113.05 (19)
H14A—C14A—H14B	107.7	N2B—C15B—H15C	109.0
N2A—C15A—C14A	110.00 (18)	C14B—C15B—H15C	109.0
N2A—C15A—H15A	109.7	N2B—C15B—H15D	109.0
C14A—C15A—H15A	109.7	C14B—C15B—H15D	109.0
N2A—C15A—H15B	109.7	H15C—C15B—H15D	107.8
C14A—C15A—H15B	109.7	H11W—O1W—H12W	102 (3)
H15A—C15A—H15B	108.2	H21W—O2W—H22W	104 (3)
C9B—O3B—C10B	115.0 (2)	H31W—O3W—H32W	106 (3)
C12B—O4B—C11B	112.4 (2)
N2A—C8A—C9A—O3A	−49.3 (3)	N2B—C8B—C9B—O3B	−53.1 (3)
C8A—C9A—O3A—C10A	−72.5 (2)	C8B—C9B—O3B—C10B	−79.4 (2)
C9A—O3A—C10A—C11A	132.0 (2)	C9B—O3B—C10B—C11B	126.9 (2)
O3A—C10A—C11A—O4A	−62.7 (3)	O3B—C10B—C11B—O4B	−70.5 (3)
C10A—C11A—O4A—C12A	175.4 (2)	C10B—C11B—O4B—C12B	179.4 (2)
C11A—O4A—C12A—C13A	−175.8 (2)	C11B—O4B—C12B—C13B	178.4 (2)
O4A—C12A—C13A—O5A	61.1 (3)	O4B—C12B—C13B—O5B	57.9 (3)
C12A—C13A—O5A—C14A	−127.9 (2)	C12B—C13B—O5B—C14B	−105.2 (3)
C13A—O5A—C14A—C15A	71.6 (2)	C13B—O5B—C14B—C15B	145.6 (2)
O5A—C14A—C15A—N2A	53.3 (2)	O5B—C14B—C15B—N2B	−71.8 (3)
C14A—C15A—N2A—C8A	−172.37 (18)	C14B—C15B—N2B—C8B	−74.1 (3)
C15A—N2A—C8A—C9A	166.3 (2)	C15B—N2B—C8B—C9B	−179.96 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1···O2B	0.89 (2)	2.14 (2)	3.015 (3)	168 (2)
N1A—H2···O1A^i	0.88 (2)	2.18 (2)	3.024 (3)	159 (2)
N2A—H3···O2A	0.94 (2)	1.77 (2)	2.697 (2)	170 (2)
N2A—H4···O4A	0.92 (2)	2.09 (2)	2.847 (2)	139 (2)
N2A—H4···O5A	0.92 (2)	2.45 (2)	2.839 (2)	106 (1)
C9A—H9A···O1A	0.97	2.46	3.305 (3)	146
N1B—H5···O2A^ii	0.90 (2)	2.12 (2)	3.011 (3)	169 (2)
N1B—H6···O2W^iii	0.90 (2)	2.18 (2)	3.065 (3)	167 (2)
N2B—H7···O4B	0.91 (2)	2.46 (2)	3.126 (2)	131 (2)
N2B—H7···O1W^iv	0.91 (2)	2.55 (2)	3.183 (3)	127 (2)
N2B—H8···O2B	0.94 (2)	1.80 (2)	2.735 (2)	170 (2)
N2B—H8···O1B	0.94 (2)	2.60 (2)	3.324 (3)	134 (2)
C9B—H9C···O1B	0.97	2.48	3.280 (3)	140
O1W—H11W···O5B^v	0.92 (2)	2.20 (3)	2.943 (3)	138 (4)
O1W—H12W···O3W	0.93 (2)	1.83 (2)	2.736 (3)	166 (4)
O2W—H21W···O1B	0.86 (2)	1.92 (2)	2.770 (3)	167 (3)
O2W—H22W···O1W	0.88 (2)	1.98 (3)	2.846 (3)	171 (3)
O3W—H31W···O2B^v	0.84 (2)	1.92 (2)	2.751 (3)	170 (3)
O3W—H32W···O1A^vi	0.83 (2)	1.94 (2)	2.770 (3)	173 (3)

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