Non-classical hydrogen bonding involving bound diazides in an inositol derivative

The inositol derivative 1D-1,2-diazido-1,2-dide­oxy-3,4,5,6-tetra-O-benzyl-myo-inositol diethyl ether 0.6-solvate, C₃₄H₃₄N₆O₄·0.6C₄H₁₀O, packs with weak and unusual C—H...N,O hydrogen bonds and C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 88 K
• Mean [sigma](C-C) = 0.016 Å
• Disorder in solvent or counterion
• R factor = 0.053
• wR factor = 0.127
• Data-to-parameter ratio = 9.3

checkCIF/PLATON results

No syntax errors found



Alert level A
RINTA01_ALERT_3_A  The value of Rint is greater than 0.20
            Rint given   0.328

Author Response: ... Reflections were affected by surface powder diffraction. Subsequent downweighting was applied by the processing program.

PLAT020_ALERT_3_A The value of Rint is greater than 0.10 .........       0.33

Author Response: ... Reflections were affected by surface powder diffraction. Subsequent downweighting was applied by the processing program.

PLAT026_ALERT_3_A Ratio Observed / Unique Reflections too Low ....         22 Perc.

Author Response: ... The best crystals that could be obtained diffracted weakly, consistent with maximum size and occluded partial disordered solvent.

PLAT093_ALERT_1_A No su's on H-atoms, but refinement reported as .      mixed
PLAT432_ALERT_2_A Short Inter X...Y Contact  C33    ..  C61     ..       2.65 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT432_ALERT_2_A Short Inter X...Y Contact  C34    ..  C61     ..       2.65 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT432_ALERT_2_A Short Inter X...Y Contact  C55    ..  C61     ..       2.15 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT432_ALERT_2_A Short Inter X...Y Contact  C57    ..  C61     ..       2.14 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.597     0.986
            Tmin(prime) and Tmax expected:      0.960     0.986
            RR(prime) =      0.622
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.62
PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) .......          2
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C30
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C40
PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         16
PLAT432_ALERT_2_B Short Inter X...Y Contact  C25    ..  C61     ..       2.97 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT432_ALERT_2_B Short Inter X...Y Contact  C51    ..  C61     ..       2.95 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT432_ALERT_2_B Short Inter X...Y Contact  C52    ..  C61     ..       3.08 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.082
            Value of mu given      =     0.081
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.770
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent .........          5
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.52 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C20
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C33
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C31
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C41
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      51.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C26    ..  C60     ..       3.17 Ang.

Author Response: ... These atoms are part of the model for coping with the disordered diethyl solvent; no physical significance should be attached to their relative positions.

PLAT480_ALERT_4_C Long H...A H-Bond Reported H14    ..  N3      ..       2.70 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H20B   ..  N3      ..       2.65 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.24 Ratio

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.40
           From the CIF: _reflns_number_total               4038
           Count of symmetry unique reflns         4050
           Completeness (_total/calc)             99.70%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   8 ALERT level A = In general: serious problem
   9 ALERT level B = Potentially serious problem
  19 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  20 ALERT type 2 Indicator that the structure model may be wrong or deficient
   7 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The title compound, (I), was prepared as part of a programme aimed at generating new hydrogenation catalyst ligands from inositol molecules (Gainsford et al., 2000; Falshaw et al., 1999).

The asymmetric unit of (I) contains one independent molecule, as shown in Fig. 1. The absolute configuration shown is that determined from the chemical synthesis route. There are few cyclohexane structures in the Cambridge Structural Database (CSD, Version?; Allen, 2002) with adjacent azide and O substituents, namely CSD refcodes QAPSAB and QAPSEF (Akai, Nakamura et al., 1999; Akai, Sugita et al., 1999), AZUZAW (Busscher et al., 2004) and IXEVAI (Carballido et al., 2004). The azide angular geometries C1—N1—N2 and N1—N2—N3 in (I) fall within the previously observed ranges of 114–119° and 170–174°, respectively. The cyclohexane ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.573 (9) Å, θ = 2.6 (9)° and ϕ = 347 (20)°.

Normally, inositol derivatives are strongly hydrogen-bonded, utilizing all available bound groups, e.g. O—H···O (GEGWIY; Dietrich et al., 1999) and C—H···O═C (HADKIG; Steiner et al., 1993). Although the crystals of (I) were weakly diffracting, the crystal packing stability has again been assisted by definite, though weak, non-classical hydrogen bonding involving C—H···X (where X is O or N_azide) and C—H···π interactions, as detailed in Table 2. These forces are sufficient to stabilize a partial molecule of the crystallizing solvent diethyl ether in the lattice (estimated as 0.6 of a molecule).

There are two types of C—H···N_azide interactions in the structure of (I). One was unexpected, being to the inositol ring-bound atom N4, while the other two were to the terminal azide atom N3. The former have rarely been observed, according to a CSD search, with only one occurrence noted in SUMRAT (Goulaouic et al., 1993), with H···N = 2.67 Å and C—H···N = 131°. There are currently five instances of C—H···N_terminal interactions. Three examples are ZDGPLN (Schmidt et al., 1980), MIYKIO (Barnes et al., 2002) and YASBAW (Humphreys et al., 2005) with H···N values of 2.62, 2.59 and 2.47 Å, respectively, and C—H···N angles of 127, 146 and 161°, respectively. In the last of these structures, the interaction was apparently insufficient to reduce the disorder found in the azide group.

The C—H···π interactions listed in Table 2 fit within the normal applied H···Cg limit of 3 Å. From the interaction distances, it seems highly likely that there is also a C—H···O hydrogen bond to the disordered diethyl ether solvent, with C26—H26···O(C60) = 2.49 Å, C26···O = 3.17 (9) Å and C—H···O = 138°.

The combined weak interactions give three-dimensional stability to the crystal structure, although it is difficult to show this meaningfully in a packing diagram. Instead, Fig. 2 (Mercury; Bruno et al., 2002), shows the full interaction commitments of all the bound groups to the inositol as dotted bonds, with the disordered solvent molecules represented by one atom, O(C60) (see Experimental).

S2. Experimental

1D-3,4,5,6-Tetra-O-benzy-myo-inositol was treated with methanesulfonyl chloride in pyridine overnight at room temperature to give the 1,2-dimesylate, which was then subjected to a displacement reaction using sodium azide in dimethylformamide overnight at 383 K. [Please give brief details of quantities] Crystals of the title compound were isolated from diethyl ether.

S3. Refinement

All non-H atoms except C23 and C24 were refined with anisotropic displacement parameters. Friedel-related reflections were merged. The H atoms of the amino (N1) and hydroxyl (O1) atoms were positionally refined. All C-bound H atoms were constrained to their expected geometries, with C—H(methyl) = 0.98 Å and the remaining C—H = 1.0 Å. For all H atoms, U_iso(H) = 1.2U_eq(parent atom). The disordered diethyl ether was modelled with density at 11 atomic sites using C atoms only and a common U_iso; no extra O or H atoms were included for the ether solvate. Models of diethyl ether in two main orientations fit on these positions, but no rational model could be constructed. On the basis of the total electron density, about 0.62 of a diethyl ether molecule per asymmetric unit was found.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Intermolecular interactions (dotted lines) in (I). Contact atoms are shown as spheres. See text for discussion of O(C60). [Symmetry codes are as given in Table 2; additionally: (iv) 3/2 − x, 1 − y, −1/2 + z].

1D-1,2-diazido-1,2-dideoxy-3,4,5,6-tetra-O-benzyl-myo-inositol diethyl ether 0.6-solvate

Crystal data

C34H34N6O4·0.6C4H10O	F(000) = 1356
Mr = 655.53	Dx = 1.241 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 895 reflections
a = 9.006 (3) Å	θ = 2.6–14.6°
b = 15.324 (6) Å	µ = 0.08 mm^−1
c = 25.424 (11) Å	T = 88 K
V = 3509 (2) Å^3	Needle, colourless
Z = 4	0.50 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4038 independent reflections
Radiation source: fine-focus sealed tube	908 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.328
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 2.1°
ϕ and ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 1996)	k = −19→19
Tmin = 0.597, Tmax = 0.986	l = −31→28
19603 measured reflections

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) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 0.77	w = 1/[σ^2(Fo^2) + (0.0367P)^2] where P = (Fo^2 + 2Fc^2)/3
4038 reflections	(Δ/σ)max = 0.001
432 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

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)
O1	0.7436 (6)	0.3110 (4)	0.1485 (2)	0.0547 (17)
O2	0.7278 (6)	0.1551 (4)	0.0859 (2)	0.0522 (17)
O3	0.8286 (5)	0.1748 (4)	−0.0209 (2)	0.0477 (16)
O4	0.7249 (6)	0.3301 (3)	−0.0704 (2)	0.0451 (15)
N1	0.7476 (11)	0.4853 (7)	−0.0070 (3)	0.076 (3)
N2	0.6674 (12)	0.5128 (6)	−0.0405 (4)	0.080 (3)
N3	0.5965 (14)	0.5481 (7)	−0.0733 (4)	0.105 (4)
N4	0.8966 (10)	0.4188 (6)	0.0776 (3)	0.067 (3)
N5	0.9346 (8)	0.4555 (7)	0.1199 (4)	0.076 (3)
N6	0.9805 (10)	0.4868 (7)	0.1563 (4)	0.095 (4)
C1	0.6971 (9)	0.3995 (6)	0.0131 (3)	0.045 (2)
H1	0.5874	0.3930	0.0082	0.054*
C2	0.7362 (10)	0.3986 (6)	0.0714 (3)	0.049 (2)
H2	0.6763	0.4441	0.0900	0.058*
C3	0.7012 (9)	0.3103 (6)	0.0944 (4)	0.050 (3)
H3	0.5916	0.3008	0.0922	0.060*
C4	0.7785 (9)	0.2368 (6)	0.0649 (3)	0.049 (2)
H4	0.8883	0.2417	0.0700	0.058*
C5	0.7432 (9)	0.2396 (5)	0.0064 (3)	0.044 (2)
H5	0.6351	0.2272	0.0012	0.053*
C6	0.7795 (9)	0.3291 (6)	−0.0171 (3)	0.046 (2)
H6	0.8889	0.3401	−0.0163	0.056*
C10	0.6367 (10)	0.2744 (6)	0.1831 (3)	0.060 (3)
H10A	0.6218	0.2118	0.1751	0.073*
H10B	0.5404	0.3049	0.1793	0.073*
C11	0.6970 (10)	0.2856 (8)	0.2388 (4)	0.057 (3)
C12	0.7496 (10)	0.3635 (7)	0.2570 (4)	0.061 (3)
H12	0.7446	0.4136	0.2351	0.073*
C13	0.8094 (11)	0.3703 (7)	0.3062 (4)	0.072 (3)
H13	0.8445	0.4251	0.3185	0.086*
C14	0.8187 (11)	0.2975 (8)	0.3382 (4)	0.074 (3)
H14	0.8598	0.3023	0.3725	0.089*
C15	0.7697 (12)	0.2198 (7)	0.3208 (4)	0.082 (3)
H15	0.7764	0.1700	0.3430	0.098*
C16	0.7088 (9)	0.2114 (7)	0.2702 (4)	0.067 (3)
H16	0.6762	0.1562	0.2577	0.080*
C20	0.8410 (11)	0.1078 (7)	0.1139 (4)	0.096 (4)
H20A	0.8894	0.1462	0.1401	0.115*
H20B	0.9177	0.0864	0.0892	0.115*
C21	0.7654 (16)	0.0311 (8)	0.1413 (5)	0.088 (4)
C22	0.8293 (11)	0.0112 (7)	0.1900 (5)	0.090 (4)
H22	0.9091	0.0457	0.2029	0.108*
C23	0.7766 (14)	−0.0590 (7)	0.2197 (5)	0.106 (4)*
H23	0.8199	−0.0742	0.2526	0.127*
C24	0.6635 (15)	−0.1032 (7)	0.1999 (5)	0.107 (5)*
H24	0.6271	−0.1507	0.2201	0.129*
C25	0.5942 (13)	−0.0871 (9)	0.1531 (6)	0.111 (4)
H25	0.5120	−0.1208	0.1415	0.133*
C26	0.6519 (14)	−0.0166 (9)	0.1225 (6)	0.106 (5)
H26	0.6105	−0.0035	0.0890	0.127*
C30	0.7428 (11)	0.1059 (7)	−0.0402 (4)	0.094 (4)
H30A	0.6617	0.1298	−0.0622	0.113*
H30B	0.6969	0.0746	−0.0102	0.113*
C31	0.8306 (11)	0.0438 (8)	−0.0716 (6)	0.068 (4)
C32	0.8859 (13)	−0.0288 (10)	−0.0474 (5)	0.082 (4)
H32	0.8670	−0.0383	−0.0111	0.099*
C33	0.9672 (17)	−0.0869 (10)	−0.0747 (7)	0.109 (5)
H33	1.0062	−0.1359	−0.0563	0.131*
C34	0.9964 (12)	−0.0800 (9)	−0.1260 (7)	0.092 (4)
H34	1.0544	−0.1229	−0.1435	0.110*
C35	0.9387 (13)	−0.0068 (11)	−0.1541 (4)	0.078 (3)
H35	0.9548	−0.0002	−0.1908	0.093*
C36	0.8576 (13)	0.0548 (8)	−0.1254 (6)	0.079 (4)
H36	0.8202	0.1051	−0.1428	0.094*
C40	0.8304 (10)	0.3439 (7)	−0.1094 (3)	0.089 (4)
H40A	0.9110	0.3004	−0.1057	0.107*
H40B	0.8743	0.4027	−0.1051	0.107*
C41	0.7624 (11)	0.3364 (7)	−0.1631 (3)	0.050 (3)
C42	0.6582 (11)	0.2761 (6)	−0.1741 (4)	0.053 (3)
H42	0.6249	0.2376	−0.1473	0.064*
C43	0.5992 (11)	0.2697 (6)	−0.2243 (5)	0.068 (3)
H43	0.5252	0.2272	−0.2316	0.081*
C44	0.6467 (12)	0.3238 (8)	−0.2628 (4)	0.074 (3)
H44	0.6069	0.3188	−0.2973	0.089*
C45	0.7535 (13)	0.3865 (6)	−0.2520 (4)	0.073 (3)
H45	0.7852	0.4255	−0.2788	0.088*
C46	0.8135 (11)	0.3919 (6)	−0.2021 (4)	0.064 (3)
H46	0.8890	0.4333	−0.1946	0.076*
C51	0.541 (5)	−0.171 (4)	−0.001 (2)	0.205 (6)*	0.65 (5)
C52	0.387 (4)	−0.170 (2)	−0.0678 (14)	0.205 (6)*	0.73 (4)
C53	0.389 (4)	−0.220 (3)	−0.036 (2)	0.205 (6)*	0.63 (4)
C54	0.508 (4)	−0.1490 (19)	−0.0428 (19)	0.205 (6)*	0.71 (4)
C55	0.305 (4)	−0.254 (2)	−0.0731 (15)	0.205 (6)*	0.63 (3)
C56	0.657 (7)	−0.230 (3)	−0.009 (2)	0.205 (6)*	0.45 (3)
C57	0.218 (5)	−0.285 (2)	−0.038 (2)	0.205 (6)*	0.50 (3)
C58	0.304 (7)	−0.223 (3)	0.0128 (17)	0.205 (6)*	0.44 (3)
C59	0.438 (7)	−0.163 (4)	0.042 (3)	0.205 (6)*	0.32 (3)
C60	0.578 (9)	−0.102 (8)	0.012 (3)	0.205 (6)*	0.22 (3)
C61	0.081 (13)	−0.240 (8)	−0.101 (5)	0.205 (6)*	0.132 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.046 (4)	0.083 (5)	0.035 (4)	0.002 (4)	0.010 (3)	0.009 (4)
O2	0.036 (4)	0.060 (5)	0.061 (4)	−0.002 (3)	0.001 (3)	0.019 (4)
O3	0.031 (4)	0.057 (4)	0.055 (4)	−0.011 (4)	−0.005 (3)	0.000 (4)
O4	0.035 (4)	0.061 (4)	0.040 (4)	0.002 (3)	0.003 (3)	−0.004 (4)
N1	0.094 (8)	0.083 (8)	0.050 (7)	0.011 (6)	−0.004 (6)	0.002 (6)
N2	0.097 (11)	0.059 (9)	0.084 (11)	−0.024 (7)	0.039 (8)	−0.013 (8)
N3	0.151 (11)	0.084 (9)	0.079 (10)	−0.024 (7)	0.013 (7)	0.002 (6)
N4	0.069 (7)	0.085 (7)	0.046 (6)	0.000 (5)	0.013 (5)	0.003 (5)
N5	0.032 (6)	0.134 (11)	0.061 (8)	−0.002 (6)	0.012 (6)	0.000 (8)
N6	0.064 (7)	0.147 (10)	0.073 (8)	−0.011 (6)	0.012 (5)	−0.042 (7)
C1	0.038 (6)	0.037 (6)	0.059 (7)	−0.003 (5)	0.001 (5)	0.008 (6)
C2	0.022 (6)	0.073 (8)	0.051 (7)	0.003 (5)	0.006 (5)	−0.005 (6)
C3	0.042 (7)	0.056 (7)	0.052 (7)	−0.007 (5)	0.002 (5)	0.020 (6)
C4	0.029 (6)	0.065 (8)	0.053 (7)	−0.001 (5)	−0.007 (5)	0.007 (6)
C5	0.029 (6)	0.054 (7)	0.049 (7)	0.010 (5)	−0.005 (5)	−0.009 (6)
C6	0.039 (6)	0.045 (6)	0.055 (7)	−0.001 (5)	0.011 (5)	−0.003 (6)
C10	0.051 (7)	0.079 (8)	0.051 (7)	−0.001 (6)	0.010 (6)	0.002 (6)
C11	0.053 (7)	0.060 (8)	0.058 (8)	−0.003 (6)	0.006 (6)	0.008 (7)
C12	0.057 (8)	0.074 (9)	0.052 (8)	0.012 (7)	0.006 (6)	0.008 (6)
C13	0.084 (9)	0.081 (10)	0.050 (8)	0.013 (7)	0.019 (7)	−0.002 (7)
C14	0.090 (9)	0.082 (9)	0.049 (7)	−0.024 (7)	−0.018 (6)	−0.005 (8)
C15	0.110 (9)	0.081 (9)	0.054 (8)	−0.029 (8)	0.008 (7)	0.010 (6)
C16	0.054 (7)	0.093 (10)	0.054 (7)	−0.019 (6)	−0.007 (5)	−0.019 (7)
C20	0.054 (8)	0.096 (9)	0.138 (11)	0.020 (7)	0.012 (7)	0.073 (8)
C21	0.093 (12)	0.083 (11)	0.087 (10)	0.057 (9)	0.015 (9)	0.030 (8)
C22	0.085 (9)	0.071 (9)	0.113 (10)	−0.020 (8)	0.034 (8)	−0.008 (8)
C25	0.047 (9)	0.120 (11)	0.165 (15)	−0.003 (8)	0.033 (9)	−0.009 (10)
C26	0.048 (10)	0.108 (12)	0.162 (15)	0.009 (8)	0.017 (9)	−0.031 (11)
C30	0.068 (9)	0.072 (8)	0.141 (11)	−0.006 (8)	0.030 (8)	−0.019 (8)
C31	0.048 (8)	0.042 (9)	0.114 (13)	−0.016 (7)	−0.017 (8)	0.003 (9)
C32	0.075 (10)	0.081 (11)	0.091 (11)	−0.032 (8)	0.009 (8)	−0.026 (11)
C33	0.145 (14)	0.088 (12)	0.094 (13)	−0.029 (11)	−0.026 (11)	0.029 (11)
C34	0.086 (10)	0.068 (11)	0.121 (14)	−0.014 (8)	−0.012 (10)	−0.024 (10)
C35	0.066 (9)	0.111 (12)	0.057 (9)	−0.020 (8)	−0.003 (7)	0.002 (10)
C36	0.057 (9)	0.092 (11)	0.087 (11)	−0.012 (8)	−0.023 (7)	0.004 (10)
C40	0.058 (8)	0.169 (11)	0.039 (7)	−0.013 (8)	−0.001 (6)	0.012 (7)
C41	0.039 (7)	0.075 (8)	0.038 (6)	0.003 (6)	0.013 (5)	−0.001 (6)
C42	0.042 (7)	0.065 (8)	0.053 (8)	0.010 (6)	0.000 (5)	0.031 (6)
C43	0.075 (8)	0.042 (8)	0.086 (9)	−0.015 (6)	0.021 (7)	−0.006 (7)
C44	0.086 (9)	0.087 (10)	0.049 (8)	−0.006 (8)	−0.011 (6)	−0.021 (8)
C45	0.103 (10)	0.067 (8)	0.050 (8)	−0.004 (8)	0.003 (7)	0.013 (6)
C46	0.070 (8)	0.067 (8)	0.053 (8)	−0.013 (6)	0.002 (6)	−0.015 (6)

Geometric parameters (Å, º)

O1—C10	1.418 (8)	C23—H23	0.9500
O1—C3	1.429 (8)	C24—C25	1.367 (14)
O2—C4	1.435 (8)	C24—H24	0.9500
O2—C20	1.440 (9)	C25—C26	1.430 (14)
O3—C30	1.397 (9)	C25—H25	0.9500
O3—C5	1.435 (8)	C26—H26	0.9500
O4—C40	1.389 (8)	C30—C31	1.474 (13)
O4—C6	1.442 (8)	C30—H30A	0.9900
N1—N2	1.194 (11)	C30—H30B	0.9900
N1—C1	1.482 (10)	C31—C32	1.365 (13)
N2—N3	1.180 (11)	C31—C36	1.400 (12)
N4—N5	1.261 (10)	C32—C33	1.345 (14)
N4—C2	1.486 (10)	C32—H32	0.9500
N5—N6	1.122 (10)	C33—C34	1.335 (13)
C1—C6	1.518 (9)	C33—H33	0.9500
C1—C2	1.522 (9)	C34—C35	1.427 (12)
C1—H1	1.0000	C34—H34	0.9500
C2—C3	1.507 (10)	C35—C36	1.399 (13)
C2—H2	1.0000	C35—H35	0.9500
C3—C4	1.522 (10)	C36—H36	0.9500
C3—H3	1.0000	C40—C41	1.500 (10)
C4—C5	1.520 (9)	C40—H40A	0.9900
C4—H4	1.0000	C40—H40B	0.9900
C5—C6	1.532 (9)	C41—C42	1.347 (11)
C5—H5	1.0000	C41—C46	1.386 (10)
C6—H6	1.0000	C42—C43	1.385 (11)
C10—C11	1.526 (11)	C42—H42	0.9500
C10—H10A	0.9900	C43—C44	1.353 (11)
C10—H10B	0.9900	C43—H43	0.9500
C11—C12	1.364 (10)	C44—C45	1.387 (11)
C11—C16	1.394 (10)	C44—H44	0.9500
C12—C13	1.367 (11)	C45—C46	1.381 (11)
C12—H12	0.9500	C45—H45	0.9500
C13—C14	1.383 (10)	C46—H46	0.9500
C13—H13	0.9500	C51—C56	1.40 (6)
C14—C15	1.344 (10)	C51—C59	1.44 (6)
C14—H14	0.9500	C52—C54	1.31 (4)
C15—C16	1.404 (10)	C52—C55	1.49 (5)
C15—H15	0.9500	C53—C55	1.31 (4)
C16—H16	0.9500	C53—C58	1.47 (5)
C20—C21	1.528 (13)	C53—C54	1.54 (5)
C20—H20A	0.9900	C54—C60	1.69 (11)
C20—H20B	0.9900	C55—C57	1.27 (5)
C21—C26	1.344 (14)	C56—C57^i	1.35 (5)
C21—C22	1.397 (13)	C56—C58^i	1.50 (6)
C22—C23	1.399 (12)	C57—C56^ii	1.35 (5)
C22—H22	0.9500	C58—C56^ii	1.50 (6)
C23—C24	1.323 (13)
C10—O1—C3	114.4 (6)	C21—C20—H20A	110.2
C4—O2—C20	113.5 (7)	O2—C20—H20B	110.2
C30—O3—C5	113.3 (7)	C21—C20—H20B	110.2
C40—O4—C6	116.1 (6)	H20A—C20—H20B	108.5
N2—N1—C1	111.9 (10)	C26—C21—C22	120.8 (13)
N3—N2—N1	172.9 (13)	C26—C21—C20	126.4 (14)
N5—N4—C2	116.6 (8)	C22—C21—C20	112.8 (14)
N6—N5—N4	174.1 (11)	C21—C22—C23	120.4 (12)
N1—C1—C6	107.7 (7)	C21—C22—H22	119.8
N1—C1—C2	105.8 (8)	C23—C22—H22	119.8
C6—C1—C2	111.9 (7)	C24—C23—C22	116.7 (12)
N1—C1—H1	110.4	C24—C23—H23	121.7
C6—C1—H1	110.4	C22—C23—H23	121.7
C2—C1—H1	110.4	C23—C24—C25	126.2 (13)
N4—C2—C3	110.4 (7)	C23—C24—H24	116.9
N4—C2—C1	109.1 (7)	C25—C24—H24	116.9
C3—C2—C1	109.7 (8)	C24—C25—C26	116.4 (13)
N4—C2—H2	109.2	C24—C25—H25	121.8
C3—C2—H2	109.2	C26—C25—H25	121.8
C1—C2—H2	109.2	C21—C26—C25	119.5 (14)
O1—C3—C2	108.2 (7)	C21—C26—H26	120.3
O1—C3—C4	111.0 (7)	C25—C26—H26	120.3
C2—C3—C4	112.2 (7)	O3—C30—C31	112.5 (8)
O1—C3—H3	108.5	O3—C30—H30A	109.1
C2—C3—H3	108.5	C31—C30—H30A	109.1
C4—C3—H3	108.5	O3—C30—H30B	109.1
O2—C4—C5	108.8 (7)	C31—C30—H30B	109.1
O2—C4—C3	108.5 (7)	H30A—C30—H30B	107.8
C5—C4—C3	111.4 (8)	C32—C31—C36	118.3 (12)
O2—C4—H4	109.4	C32—C31—C30	118.6 (15)
C5—C4—H4	109.4	C36—C31—C30	123.0 (14)
C3—C4—H4	109.4	C33—C32—C31	120.4 (14)
O3—C5—C4	110.0 (7)	C33—C32—H32	119.8
O3—C5—C6	108.4 (7)	C31—C32—H32	119.8
C4—C5—C6	111.2 (7)	C34—C33—C32	123.9 (16)
O3—C5—H5	109.1	C34—C33—H33	118.1
C4—C5—H5	109.1	C32—C33—H33	118.1
C6—C5—H5	109.1	C33—C34—C35	118.7 (14)
O4—C6—C1	107.6 (7)	C33—C34—H34	120.7
O4—C6—C5	107.6 (7)	C35—C34—H34	120.7
C1—C6—C5	109.5 (7)	C36—C35—C34	117.4 (11)
O4—C6—H6	110.7	C36—C35—H35	121.3
C1—C6—H6	110.7	C34—C35—H35	121.3
C5—C6—H6	110.7	C35—C36—C31	121.2 (12)
O1—C10—C11	106.8 (7)	C35—C36—H36	119.4
O1—C10—H10A	110.4	C31—C36—H36	119.4
C11—C10—H10A	110.4	O4—C40—C41	111.0 (7)
O1—C10—H10B	110.4	O4—C40—H40A	109.4
C11—C10—H10B	110.4	C41—C40—H40A	109.4
H10A—C10—H10B	108.6	O4—C40—H40B	109.4
C12—C11—C16	119.5 (9)	C41—C40—H40B	109.4
C12—C11—C10	122.4 (10)	H40A—C40—H40B	108.0
C16—C11—C10	117.8 (10)	C42—C41—C46	120.2 (9)
C11—C12—C13	120.9 (10)	C42—C41—C40	121.8 (10)
C11—C12—H12	119.5	C46—C41—C40	118.0 (10)
C13—C12—H12	119.5	C41—C42—C43	120.5 (9)
C12—C13—C14	120.0 (10)	C41—C42—H42	119.8
C12—C13—H13	120.0	C43—C42—H42	119.8
C14—C13—H13	120.0	C44—C43—C42	120.2 (9)
C15—C14—C13	120.1 (10)	C44—C43—H43	119.9
C15—C14—H14	120.0	C42—C43—H43	119.9
C13—C14—H14	120.0	C43—C44—C45	120.0 (9)
C14—C15—C16	120.7 (10)	C43—C44—H44	120.0
C14—C15—H15	119.6	C45—C44—H44	120.0
C16—C15—H15	119.6	C46—C45—C44	119.7 (9)
C11—C16—C15	118.7 (9)	C46—C45—H45	120.2
C11—C16—H16	120.7	C44—C45—H45	120.2
C15—C16—H16	120.7	C45—C46—C41	119.4 (9)
O2—C20—C21	107.3 (9)	C45—C46—H46	120.3
O2—C20—H20A	110.2	C41—C46—H46	120.3
N2—N1—C1—C6	94.6 (10)	C10—C11—C12—C13	−176.9 (8)
N2—N1—C1—C2	−145.5 (9)	C11—C12—C13—C14	0.7 (14)
N5—N4—C2—C3	−88.0 (10)	C12—C13—C14—C15	0.3 (15)
N5—N4—C2—C1	151.4 (8)	C13—C14—C15—C16	0.1 (16)
N1—C1—C2—N4	−53.9 (9)	C12—C11—C16—C15	2.4 (13)
C6—C1—C2—N4	63.2 (9)	C10—C11—C16—C15	177.4 (8)
N1—C1—C2—C3	−175.0 (7)	C14—C15—C16—C11	−1.4 (14)
C6—C1—C2—C3	−57.9 (9)	C4—O2—C20—C21	170.8 (8)
C10—O1—C3—C2	134.6 (7)	O2—C20—C21—C26	36.3 (15)
C10—O1—C3—C4	−101.9 (8)	O2—C20—C21—C22	−145.3 (9)
N4—C2—C3—O1	58.0 (9)	C26—C21—C22—C23	0.4 (17)
C1—C2—C3—O1	178.2 (6)	C20—C21—C22—C23	−178.1 (9)
N4—C2—C3—C4	−64.8 (10)	C21—C22—C23—C24	−1.3 (15)
C1—C2—C3—C4	55.5 (9)	C22—C23—C24—C25	0.4 (17)
C20—O2—C4—C5	126.6 (8)	C23—C24—C25—C26	1.3 (18)
C20—O2—C4—C3	−112.0 (8)	C22—C21—C26—C25	1.4 (18)
O1—C3—C4—O2	64.5 (8)	C20—C21—C26—C25	179.6 (9)
C2—C3—C4—O2	−174.4 (7)	C24—C25—C26—C21	−2.1 (17)
O1—C3—C4—C5	−175.8 (7)	C5—O3—C30—C31	175.5 (9)
C2—C3—C4—C5	−54.7 (10)	O3—C30—C31—C32	95.1 (11)
C30—O3—C5—C4	110.5 (8)	O3—C30—C31—C36	−86.1 (12)
C30—O3—C5—C6	−127.7 (8)	C36—C31—C32—C33	1.5 (15)
O2—C4—C5—O3	−66.0 (8)	C30—C31—C32—C33	−179.7 (10)
C3—C4—C5—O3	174.5 (7)	C31—C32—C33—C34	−1.7 (19)
O2—C4—C5—C6	173.9 (7)	C32—C33—C34—C35	0.0 (19)
C3—C4—C5—C6	54.4 (9)	C33—C34—C35—C36	1.7 (16)
C40—O4—C6—C1	122.1 (8)	C34—C35—C36—C31	−1.8 (16)
C40—O4—C6—C5	−119.9 (8)	C32—C31—C36—C35	0.3 (15)
N1—C1—C6—O4	−69.3 (8)	C30—C31—C36—C35	−178.5 (10)
C2—C1—C6—O4	174.8 (7)	C6—O4—C40—C41	175.5 (7)
N1—C1—C6—C5	174.0 (7)	O4—C40—C41—C42	−38.5 (13)
C2—C1—C6—C5	58.1 (9)	O4—C40—C41—C46	143.5 (9)
O3—C5—C6—O4	66.5 (8)	C46—C41—C42—C43	−1.0 (13)
C4—C5—C6—O4	−172.5 (6)	C40—C41—C42—C43	−178.9 (9)
O3—C5—C6—C1	−176.9 (7)	C41—C42—C43—C44	0.5 (14)
C4—C5—C6—C1	−55.8 (9)	C42—C43—C44—C45	−0.7 (15)
C3—O1—C10—C11	−176.8 (7)	C43—C44—C45—C46	1.6 (15)
O1—C10—C11—C12	49.4 (11)	C44—C45—C46—C41	−2.1 (14)
O1—C10—C11—C16	−125.5 (8)	C42—C41—C46—C45	1.8 (14)
C16—C11—C12—C13	−2.1 (14)	C40—C41—C46—C45	179.8 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg1^iii	1.0	2.64	3.510 (10)	146
C43—H43···Cg2^iii	0.95	2.82	3.597 (11)	140
C1—H1···O3^iii	1.00	2.57	3.514 (10)	157
C30—H30A···N4^iii	0.99	2.53	3.282 (13)	132
C14—H14···N3^iv	0.95	2.70	3.353 (16)	126
C20—H20B···N3^v	0.99	2.65	3.474 (16)	141

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