Three related benzoannelated diaza­polyether macrocycles: effects of macrocycle ring size and position of benzo groups on hydrogen bonding of the amine H atoms

The benzoannelated diaza­polyether macrocycles 6,7,9,10,17,18-hexa­hydro-5H,11H-8,16,19-trioxa-5,11-diaza­dibenzo­[a,g]­cyclo­penta­decene, C₁₈H₂₂N₂O₃, (I), 6,7,9,10,12,13,20,21-octa­hydro-5H,14H-8,11,19,22-tetra­oxa-5,14-diaza­dibenzo­[a,g]­cyclo­octa­decene, C₂₀H₂₆N₂O₄, (II), and 6,7,9,10,17,18,20,21-octa­hydro-16H,22H-5,8,11,19-tetra­oxa-16,22-diaza­dibenzo­[a,j]­cyclo­octa­decene 0.3-hydrate, C₂₀H₂₆N₂O₄·0.304H₂O, (III), show different patterns of hydrogen bonding. In (I), the amine H atoms participate only in intra­molecular hydrogen bonds with ether O atoms. In (II), the amine H atoms form intra­molecular hydrogen bonds with the phen­oxy ether O atoms and inter­molecular hydrogen bonds with alkyl ether O atoms in an adjacent mol­ecule, forming a chain linking the macrocycles together via an R₂²(10) motif. Mol­ecules of (II) were found on a crystallographic twofold axis. In (III), the amine H atoms participate in a hydrogen-bond network with adjacent ether O atoms and with a water mol­ecule [having a partial occupancy of 0.304 (6)] that links the mol­ecules together via a C₂²(7) motif.

S1. Comment

Macrocyclic diaminopolyethers, which serve as precursors in the synthesis of cryptands, also are of interest for their potential as receptors for molecules and anions (Kang et al., 2006). In the process of preparing cryptands with aniline-type nitrogen as the bridgehead atoms we have isolated several related benzoannelated macrocyclic diamines, and we report the structures of (I)–(III) here. These closely related compounds reveal the effects of ring size [comparing (I) and (II)] and position of the benzo groups [comparing (II) and (III)] on the orientation of the NH H atoms, an important consideration for the design of anion and molecular receptors. Among the factors that contribute to the conformation of the macrocycle, and thus the orientation of the NH H atoms, are the torsion angles for the X—CH₂—CH₂—O (X = N and O) segments, macrocycle ring size and the position of the benzo groups in the macrocycle backbone. For (I)–(III) the torsion angles for the alkyl X—CH₂—CH₂—O groups lie in the range 54.77 (13)–76.9 (6)° [cf. values in CIF, should this be 55.00 (15)–74.6 (5)?], thus adopting the gauche conformation preferred when such subunits contain N or O atoms (Herceg & Weiss, 1970; Wolf et al., 1987). The N—C═C—O torsion angles for the heteroatoms attached to the benzene ring are geometrically restricted and range from 1.50 (6)° to 6.23 (14)° [or 1.6 (6)–6.27 (18)?]. The N atoms are essentially coplanar with the associated benzo group [with deviations of 0.0055 (13)–0.071 (6) Å], while the amino H atoms show a slightly greater range of deviation (0.0478 (13)–0.193 (6) Å]. Therefore, the orientation of the NH H atoms will be defined by the associated benzo group, and, as shown in Figs. 1–3, the NH H atoms have an endodentate conformation with respect to the macrocycle cavity.

For (I) the gauche conformation of the X—CH₂—CH₂—O subunits, the smaller ring size and the short five-atom bridge (CCOCC) connecting atoms N5 and N11 result in the molecule adopting a relatively flat conformation (Fig. 1), although the least-squares plane defined by the atoms N5, O8, N11, O16 and O19 [the mean deviation is 0.4288 (14) Å] is the least well defined among the three compounds. Benzene rings A and B have dihedral angles of 28.5 (2) and 137.7 (2)°, respectively, with the plane defined by the heteroatoms and 166.2 (2)° with each other. Atom H5 forms hydrogen bonds with atoms O8 and O19, while H11 has reasonable hydrogen bond geometry only with O16 (Fig. 1 and Table 1).

Molecule (II) lies on a twofold rotation axis. The eight-atom chain (CCOCCOCC) between the N atoms allows the benzo groups to rotate out the plane defined by atoms N5, O8 and O22 [the mean deviation is 0.2513 (12) Å] to a much greater extent than for (I). The resulting conformation has the benzo groups on opposite sides of the hetero-atom plane (Fig. 4), forming a dihedral angle of 72.9 (2)° with one another and 112.1 (2)° with the hetero-atom plane. As a result, one NH H atom is oriented above and the other below the hetero-atom plane. Each forms an intramolecular hydrogen bond with the proximal phenoxy ether O atom (Fig. 2 and Table 2). In addition, each NH H atom forms a hydrogen bond to ether atom O8(1 - x, 1 - y, 1 - z) in an adjacent molecule, linking the macrocycles together in a chain-like fashion via an R₂²(10) motif (Bernstein et al., 1995) along the c axis (Fig. 4).

The macrocycle ring size of (III) is the same as that of (II) but the position of the benzo groups and N atoms in the ring differs, and a molecule of water [with a fractional occupancy of 0.304 (6)] is present above the center of the macrocycle cavity. The positions of the benzo groups and gauche conformation of all the X—CH₂—CH₂—O subunits allow the molecule to adopt a folded conformation defined by an axis passing through O8 and O19 (Fig. 5). The benzo groups are located on the same side of the plane defined by atoms O5, O8, O11, N16, O19 and N22 [the mean deviation is 0.0557 (6) Å]. Benzene rings A and B form dihedral angles of 33.5 (2) and 148.0 (2)°, respectively, with the hetero-atom plane and 114.6 (2)° with one another. Both NH H atoms are on the same side of the macrocycle plane and are oriented toward, but above, the center of the cavity. Each NH H atom forms an intramolecular hydrogen bond with the adjacent phenoxy ether O atom (Fig. 3 and Table 3). In addition, both NH H atoms interact with atom O1S of the water molecule. Atom H1S1 forms a hydrogen bond to atom O8, while H1S2 forms a hydrogen bond with atom O19(x, 1 + y, z) in an adjacent molecule, linking the crown ethers in a chain via a C₂²(7) motif (Bernstein et al., 1995) along the b axis (Fig. 5).

The NH H atoms for (I)–(III) all form weak intramolecular hydrogen bonds with one or more ether O atoms in the macrocycle; however, the N—H···O angles [106.0 (14)–116 (3)°] cannot achieve optimal geometry due to conformational restrictions imposed by the ring structure and the presence of the benzo groups in the macrocycle backbone. The intermolecular N—H···O angels for (III) [152 (4)–173 (13)°] fall in the conventional range except for O1S—H1S···O11 [117 (11)°], while those for (II) [134.9 (11)°] are somewhat lower. Comparison of the structural characteristics of (I)–(III) suggests that a macrocycle with NH groups separated by a five-atom bridge and a ring size of 18 atoms, as in (III), provides hydrogen-bond donors with the spacing and orientation suitable to interact preferably with an external hydrogen-bond acceptor guest.

Related literature

For related literature, see: Aguilar et al. (2001); Bernstein et al. (1995); Crossley et al. (1994); Dietrich et al. (1973); Flack & Schwarzenbach (1988); Formanovskii & Murakhovskaya (1985); Formanovskii et al. (1988); Herceg & Weiss (1970); Kang et al. (2006); Lockhart & Thompson (1977); Smith et al. (1986, 1988, 2006); Wolf, Hartman, Storey, Foxman & Cooper (1987).

S2. Experimental

Monocyclic diamines (I), (II) and (III) were prepared by condensation of the appropriate α,ω-polyoxadianiline with the corresponding diacid chloride ether under high-dilution conditions (Dietrich et al., 1973) according to reported methods (Lockhart & Thompson, 1977; Aguilar et al., 2001; Formanovskii & Murakhovskaya, 1985; Formanovskii et al., 1988; Crossley et al., 1994). The resulting dilactams were purified by recrystallization from ethanol [for (I) and (II)] or benzene/toluene [for (III)] (Smith et al., 2006). Reduction of the dilactams using BH₃ in THF and subsequent work-up (Smith et al., 1986, 1988) gave the title compounds. Compound (I) was obtained in 58% overall yield; ESI–MS: m/z = 315.2 (M+H⁺), 337.2 (M+Na⁺), 651.4 (2M+Na⁺). Compound (II) was obtained in 51% overall yield; ESI–MS: m/z = 359.2 (M+H⁺), 381.2 (M+Na⁺). Compound (III) was obtained in 70% overall yield; ESI–MS: m/z = 359.2 (M+H⁺), 381.2 (M+Na⁺). ¹H NMR spectra were consistent with previously reported values for (I) (Formanovskii & Murakhovskaya, 1985) and (III) (Aguilar et al., 2001). Crystals suitable for X-ray crystallographic analysis were grown by vapor diffusion of heptane into a solution of (I) in benzene, by vapor diffusion of water into a solution of (II) in benzene, and by slow evaporation of a solution of (III) in methanol.

S3. Refinement

H atoms attached to C were positioned geometrically and refined using a riding model, with C—H distances of 0.95 (phenyl) or 0.99 Å (ethylene). H atoms attached to N or O atoms were located initially in a difference map and refined independently in (I) and (II) and with distances restraints applied in (III). The U_iso(H) parameters for all H atoms were set to 1.2U_eq(C,N,O). The water O atom in (III) was located in a difference map. After initial refinements that lead to an implausibly large displacement parameter for this O atom, the occupancy of the atom was refined with a fixed displacement parameter. After a converged refinement with both occupancy and isotropic displacement parameter for the water O atom, a difference map revealed two peaks in chemically reasonable positions for the H atoms. The positional parameters of the water H atoms were restrained to be 0.82 (2) Å and have a nearly tetrahedral angle in the molecule. The N—H bonds in (III) were restrained to be 0.85 (2) Å. One polar axis restraint for (III) was applied in the manner of Flack & Schwarzenbach (1988).

Computing details

For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The molecular structure of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a chain of hydrogen-bonded R2^2(10) rings along the c axis. H atoms attached to C atoms have been omitted for clarity. Atoms marked with an asterisk (*) are related by the symmetry operation (1 - x, 1 - y, 1 - z). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded C2^2(7) chain along the b axis involving the amine H atoms, water molecule and ether O atom. Atoms marked with an asterisk (*) or a hash (#) are related by the symmetry operations (x, 1 + y, z) and (x, 1 - y, z), respectively. H atoms attached to carbon have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.

(I) 6,7,9,10,17,18-hexahydro-5H,11H-8,16,19-trioxa-5,11- diazadibenzo[a,g]cyclopentadecene

Crystal data

C18H22N2O3	F(000) = 672
Mr = 314.38	Dx = 1.316 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5823 reflections
a = 7.8995 (8) Å	θ = 3.2–26.9°
b = 9.5228 (10) Å	µ = 0.09 mm^−1
c = 21.093 (2) Å	T = 100 K
V = 1586.7 (3) Å^3	Prism, colourless
Z = 4	0.32 × 0.26 × 0.20 mm

Data collection

Bruker APEX CCD diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1788 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→9
Tmin = 0.971, Tmax = 0.984	k = −11→11
16397 measured reflections	l = −25→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.240P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1809 reflections	Δρmax = 0.17 e Å^−3
215 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

Special details

Experimental. All intensity X-ray data were collected on a Bruker diffractometer with a D8 goniometer, an APEX CCD detector, a sealed-tube Mo Kα source, and an Oxford Cryosystems Cryostream 700 low temperature device (Bruker, 1998).

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. Although the Flack parameter was refined, the lack of a strong anomalous scatter makes this parameter inappropriate. The Friedel related data were merged.

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

	x	y	z	Uiso*/Ueq
C1	0.34334 (19)	0.51249 (16)	0.31794 (7)	0.0241 (3)
H1	0.2496	0.4506	0.3140	0.029*
C2	0.3866 (2)	0.60177 (16)	0.26794 (7)	0.0267 (3)
H2	0.3225	0.6010	0.2298	0.032*
C3	0.5232 (2)	0.69111 (16)	0.27429 (7)	0.0268 (3)
H3	0.5529	0.7514	0.2402	0.032*
C4	0.6182 (2)	0.69411 (16)	0.33005 (7)	0.0248 (3)
H4	0.7115	0.7565	0.3336	0.030*
N5	0.66061 (16)	0.60605 (13)	0.43879 (6)	0.0220 (3)
H5	0.635 (2)	0.531 (2)	0.4616 (8)	0.026*
C6	0.83714 (19)	0.64872 (16)	0.44346 (7)	0.0258 (3)
H6A	0.8511	0.7450	0.4266	0.031*
H6B	0.9091	0.5845	0.4182	0.031*
C7	0.8900 (2)	0.64430 (16)	0.51234 (7)	0.0264 (3)
H7A	1.0123	0.6652	0.5163	0.032*
H7B	0.8261	0.7152	0.5369	0.032*
O8	0.85488 (13)	0.50656 (10)	0.53601 (5)	0.0231 (2)
C9	0.87951 (19)	0.49346 (17)	0.60301 (7)	0.0254 (3)
H9A	0.9929	0.5302	0.6142	0.031*
H9B	0.8761	0.3929	0.6148	0.031*
C10	0.74524 (18)	0.57277 (16)	0.64093 (7)	0.0248 (3)
H10A	0.7635	0.5549	0.6867	0.030*
H10B	0.7595	0.6748	0.6336	0.030*
N11	0.57172 (16)	0.53277 (14)	0.62434 (6)	0.0221 (3)
H11	0.549 (2)	0.551 (2)	0.5837 (8)	0.027*
C12	0.55390 (18)	0.33648 (16)	0.70008 (7)	0.0223 (3)
H12	0.6409	0.3763	0.7254	0.027*
C13	0.47728 (19)	0.21172 (15)	0.71933 (6)	0.0237 (3)
H13	0.5124	0.1674	0.7575	0.028*
C14	0.3503 (2)	0.15238 (15)	0.68306 (6)	0.0236 (3)
H14	0.2986	0.0671	0.6961	0.028*
C15	0.29838 (19)	0.21812 (15)	0.62724 (6)	0.0217 (3)
H15	0.2100	0.1782	0.6026	0.026*
O16	0.33415 (14)	0.41261 (10)	0.55285 (4)	0.0218 (2)
C17	0.23723 (18)	0.33597 (15)	0.50683 (6)	0.0198 (3)
H17A	0.1197	0.3231	0.5220	0.024*
H17B	0.2879	0.2422	0.4998	0.024*
C18	0.23809 (17)	0.41882 (15)	0.44624 (6)	0.0209 (3)
H18A	0.1632	0.3738	0.4146	0.025*
H18B	0.1966	0.5154	0.4541	0.025*
O19	0.40834 (12)	0.42266 (11)	0.42325 (5)	0.0229 (2)
C20	0.43795 (18)	0.51466 (15)	0.37326 (7)	0.0210 (3)
C21	0.57665 (17)	0.60541 (15)	0.38088 (7)	0.0206 (3)
C22	0.50516 (18)	0.40398 (14)	0.64422 (6)	0.0196 (3)
C23	0.37543 (18)	0.34158 (14)	0.60772 (6)	0.0195 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0235 (7)	0.0238 (7)	0.0251 (7)	0.0028 (6)	0.0005 (6)	0.0012 (6)
C2	0.0296 (7)	0.0274 (7)	0.0232 (7)	0.0083 (7)	0.0008 (6)	0.0027 (6)
C3	0.0302 (8)	0.0251 (7)	0.0251 (7)	0.0079 (7)	0.0085 (6)	0.0056 (6)
C4	0.0239 (7)	0.0206 (7)	0.0299 (7)	0.0026 (6)	0.0063 (6)	0.0021 (6)
N5	0.0204 (6)	0.0201 (6)	0.0254 (6)	−0.0007 (5)	0.0019 (5)	0.0006 (5)
C6	0.0226 (7)	0.0255 (7)	0.0293 (7)	−0.0055 (6)	0.0024 (6)	−0.0022 (6)
C7	0.0251 (7)	0.0232 (7)	0.0309 (7)	−0.0065 (7)	0.0016 (6)	−0.0049 (6)
O8	0.0236 (5)	0.0216 (5)	0.0242 (5)	−0.0016 (4)	−0.0022 (4)	−0.0043 (4)
C9	0.0215 (7)	0.0288 (8)	0.0260 (7)	−0.0012 (6)	−0.0049 (6)	−0.0040 (6)
C10	0.0241 (7)	0.0247 (7)	0.0256 (7)	−0.0061 (7)	−0.0011 (6)	−0.0048 (6)
N11	0.0224 (6)	0.0208 (6)	0.0232 (6)	−0.0031 (5)	−0.0020 (5)	−0.0006 (5)
C12	0.0202 (6)	0.0251 (7)	0.0215 (6)	0.0018 (6)	−0.0025 (5)	−0.0046 (6)
C13	0.0268 (8)	0.0248 (7)	0.0196 (6)	0.0047 (7)	−0.0004 (6)	0.0005 (6)
C14	0.0281 (7)	0.0197 (7)	0.0232 (6)	−0.0022 (6)	0.0036 (6)	−0.0005 (5)
C15	0.0221 (7)	0.0217 (6)	0.0211 (6)	−0.0032 (6)	−0.0003 (5)	−0.0028 (6)
O16	0.0270 (5)	0.0191 (5)	0.0194 (5)	−0.0040 (4)	−0.0046 (4)	−0.0002 (4)
C17	0.0174 (6)	0.0232 (7)	0.0189 (6)	−0.0035 (6)	−0.0006 (5)	−0.0019 (5)
C18	0.0157 (6)	0.0246 (7)	0.0224 (6)	−0.0001 (6)	−0.0007 (5)	0.0006 (6)
O19	0.0171 (5)	0.0268 (5)	0.0249 (5)	0.0016 (4)	0.0019 (4)	0.0079 (4)
C20	0.0210 (7)	0.0193 (6)	0.0228 (6)	0.0047 (6)	0.0038 (5)	0.0027 (6)
C21	0.0203 (6)	0.0179 (6)	0.0236 (6)	0.0058 (6)	0.0051 (5)	−0.0014 (5)
C22	0.0181 (6)	0.0183 (6)	0.0225 (6)	0.0006 (6)	0.0024 (5)	−0.0048 (5)
C23	0.0214 (7)	0.0188 (6)	0.0183 (6)	0.0027 (6)	−0.0001 (5)	−0.0030 (5)

Geometric parameters (Å, º)

C1—C20	1.386 (2)	C10—H10B	0.9900
C1—C2	1.397 (2)	N11—C22	1.3988 (19)
C1—H1	0.9500	N11—H11	0.893 (17)
C2—C3	1.380 (2)	C12—C13	1.394 (2)
C2—H2	0.9500	C12—C22	1.396 (2)
C3—C4	1.396 (2)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.382 (2)
C4—C21	1.4037 (19)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.395 (2)
N5—C21	1.3900 (18)	C14—H14	0.9500
N5—C6	1.4558 (19)	C15—C23	1.386 (2)
N5—H5	0.887 (19)	C15—H15	0.9500
C6—C7	1.512 (2)	O16—C23	1.3796 (16)
C6—H6A	0.9900	O16—C17	1.4357 (16)
C6—H6B	0.9900	C17—C18	1.5018 (18)
C7—O8	1.4306 (18)	C17—H17A	0.9900
C7—H7A	0.9900	C17—H17B	0.9900
C7—H7B	0.9900	C18—O19	1.4301 (16)
O8—C9	1.4319 (17)	C18—H18A	0.9900
C9—C10	1.528 (2)	C18—H18B	0.9900
C9—H9A	0.9900	O19—C20	1.3906 (17)
C9—H9B	0.9900	C20—C21	1.405 (2)
C10—N11	1.4651 (18)	C22—C23	1.4129 (19)
C10—H10A	0.9900
C20—C1—C2	119.63 (14)	C22—N11—H11	112.7 (12)
C20—C1—H1	120.2	C10—N11—H11	111.5 (12)
C2—C1—H1	120.2	C13—C12—C22	121.23 (14)
C3—C2—C1	119.55 (14)	C13—C12—H12	119.4
C3—C2—H2	120.2	C22—C12—H12	119.4
C1—C2—H2	120.2	C14—C13—C12	120.16 (13)
C2—C3—C4	120.97 (13)	C14—C13—H13	119.9
C2—C3—H3	119.5	C12—C13—H13	119.9
C4—C3—H3	119.5	C13—C14—C15	119.81 (13)
C3—C4—C21	120.38 (14)	C13—C14—H14	120.1
C3—C4—H4	119.8	C15—C14—H14	120.1
C21—C4—H4	119.8	C23—C15—C14	120.13 (13)
C21—N5—C6	121.18 (12)	C23—C15—H15	119.9
C21—N5—H5	111.5 (12)	C14—C15—H15	119.9
C6—N5—H5	113.8 (12)	C23—O16—C17	116.36 (10)
N5—C6—C7	108.76 (12)	O16—C17—C18	107.81 (11)
N5—C6—H6A	109.9	O16—C17—H17A	110.1
C7—C6—H6A	109.9	C18—C17—H17A	110.1
N5—C6—H6B	109.9	O16—C17—H17B	110.1
C7—C6—H6B	109.9	C18—C17—H17B	110.1
H6A—C6—H6B	108.3	H17A—C17—H17B	108.5
O8—C7—C6	107.91 (12)	O19—C18—C17	107.84 (11)
O8—C7—H7A	110.1	O19—C18—H18A	110.1
C6—C7—H7A	110.1	C17—C18—H18A	110.1
O8—C7—H7B	110.1	O19—C18—H18B	110.1
C6—C7—H7B	110.1	C17—C18—H18B	110.1
H7A—C7—H7B	108.4	H18A—C18—H18B	108.5
C7—O8—C9	113.46 (11)	C20—O19—C18	115.56 (10)
O8—C9—C10	112.28 (12)	C1—C20—O19	122.57 (13)
O8—C9—H9A	109.1	C1—C20—C21	121.74 (13)
C10—C9—H9A	109.1	O19—C20—C21	115.60 (12)
O8—C9—H9B	109.1	N5—C21—C4	123.85 (13)
C10—C9—H9B	109.1	N5—C21—C20	118.38 (13)
H9A—C9—H9B	107.9	C4—C21—C20	117.73 (13)
N11—C10—C9	113.32 (12)	C12—C22—N11	123.57 (13)
N11—C10—H10A	108.9	C12—C22—C23	117.79 (13)
C9—C10—H10A	108.9	N11—C22—C23	118.56 (13)
N11—C10—H10B	108.9	O16—C23—C15	124.14 (12)
C9—C10—H10B	108.9	O16—C23—C22	114.99 (12)
H10A—C10—H10B	107.7	C15—C23—C22	120.88 (13)
C22—N11—C10	120.53 (13)
C20—C1—C2—C3	0.0 (2)	C6—N5—C21—C20	154.70 (13)
C1—C2—C3—C4	−0.3 (2)	C3—C4—C21—N5	−177.33 (13)
C2—C3—C4—C21	0.2 (2)	C3—C4—C21—C20	0.2 (2)
C21—N5—C6—C7	177.61 (13)	C1—C20—C21—N5	177.12 (13)
N5—C6—C7—O8	55.00 (15)	O19—C20—C21—N5	−6.27 (18)
C6—C7—O8—C9	−172.63 (12)	C1—C20—C21—C4	−0.5 (2)
C7—O8—C9—C10	70.25 (16)	O19—C20—C21—C4	176.07 (12)
O8—C9—C10—N11	54.75 (17)	C13—C12—C22—N11	176.67 (13)
C9—C10—N11—C22	74.11 (17)	C13—C12—C22—C23	0.0 (2)
C22—C12—C13—C14	−0.1 (2)	C10—N11—C22—C12	30.1 (2)
C12—C13—C14—C15	−0.3 (2)	C10—N11—C22—C23	−153.20 (13)
C13—C14—C15—C23	0.9 (2)	C17—O16—C23—C15	−15.83 (19)
C23—O16—C17—C18	−168.02 (11)	C17—O16—C23—C22	164.22 (12)
O16—C17—C18—O19	65.29 (14)	C14—C15—C23—O16	179.01 (13)
C17—C18—O19—C20	−169.60 (11)	C14—C15—C23—C22	−1.0 (2)
C2—C1—C20—O19	−175.91 (13)	C12—C22—C23—O16	−179.44 (12)
C2—C1—C20—C21	0.5 (2)	N11—C22—C23—O16	3.68 (18)
C18—O19—C20—C1	−53.32 (18)	C12—C22—C23—C15	0.6 (2)
C18—O19—C20—C21	130.10 (13)	N11—C22—C23—C15	−176.28 (12)
C6—N5—C21—C4	−27.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O8	0.887 (19)	2.349 (18)	2.7310 (16)	106.0 (14)
N5—H5···O19	0.887 (19)	2.220 (19)	2.6699 (17)	111.0 (14)
N11—H11···O16	0.893 (17)	2.246 (18)	2.6655 (16)	108.3 (14)

(II) 6,7,9,10,12,13,20,21-octahydro-5H,14H-8,11,19,22-tetraoxa- 5,14-diazadibenzo[a,g]cyclooctadecene

Crystal data

C20H26N2O4	F(000) = 768
Mr = 358.43	Dx = 1.272 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5690 reflections
a = 11.837 (2) Å	θ = 2.1–26.4°
b = 18.116 (3) Å	µ = 0.09 mm^−1
c = 9.2565 (18) Å	T = 120 K
β = 109.485 (5)°	Prism, colourless
V = 1871.3 (6) Å^3	0.28 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker APEX CCD diffractometer	1839 independent reflections
Radiation source: fine-focus sealed tube	1726 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −14→14
Tmin = 0.973, Tmax = 0.989	k = −22→22
9314 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 1.P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1839 reflections	Δρmax = 0.24 e Å^−3
122 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (10)

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
C1	0.18564 (9)	0.31043 (6)	0.63215 (11)	0.0262 (2)
H1	0.2085	0.2682	0.6961	0.031*
C2	0.06692 (10)	0.33518 (6)	0.58493 (12)	0.0302 (3)
H2	0.0092	0.3101	0.6177	0.036*
C3	0.03388 (9)	0.39600 (6)	0.49067 (13)	0.0300 (3)
H3	−0.0468	0.4127	0.4585	0.036*
C4	0.11801 (9)	0.43320 (6)	0.44222 (12)	0.0254 (2)
H4	0.0939	0.4750	0.3772	0.030*
N5	0.32358 (8)	0.44260 (5)	0.44061 (10)	0.0237 (2)
H5	0.3953 (12)	0.4283 (7)	0.4856 (14)	0.028*
C6	0.30872 (9)	0.51483 (6)	0.36939 (11)	0.0250 (2)
H6A	0.2312	0.5161	0.2844	0.030*
H6B	0.3731	0.5224	0.3247	0.030*
C7	0.31192 (9)	0.57776 (6)	0.47855 (12)	0.0258 (2)
H7A	0.2899	0.6246	0.4208	0.031*
H7B	0.2536	0.5685	0.5322	0.031*
O8	0.42944 (6)	0.58316 (4)	0.58670 (8)	0.0255 (2)
C9	0.43885 (10)	0.64274 (6)	0.68967 (12)	0.0280 (3)
H9A	0.3767	0.6379	0.7389	0.034*
H9B	0.4256	0.6900	0.6328	0.034*
C21	0.43311 (9)	0.26993 (5)	0.73029 (11)	0.0239 (2)
H21A	0.3988	0.2227	0.6812	0.029*
H21B	0.4113	0.2766	0.8238	0.029*
O22	0.38886 (6)	0.33012 (4)	0.62683 (8)	0.0249 (2)
C23	0.26966 (9)	0.34751 (5)	0.58562 (10)	0.0216 (2)
C24	0.23705 (8)	0.40991 (5)	0.48789 (11)	0.0208 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0311 (5)	0.0257 (5)	0.0206 (5)	−0.0069 (4)	0.0070 (4)	−0.0027 (4)
C2	0.0293 (5)	0.0345 (6)	0.0308 (5)	−0.0102 (4)	0.0152 (4)	−0.0074 (4)
C3	0.0223 (5)	0.0325 (6)	0.0362 (6)	−0.0007 (4)	0.0109 (4)	−0.0081 (4)
C4	0.0232 (5)	0.0245 (5)	0.0270 (5)	0.0013 (4)	0.0063 (4)	−0.0027 (4)
N5	0.0197 (4)	0.0242 (5)	0.0263 (4)	0.0023 (3)	0.0066 (3)	0.0044 (3)
C6	0.0247 (5)	0.0266 (5)	0.0227 (5)	0.0004 (4)	0.0064 (4)	0.0057 (4)
C7	0.0237 (5)	0.0240 (5)	0.0288 (5)	0.0032 (4)	0.0074 (4)	0.0066 (4)
O8	0.0238 (4)	0.0258 (4)	0.0266 (4)	0.0008 (3)	0.0081 (3)	−0.0013 (3)
C9	0.0356 (6)	0.0218 (5)	0.0277 (5)	0.0032 (4)	0.0121 (5)	0.0019 (4)
C21	0.0290 (6)	0.0183 (5)	0.0202 (5)	−0.0010 (4)	0.0027 (4)	0.0013 (4)
O22	0.0218 (4)	0.0231 (4)	0.0258 (4)	−0.0008 (3)	0.0026 (3)	0.0053 (3)
C23	0.0222 (5)	0.0223 (5)	0.0179 (4)	−0.0024 (4)	0.0035 (4)	−0.0047 (3)
C24	0.0219 (5)	0.0217 (5)	0.0182 (4)	−0.0015 (4)	0.0057 (4)	−0.0041 (4)

Geometric parameters (Å, º)

C1—C23	1.3826 (14)	C6—H6B	0.9900
C1—C2	1.3990 (15)	C7—O8	1.4205 (12)
C1—H1	0.9500	C7—H7A	0.9900
C2—C3	1.3786 (16)	C7—H7B	0.9900
C2—H2	0.9500	O8—C9	1.4196 (12)
C3—C4	1.3946 (15)	C9—C9^i	1.505 (2)
C3—H3	0.9500	C9—H9A	0.9900
C4—C24	1.3946 (14)	C9—H9B	0.9900
C4—H4	0.9500	C21—O22	1.4303 (11)
N5—C24	1.3749 (13)	C21—C21^i	1.502 (2)
N5—C6	1.4493 (13)	C21—H21A	0.9900
N5—H5	0.851 (14)	C21—H21B	0.9900
C6—C7	1.5155 (14)	O22—C23	1.3699 (12)
C6—H6A	0.9900	C23—C24	1.4185 (14)
C23—C1—C2	119.93 (10)	O8—C7—H7B	109.9
C23—C1—H1	120.0	C6—C7—H7B	109.9
C2—C1—H1	120.0	H7A—C7—H7B	108.3
C3—C2—C1	119.81 (9)	C9—O8—C7	111.39 (8)
C3—C2—H2	120.1	O8—C9—C9^i	109.81 (8)
C1—C2—H2	120.1	O8—C9—H9A	109.7
C2—C3—C4	120.50 (10)	C9^i—C9—H9A	109.7
C2—C3—H3	119.8	O8—C9—H9B	109.7
C4—C3—H3	119.8	C9^i—C9—H9B	109.7
C24—C4—C3	120.93 (10)	H9A—C9—H9B	108.2
C24—C4—H4	119.5	O22—C21—C21^i	106.48 (7)
C3—C4—H4	119.5	O22—C21—H21A	110.4
C24—N5—C6	122.91 (8)	C21^i—C21—H21A	110.4
C24—N5—H5	116.1 (9)	O22—C21—H21B	110.4
C6—N5—H5	116.6 (9)	C21^i—C21—H21B	110.4
N5—C6—C7	113.81 (8)	H21A—C21—H21B	108.6
N5—C6—H6A	108.8	C23—O22—C21	118.35 (8)
C7—C6—H6A	108.8	O22—C23—C1	125.63 (9)
N5—C6—H6B	108.8	O22—C23—C24	113.38 (8)
C7—C6—H6B	108.8	C1—C23—C24	120.99 (9)
H6A—C6—H6B	107.7	N5—C24—C4	123.91 (9)
O8—C7—C6	108.81 (8)	N5—C24—C23	118.23 (9)
O8—C7—H7A	109.9	C4—C24—C23	117.83 (9)
C6—C7—H7A	109.9
C23—C1—C2—C3	0.74 (15)	C2—C1—C23—O22	178.24 (9)
C1—C2—C3—C4	−0.14 (15)	C2—C1—C23—C24	−1.14 (15)
C2—C3—C4—C24	−0.06 (15)	C6—N5—C24—C4	15.54 (15)
C24—N5—C6—C7	70.84 (12)	C6—N5—C24—C23	−166.26 (9)
N5—C6—C7—O8	67.58 (10)	C3—C4—C24—N5	177.90 (9)
C6—C7—O8—C9	178.31 (8)	C3—C4—C24—C23	−0.31 (14)
C7—O8—C9—C9^i	175.21 (9)	O22—C23—C24—N5	3.15 (12)
C21^i—C21—O22—C23	−173.01 (8)	C1—C23—C24—N5	−177.40 (9)
C21—O22—C23—C1	−1.91 (14)	O22—C23—C24—C4	−178.54 (8)
C21—O22—C23—C24	177.52 (8)	C1—C23—C24—C4	0.91 (14)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O8^ii	0.851 (14)	2.392 (13)	3.0530 (12)	134.9 (11)
N5—H5···O22	0.851 (14)	2.223 (13)	2.6138 (11)	107.9 (10)

Symmetry code: (ii) −x+1, −y+1, −z+1.

(III) 6,7,9,10,17,18,20,21-octahydro-16H,22H-5,8,11,19-tetraoxa-16,22- diazadibenzo[a,j]cyclooctadecene 0.3-hydrate

Crystal data

C20H26N2O4·0.304H2O	F(000) = 390
Mr = 363.92	Dx = 1.287 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 13.507 (8) Å	Cell parameters from 972 reflections
b = 5.133 (3) Å	θ = 2.6–24.6°
c = 14.644 (8) Å	µ = 0.09 mm^−1
β = 112.336 (9)°	T = 100 K
V = 939.1 (9) Å^3	Needle, colourless
Z = 2	0.22 × 0.05 × 0.04 mm

Data collection

Bruker APEX CCD diffractometer	2037 independent reflections
Radiation source: fine-focus sealed tube	1223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −16→16
Tmin = 0.979, Tmax = 0.997	k = −5→6
4546 measured reflections	l = −18→14

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) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.032P)^2] where P = (Fo^2 + 2Fc^2)/3
2037 reflections	(Δ/σ)max < 0.001
257 parameters	Δρmax = 0.23 e Å^−3
6 restraints	Δρmin = −0.20 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. Although the Flack parameter was refined, the lack of a strong anomalous scatter makes this parameter inappropriate. The Friedel related data were merged.

Restraints on the N—H and O—H distances were required.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6694 (4)	0.2589 (10)	1.1212 (3)	0.0355 (13)
H1	0.6153	0.1293	1.0987	0.043*
C2	0.7342 (4)	0.2733 (10)	1.2211 (3)	0.0357 (13)
H2	0.7242	0.1539	1.2664	0.043*
C3	0.8125 (4)	0.4597 (11)	1.2542 (3)	0.0340 (13)
H3	0.8563	0.4701	1.3224	0.041*
C4	0.8282 (4)	0.6343 (10)	1.1877 (3)	0.0331 (13)
H4	0.8827	0.7628	1.2106	0.040*
O5	0.7732 (2)	0.7817 (6)	1.0176 (2)	0.0330 (8)
C6	0.8615 (3)	0.9623 (10)	1.0469 (3)	0.0284 (12)
H6A	0.9301	0.8671	1.0757	0.034*
H6B	0.8562	1.0844	1.0972	0.034*
C7	0.8565 (4)	1.1092 (10)	0.9569 (3)	0.0296 (12)
H7A	0.7837	1.1807	0.9223	0.036*
H7B	0.9077	1.2562	0.9762	0.036*
O8	0.8825 (2)	0.9370 (7)	0.89319 (19)	0.0329 (8)
C9	0.8712 (4)	1.0595 (9)	0.8038 (3)	0.0264 (12)
H9A	0.9166	1.2175	0.8174	0.032*
H9B	0.7958	1.1131	0.7684	0.032*
C10	0.9037 (3)	0.8757 (9)	0.7409 (3)	0.0260 (12)
H10A	0.9174	0.9730	0.6885	0.031*
H10B	0.9701	0.7829	0.7816	0.031*
O11	0.8187 (2)	0.6939 (6)	0.6979 (2)	0.0315 (8)
C12	0.9164 (4)	0.4963 (9)	0.6039 (3)	0.0323 (13)
H12	0.9764	0.6077	0.6333	0.039*
C13	0.9170 (4)	0.3112 (9)	0.5354 (3)	0.0312 (12)
H13	0.9769	0.2980	0.5167	0.037*
C14	0.8319 (4)	0.1473 (10)	0.4944 (3)	0.0343 (12)
H14	0.8335	0.0200	0.4479	0.041*
C15	0.7425 (4)	0.1646 (10)	0.5200 (3)	0.0324 (12)
H15	0.6840	0.0490	0.4911	0.039*
N16	0.6530 (3)	0.3813 (8)	0.6161 (2)	0.0254 (9)
H16	0.670 (3)	0.484 (7)	0.666 (2)	0.030*
C17	0.5757 (3)	0.1761 (10)	0.5971 (3)	0.0327 (12)
H17A	0.6130	0.0084	0.6205	0.039*
H17B	0.5344	0.1620	0.5251	0.039*
C18	0.5006 (3)	0.2295 (10)	0.6490 (3)	0.0325 (12)
H18A	0.4716	0.4083	0.6335	0.039*
H18B	0.4399	0.1058	0.6256	0.039*
O19	0.5558 (2)	0.2027 (7)	0.7526 (2)	0.0371 (9)
C20	0.4862 (3)	0.2611 (10)	0.8032 (3)	0.0326 (12)
H20A	0.4229	0.1454	0.7789	0.039*
H20B	0.4611	0.4435	0.7896	0.039*
C21	0.5446 (3)	0.2233 (10)	0.9127 (3)	0.0321 (12)
H21A	0.4922	0.2162	0.9450	0.038*
H21B	0.5838	0.0557	0.9251	0.038*
N22	0.6186 (3)	0.4321 (8)	0.9545 (2)	0.0269 (10)
H22	0.650 (3)	0.523 (7)	0.925 (3)	0.032*
C23	0.6832 (3)	0.4316 (9)	1.0546 (3)	0.0258 (11)
C24	0.7644 (4)	0.6197 (9)	1.0891 (3)	0.0254 (12)
C25	0.8270 (4)	0.5186 (9)	0.6298 (3)	0.0254 (12)
C26	0.7392 (3)	0.3500 (9)	0.5874 (3)	0.0259 (12)
O1S	0.6568 (8)	0.703 (2)	0.7943 (8)	0.032 (4)	0.304 (6)
H1S	0.7225 (19)	0.72 (2)	0.818 (9)	0.038*	0.304 (6)
H2S	0.623 (8)	0.840 (14)	0.779 (10)	0.038*	0.304 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.045 (3)	0.040 (4)	0.030 (3)	−0.005 (3)	0.024 (3)	−0.003 (3)
C2	0.037 (3)	0.045 (3)	0.028 (3)	0.005 (3)	0.016 (2)	0.008 (3)
C3	0.038 (3)	0.043 (3)	0.019 (3)	0.009 (3)	0.008 (2)	0.003 (3)
C4	0.030 (3)	0.039 (3)	0.030 (3)	0.002 (3)	0.010 (2)	−0.002 (3)
O5	0.040 (2)	0.033 (2)	0.0262 (18)	−0.0023 (17)	0.0134 (16)	0.0036 (16)
C6	0.026 (3)	0.031 (3)	0.027 (3)	−0.003 (3)	0.008 (2)	−0.002 (2)
C7	0.032 (3)	0.032 (3)	0.026 (3)	−0.003 (2)	0.012 (2)	−0.002 (2)
O8	0.045 (2)	0.035 (2)	0.0232 (17)	0.0066 (17)	0.0183 (16)	0.0059 (17)
C9	0.031 (3)	0.027 (3)	0.019 (3)	−0.002 (2)	0.006 (2)	−0.002 (2)
C10	0.023 (3)	0.028 (3)	0.023 (3)	−0.002 (2)	0.004 (2)	0.002 (2)
O11	0.040 (2)	0.030 (2)	0.0269 (17)	−0.0042 (18)	0.0152 (16)	−0.0038 (16)
C12	0.046 (3)	0.027 (3)	0.027 (3)	0.000 (3)	0.018 (3)	0.007 (2)
C13	0.046 (3)	0.028 (3)	0.030 (3)	0.005 (3)	0.026 (3)	0.008 (2)
C14	0.048 (3)	0.032 (3)	0.028 (3)	0.009 (3)	0.019 (3)	0.003 (3)
C15	0.037 (3)	0.034 (3)	0.023 (3)	0.002 (3)	0.009 (2)	−0.002 (3)
N16	0.026 (2)	0.024 (2)	0.023 (2)	−0.003 (2)	0.006 (2)	−0.0111 (19)
C17	0.035 (3)	0.035 (3)	0.025 (3)	0.000 (3)	0.007 (2)	−0.002 (2)
C18	0.027 (3)	0.039 (3)	0.026 (3)	−0.004 (3)	0.003 (2)	−0.002 (3)
O19	0.0320 (18)	0.054 (2)	0.0220 (17)	0.0037 (19)	0.0059 (16)	−0.0026 (18)
C20	0.030 (3)	0.039 (3)	0.031 (3)	0.000 (2)	0.014 (2)	−0.001 (3)
C21	0.030 (3)	0.038 (3)	0.028 (3)	−0.003 (3)	0.010 (2)	0.003 (3)
N22	0.030 (2)	0.035 (3)	0.017 (2)	−0.010 (2)	0.0096 (19)	0.0043 (19)
C23	0.027 (3)	0.024 (3)	0.027 (3)	0.007 (2)	0.012 (2)	−0.003 (2)
C24	0.031 (3)	0.028 (3)	0.020 (3)	0.005 (3)	0.013 (2)	0.003 (2)
C25	0.040 (3)	0.019 (3)	0.019 (3)	−0.001 (2)	0.013 (2)	−0.002 (2)
C26	0.030 (3)	0.026 (3)	0.019 (3)	0.003 (2)	0.006 (2)	0.002 (2)
O1S	0.039 (7)	0.032 (8)	0.028 (7)	−0.002 (6)	0.016 (6)	0.003 (6)

Geometric parameters (Å, º)

C1—C23	1.382 (6)	C13—C14	1.365 (6)
C1—C2	1.393 (6)	C13—H13	0.9500
C1—H1	0.9500	C14—C15	1.396 (6)
C2—C3	1.371 (7)	C14—H14	0.9500
C2—H2	0.9500	C15—C26	1.384 (6)
C3—C4	1.397 (6)	C15—H15	0.9500
C3—H3	0.9500	N16—C26	1.390 (5)
C4—C24	1.373 (5)	N16—C17	1.433 (6)
C4—H4	0.9500	N16—H16	0.861 (19)
O5—C24	1.378 (5)	C17—C18	1.506 (5)
O5—C6	1.441 (5)	C17—H17A	0.9900
C6—C7	1.498 (5)	C17—H17B	0.9900
C6—H6A	0.9900	C18—O19	1.419 (4)
C6—H6B	0.9900	C18—H18A	0.9900
C7—O8	1.423 (5)	C18—H18B	0.9900
C7—H7A	0.9900	O19—C20	1.432 (4)
C7—H7B	0.9900	C20—C21	1.507 (5)
O8—C9	1.407 (4)	C20—H20A	0.9900
C9—C10	1.495 (5)	C20—H20B	0.9900
C9—H9A	0.9900	C21—N22	1.434 (6)
C9—H9B	0.9900	C21—H21A	0.9900
C10—O11	1.427 (5)	C21—H21B	0.9900
C10—H10A	0.9900	N22—C23	1.393 (5)
C10—H10B	0.9900	N22—H22	0.842 (19)
O11—C25	1.379 (5)	C23—C24	1.403 (6)
C12—C13	1.385 (6)	C25—C26	1.407 (6)
C12—C25	1.400 (6)	O1S—H1S	0.83 (2)
C12—H12	0.9500	O1S—H2S	0.82 (2)
C23—C1—C2	120.5 (5)	C26—C15—C14	120.1 (5)
C23—C1—H1	119.7	C26—C15—H15	120.0
C2—C1—H1	119.7	C14—C15—H15	120.0
C3—C2—C1	120.0 (5)	C26—N16—C17	119.2 (4)
C3—C2—H2	120.0	C26—N16—H16	110 (3)
C1—C2—H2	120.0	C17—N16—H16	123 (3)
C2—C3—C4	120.2 (4)	N16—C17—C18	110.4 (4)
C2—C3—H3	119.9	N16—C17—H17A	109.6
C4—C3—H3	119.9	C18—C17—H17A	109.6
C24—C4—C3	119.8 (5)	N16—C17—H17B	109.6
C24—C4—H4	120.1	C18—C17—H17B	109.6
C3—C4—H4	120.1	H17A—C17—H17B	108.1
C24—O5—C6	117.5 (3)	O19—C18—C17	110.0 (3)
O5—C6—C7	107.8 (3)	O19—C18—H18A	109.7
O5—C6—H6A	110.1	C17—C18—H18A	109.7
C7—C6—H6A	110.1	O19—C18—H18B	109.7
O5—C6—H6B	110.1	C17—C18—H18B	109.7
C7—C6—H6B	110.1	H18A—C18—H18B	108.2
H6A—C6—H6B	108.5	C18—O19—C20	110.6 (3)
O8—C7—C6	109.0 (4)	O19—C20—C21	110.1 (4)
O8—C7—H7A	109.9	O19—C20—H20A	109.6
C6—C7—H7A	109.9	C21—C20—H20A	109.6
O8—C7—H7B	109.9	O19—C20—H20B	109.6
C6—C7—H7B	109.9	C21—C20—H20B	109.6
H7A—C7—H7B	108.3	H20A—C20—H20B	108.2
C9—O8—C7	111.5 (3)	N22—C21—C20	110.8 (4)
O8—C9—C10	109.7 (4)	N22—C21—H21A	109.5
O8—C9—H9A	109.7	C20—C21—H21A	109.5
C10—C9—H9A	109.7	N22—C21—H21B	109.5
O8—C9—H9B	109.7	C20—C21—H21B	109.5
C10—C9—H9B	109.7	H21A—C21—H21B	108.1
H9A—C9—H9B	108.2	C23—N22—C21	120.3 (4)
O11—C10—C9	108.0 (3)	C23—N22—H22	108 (3)
O11—C10—H10A	110.1	C21—N22—H22	127 (3)
C9—C10—H10A	110.1	C1—C23—N22	123.1 (4)
O11—C10—H10B	110.1	C1—C23—C24	118.9 (4)
C9—C10—H10B	110.1	N22—C23—C24	118.0 (4)
H10A—C10—H10B	108.4	C4—C24—O5	124.5 (4)
C25—O11—C10	118.3 (3)	C4—C24—C23	120.6 (4)
C13—C12—C25	119.6 (5)	O5—C24—C23	115.0 (4)
C13—C12—H12	120.2	O11—C25—C12	124.3 (4)
C25—C12—H12	120.2	O11—C25—C26	115.6 (4)
C14—C13—C12	120.4 (4)	C12—C25—C26	120.0 (4)
C14—C13—H13	119.8	C15—C26—N16	123.6 (4)
C12—C13—H13	119.8	C15—C26—C25	119.1 (4)
C13—C14—C15	120.8 (5)	N16—C26—C25	117.3 (4)
C13—C14—H14	119.6	H1S—O1S—H2S	114 (6)
C15—C14—H14	119.6
C23—C1—C2—C3	0.0 (7)	C21—N22—C23—C24	171.3 (4)
C1—C2—C3—C4	−0.5 (7)	C3—C4—C24—O5	−179.9 (4)
C2—C3—C4—C24	0.4 (7)	C3—C4—C24—C23	0.4 (7)
C24—O5—C6—C7	178.0 (3)	C6—O5—C24—C4	6.0 (6)
O5—C6—C7—O8	−69.7 (4)	C6—O5—C24—C23	−174.2 (4)
C6—C7—O8—C9	175.5 (4)	C1—C23—C24—C4	−0.9 (6)
C7—O8—C9—C10	177.6 (3)	N22—C23—C24—C4	177.8 (4)
O8—C9—C10—O11	77.0 (4)	C1—C23—C24—O5	179.3 (4)
C9—C10—O11—C25	174.4 (3)	N22—C23—C24—O5	−2.0 (6)
C25—C12—C13—C14	−1.3 (6)	C10—O11—C25—C12	3.9 (6)
C12—C13—C14—C15	0.6 (7)	C10—O11—C25—C26	−177.9 (4)
C13—C14—C15—C26	0.2 (7)	C13—C12—C25—O11	179.2 (4)
C26—N16—C17—C18	170.3 (4)	C13—C12—C25—C26	1.2 (6)
N16—C17—C18—O19	−69.9 (5)	C14—C15—C26—N16	179.4 (4)
C17—C18—O19—C20	178.2 (4)	C14—C15—C26—C25	−0.3 (6)
C18—O19—C20—C21	178.1 (4)	C17—N16—C26—C15	16.9 (6)
O19—C20—C21—N22	74.6 (5)	C17—N16—C26—C25	−163.3 (4)
C20—C21—N22—C23	−178.2 (4)	O11—C25—C26—C15	−178.6 (4)
C2—C1—C23—N22	−177.9 (4)	C12—C25—C26—C15	−0.4 (6)
C2—C1—C23—C24	0.7 (6)	O11—C25—C26—N16	1.6 (6)
C21—N22—C23—C1	−10.1 (6)	C12—C25—C26—N16	179.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N16—H16···O11	0.86 (2)	2.17 (4)	2.643 (5)	114 (3)
N16—H16···O1S	0.86 (2)	2.25 (3)	3.073 (11)	160 (4)
N22—H22···O5	0.84 (2)	2.16 (4)	2.639 (5)	116 (3)
N22—H22···O1S	0.84 (2)	2.17 (3)	2.937 (11)	152 (4)
O1S—H1S···O8	0.83 (2)	2.30 (6)	3.078 (10)	157 (12)
O1S—H1S···O11	0.83 (2)	2.56 (12)	3.021 (10)	117 (11)
O1S—H2S···O19^i	0.82 (2)	2.04 (3)	2.859 (12)	173 (13)

Symmetry code: (i) x, y+1, z.