A Schiff base lateral macrobicycle derived from 4,13-diaza-18-crown-6 in its protonated form

In the structure of the title compound, 28,31,36,39-tetraoxa-9,17,42-triaza-1,25-diazoniapentacyclo[23.8.5.1^11,15.0^3,8.0^18,23]nonatriaconta-3,5,7,9,11,13,15,16,18,20,22-undecene bis(perchlorate), C₃₃H₄₃N₅O₄²⁺·2ClO₄^- or (H₂L)(ClO₄)₂, the cation and one of the two independent anions lie on crystallographic twofold axes, while the second perchlorate anion is disordered about a centre of inversion. The conformation of the macrobicycle L is conditioned by two strong intramolecular hydrogen-bonding interactions involving the pivot and imine N atoms, and is quite different from that observed when a metal ion is placed inside its cavity. The two imine groups are not coplanar with the pyridine moiety, and the deviation from planarity is considerably larger than that found in the corresponding Ba complex. Moreover, the fold of the macrobicycle in H₂L²⁺ causes a significant approach of the two pivot N atoms compared with their disposition in the Ba complex. This is the first X-ray crystal structure analysis of an uncoordinated Schiff base lateral macrobicycle.

S1. Comment

Macrocyclic compounds have been studied extensively from many different points of view, such as molecular recognition, artificial catalysis and supramolecular structure. Our current research interest in this field includes the design of novel macrobicyclic architectures. According to the number of connecting bridges used for their construction and the nature of the subunits used as building blocks, two different kinds of macrobicyclic structures may be envisaged, namely axial macrobicycles, which result from a coaxial arrangement of two tripodal subunits linked by three bridges, and lateral macrobicycles, which are dissymmetrical molecules structurally based on the combination of two different binding units, one chelating and one macrocyclic (Lehn, 1980). We have reported a novel family of Schiff base lateral macrobicycles containing two different binding units, namely a rigid unsaturated N₂X set (X = N or O) and a flexible cyclic N₂On set linked by aromatic bridges (Esteban et al., 1999). These macrobicycles are structurally derived from bibracchial lariat ethers incorporating pendant aniline moieties, and constitute the first examples of lateral macrobicycles containing imine groups. This type of Schiff base lateral macrobicyclic architecture cannot be prepared by direct reaction between the organic precursors. However, some metal ions can template the corresponding reactions, thereby allowing access to the desired macrobicycles in high yields (Platas-Iglesias et al., 2003), although in all cases the metal ion acts as a permanent template, remaining trapped in the macrobicyclic cavity. Thus, to date, all the X-ray crystal structures described for this type of lateral macrobicycle correspond to their metal-coordinated form. We have found that addition of perchloric acid to the Pb complex of L causes the demetallation of the complex, yielding the macrobicycle L in its protonated form, (H₂L)(ClO₄)₂, (I). Here, we describe the structure of (I), which represents the first X-ray structure determination of an uncoordinated Schiff base lateral macrobicycle.

The asymmetric unit of (I) comprises a half-molecule of the cation (H₂L)²⁺, and half molecules of two crystallographically independent perchlorate anions. The cation and one of the anions (Cl2) are located on twofold axes, while the second perchlorate is situated on a centre of symmetry, with half-occupied disordered O sites. Fig. 1 shows the structure of (I), while selected bond lengths and angles are given in Table 1. The bond lengths and angles do not show any significant deviation from the expected values. The N2═C4 distance of 1.261 (3) Å is consistent with an imine group, and the bond angle of 119.8 (2)° for C4—N2—C5 confirms the sp² character of atom N2.

The conformation of the macrobicycle L in (I) is conditioned by two strong intramolecular hydrogen-bonding interactions involving the pivot and imine N atoms [N2···N1 2.743 (3) Å; Table 2], and in fact this conformation is quite different from that observed when a metal ion is placed inside its cavity (Avecilla et al., 2003). The lateral aromatic rings of (H₂L)²⁺ form a dihedral angle of 85.32 (9)°, whereas the plane of the pyridine ring forms a dihedral angle of 54.87 (10)° with the plane containing the benzene ring. The imine groups are not coplanar with the pyridine moiety, as indicated by the dihedral angle N2—C4—C3—N3 of 15.7 (5)°. This deviation from planarity is considerably greater than that found in the corresponding Ba complex (Avecilla et al., 2003). Moreover, the fold of the macrobicycle causes an important approach between the two pivot N atoms [N1···N1A 5.257 (5) Å], which are 6.384 (4) Å apart when a Ba ion is trapped in the macrobicyclic cavity (Avecilla et al., 2003). Moreover, the distance between the two imine N atoms (N2 and N2A) is 5.138 (4) Å, ca 0.35 Å longer than that found in [Ba(L)]²⁺.

S2. Experimental

Single crystals of (H₂L)(ClO₄)₂ suitable for X-ray crystallography were grown by addition of a dilute solution of perchloric acid in acetonitrile to a solution of [Pb(L)](ClO₄)₂ 0.5H₂O in the same solvent (molar ratio 2:1), followed by slow diffusion of diethyl ether into the resultant solution.

S3. Refinement

The O atoms of one perchlorate anion were disordered (site-occupancy factor 0.5 for atoms O5A, O6A, O5B and O6B). 42 restraints were imposed and applied to the Cl—O bonds of the perchlorate anion. Atom H1N, which is involved in an intramolecular hydrogen bond, was found in a difference electron-density map and then refined riding on the coordinates of atom N1. The positions of all other H atoms were calculated geometrically and a riding model was used in their refinement, with C—H distances in the range 0.93–0.97 Å and with U_iso(H) = 1.2U_eq(C). Please check added text.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of the (H2L)^2+ cation of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Atoms labelled with the suffix A are at the symmetry position (2 − x, y, 3/2 − z).

28,31,36,39-tetraoxa-9,17,42-pentaaza-1,25- diazoniapentacyclo[23.8.5.1^11,15.0^3,8.0^18,23]nonatriaconta- 3,5,7,9,11,13,15,16,18,20,22-undecane bis(perchlorate)

Crystal data

C33H43N5O4^2+·2ClO4^−	F(000) = 1624
Mr = 772.62	Dx = 1.374 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 951 reflections
a = 9.5092 (2) Å	θ = 2.9–28.2°
b = 19.1979 (2) Å	µ = 0.24 mm^−1
c = 20.6024 (5) Å	T = 298 K
β = 96.880 (1)°	Block-like, colourless
V = 3734.02 (13) Å^3	0.40 × 0.35 × 0.30 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	4630 independent reflections
Radiation source: fine-focus sealed tube	2771 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.910, Tmax = 0.931	k = −23→25
13616 measured reflections	l = −21→27

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)] = 0.068	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.214	w = 1/[σ^2(Fo^2) + (0.101P)^2 + 2.7759P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
4630 reflections	Δρmax = 0.66 e Å^−3
262 parameters	Δρmin = −0.59 e Å^−3
42 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0030 (7)

Special details

Experimental. Data were collected using a Bruker SMART CCD based diffractometer operating at room temperature. Data were measured using phi–omega scans of 0.3 degrees per frame for 10 s. A total of 1321 frames were collected. The first 50 frames were recollected at the end of the measurement.

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	Occ. (<1)
Cl1	0.5000	0.0000	0.5000	0.0839 (5)
N1	0.7818 (3)	0.15351 (12)	0.65871 (12)	0.0480 (6)
H1N	0.866 (3)	0.1740 (15)	0.6690 (14)	0.045 (8)*
O1	0.6776 (2)	0.12211 (12)	0.79851 (11)	0.0662 (6)
C1	1.0000	0.4646 (2)	0.7500	0.0716 (14)
H1	1.0000	0.5130	0.7500	0.086*
O2	1.0385 (2)	0.08667 (11)	0.65184 (11)	0.0589 (6)
N2	0.9614 (2)	0.25529 (12)	0.62443 (10)	0.0458 (6)
C2	1.0038 (4)	0.42756 (16)	0.69360 (16)	0.0636 (9)
H2	1.0079	0.4508	0.6542	0.076*
Cl2	0.0000	0.12911 (7)	0.2500	0.1179 (8)
O3	−0.0987 (6)	0.0885 (3)	0.2730 (2)	0.195 (3)
O4	0.0523 (9)	0.1703 (3)	0.2990 (3)	0.250 (3)
N3	1.0000	0.31829 (15)	0.7500	0.0454 (7)
C3	1.0015 (3)	0.35532 (15)	0.69512 (13)	0.0494 (7)
C4	0.9968 (3)	0.31833 (15)	0.63209 (13)	0.0534 (7)
H4	1.0212	0.3428	0.5961	0.064*
O5A	0.6111 (9)	0.0222 (4)	0.4623 (3)	0.121 (3)	0.5
O6A	0.5307 (11)	0.0255 (4)	0.5609 (3)	0.109 (3)	0.5
O5B	0.3751 (11)	0.0091 (7)	0.4625 (7)	0.182 (6)	0.5
O6B	0.5286 (8)	−0.0780 (3)	0.5039 (3)	0.113 (3)	0.5
C5	0.9559 (3)	0.22416 (15)	0.56137 (13)	0.0485 (7)
C6	1.0558 (4)	0.23595 (19)	0.51909 (15)	0.0634 (8)
H6	1.1293	0.2673	0.5302	0.076*
C7	1.0458 (4)	0.2005 (2)	0.45964 (17)	0.0748 (10)
H7	1.1127	0.2086	0.4311	0.090*
C8	0.9390 (5)	0.1541 (2)	0.44289 (17)	0.0790 (11)
H8	0.9332	0.1307	0.4032	0.095*
C9	0.8397 (4)	0.14216 (18)	0.48519 (17)	0.0703 (10)
H9	0.7670	0.1105	0.4736	0.084*
C10	0.8463 (3)	0.17655 (15)	0.54461 (14)	0.0528 (7)
C11	0.7312 (3)	0.16729 (17)	0.58765 (15)	0.0575 (8)
H11A	0.6715	0.1288	0.5709	0.069*
H11B	0.6731	0.2089	0.5848	0.069*
C12	0.6853 (3)	0.18867 (18)	0.70118 (16)	0.0595 (8)
H12A	0.6774	0.2375	0.6892	0.071*
H12B	0.5917	0.1682	0.6924	0.071*
C13	0.7330 (3)	0.18359 (17)	0.77315 (16)	0.0599 (8)
H13A	0.8357	0.1827	0.7806	0.072*
H13B	0.7004	0.2240	0.7953	0.072*
C14	0.7251 (4)	0.1113 (2)	0.86613 (17)	0.0726 (10)
H14A	0.6463	0.0948	0.8878	0.087*
H14B	0.7562	0.1554	0.8858	0.087*
C15	0.8040 (3)	0.07773 (16)	0.67470 (17)	0.0600 (8)
H15A	0.7153	0.0530	0.6640	0.072*
H15B	0.8325	0.0727	0.7213	0.072*
C16	0.9148 (4)	0.04578 (16)	0.63783 (18)	0.0628 (8)
H16A	0.9332	−0.0020	0.6518	0.075*
H16B	0.8836	0.0460	0.5913	0.075*
C17	1.1568 (4)	0.0602 (2)	0.62295 (19)	0.0724 (10)
H17A	1.1308	0.0531	0.5765	0.087*
H17B	1.1862	0.0158	0.6426	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1164 (12)	0.0894 (10)	0.0459 (6)	−0.0572 (8)	0.0100 (7)	−0.0073 (6)
N1	0.0417 (12)	0.0476 (13)	0.0536 (14)	−0.0071 (10)	0.0015 (10)	0.0013 (11)
O1	0.0546 (12)	0.0776 (16)	0.0673 (15)	−0.0174 (11)	0.0105 (11)	0.0074 (11)
C1	0.115 (4)	0.037 (2)	0.063 (3)	0.000	0.009 (3)	0.000
O2	0.0565 (12)	0.0527 (12)	0.0680 (14)	0.0043 (10)	0.0097 (10)	−0.0114 (10)
N2	0.0511 (13)	0.0466 (13)	0.0390 (12)	−0.0058 (10)	0.0030 (10)	−0.0024 (9)
C2	0.097 (2)	0.0437 (16)	0.0496 (17)	−0.0106 (16)	0.0054 (16)	0.0055 (13)
Cl2	0.233 (2)	0.0484 (7)	0.0882 (11)	0.000	0.0853 (13)	0.000
O3	0.205 (5)	0.223 (5)	0.149 (4)	−0.102 (4)	−0.010 (3)	0.077 (4)
O4	0.366 (7)	0.206 (5)	0.208 (4)	−0.158 (5)	0.166 (5)	−0.130 (4)
N3	0.0579 (19)	0.0367 (16)	0.0406 (17)	0.000	0.0022 (14)	0.000
C3	0.0633 (17)	0.0426 (15)	0.0416 (15)	−0.0102 (12)	0.0034 (12)	0.0006 (11)
C4	0.0737 (19)	0.0485 (16)	0.0374 (14)	−0.0133 (14)	0.0046 (13)	0.0007 (12)
O5A	0.178 (7)	0.095 (5)	0.106 (5)	−0.042 (5)	0.078 (5)	0.001 (4)
O6A	0.147 (7)	0.121 (6)	0.060 (4)	−0.027 (5)	0.019 (4)	−0.025 (3)
O5B	0.124 (8)	0.191 (10)	0.213 (13)	−0.024 (7)	−0.056 (8)	0.030 (9)
O6B	0.170 (7)	0.072 (4)	0.098 (5)	−0.040 (4)	0.015 (4)	0.003 (3)
C5	0.0571 (16)	0.0492 (15)	0.0377 (14)	−0.0036 (13)	−0.0001 (12)	−0.0027 (11)
C6	0.068 (2)	0.075 (2)	0.0481 (17)	−0.0084 (17)	0.0073 (15)	−0.0041 (15)
C7	0.088 (3)	0.088 (3)	0.0504 (19)	0.006 (2)	0.0179 (18)	−0.0049 (18)
C8	0.110 (3)	0.076 (2)	0.0499 (19)	0.005 (2)	0.004 (2)	−0.0163 (17)
C9	0.092 (3)	0.058 (2)	0.056 (2)	−0.0075 (18)	−0.0094 (18)	−0.0101 (15)
C10	0.0627 (18)	0.0472 (16)	0.0455 (16)	−0.0019 (13)	−0.0061 (13)	−0.0016 (12)
C11	0.0512 (16)	0.0605 (18)	0.0572 (18)	−0.0087 (14)	−0.0088 (13)	0.0020 (14)
C12	0.0475 (16)	0.0629 (19)	0.069 (2)	0.0061 (14)	0.0117 (14)	0.0041 (15)
C13	0.0538 (17)	0.0609 (19)	0.067 (2)	−0.0038 (15)	0.0153 (15)	−0.0005 (15)
C14	0.060 (2)	0.099 (3)	0.062 (2)	−0.0094 (19)	0.0176 (16)	0.0110 (19)
C15	0.0630 (19)	0.0471 (17)	0.070 (2)	−0.0068 (14)	0.0082 (16)	0.0061 (14)
C16	0.075 (2)	0.0417 (16)	0.072 (2)	−0.0026 (14)	0.0067 (17)	−0.0028 (14)
C17	0.072 (2)	0.079 (2)	0.067 (2)	0.0140 (19)	0.0122 (17)	−0.0169 (18)

Geometric parameters (Å, º)

Cl1—O6A	1.346 (5)	C6—C7	1.394 (5)
Cl1—O5A	1.448 (6)	C6—H6	0.9300
Cl1—O5B	1.348 (8)	C7—C8	1.364 (6)
Cl1—O6B	1.522 (6)	C7—H7	0.9300
N1—C15	1.501 (4)	C8—C9	1.379 (6)
N1—C12	1.501 (4)	C8—H8	0.9300
N1—C11	1.509 (4)	C9—C10	1.386 (4)
N1—N1^i	5.257 (5)	C9—H9	0.9300
N1—H1N	0.89 (3)	C10—C11	1.500 (4)
O1—C13	1.418 (4)	C11—H11A	0.9700
O1—C14	1.427 (4)	C11—H11B	0.9700
C1—C2	1.366 (4)	C12—C13	1.501 (4)
C1—H1	0.9300	C12—H12A	0.9700
O2—C16	1.414 (4)	C12—H12B	0.9700
O2—C17	1.428 (4)	C13—H13A	0.9700
N2—C4	1.261 (3)	C13—H13B	0.9700
N2—C5	1.425 (3)	C14—C17^i	1.488 (5)
N2—N2^i	5.138 (4)	C14—H14A	0.9700
C2—C3	1.387 (4)	C14—H14B	0.9700
C2—H2	0.9300	C15—C16	1.502 (5)
Cl2—O4	1.331 (5)	C15—H15A	0.9700
Cl2—O3	1.350 (4)	C15—H15B	0.9700
N3—C3	1.337 (3)	C16—H16A	0.9700
C3—C4	1.476 (4)	C16—H16B	0.9700
C4—H4	0.9300	C17—C14^i	1.488 (5)
C5—C6	1.383 (4)	C17—H17A	0.9700
C5—C10	1.398 (4)	C17—H17B	0.9700
O6A—Cl1—O5B	124.4 (6)	C10—C9—H9	119.4
O6A—Cl1—O5A	107.6 (5)	C9—C10—C5	118.9 (3)
O5B—Cl1—O5A	107.7 (7)	C9—C10—C11	120.4 (3)
O6A—Cl1—O6B	107.0 (5)	C5—C10—C11	120.4 (3)
O5B—Cl1—O6B	107.2 (6)	C10—C11—N1	115.1 (2)
O5A—Cl1—O6B	100.4 (4)	C10—C11—H11A	108.5
C15—N1—C12	112.8 (2)	N1—C11—H11A	108.5
C15—N1—C11	113.8 (2)	C10—C11—H11B	108.5
C12—N1—C11	109.9 (2)	N1—C11—H11B	108.5
C15—N1—H1N	106.1 (18)	H11A—C11—H11B	107.5
C12—N1—H1N	104.8 (18)	C13—C12—N1	114.4 (2)
C11—N1—H1N	108.9 (18)	C13—C12—H12A	108.7
C13—O1—C14	113.1 (3)	N1—C12—H12A	108.7
C2—C1—C2^i	117.3 (4)	C13—C12—H12B	108.7
C2—C1—H1	121.3	N1—C12—H12B	108.7
C2^i—C1—H1	121.3	H12A—C12—H12B	107.6
C16—O2—C17	113.3 (2)	O1—C13—C12	109.7 (3)
C4—N2—C5	119.8 (2)	O1—C13—H13A	109.7
C1—C2—C3	119.9 (3)	C12—C13—H13A	109.7
C1—C2—H2	120.0	O1—C13—H13B	109.7
C3—C2—H2	120.0	C12—C13—H13B	109.7
O4—Cl2—O4^ii	107.2 (7)	H13A—C13—H13B	108.2
O4—Cl2—O3^ii	113.4 (4)	O1—C14—C17^i	112.9 (3)
O4—Cl2—O3	106.8 (3)	O1—C14—H14A	109.0
O3^ii—Cl2—O3	109.4 (6)	C17^i—C14—H14A	109.0
C3—N3—C3^i	115.8 (3)	O1—C14—H14B	109.0
N3—C3—C2	123.5 (3)	C17^i—C14—H14B	109.0
N3—C3—C4	119.1 (2)	H14A—C14—H14B	107.8
C2—C3—C4	117.4 (3)	N1—C15—C16	111.9 (3)
N2—C4—C3	123.5 (3)	N1—C15—H15A	109.2
N2—C4—H4	118.3	C16—C15—H15A	109.2
C3—C4—H4	118.3	N1—C15—H15B	109.2
C6—C5—C10	120.0 (3)	C16—C15—H15B	109.2
C6—C5—N2	123.6 (3)	H15A—C15—H15B	107.9
C10—C5—N2	116.4 (3)	O2—C16—C15	106.7 (2)
C5—C6—C7	119.6 (3)	O2—C16—H16A	110.4
C5—C6—H6	120.2	C15—C16—H16A	110.4
C7—C6—H6	120.2	O2—C16—H16B	110.4
C8—C7—C6	120.8 (3)	C15—C16—H16B	110.4
C8—C7—H7	119.6	H16A—C16—H16B	108.6
C6—C7—H7	119.6	O2—C17—C14^i	108.7 (3)
C7—C8—C9	119.6 (3)	O2—C17—H17A	109.9
C7—C8—H8	120.2	C14^i—C17—H17A	109.9
C9—C8—H8	120.2	O2—C17—H17B	109.9
C8—C9—C10	121.1 (3)	C14^i—C17—H17B	109.9
C8—C9—H9	119.4	H17A—C17—H17B	108.3
C2^i—C1—C2—C3	1.0 (2)	N2—C5—C10—C9	−177.0 (3)
C3^i—N3—C3—C2	1.1 (3)	C6—C5—C10—C11	−175.4 (3)
C3^i—N3—C3—C4	−177.3 (3)	N2—C5—C10—C11	8.1 (4)
C1—C2—C3—N3	−2.1 (5)	C9—C10—C11—N1	133.2 (3)
C1—C2—C3—C4	176.3 (3)	C5—C10—C11—N1	−51.9 (4)
C5—N2—C4—C3	178.2 (3)	C15—N1—C11—C10	−88.6 (3)
N2^i—N2—C4—C3	−14.8 (3)	C12—N1—C11—C10	143.8 (3)
N3—C3—C4—N2	15.7 (5)	C15—N1—C12—C13	57.0 (3)
C2—C3—C4—N2	−162.8 (3)	C11—N1—C12—C13	−174.9 (3)
C4—N2—C5—C6	41.0 (4)	C14—O1—C13—C12	176.5 (3)
C4—N2—C5—C10	−142.6 (3)	N1—C12—C13—O1	−88.8 (3)
C10—C5—C6—C7	0.5 (5)	C13—O1—C14—C17^i	−99.8 (4)
N2—C5—C6—C7	176.8 (3)	C12—N1—C15—C16	−172.7 (3)
C5—C6—C7—C8	−0.3 (6)	C11—N1—C15—C16	61.2 (3)
C6—C7—C8—C9	0.1 (6)	N1^i—N1—C15—C16	−84.2 (2)
C7—C8—C9—C10	0.0 (6)	C17—O2—C16—C15	176.6 (3)
C8—C9—C10—C5	0.1 (5)	N1—C15—C16—O2	55.1 (3)
C8—C9—C10—C11	175.1 (3)	C16—O2—C17—C14^i	173.2 (3)
C6—C5—C10—C9	−0.4 (5)	N2—C4—C3—N3	15.7 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.89 (3)	2.07 (3)	2.743 (3)	131 (2)