Difur­aza­no­[3,4-b:3',4'-f]-4,5-di­aza-1,8-dioxa­cyclo­dodecine and an acyclic analogue

The novel title fur­azan-containing macrocycle (systematic name: 6,9,14,17-tetraoxa-2,3,5,7,16,18-hexa­aza­tri­cyclo­[13.3.0.0^4,8]­octadeca-4,7,15,18-tetraene), C₈H₁₀N₆O₄, (I), is the first macrocycle where the fur­azan rings are connected via a hydrazine group. In spite of the strain in the 12-membered macrocycle of (I), the geometry of the fur­azan fragment is the same in (I) and in its acyclic analogue 1,8-bis(5-amino­fur­azan-4-yl­oxy)-3,6-dioxaoctane, C₁₀H₁₆N₆O₆, (II). In both compounds, the participation of the fur­azan rings in intermolecular hydrogen bonding equalizes the N-O bonds within the fur­azan rings, in contrast with rings which do not participate in such interactions.

S1. Comment

Furazan derivatives have potential as high-energy materials (Coburn, 1968; Beal & Brill, 2000), and it has been shown that these compounds are useful as ingredients of explosives and rocket propellants (Sheremetev et al., 1996; Batog et al., 1998). At the same time, furazan-containing macrocycles have exhibited interesting biological and pharmacological properties, for instance as effective inhibitors of soluble guanylate cyclase (Kots et al., 1999; Sheremetev et al., 2000). Recently, we have been involved in the construction of furazan-containing macrocycles (Sheremetev, Shatunova et al., 2004; Sheremetev, Ivanova et al., 2004), in which the macrocyclic furazan fragments are linked by a rigid azo group.

In the present paper, we discuss the structure of a new 12-membered macrocycle containing two furazan rings linked by the less rigid –NH—NH– group, namely difurazano[3,4 − b:3',4'-f]-4,5-diaza-1,8-dioxacyclododecine, (I). We also describe the structure of 1,8-bis(3-aminofurazan-4-yloxy)-3,6-dioxaoctane, (II), which is an acyclic analogue of (I). We are interested in the influence of steric factors, caused by the macrocyclic structure of the molecule, on the geometry of the furazan rings. Compound (II) is not an exact acyclic analogue of (I) because the former contains the additional O5—C7—C8—O6 fragment, but this fragment should not influence the geometry of the furazan rings, because it is remote from them. \sch

Ellipsoid plots of molecules of (I) and (II) is presented in Figs. 1 and 2, respectively. Due to the incorporation of the hydrazine group, the molecule of (I) is nonplanar, unlike previously studied macrocycles, where the furazan rings were connected via an azo group (Sheremetev et al., 2002, 2003) or an ether O atom (Averkiev et al., 2003). The dihedral angle between the furazan rings in (I) is 99.0° (Fig. 1). The molecule of (II) is also nonplanar and adopts a crimped shape (Figure 2).

The strain in the macrocycle of (I) is evident from the increased bond angles at atoms C6, C7 and C8 [113.8 (2), 114.9 (2) and 111.8 (2)°, respectively] relative to the ideal tetrahedral angle. However, the bond angles at atoms O1 and O2 are not increased in comparison with those in (II): in both compounds, these are between 115 and 116°. Perhaps the slight lengthening of the C—C bonds within the furazan rings in (I), to 1.443 (2) Å for C1—C2 and 1.437 (2) Å for C3—C4, in comparison with 1.429 (2) and 1.423 (3) Å for the respective analogous bonds in (II) and the standard database value of 1.428 Å (Allen et al., 1987), may be explained by the strained structure of (I) (Tables 1 and 3).

In spite of possible conjugation between the lone pairs of the N atoms and the π system of the furazan rings, the configuration around atoms N1 and N2 is noticeably non-planar. The sum of the bond angles is 346 (2)° for N1 and 341 (2)° for N2 in (I), and 348 (2)° for N1 and 345 (2)° for N2 in (II). The trigonal configuration of the N atoms in (I) cannot be explained by steric interactions with neighbouring alkoxy substituents (Borbulevych et al., 2002), because deviation from planarity does not affect the N1—H1A···O1 and N2—H2A···O2 intramolecular contacts (2.67 and 2.65 Å, respectively). The corresponding N—H···O distances for the calculated planar configuration of an N atom are 2.68 and 2.67 Å, and are very close to the sum of the van der Waals radii of O and H atoms (2.65 Å; Rowland & Taylor, 1996). In (I), the non-planar coordination at N1 and N2 can be attributed in part to the cyclic structure of the molecule. In both compounds, the bond angles at the O atoms of the methoxy fragments [115.2 (2)–116.5 (2)°] are slightly wider than the average value of 112.9° we find for the unconjugated C—O—C fragment in the Cambridge Structural Database (CSD, Version?; Allen, 2002).

Analysis of the furazan geometry in (I) and (II) reveals the unexpected feature that, in each compound, the geometries of the two chemically equivalent furazan rings are slightly different. It might be expected that the lengths of the N—O bonds close to the alkoxy substituents should be about 1.379–1.390 Å, as we reported previously (Averkiev et al., 2003), while the lengths of the N—O bonds close to an amino or hydrazine group should be about 1.400–1.411 Å, according to our analysis of aminofurazan fragments in the CSD. However, only the C3—N5—O4—N6—C4 furazan rings in both compounds show the expected lengths for the N—O bonds: N5—O4 is elongated to 1.410 (2) Å in (I) and 1.411 (3) Å in (II), while N6—O4 is shortened to 1.391 (3) Å in (I) and 1.393 (3) Å in (II). Meanwhile, the N3—O3 and N4—O3 bonds in both compounds are unexpectedly equal, at 1.399 (2) and 1.395 (2) Å, respectively, for (I), and 1.403 and 1.403 Å, respectively, for (II). The only explanation which we can suggest is participation of atoms N3 and N4 in both compounds in the intermolecular hydrogen bonds (see below).

Molecules of (I) are arranged in centrosymmetrical dimers linked by N1—H1···N3 hydrogen bonds. These dimers are arranged into crimped layers by another hydrogen bond, N2—H2···N4 (Table 2, Fig. 3). These layers are parallel to the (1 0 1) plane. Molecules of (II) are arranged in helices along the b direction. All molecules in a helix are translationally identical, hence each molecule composes one coil of the helix. Two intermolecular hydrogen bonds, namely N2—H2B···O5 and N2—H2A···N4, were found inside each helix (Table 4). Each helix is connected by N1—H1A···N3 hydrogen bonds to the neighbouring helix, symmetrically related by 2₁ screw axes (Fig. 4). As can be seen from the pattern of hydrogen bonds, for both compounds (I) and (II), one furazan ring (C1—C2—N3—O3—N4, denoted by 'a' in Figs. 3 and 4) participates in intermolecular hydrogen bonding via both N atoms, while the other furazan ring (C3—C4—N6—O4—N5, denoted by 'b') does not participate in hydrogen bonding. We believe that it is due to this hydrogen bonding that the N—O bonds in the C1—C2—N3—O3—N4 ring are equalized.

S2. Experimental

Compound (I) (m.p. 333–334 K) was obtained in 40% yield using the literature procedures of Kharitinova et al. (1991) and Shatunova & Sheremetev (1995). X-ray quality crystals of (I) were grown by slow evaporation of a methanol solution at room temperature. Using the previously reported procedure of Poncio & Avogadro (1923), compound (II) (m.p. 453–454 K) was obtained in 52% yield by reduction of the N═N bond in the corresponding azomacrocycle [1,2] with phenyl hydrazine in Et₂O at room temperature. Separation of (II) by flash chromatography followed by recrystallization from AcOH solution afforded X-ray quality crystals.

Computing details

Data collection: SMART (Bruker, 1998) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SAINT-Plus (Bruker, 1998) for (I); CAD-4 Software for (II). Data reduction: SAINT-Plus for (I); XCAD4 (Harms, 1996) for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A general view of (I), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A general view of (II), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level.
	Fig. 3. The hydrogen-bonding scheme in (I) [symmetry codes (i) and (ii) are as given in Table 2].
	Fig. 4. The hydrogen-bonding scheme in (II) [symmetry codes (i), (ii) and (iii) are as given in Table 4].

(I) 6,9,14,17-tetraoxa-2,3,5,7,16,18-hexaazatricyclo[13.3.0.0^4,8]octadeca- 4,7,15,18-tetraene

Crystal data

C8H10N6O4	F(000) = 528
Mr = 254.22	Dx = 1.558 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 908 reflections
a = 8.3331 (12) Å	θ = 3–29°
b = 14.695 (2) Å	µ = 0.13 mm^−1
c = 9.2384 (13) Å	T = 110 K
β = 106.619 (3)°	Rectangular prism, colourless
V = 1084.1 (3) Å^3	0.4 × 0.3 × 0.3 mm
Z = 4

Data collection

Bruker SMART1000 CCD area-detector diffractometer	2100 independent reflections
Radiation source: fine-focus sealed tube	1757 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→8
Tmin = 0.882, Tmax = 0.965	k = −16→18
4776 measured reflections	l = −9→11

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)] = 0.056	Hydrogen site location: difference Fourier map
wR(F^2) = 0.171	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1347P)^2] where P = (Fo^2 + 2Fc^2)/3
2100 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.34 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
O1	0.48627 (16)	0.22906 (8)	0.72669 (14)	0.0239 (4)
N1	0.59616 (19)	0.42285 (11)	0.69846 (17)	0.0232 (4)
C1	0.4954 (2)	0.36905 (11)	0.58685 (19)	0.0211 (4)
H1	0.592 (3)	0.4787 (16)	0.682 (3)	0.032 (6)*
O2	0.51203 (16)	0.27300 (8)	1.05979 (14)	0.0266 (4)
N2	0.6012 (2)	0.40317 (10)	0.84990 (17)	0.0233 (4)
C2	0.4487 (2)	0.27524 (11)	0.59753 (19)	0.0205 (4)
H2	0.664 (3)	0.3558 (14)	0.885 (2)	0.026 (5)*
O3	0.35966 (15)	0.31780 (8)	0.36702 (13)	0.0253 (4)
N3	0.43830 (19)	0.39450 (10)	0.44589 (16)	0.0238 (4)
C3	0.4506 (2)	0.40055 (12)	0.88437 (19)	0.0235 (4)
O4	0.20130 (16)	0.42704 (10)	0.89576 (15)	0.0308 (4)
N4	0.36684 (19)	0.24461 (10)	0.46486 (16)	0.0231 (4)
C4	0.4080 (2)	0.33823 (12)	0.98749 (19)	0.0245 (4)
C5	0.4478 (3)	0.13186 (12)	0.7157 (2)	0.0245 (4)
N5	0.32493 (19)	0.45487 (10)	0.82804 (17)	0.0276 (4)
H5B	0.524 (2)	0.1027 (12)	0.664 (2)	0.017 (5)*
H5A	0.331 (3)	0.1261 (13)	0.658 (3)	0.028 (5)*
C6	0.4773 (2)	0.09709 (12)	0.8751 (2)	0.0233 (4)
N6	0.2576 (2)	0.35470 (11)	0.99436 (18)	0.0300 (4)
H6B	0.468 (2)	0.0322 (14)	0.866 (2)	0.027 (5)*
H6A	0.588 (3)	0.1094 (14)	0.936 (2)	0.022 (5)*
C7	0.3523 (2)	0.13480 (12)	0.9554 (2)	0.0266 (5)
H7B	0.265 (3)	0.1716 (14)	0.881 (3)	0.032 (6)*
H7A	0.289 (3)	0.0857 (14)	0.986 (3)	0.030 (5)*
C8	0.4304 (3)	0.19079 (13)	1.0952 (2)	0.0295 (5)
H8B	0.522 (3)	0.1545 (17)	1.168 (3)	0.040 (6)*
H8A	0.350 (3)	0.2103 (16)	1.150 (3)	0.036 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0333 (8)	0.0239 (7)	0.0137 (6)	−0.0031 (5)	0.0054 (5)	0.0020 (5)
N1	0.0299 (9)	0.0246 (8)	0.0151 (8)	−0.0031 (6)	0.0063 (6)	0.0015 (6)
C1	0.0224 (9)	0.0250 (9)	0.0162 (8)	0.0003 (7)	0.0062 (7)	−0.0004 (7)
O2	0.0319 (8)	0.0288 (7)	0.0192 (7)	0.0007 (5)	0.0074 (6)	0.0041 (5)
N2	0.0294 (9)	0.0263 (8)	0.0142 (8)	0.0013 (6)	0.0064 (7)	0.0017 (6)
C2	0.0218 (9)	0.0254 (9)	0.0159 (9)	0.0003 (6)	0.0076 (7)	0.0005 (6)
O3	0.0343 (8)	0.0258 (7)	0.0147 (6)	−0.0028 (5)	0.0054 (6)	0.0011 (5)
N3	0.0292 (8)	0.0261 (8)	0.0159 (8)	−0.0027 (6)	0.0060 (6)	−0.0009 (6)
C3	0.0292 (10)	0.0270 (9)	0.0129 (8)	−0.0007 (7)	0.0037 (7)	−0.0045 (6)
O4	0.0272 (7)	0.0391 (8)	0.0263 (7)	0.0048 (5)	0.0083 (6)	0.0001 (6)
N4	0.0274 (8)	0.0273 (8)	0.0151 (8)	−0.0010 (6)	0.0068 (7)	0.0027 (6)
C4	0.0297 (10)	0.0292 (9)	0.0147 (8)	0.0015 (7)	0.0064 (7)	−0.0014 (7)
C5	0.0333 (11)	0.0221 (9)	0.0186 (9)	−0.0031 (7)	0.0084 (8)	−0.0009 (7)
N5	0.0321 (9)	0.0296 (9)	0.0211 (8)	0.0019 (7)	0.0077 (7)	−0.0010 (6)
C6	0.0275 (10)	0.0251 (10)	0.0180 (9)	0.0019 (7)	0.0078 (8)	0.0033 (7)
N6	0.0335 (9)	0.0368 (9)	0.0212 (8)	0.0009 (7)	0.0100 (7)	−0.0002 (7)
C7	0.0299 (10)	0.0292 (10)	0.0229 (10)	0.0000 (8)	0.0113 (8)	0.0018 (7)
C8	0.0380 (12)	0.0325 (11)	0.0207 (9)	−0.0027 (8)	0.0125 (9)	0.0055 (7)

Geometric parameters (Å, º)

O1—C2	1.330 (2)	C3—C4	1.437 (2)
O1—C5	1.461 (2)	O4—N6	1.391 (2)
N1—C1	1.378 (2)	O4—N5	1.410 (2)
N1—N2	1.417 (2)	C4—N6	1.296 (2)
N1—H1	0.83 (2)	C5—C6	1.512 (2)
C1—N3	1.307 (2)	C5—H5B	1.00 (2)
C1—C2	1.443 (2)	C5—H5A	0.97 (2)
O2—C4	1.336 (2)	C6—C7	1.544 (2)
O2—C8	1.469 (2)	C6—H6B	0.96 (2)
N2—C3	1.381 (2)	C6—H6A	0.95 (2)
N2—H2	0.87 (2)	C7—C8	1.512 (3)
C2—N4	1.301 (2)	C7—H7B	1.01 (2)
O3—N4	1.3951 (18)	C7—H7A	0.98 (2)
O3—N3	1.3991 (19)	C8—H8B	1.01 (3)
C3—N5	1.301 (2)	C8—H8A	0.99 (2)
C2—O1—C5	116.48 (14)	O1—C5—H5B	107.2 (10)
C1—N1—N2	117.47 (14)	C6—C5—H5B	112.1 (11)
C1—N1—H1	116.4 (16)	O1—C5—H5A	106.8 (12)
N2—N1—H1	111.7 (16)	C6—C5—H5A	111.4 (13)
N3—C1—N1	123.50 (15)	H5B—C5—H5A	112.0 (17)
N3—C1—C2	108.24 (15)	C3—N5—O4	104.56 (14)
N1—C1—C2	127.99 (15)	C5—C6—C7	113.77 (15)
C4—O2—C8	115.19 (15)	C5—C6—H6B	105.5 (13)
C3—N2—N1	117.45 (14)	C7—C6—H6B	110.6 (12)
C3—N2—H2	112.3 (14)	C5—C6—H6A	111.8 (13)
N1—N2—H2	111.7 (14)	C7—C6—H6A	108.8 (13)
N4—C2—O1	126.46 (16)	H6B—C6—H6A	106.1 (17)
N4—C2—C1	110.19 (15)	C4—N6—O4	105.08 (14)
O1—C2—C1	123.35 (16)	C8—C7—C6	114.89 (16)
N4—O3—N3	110.90 (12)	C8—C7—H7B	110.1 (12)
C1—N3—O3	105.74 (13)	C6—C7—H7B	108.6 (12)
N5—C3—N2	124.85 (16)	C8—C7—H7A	106.6 (13)
N5—C3—C4	109.42 (16)	C6—C7—H7A	111.5 (13)
N2—C3—C4	125.73 (16)	H7B—C7—H7A	104.6 (17)
N6—O4—N5	111.10 (13)	O2—C8—C7	111.78 (15)
C2—N4—O3	104.92 (14)	O2—C8—H8B	105.6 (13)
N6—C4—O2	127.45 (16)	C7—C8—H8B	109.7 (14)
N6—C4—C3	109.85 (16)	O2—C8—H8A	107.5 (13)
O2—C4—C3	122.69 (15)	C7—C8—H8A	113.7 (13)
O1—C5—C6	106.95 (14)	H8B—C8—H8A	108 (2)
N2—N1—C1—N3	158.21 (17)	C8—O2—C4—N6	28.3 (2)
N2—N1—C1—C2	−28.6 (2)	C8—O2—C4—C3	−150.06 (17)
C1—N1—N2—C3	−54.6 (2)	N5—C3—C4—N6	−0.2 (2)
C5—O1—C2—N4	7.2 (3)	N2—C3—C4—N6	179.60 (16)
C5—O1—C2—C1	−172.84 (15)	N5—C3—C4—O2	178.41 (15)
N3—C1—C2—N4	0.8 (2)	N2—C3—C4—O2	−1.8 (3)
N1—C1—C2—N4	−173.18 (16)	C2—O1—C5—C6	−172.00 (14)
N3—C1—C2—O1	−179.18 (15)	N2—C3—N5—O4	−179.80 (15)
N1—C1—C2—O1	6.8 (3)	C4—C3—N5—O4	0.04 (19)
N1—C1—N3—O3	173.05 (15)	N6—O4—N5—C3	0.16 (19)
C2—C1—N3—O3	−1.27 (18)	O1—C5—C6—C7	67.3 (2)
N4—O3—N3—C1	1.36 (17)	O2—C4—N6—O4	−178.24 (16)
N1—N2—C3—N5	−37.7 (2)	C3—C4—N6—O4	0.32 (19)
N1—N2—C3—C4	142.53 (17)	N5—O4—N6—C4	−0.31 (19)
O1—C2—N4—O3	−179.96 (15)	C5—C6—C7—C8	−117.93 (18)
C1—C2—N4—O3	0.05 (18)	C4—O2—C8—C7	72.4 (2)
N3—O3—N4—C2	−0.85 (17)	C6—C7—C8—O2	62.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3^i	0.83 (2)	2.18 (2)	2.974 (2)	159 (2)
N2—H2···N4^ii	0.87 (2)	2.21 (2)	3.066 (2)	167 (2)

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

(II) 1,8-bis(5-aminofurazan-4-yloxy)-3,6-dioxaoctane

Crystal data

C10H16N6O6	F(000) = 1328
Mr = 316.29	Dx = 1.422 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 24 reflections
a = 31.363 (6) Å	θ = 11–13°
b = 6.0550 (12) Å	µ = 0.12 mm^−1
c = 15.724 (3) Å	T = 293 K
β = 98.34 (3)°	Plate, colourless
V = 2954.5 (10) Å^3	0.4 × 0.3 × 0.1 mm
Z = 8

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.032
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 1.3°
Graphite monochromator	h = 0→36
θ/5/3θ scans	k = 0→7
2742 measured reflections	l = −19→18
2689 independent reflections	2 standard reflections every 98 reflections
1877 reflections with I > 2σ(I)	intensity decay: 2.5%

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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F^2) = 0.109	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 0.8023P] where P = (Fo^2 + 2Fc^2)/3
2689 reflections	(Δ/σ)max = 0.003
263 parameters	Δρmax = 0.13 e Å^−3
0 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.

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
O1	0.19740 (4)	1.1127 (2)	0.97158 (7)	0.0507 (3)
C1	0.22406 (5)	1.0840 (3)	1.12314 (11)	0.0458 (4)
N1	0.24128 (6)	0.8782 (3)	1.12226 (14)	0.0619 (5)
H1B	0.2303 (7)	0.795 (4)	1.0797 (15)	0.076 (7)*
H1A	0.2478 (7)	0.817 (4)	1.1754 (15)	0.076 (7)*
O2	0.07060 (4)	0.1731 (2)	0.97335 (8)	0.0556 (4)
C2	0.20301 (5)	1.1998 (3)	1.04963 (11)	0.0430 (4)
N2	0.12744 (6)	−0.1970 (3)	1.03077 (13)	0.0633 (5)
H2B	0.1250 (8)	−0.161 (4)	0.9746 (17)	0.084 (8)*
H2A	0.1359 (8)	−0.322 (5)	1.0472 (17)	0.089 (9)*
O3	0.20592 (5)	1.4085 (2)	1.15965 (9)	0.0671 (4)
C3	0.09335 (7)	−0.1334 (3)	1.06773 (11)	0.0527 (5)
N3	0.22613 (5)	1.2113 (2)	1.18994 (10)	0.0581 (4)
O4	0.04648 (6)	−0.0890 (3)	1.15384 (10)	0.0854 (5)
C4	0.06630 (6)	0.0508 (3)	1.04223 (11)	0.0516 (5)
N4	0.19181 (5)	1.3947 (2)	1.07096 (10)	0.0565 (4)
O5	0.13116 (4)	0.9305 (2)	0.84603 (8)	0.0577 (4)
C5	0.17042 (6)	1.2388 (3)	0.90513 (12)	0.0494 (4)
N5	0.08103 (7)	−0.2211 (3)	1.13531 (11)	0.0750 (6)
H5B	0.1440 (6)	1.281 (3)	0.9285 (12)	0.054 (5)*
H5A	0.1870 (7)	1.363 (4)	0.8911 (13)	0.068 (6)*
O6	0.08103 (4)	0.5458 (2)	0.86325 (8)	0.0567 (4)
C6	0.16108 (7)	1.0920 (4)	0.82892 (12)	0.0539 (5)
N6	0.03811 (6)	0.0802 (3)	1.09374 (12)	0.0700 (5)
H6B	0.1497 (6)	1.183 (3)	0.7807 (13)	0.056 (5)*
H6A	0.1876 (7)	1.030 (3)	0.8164 (12)	0.063 (6)*
C7	0.12208 (7)	0.7688 (3)	0.78049 (12)	0.0567 (5)
H7B	0.1212 (6)	0.835 (3)	0.7243 (13)	0.058 (5)*
H7A	0.1448 (7)	0.657 (4)	0.7857 (13)	0.067 (6)*
C8	0.07933 (7)	0.6664 (4)	0.78572 (13)	0.0602 (5)
H8B	0.0724 (8)	0.573 (4)	0.7351 (15)	0.084 (7)*
H8A	0.0550 (7)	0.779 (4)	0.7816 (13)	0.072 (6)*
C9	0.04152 (6)	0.4345 (4)	0.86763 (15)	0.0620 (5)
H9B	0.0373 (7)	0.312 (4)	0.8233 (14)	0.067 (6)*
H9A	0.0176 (8)	0.541 (4)	0.8526 (15)	0.080 (7)*
C10	0.04009 (7)	0.3519 (3)	0.95580 (14)	0.0583 (5)
H10B	0.0102 (7)	0.287 (4)	0.9614 (13)	0.072 (6)*
H10A	0.0486 (6)	0.468 (4)	1.0001 (14)	0.066 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0548 (7)	0.0442 (7)	0.0498 (7)	0.0069 (6)	−0.0035 (5)	0.0013 (6)
C1	0.0465 (9)	0.0360 (9)	0.0526 (10)	−0.0066 (7)	−0.0003 (7)	0.0053 (8)
N1	0.0789 (12)	0.0383 (9)	0.0626 (11)	0.0067 (8)	−0.0096 (9)	0.0061 (9)
O2	0.0570 (7)	0.0526 (8)	0.0592 (8)	0.0085 (6)	0.0150 (6)	0.0066 (6)
C2	0.0413 (9)	0.0352 (9)	0.0510 (10)	−0.0044 (7)	0.0014 (7)	0.0016 (8)
N2	0.0801 (13)	0.0500 (11)	0.0567 (11)	0.0049 (9)	0.0001 (9)	0.0105 (9)
O3	0.0940 (11)	0.0436 (7)	0.0596 (8)	0.0083 (7)	−0.0027 (7)	−0.0053 (6)
C3	0.0709 (13)	0.0455 (10)	0.0392 (9)	−0.0176 (9)	−0.0004 (9)	−0.0033 (8)
N3	0.0744 (11)	0.0423 (8)	0.0541 (9)	−0.0035 (8)	−0.0024 (8)	0.0027 (7)
O4	0.1104 (13)	0.0976 (12)	0.0531 (9)	−0.0378 (11)	0.0280 (9)	−0.0045 (9)
C4	0.0575 (11)	0.0542 (11)	0.0434 (9)	−0.0177 (9)	0.0079 (8)	−0.0090 (8)
N4	0.0684 (10)	0.0385 (8)	0.0591 (10)	0.0048 (7)	−0.0022 (8)	−0.0003 (7)
O5	0.0711 (9)	0.0558 (8)	0.0467 (7)	−0.0156 (7)	0.0104 (6)	−0.0050 (6)
C5	0.0465 (10)	0.0463 (11)	0.0528 (10)	0.0006 (9)	−0.0021 (8)	0.0088 (8)
N5	0.1068 (15)	0.0697 (12)	0.0474 (9)	−0.0275 (11)	0.0079 (9)	0.0026 (9)
O6	0.0551 (8)	0.0481 (7)	0.0619 (8)	−0.0019 (6)	−0.0085 (6)	0.0098 (6)
C6	0.0581 (11)	0.0555 (11)	0.0473 (11)	−0.0034 (10)	0.0053 (9)	0.0097 (9)
N6	0.0773 (12)	0.0757 (12)	0.0606 (10)	−0.0200 (10)	0.0226 (9)	−0.0158 (10)
C7	0.0784 (14)	0.0471 (11)	0.0431 (11)	0.0055 (10)	0.0040 (9)	−0.0015 (9)
C8	0.0738 (14)	0.0483 (11)	0.0523 (11)	−0.0020 (10)	−0.0118 (10)	0.0003 (9)
C9	0.0498 (11)	0.0513 (12)	0.0792 (14)	−0.0014 (10)	−0.0103 (10)	0.0010 (11)
C10	0.0486 (11)	0.0484 (11)	0.0781 (14)	0.0018 (9)	0.0098 (10)	−0.0065 (10)

Geometric parameters (Å, º)

O1—C2	1.324 (2)	O5—C6	1.408 (2)
O1—C5	1.461 (2)	O5—C7	1.420 (2)
C1—N3	1.297 (2)	C5—C6	1.487 (3)
C1—N1	1.360 (2)	C5—H5B	0.987 (19)
C1—C2	1.429 (2)	C5—H5A	0.96 (2)
N1—H1B	0.87 (2)	O6—C8	1.415 (2)
N1—H1A	0.91 (2)	O6—C9	1.421 (2)
O2—C4	1.335 (2)	C6—H6B	0.96 (2)
O2—C10	1.445 (2)	C6—H6A	0.96 (2)
C2—N4	1.290 (2)	C7—C8	1.490 (3)
N2—C3	1.345 (3)	C7—H7B	0.97 (2)
N2—H2B	0.90 (3)	C7—H7A	0.98 (2)
N2—H2A	0.83 (3)	C8—H8B	0.97 (3)
O3—N3	1.402 (2)	C8—H8A	1.02 (2)
O3—N4	1.403 (2)	C9—C10	1.481 (3)
C3—N5	1.296 (2)	C9—H9B	1.01 (2)
C3—C4	1.423 (3)	C9—H9A	0.99 (2)
O4—N6	1.393 (3)	C10—H10B	1.03 (2)
O4—N5	1.411 (3)	C10—H10A	1.00 (2)
C4—N6	1.295 (2)
C2—O1—C5	116.12 (14)	C8—O6—C9	111.25 (15)
N3—C1—N1	125.45 (17)	O5—C6—C5	108.65 (15)
N3—C1—C2	109.07 (15)	O5—C6—H6B	111.4 (11)
N1—C1—C2	125.39 (18)	C5—C6—H6B	107.5 (12)
C1—N1—H1B	115.2 (16)	O5—C6—H6A	112.9 (12)
C1—N1—H1A	113.7 (15)	C5—C6—H6A	108.9 (12)
H1B—N1—H1A	119 (2)	H6B—C6—H6A	107.3 (16)
C4—O2—C10	115.37 (15)	C4—N6—O4	104.18 (18)
N4—C2—O1	126.94 (16)	O5—C7—C8	109.52 (17)
N4—C2—C1	110.47 (16)	O5—C7—H7B	110.6 (12)
O1—C2—C1	122.57 (15)	C8—C7—H7B	108.5 (11)
C3—N2—H2B	113.2 (16)	O5—C7—H7A	110.4 (12)
C3—N2—H2A	111.4 (17)	C8—C7—H7A	111.0 (12)
H2B—N2—H2A	120 (2)	H7B—C7—H7A	106.7 (16)
N3—O3—N4	110.40 (13)	O6—C8—C7	109.90 (16)
N5—C3—N2	125.9 (2)	O6—C8—H8B	112.4 (14)
N5—C3—C4	108.4 (2)	C7—C8—H8B	106.9 (14)
N2—C3—C4	125.54 (18)	O6—C8—H8A	109.5 (12)
C1—N3—O3	105.30 (14)	C7—C8—H8A	112.9 (12)
N6—O4—N5	110.59 (14)	H8B—C8—H8A	105.1 (18)
N6—C4—O2	126.14 (19)	O6—C9—C10	110.54 (17)
N6—C4—C3	111.37 (18)	O6—C9—H9B	110.0 (12)
O2—C4—C3	122.48 (17)	C10—C9—H9B	112.3 (12)
C2—N4—O3	104.75 (14)	O6—C9—H9A	108.4 (13)
C6—O5—C7	114.16 (14)	C10—C9—H9A	108.6 (13)
O1—C5—C6	106.86 (16)	H9B—C9—H9A	106.9 (17)
O1—C5—H5B	107.5 (11)	O2—C10—C9	108.83 (17)
C6—C5—H5B	112.2 (11)	O2—C10—H10B	106.6 (12)
O1—C5—H5A	107.3 (13)	C9—C10—H10B	111.0 (12)
C6—C5—H5A	109.6 (12)	O2—C10—H10A	107.0 (12)
H5B—C5—H5A	113.1 (17)	C9—C10—H10A	111.8 (12)
C3—N5—O4	105.43 (18)	H10B—C10—H10A	111.3 (17)
C5—O1—C2—N4	−9.3 (2)	N3—O3—N4—C2	0.00 (19)
C5—O1—C2—C1	172.18 (16)	C2—O1—C5—C6	−168.47 (15)
N3—C1—C2—N4	−0.7 (2)	N2—C3—N5—O4	175.28 (17)
N1—C1—C2—N4	−177.35 (17)	C4—C3—N5—O4	−1.2 (2)
N3—C1—C2—O1	178.03 (15)	N6—O4—N5—C3	0.9 (2)
N1—C1—C2—O1	1.4 (3)	C7—O5—C6—C5	−175.31 (16)
N1—C1—N3—O3	177.29 (17)	O1—C5—C6—O5	73.4 (2)
C2—C1—N3—O3	0.68 (19)	O2—C4—N6—O4	179.39 (16)
N4—O3—N3—C1	−0.45 (19)	C3—C4—N6—O4	−0.5 (2)
C10—O2—C4—N6	−0.8 (3)	N5—O4—N6—C4	−0.2 (2)
C10—O2—C4—C3	179.10 (16)	C6—O5—C7—C8	−157.18 (17)
N5—C3—C4—N6	1.1 (2)	C9—O6—C8—C7	−176.28 (17)
N2—C3—C4—N6	−175.30 (18)	O5—C7—C8—O6	−65.9 (2)
N5—C3—C4—O2	−178.79 (16)	C8—O6—C9—C10	−167.23 (17)
N2—C3—C4—O2	4.8 (3)	C4—O2—C10—C9	−165.85 (15)
O1—C2—N4—O3	−178.28 (16)	O6—C9—C10—O2	−69.8 (2)
C1—C2—N4—O3	0.42 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3^i	0.91 (2)	2.25 (2)	3.148 (3)	169 (2)
N2—H2B···O5^ii	0.90 (3)	2.13 (3)	3.024 (2)	170 (2)
N2—H2A···N4^iii	0.83 (3)	2.44 (3)	3.196 (3)	151 (2)

Symmetry codes: (i) −x+1/2, y−1/2, −z+5/2; (ii) x, y−1, z; (iii) x, y−2, z.