(E)-2-[1,3-Dihydr­oxy-2-(hydroxy­meth­yl)propan-2-ylamino­methyl­ene]-4-[(4-ethyl­phen­yl)diazen­yl]-6-methoxy­cyclo­hexa­none

The title compound, C₂₀H₂₅N₃O₅, adopts the keto–amine tautomeric form and displays the characteristic features of azobenzene derivatives. Intra­molecular N—H...O and O—H...O and inter­molecular O—H...O inter­actions influence the conformation of the mol­ecules and the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.058
• wR factor = 0.174
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT432_ALERT_2_A Short Inter X...Y Contact  C1B    ..  C5B     ..       2.65 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.55 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.32 Ratio
PLAT417_ALERT_2_B Short Inter D-H..H-D       H3A    ..  H4      ..       1.31 Ang.
PLAT432_ALERT_2_B Short Inter X...Y Contact  C1B    ..  C4B     ..       2.94 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

PLAT432_ALERT_2_B Short Inter X...Y Contact  C4B    ..  C4B     ..       3.00 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

PLAT432_ALERT_2_B Short Inter X...Y Contact  C5A    ..  C7A     ..       3.08 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

PLAT432_ALERT_2_B Short Inter X...Y Contact  C5C    ..  C8C     ..       3.02 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -0.606
            Test value =     -0.600
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............      -0.61 e/A   3
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.85 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N1
PLAT301_ALERT_3_C Main Residue  Disorder .........................      18.00 Perc.
PLAT414_ALERT_2_C Short Intra D-H..H-X       H5     ..  H19B    ..       1.95 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C5C    ..  C7C     ..       3.13 Ang.

Author Response: Although the complicated disorder (the temperature was 150 K) of the 4-ethyl phenyl group was studied in three different orientations, a good matching could not have been achieved and so some contact length are not reasonable.

PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         15

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

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

---

S1. Comment

Azo compounds are the most widely used class of dyes, owing to their versatile application in various fields, such as the dyeing of textiles and fibres, the colouring of different materials, and high-technology areas, such as electro-optical devices and ink-jet printers (Peters & Freeman, 1991). There is interest in Schiff base ligands and their complexes with regards to their impressive antitumour activities (Zhou et al., 2000). Schiff base compounds can be classified by their photochromic and thermochromic characteristics (Cohen et al., 1964; Moustakali et al., 1978; Hadjoudis et al., 1987). On the basis of studies of some thermochromic and photochromic Schiff base compounds, it has been proposed that molecules exhibiting monochromism are planar, while those exhibiting photochromism are non-planar (Moustakali et al., 1978).

ο-Hydroxyarylidene Schiff bases display two possible tautomeric forms, namely, phenol–imine and keto–amine. In the solid state, the keto–amine tautomer has been found in naphthaldimine (Hökelek et al., 2000; Ünver et al., 2002), while the phenol–imine tautomer is found in salicylaldimine Schiff bases (Yıldız et al., 1998; Elmalı & Elerman, 1998; Dey et al., 2001; Yang & Vittal, 2003; Karadayı et al., 2003).

The molecular structure of (I), with the atom-labelling scheme, is shown in Fig. 1. The –N═N– double bond length [1.232 (3) Å] is comparable to the same bond length [1.223 (7) Å] of azo compound 2-hydroxy-5-{[4-(2-pyridinylamino)sulfonyl]phenyl}azobenzoic acid (van der Sluis et al., 1990). In the molecule of (I), the C12═O2, N2—C9 and C11—C16 bond lengths (Table 1) agree with the corresponding distances in 4-[(3-chlorophenyl)diazenyl]-2- {[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5- dien-1(2H)-one [1.286 (2), 1.414 (2) and 1.411 (3) Å; Odabaşoğlu et al., 2003].

The intra- and intermolecular hydrogen bonding in (I) is shown in Fig. 2 and the geometric values are given in Table 2. Atom H3 bonded to N3 forms a strong intramolecular hydrogen bond,with atom O2, with an N···O distance of 2.603 (2) Å, as in our previous work (Odabaşoğlu, et al., 2003).

S2. Experimental

The title compound, (I), was prepared as described by Odabaşoğlu et al. (2003), using o-vanillin, 4-ethylaniline and tris(hydroxymethyl)aminomethane as starting materials. The product was recrystallized from ethanol and well shaped crystals of (I) were obtained by slow evaporation of an ethanol solution (yield 80%, m.p. 453–455 K).

S3. Refinement

The high s.u. values and high displacement parameters of some atoms in the molecule are likely caused by some disorder of the 4-ethyl phenyl group. This disorder was studied in three different orientations of the CA, CB and CC groups (CA = C1A–C8A, CB = C1B–C8B and CC = C1C–C8C) with occupancy factors of 0.329 (3), 0.351 (3) and 0.320 (4). An H atom is located on N3 rather than on O2, thus confirming a preference for the keto–amine tautomer in the solid state. All H atoms were refined using a riding model, with C—H = 0.93–0.97 Å, N—H = 0.86 Å and O—H = 0.82 Å. The constraint U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl and hydroxyl carrier) was applied. Please check changes to text.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); 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: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids. Only the major disorder components are indicated.
	Fig. 2. A packing diagram for (I), showing hydrogen bonds as dashed lines, with the major disorder components. Non-hydrogen-bonding H atoms have been omitted for clarity.

(E)-2-[1,3-Dihydroxy-2-(hydroxymethyl)propan-2-ylaminomethylene]-4-[(4- ethylphenyl)diazenyl]-6-methoxycyclohexanone

Crystal data

C20H25N3O5	F(000) = 824
Mr = 387.43	Dx = 1.345 Mg m^−3
Monoclinic, P21/c	Melting point = 453–455 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 17.0925 (16) Å	Cell parameters from 14646 reflections
b = 10.6353 (6) Å	θ = 1.9–28.8°
c = 10.6634 (9) Å	µ = 0.10 mm^−1
β = 99.263 (7)°	T = 150 K
V = 1913.2 (3) Å^3	Prism, yellow
Z = 4	0.42 × 0.29 × 0.15 mm

Data collection

Stoe IPDS-II diffractometer	2603 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 26.0°, θmin = 2.3°
Detector resolution: 6.67 pixels mm^-1	h = −21→21
ω scans	k = −13→13
16869 measured reflections	l = −12→13
3769 independent 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1061P)^2 + 0.2543P] where P = (Fo^2 + 2Fc^2)/3
3769 reflections	(Δ/σ)max < 0.001
299 parameters	Δρmax = 0.58 e Å^−3
127 restraints	Δρmin = −0.61 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	Occ. (<1)
C3A	0.5935 (6)	0.5683 (8)	0.8928 (10)	0.0301 (7)	0.329 (3)
C4A	0.5523 (4)	0.4606 (8)	0.8558 (7)	0.0301 (7)	0.329 (3)
H4A	0.5640	0.3874	0.9029	0.036*	0.329 (3)
C5A	0.4942 (4)	0.4582 (8)	0.7508 (8)	0.0301 (7)	0.329 (3)
H5A	0.4674	0.3835	0.7281	0.036*	0.329 (3)
C6A	0.4747 (9)	0.5651 (13)	0.6778 (14)	0.0301 (7)	0.329 (3)
C7A	0.5190 (4)	0.6733 (7)	0.7081 (8)	0.0301 (7)	0.329 (3)
H7A	0.5103	0.7439	0.6562	0.036*	0.329 (3)
C8A	0.5768 (4)	0.6759 (7)	0.8167 (9)	0.0301 (7)	0.329 (3)
H8A	0.6047	0.7499	0.8390	0.036*	0.329 (3)
C2A	0.6557 (11)	0.5769 (15)	1.0033 (17)	0.0408 (11)	0.329 (3)
H2A1	0.6422	0.6463	1.0548	0.049*	0.329 (3)
H2A2	0.7042	0.6000	0.9728	0.049*	0.329 (3)
C1A	0.6747 (7)	0.4644 (12)	1.0911 (11)	0.0408 (11)	0.329 (3)
H1A1	0.7175	0.4854	1.1577	0.061*	0.329 (3)
H1A2	0.6899	0.3944	1.0435	0.061*	0.329 (3)
H1A3	0.6287	0.4423	1.1276	0.061*	0.329 (3)
C3B	0.5861 (6)	0.6041 (8)	0.8708 (10)	0.0301 (7)	0.351 (3)
C4B	0.5044 (4)	0.5817 (6)	0.8866 (7)	0.0301 (7)	0.351 (3)
H4B	0.4925	0.5680	0.9676	0.036*	0.351 (3)
C5B	0.4441 (4)	0.5803 (6)	0.7831 (7)	0.0301 (7)	0.351 (3)
H5B	0.3919	0.5652	0.7934	0.036*	0.351 (3)
C6B	0.4632 (12)	0.6015 (16)	0.666 (2)	0.0301 (7)	0.351 (3)
C7B	0.5385 (4)	0.6328 (7)	0.6493 (8)	0.0301 (7)	0.351 (3)
H7B	0.5492	0.6541	0.5692	0.036*	0.351 (3)
C8B	0.5987 (4)	0.6323 (7)	0.7544 (7)	0.0301 (7)	0.351 (3)
H8B	0.6499	0.6524	0.7424	0.036*	0.351 (3)
C2B	0.6512 (10)	0.5988 (14)	0.9883 (16)	0.0408 (11)	0.351 (3)
H2B1	0.6408	0.6624	1.0488	0.049*	0.351 (3)
H2B2	0.7020	0.6175	0.9632	0.049*	0.351 (3)
C1B	0.6552 (6)	0.4645 (11)	1.0547 (10)	0.0408 (11)	0.351 (3)
H1B1	0.6965	0.4645	1.1274	0.061*	0.351 (3)
H1B2	0.6663	0.4015	0.9955	0.061*	0.351 (3)
H1B3	0.6053	0.4465	1.0812	0.061*	0.351 (3)
C3C	0.5622 (5)	0.6560 (10)	0.8950 (8)	0.036 (2)	0.320 (4)
C4C	0.5563 (4)	0.5461 (9)	0.8255 (8)	0.035 (2)	0.320 (4)
H4C	0.5904	0.4797	0.8518	0.042*	0.320 (4)
C5C	0.4995 (5)	0.5331 (9)	0.7156 (8)	0.026 (2)	0.320 (4)
H5C	0.4960	0.4579	0.6706	0.031*	0.320 (4)
C6C	0.4489 (7)	0.6302 (12)	0.6737 (15)	0.026 (3)	0.320 (4)
C7C	0.4587 (5)	0.7479 (7)	0.7403 (8)	0.034 (2)	0.320 (4)
H7C	0.4284	0.8174	0.7098	0.041*	0.320 (4)
C8C	0.5135 (5)	0.7570 (8)	0.8500 (8)	0.038 (2)	0.320 (4)
H8C	0.5180	0.8322	0.8951	0.046*	0.320 (4)
C2C	0.6137 (5)	0.6733 (9)	1.0275 (9)	0.0408 (11)	0.320 (4)
H2C1	0.6313	0.7599	1.0377	0.049*	0.320 (4)
H2C2	0.5822	0.6547	1.0932	0.049*	0.320 (4)
C1C	0.6850 (6)	0.5869 (10)	1.0418 (10)	0.0408 (11)	0.320 (4)
H1C1	0.7163	0.5986	1.1242	0.061*	0.320 (4)
H1C2	0.7165	0.6062	0.9775	0.061*	0.320 (4)
H1C3	0.6675	0.5011	1.0328	0.061*	0.320 (4)
C15	0.2456 (2)	0.7468 (3)	0.1514 (4)	0.0723 (2)
H15A	0.2291	0.7900	0.0725	0.108*
H15B	0.3024	0.7420	0.1680	0.108*
H15C	0.2271	0.7917	0.2190	0.108*
C9	0.29527 (15)	0.4942 (3)	0.4578 (2)	0.0320 (6)
C10	0.24873 (15)	0.3900 (2)	0.4571 (2)	0.0309 (6)
H10	0.2532	0.3395	0.5291	0.037*
C11	0.19368 (13)	0.3578 (2)	0.3479 (2)	0.0229 (5)
C12	0.18655 (13)	0.4346 (2)	0.2372 (2)	0.0222 (5)
C13	0.23126 (15)	0.5498 (2)	0.2480 (2)	0.0307 (6)
C14	0.28533 (16)	0.5770 (3)	0.3526 (3)	0.0364 (6)
H14	0.3157	0.6498	0.3550	0.044*
C16	0.14711 (14)	0.2483 (2)	0.3498 (2)	0.0247 (5)
H16	0.1530	0.2004	0.4237	0.030*
C17	0.04341 (13)	0.10209 (19)	0.2413 (2)	0.0204 (5)
C18	−0.03980 (13)	0.1490 (2)	0.1843 (2)	0.0233 (5)
H18A	−0.0739	0.0775	0.1588	0.028*
H18B	−0.0622	0.1955	0.2483	0.028*
C19	0.07655 (14)	0.0103 (2)	0.1529 (2)	0.0234 (5)
H19A	0.0765	0.0486	0.0704	0.028*
H19B	0.1306	−0.0125	0.1881	0.028*
C20	0.03705 (14)	0.0412 (2)	0.3686 (2)	0.0226 (5)
H20A	0.0334	0.1067	0.4307	0.027*
H20B	−0.0114	−0.0077	0.3598	0.027*
N1	0.40267 (18)	0.5932 (3)	0.5619 (2)	0.06047 (14)
N2	0.35390 (14)	0.5086 (2)	0.5660 (2)	0.0418 (6)
N3	0.09626 (11)	0.21156 (16)	0.25222 (17)	0.0211 (4)
H3	0.0933	0.2577	0.1854	0.025*
O1	0.21331 (13)	0.62325 (17)	0.14344 (19)	0.0495 (6)
O2	0.14136 (9)	0.40549 (14)	0.13321 (15)	0.0243 (4)
O3	−0.03690 (9)	0.22770 (14)	0.07718 (14)	0.0248 (4)
H3A	−0.0187	0.1880	0.0226	0.037*
O4	0.02729 (10)	−0.09798 (14)	0.14105 (16)	0.0299 (4)
H4	0.0438	−0.1490	0.0939	0.045*
O5	0.10246 (9)	−0.03868 (14)	0.41504 (15)	0.0251 (4)
H5	0.1175	−0.0745	0.3552	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C4A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C5A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C6A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C7A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C8A	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C2A	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C1A	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C3B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C4B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C5B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C6B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C7B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C8B	0.0305 (12)	0.0261 (15)	0.0318 (14)	−0.0052 (10)	−0.0009 (9)	−0.0003 (10)
C2B	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C1B	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C3C	0.032 (5)	0.051 (6)	0.025 (5)	−0.023 (4)	0.003 (4)	0.008 (4)
C4C	0.023 (4)	0.045 (6)	0.036 (5)	−0.008 (4)	−0.002 (4)	0.007 (4)
C5C	0.031 (5)	0.023 (5)	0.024 (4)	0.007 (4)	0.005 (3)	−0.002 (3)
C6C	0.021 (6)	0.030 (7)	0.025 (5)	−0.004 (4)	−0.005 (4)	0.009 (5)
C7C	0.049 (5)	0.023 (4)	0.029 (4)	−0.009 (3)	0.003 (4)	−0.002 (3)
C8C	0.052 (5)	0.027 (4)	0.033 (5)	−0.019 (4)	−0.003 (4)	−0.003 (3)
C2C	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C1C	0.035 (3)	0.045 (2)	0.040 (3)	−0.006 (2)	−0.0037 (18)	−0.004 (2)
C15	0.080	0.039	0.086	−0.0311 (15)	−0.023 (2)	0.0262 (16)
C9	0.0357 (13)	0.0382 (14)	0.0219 (12)	−0.0155 (11)	0.0038 (10)	−0.0069 (10)
C10	0.0406 (14)	0.0329 (13)	0.0185 (11)	−0.0115 (11)	0.0025 (10)	−0.0004 (10)
C11	0.0274 (11)	0.0219 (11)	0.0192 (11)	−0.0052 (9)	0.0026 (9)	−0.0024 (9)
C12	0.0255 (11)	0.0192 (11)	0.0218 (11)	−0.0003 (9)	0.0032 (9)	−0.0030 (9)
C13	0.0407 (14)	0.0238 (12)	0.0272 (13)	−0.0083 (10)	0.0040 (10)	0.0029 (10)
C14	0.0467 (15)	0.0311 (13)	0.0306 (14)	−0.0191 (11)	0.0044 (11)	−0.0026 (11)
C16	0.0330 (12)	0.0220 (11)	0.0181 (11)	−0.0041 (9)	0.0009 (9)	0.0012 (9)
C17	0.0292 (12)	0.0147 (10)	0.0169 (11)	−0.0048 (8)	0.0030 (9)	−0.0009 (8)
C18	0.0302 (12)	0.0195 (11)	0.0199 (11)	−0.0033 (9)	0.0028 (9)	−0.0007 (9)
C19	0.0335 (12)	0.0181 (10)	0.0190 (11)	−0.0035 (9)	0.0051 (9)	−0.0007 (9)
C20	0.0317 (12)	0.0174 (10)	0.0188 (11)	−0.0036 (9)	0.0045 (9)	−0.0009 (8)
N1	0.072	0.070	0.034	−0.0517 (11)	−0.0052 (13)	0.0023 (13)
N2	0.0423 (13)	0.0584 (15)	0.0239 (11)	−0.0241 (11)	0.0033 (9)	−0.0104 (11)
N3	0.0297 (10)	0.0163 (9)	0.0166 (9)	−0.0051 (7)	0.0019 (7)	0.0011 (7)
O1	0.0733 (14)	0.0269 (10)	0.0412 (12)	−0.0232 (9)	−0.0123 (10)	0.0131 (8)
O2	0.0314 (9)	0.0198 (8)	0.0200 (8)	−0.0025 (6)	−0.0010 (7)	0.0023 (6)
O3	0.0374 (9)	0.0199 (8)	0.0170 (8)	0.0018 (7)	0.0036 (6)	−0.0019 (6)
O4	0.0474 (10)	0.0175 (8)	0.0257 (9)	−0.0084 (7)	0.0086 (7)	−0.0067 (7)
O5	0.0374 (9)	0.0187 (8)	0.0187 (8)	0.0022 (6)	0.0029 (7)	0.0002 (6)

Geometric parameters (Å, º)

C3A—C4A	1.368 (12)	C7C—C8C	1.378 (11)
C3A—C8A	1.406 (12)	C7C—H7C	0.9300
C3A—C2A	1.46 (2)	C8C—H8C	0.9300
C4A—C5A	1.373 (11)	C2C—C1C	1.514 (14)
C4A—H4A	0.9300	C2C—H2C1	0.9700
C5A—C6A	1.387 (15)	C2C—H2C2	0.9700
C5A—H5A	0.9300	C1C—H1C1	0.9600
C6A—C7A	1.388 (16)	C1C—H1C2	0.9600
C6A—N1	1.626 (16)	C1C—H1C3	0.9600
C7A—C8A	1.397 (11)	C15—O1	1.422 (3)
C7A—H7A	0.9300	C15—H15A	0.9600
C8A—H8A	0.9300	C15—H15B	0.9600
C2A—C1A	1.522 (16)	C15—H15C	0.9600
C2A—H2A1	0.9700	C9—C10	1.364 (3)
C2A—H2A2	0.9700	C9—N2	1.410 (3)
C1A—H1A1	0.9600	C9—C14	1.414 (4)
C1A—H1A2	0.9600	C10—C11	1.416 (3)
C1A—H1A3	0.9600	C10—H10	0.9300
C3B—C8B	1.327 (13)	C11—C16	1.413 (3)
C3B—C4B	1.452 (13)	C11—C12	1.424 (3)
C3B—C2B	1.538 (17)	C12—O2	1.283 (3)
C4B—C5B	1.384 (10)	C12—C13	1.439 (3)
C4B—H4B	0.9300	C13—O1	1.355 (3)
C5B—C6B	1.36 (2)	C13—C14	1.361 (4)
C5B—H5B	0.9300	C14—H14	0.9300
C6B—C7B	1.37 (2)	C16—N3	1.304 (3)
C6B—N1	1.40 (2)	C16—H16	0.9300
C7B—C8B	1.394 (10)	C17—N3	1.467 (3)
C7B—H7B	0.9300	C17—C20	1.524 (3)
C8B—H8B	0.9300	C17—C19	1.528 (3)
C2B—C1B	1.590 (16)	C17—C18	1.537 (3)
C2B—H2B1	0.9700	C18—O3	1.424 (3)
C2B—H2B2	0.9700	C18—H18A	0.9700
C1B—H1B1	0.9600	C18—H18B	0.9700
C1B—H1B2	0.9600	C19—O4	1.420 (3)
C1B—H1B3	0.9600	C19—H19A	0.9700
C3C—C4C	1.379 (15)	C19—H19B	0.9700
C3C—C8C	1.397 (14)	C20—O5	1.428 (3)
C3C—C2C	1.551 (12)	C20—H20A	0.9700
C4C—C5C	1.403 (13)	C20—H20B	0.9700
C4C—H4C	0.9300	N1—N2	1.232 (3)
C5C—C6C	1.374 (13)	N3—H3	0.8600
C5C—H5C	0.9300	O3—H3A	0.8200
C6C—N1	1.378 (16)	O4—H4	0.8200
C6C—C7C	1.436 (15)	O5—H5	0.8200
C4A—C3A—C8A	117.9 (9)	C7C—C8C—H8C	119.2
C4A—C3A—C2A	124.1 (9)	C3C—C8C—H8C	119.2
C8A—C3A—C2A	118.0 (9)	C1C—C2C—C3C	110.4 (8)
C3A—C4A—C5A	121.5 (8)	C1C—C2C—H2C1	109.6
C3A—C4A—H4A	119.3	C3C—C2C—H2C1	109.6
C5A—C4A—H4A	119.3	C1C—C2C—H2C2	109.6
C4A—C5A—C6A	121.3 (9)	C3C—C2C—H2C2	109.6
C4A—C5A—H5A	119.3	H2C1—C2C—H2C2	108.1
C6A—C5A—H5A	119.3	C2C—C1C—H1C1	109.5
C5A—C6A—C7A	118.4 (12)	C2C—C1C—H1C2	109.5
C5A—C6A—N1	131.4 (10)	H1C1—C1C—H1C2	109.5
C7A—C6A—N1	110.0 (10)	C2C—C1C—H1C3	109.5
C6A—C7A—C8A	119.8 (9)	H1C1—C1C—H1C3	109.5
C6A—C7A—H7A	120.1	H1C2—C1C—H1C3	109.5
C8A—C7A—H7A	120.1	O1—C15—H15A	109.5
C7A—C8A—C3A	120.9 (7)	O1—C15—H15B	109.5
C7A—C8A—H8A	119.6	H15A—C15—H15B	109.5
C3A—C8A—H8A	119.6	O1—C15—H15C	109.5
C3A—C2A—C1A	120.2 (14)	H15A—C15—H15C	109.5
C3A—C2A—H2A1	107.3	H15B—C15—H15C	109.5
C1A—C2A—H2A1	107.3	C10—C9—N2	115.5 (2)
C3A—C2A—H2A2	107.3	C10—C9—C14	120.4 (2)
C1A—C2A—H2A2	107.3	N2—C9—C14	124.1 (2)
H2A1—C2A—H2A2	106.9	C9—C10—C11	120.7 (2)
C2A—C1A—H1A1	109.5	C9—C10—H10	119.6
C2A—C1A—H1A2	109.5	C11—C10—H10	119.6
H1A1—C1A—H1A2	109.5	C16—C11—C10	119.3 (2)
C2A—C1A—H1A3	109.5	C16—C11—C12	120.75 (19)
H1A1—C1A—H1A3	109.5	C10—C11—C12	120.0 (2)
H1A2—C1A—H1A3	109.5	O2—C12—C11	122.5 (2)
C8B—C3B—C4B	116.8 (8)	O2—C12—C13	120.8 (2)
C8B—C3B—C2B	124.4 (11)	C11—C12—C13	116.6 (2)
C4B—C3B—C2B	118.8 (10)	O1—C13—C14	125.8 (2)
C5B—C4B—C3B	121.0 (8)	O1—C13—C12	112.2 (2)
C5B—C4B—H4B	119.5	C14—C13—C12	121.9 (2)
C3B—C4B—H4B	119.5	C13—C14—C9	119.8 (2)
C6B—C5B—C4B	118.2 (11)	C13—C14—H14	120.1
C6B—C5B—H5B	120.9	C9—C14—H14	120.1
C4B—C5B—H5B	120.9	N3—C16—C11	122.7 (2)
C5B—C6B—C7B	122.2 (17)	N3—C16—H16	118.7
C5B—C6B—N1	117.8 (16)	C11—C16—H16	118.7
C7B—C6B—N1	120.1 (17)	N3—C17—C20	113.45 (17)
C6B—C7B—C8B	118.7 (12)	N3—C17—C19	105.75 (17)
C6B—C7B—H7B	120.6	C20—C17—C19	111.39 (18)
C8B—C7B—H7B	120.6	N3—C17—C18	107.03 (17)
C3B—C8B—C7B	122.8 (8)	C20—C17—C18	107.20 (18)
C3B—C8B—H8B	118.6	C19—C17—C18	112.03 (18)
C7B—C8B—H8B	118.6	O3—C18—C17	111.00 (18)
C3B—C2B—C1B	111.7 (11)	O3—C18—H18A	109.4
C3B—C2B—H2B1	109.3	C17—C18—H18A	109.4
C1B—C2B—H2B1	109.3	O3—C18—H18B	109.4
C3B—C2B—H2B2	109.3	C17—C18—H18B	109.4
C1B—C2B—H2B2	109.3	H18A—C18—H18B	108.0
H2B1—C2B—H2B2	107.9	O4—C19—C17	107.44 (18)
C2B—C1B—H1B1	109.5	O4—C19—H19A	110.2
C2B—C1B—H1B2	109.5	C17—C19—H19A	110.2
H1B1—C1B—H1B2	109.5	O4—C19—H19B	110.2
C2B—C1B—H1B3	109.5	C17—C19—H19B	110.2
H1B1—C1B—H1B3	109.5	H19A—C19—H19B	108.5
H1B2—C1B—H1B3	109.5	O5—C20—C17	113.43 (19)
C4C—C3C—C8C	118.6 (7)	O5—C20—H20A	108.9
C4C—C3C—C2C	124.9 (9)	C17—C20—H20A	108.9
C8C—C3C—C2C	116.2 (9)	O5—C20—H20B	108.9
C3C—C4C—C5C	120.9 (8)	C17—C20—H20B	108.9
C3C—C4C—H4C	119.6	H20A—C20—H20B	107.7
C5C—C4C—H4C	119.6	N2—N1—C6C	118.4 (6)
C6C—C5C—C4C	120.8 (10)	N2—N1—C6B	115.9 (9)
C6C—C5C—H5C	119.6	N2—N1—C6A	105.8 (5)
C4C—C5C—H5C	119.6	N1—N2—C9	116.5 (2)
C5C—C6C—N1	108.1 (10)	C16—N3—C17	128.61 (19)
C5C—C6C—C7C	118.5 (12)	C16—N3—H3	115.7
N1—C6C—C7C	133.0 (9)	C17—N3—H3	115.7
C8C—C7C—C6C	119.4 (9)	C13—O1—C15	116.7 (2)
C8C—C7C—H7C	120.3	C18—O3—H3A	109.5
C6C—C7C—H7C	120.3	C19—O4—H4	109.5
C7C—C8C—C3C	121.6 (8)	C20—O5—H5	109.5
C8A—C3A—C4A—C5A	−2.6 (10)	O2—C12—C13—C14	−173.5 (2)
C2A—C3A—C4A—C5A	179.9 (12)	C11—C12—C13—C14	8.1 (4)
C3A—C4A—C5A—C6A	−0.1 (11)	O1—C13—C14—C9	176.9 (3)
C4A—C5A—C6A—C7A	4.3 (16)	C12—C13—C14—C9	−3.8 (4)
C4A—C5A—C6A—N1	−171.3 (9)	C10—C9—C14—C13	−2.7 (4)
C5A—C6A—C7A—C8A	−5.8 (17)	N2—C9—C14—C13	174.6 (3)
N1—C6A—C7A—C8A	170.8 (8)	C10—C11—C16—N3	−178.8 (2)
C6A—C7A—C8A—C3A	3.1 (14)	C12—C11—C16—N3	0.3 (4)
C4A—C3A—C8A—C7A	1.1 (13)	N3—C17—C18—O3	47.0 (2)
C2A—C3A—C8A—C7A	178.7 (12)	C20—C17—C18—O3	169.07 (17)
C4A—C3A—C2A—C1A	−4 (2)	C19—C17—C18—O3	−68.4 (2)
C8A—C3A—C2A—C1A	178.3 (12)	N3—C17—C19—O4	179.36 (16)
C8B—C3B—C4B—C5B	4.9 (10)	C20—C17—C19—O4	55.7 (2)
C2B—C3B—C4B—C5B	−177.3 (9)	C18—C17—C19—O4	−64.4 (2)
C3B—C4B—C5B—C6B	−0.5 (11)	N3—C17—C20—O5	−79.6 (2)
C4B—C5B—C6B—C7B	−4.8 (17)	C19—C17—C20—O5	39.5 (2)
C4B—C5B—C6B—N1	176.6 (9)	C18—C17—C20—O5	162.43 (17)
C5B—C6B—C7B—C8B	5.6 (18)	C5C—C6C—N1—N2	68.0 (11)
N1—C6B—C7B—C8B	−175.8 (9)	C7C—C6C—N1—N2	−119.9 (13)
C4B—C3B—C8B—C7B	−4.1 (12)	C5C—C6C—N1—C6B	−18 (4)
C2B—C3B—C8B—C7B	178.2 (9)	C7C—C6C—N1—C6B	154 (6)
C6B—C7B—C8B—C3B	−0.9 (14)	C5C—C6C—N1—C6A	−3.8 (11)
C8B—C3B—C2B—C1B	−122.1 (12)	C7C—C6C—N1—C6A	168 (2)
C4B—C3B—C2B—C1B	60.2 (14)	C5B—C6B—N1—N2	−38.6 (15)
C8C—C3C—C4C—C5C	−3.5 (10)	C7B—C6B—N1—N2	142.7 (10)
C2C—C3C—C4C—C5C	170.3 (8)	C5B—C6B—N1—C6C	64 (4)
C3C—C4C—C5C—C6C	0.8 (11)	C7B—C6B—N1—C6C	−115 (5)
C4C—C5C—C6C—N1	177.3 (7)	C5B—C6B—N1—C6A	−86 (5)
C4C—C5C—C6C—C7C	3.8 (16)	C7B—C6B—N1—C6A	95 (5)
C5C—C6C—C7C—C8C	−5.6 (16)	C5A—C6A—N1—N2	15.5 (15)
N1—C6C—C7C—C8C	−177.1 (11)	C7A—C6A—N1—N2	−160.4 (8)
C6C—C7C—C8C—C3C	2.9 (14)	C5A—C6A—N1—C6C	135 (2)
C4C—C3C—C8C—C7C	1.6 (12)	C7A—C6A—N1—C6C	−40.7 (12)
C2C—C3C—C8C—C7C	−172.8 (8)	C5A—C6A—N1—C6B	152 (6)
C4C—C3C—C2C—C1C	29.1 (11)	C7A—C6A—N1—C6B	−24 (5)
C8C—C3C—C2C—C1C	−156.9 (8)	C6C—N1—N2—C9	165.1 (5)
N2—C9—C10—C11	−173.0 (2)	C6B—N1—N2—C9	−176.2 (9)
C14—C9—C10—C11	4.6 (4)	C6A—N1—N2—C9	−165.2 (6)
C9—C10—C11—C16	179.2 (2)	C10—C9—N2—N1	171.4 (3)
C9—C10—C11—C12	0.1 (4)	C14—C9—N2—N1	−6.1 (4)
C16—C11—C12—O2	−3.6 (4)	C11—C16—N3—C17	−178.9 (2)
C10—C11—C12—O2	175.5 (2)	C20—C17—N3—C16	13.1 (3)
C16—C11—C12—C13	174.7 (2)	C19—C17—N3—C16	−109.3 (3)
C10—C11—C12—C13	−6.2 (3)	C18—C17—N3—C16	131.1 (2)
O2—C12—C13—O1	5.9 (3)	C14—C13—O1—C15	−9.3 (5)
C11—C12—C13—O1	−172.5 (2)	C12—C13—O1—C15	171.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.86	1.90	2.603 (2)	138
O5—H5···O4	0.82	2.55	3.062 (2)	121
O3—H3A···O4^i	0.82	1.97	2.733 (2)	153
O4—H4···O3^i	0.82	1.99	2.733 (2)	150

Symmetry code: (i) −x, −y, −z.