C.I. Pigment Red 266

C.I. Pigment Red 266, or 4-{[4-(amino­carbonyl)­phenyl]­hydraz­ono}-N-(2-methoxy­phenyl)-3-oxo-3,4-di­hydro­naph­tha­l­ene-2-carbox­amide, C₂₅H₂₀N₄O₄, adopts the keto-hydrazone tautomeric form with significant intramolecular hydrogen bonding. The mol­ecules pack to form layers involving an extensive network of intermolecular hydrogen bonds, in which the primary amide group plays a prominent role. The good technical performance of this pigment in application may be attributed principally to the pattern of intra- and intermolecular hydrogen bonding.

S1. Comment

Organic pigments are insoluble colouring materials, which are manufactured in a finely-divided crystalline form (Christie, 2002). Their application properties are dependent on chemical structure and molecular packing in the solid state in addition to particle size and shape distribution. Single-crystal X-ray crystallographic information is vital in understanding the technical performance of pigments, including colour and fastness properties, and is an essential first step in the crystal engineering of new products for improved performance.

Naphthol azo red (or Naphthol AS) pigments constitute a group of products of industrial importance for application principally in coatings and printing inks. These products can be conveniently classified into two groups. Group 1 pigments contain a single amide group and generally provide only moderate technical performance. A number of single-crystal X-ray structures of these pigments have been reported previously (Kobelt et al., 1972, 1974; Whitaker, 1977). Group 2 pigments, with additional amide or sulphonamide substituents, provide improved technical performance yet have been less extensively investigated. In the only previous study, the X-ray crystal structure of C·I. Pigment Red 208, which contains a benzimidazolone group, has shown that the molecules are linked by a network of hydrogen bonds (Paulus & Hunger, 1980), a feature that is primarily responsible for the superior technical performance of this pigment.

C·I. Pigment Red 266, (I), is in this latter group and investigation of the crystallographic features, notably hydrogen bonding, that contribute to its superior technical performance, such as lightfastness, solvent resistance and thermal stability, is of industrial interest. Compound (I) possesses both primary and secondary amide groups. The latter is a commonly-encountered structural feature in azo pigments, yet the presence of the primary amide group is unusual in commercial organic pigments.

In common with all azo pigments whose crystal structures have been previously reported (Hunger, 1999), (I) exists in the ketohydrazone tautomeric form shown. Important bond lengths that can be highlighted in this respect are N1—N2, N2—C20 and C21—O21 (Table 1), which are similar to those reported for Group 1 naphthol azo pigments (Kobelt et al., 1972, 1974) with the following ranges in bond lengths: N—N = 1.32 (1)–1.336 (8) Å, C—N = 1.322 (9)–1.33 (1) Å and C—O = 1.255 (9)–1.26 (1) Å.

The shortest of the hydrogen bonds found in (I) are intramolecular hydrogen bonds bifurcated at the acceptor end, a type of bonding that is commonly encountered in commercial azo pigments. Interatomic distances indicate strong hydrogen-bonding interactions between hydrazone atom H1 and keto atom O21, and between atom O21 and secondary amide atom H32 (Table 2). The strong hydrogen bonds involving atom O21 probably contribute to the lengthening of the C═O bond. There is also a weaker interaction between atom H32 and methoxy atom O39. Intramolecular hydrogen bonding of this type is considered vital in determining lightfastness properties by providing electronic protection of the chromophore towards photochemical degradation.

Extensive intermolecular hydrogen bonding is also observed, with the primary amide group playing a prominent role. This functional group forms a dimeric R²₂(8) hydrogen- bonded arrangement (Etter, 1990; Etter & MacDonald, 1990), with the equivalent group in another molecule related by a centre of inversion (Table 2 and Fig. 2). The hydrogen-bonded network extends beyond the eight-membered ring via an N—H···O interaction involving the primary amide atoms N18/H18B and the secondary amide atom O30ⁱ [symmetry code: (i) x − 1.5, 0.5 − y, 0.5 + z]. A longer, C—H···O interaction links atom O17 to atom H25ⁱⁱ [symmetry code: (ii) 1.5 − x, y − 0.5, 1.5 − z] in the naphthol ring system, while another intralayer C—H···O interaction involves the secondary amide atom O30 and atom H14 in a different adjacent molecule (Table 2).

The pigment molecules are associated in layers as a result of the extensive two-dimensional network of intermolecular hydrogen bonds. These sheets are not parallel to any crystallographic axis but are inclined to the c axis at an angle of 22.95 (2)°. Weaker C—H···O and C—H···N contacts between layers can also be identified. The primary amide atoms O17 and N18 have very weak intermolecular interactions with atom H11 of a phenylhydrazone ring and with atom H12 of a phenylazo ring, respectively, of molecules in the next layer (Table 2). The C16—N18···H11ⁱⁱⁱ and C16—O17···H12^iv angles at the acceptor atoms are 114 and 115°, respectively [symmmetry codes: (iii) x − 1, y, z; (iv) 1 − x, −y, 2 − z]. Enhanced technical performance, especially solvent resistance, can be attributed primarily to the extensive intermolecular association present in (I), in contrast to the situation for Group 1 products, in which the intermolecular interactions are predominantly van der Waals forces (Whitaker, 1978).

In the solid state, (I) deviates slightly from planarity, with the phenylhydrazone and anilide rings both twisted slightly with respect to the naphthol plane. The r.m.s. deviation from the least-squares molecular plane defined by all the non-H atoms is 0.0970 Å. The angle between the two fused rings of the naphthol system is 2.63 (8)°. The phenylhydrazone (C10–C15) and anilide (C33–C38) rings are angled at 10.91 (7) and 6.67 (6)°, respectively, to the mean plane of the naphthol system (C20–C29). The primary amide group is twisted by 18.57 (14)° with respect to the phenyl ring to which it is attached, possibly in order to accommodate the dimeric hydrogen bonding arrangement with its neighbour.

S2. Experimental

C·I. Pigment Red 266 was synthesized by diazotization of 4-aminobenzamide, using sodium nitrite in dilute hydrochloric acid, and reaction of the resulting diazonium salt with 3-hydroxy-N-(2-methoxyphenyl)-2-naphthalenecarboxamide (Naphthol AS—OL), using a simultaneous aqueous azo coupling procedure at pH 5–6 (Hoechst, 1974). Crystals suitable for X-ray analysis were obtained by slow cooling of a solution of the pigment in nitrobenzene, contained in a sealed tube, from 463 K.

S3. Refinement

Amide and amine H atoms were located from a difference Fourier map and their positions were refined freely. Other H-atom positions were calculated and were constrained to idealized positions with C—H distances of 0.98 (phenyl), 0.97 (methylene) and 0.96 Å (methyl). The U_iso parameters of the amino, phenyl, methylene and methyl H atoms were defined as 1.2, 1.2, 1.2 and 1.5 times U_eq of the parent atom, respectively.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids. Intramolecular hydrogen bonds are indicated by dotted lines, with the secondary longer interaction indicated by a lightly dashed line.
	Fig. 2. The primary hydrogen-bonding network in (I). Atoms labelled with the suffixes A and B are generated by the symmetry operations (-x, −y, 2 − z) and (x − 3/2, 1/2 − y, 1/2 + z).

4-{[4-(aminocarbonyl)phenyl]hydrazono}-N-(2-methoxyphenyl)-3-oxo- 3,4-dihydronaphthalene-2-carboxamide

Crystal data

C25H20N4O4	F(000) = 920
Mr = 440.45	Dx = 1.450 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 56 reflections
a = 7.254 (1) Å	θ = 6.7–30.7°
b = 24.115 (3) Å	µ = 0.10 mm^−1
c = 11.565 (2) Å	T = 160 K
β = 94.22 (1)°	Triangular plate, red
V = 2017.6 (5) Å^3	0.54 × 0.42 × 0.20 mm
Z = 4

Data collection

Bruker P4 diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = −1→8
ω scans	k = −1→28
4668 measured reflections	l = −13→13
3549 independent reflections	3 standard reflections every 97 reflections
2761 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 0.3084P] where P = (Fo^2 + 2Fc^2)/3
3549 reflections	(Δ/σ)max < 0.001
311 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.26 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
N1	0.7260 (2)	0.21014 (5)	0.81610 (12)	0.0239 (3)
H1	0.826 (3)	0.1985 (8)	0.7912 (16)	0.029*
N2	0.70924 (19)	0.26380 (5)	0.81015 (11)	0.0242 (3)
C10	0.5895 (2)	0.17576 (7)	0.85697 (14)	0.0228 (4)
C11	0.6343 (2)	0.11985 (7)	0.86939 (14)	0.0256 (4)
H11	0.7535	0.1071	0.8528	0.031*
C12	0.5056 (2)	0.08300 (6)	0.90571 (15)	0.0262 (4)
H12	0.5369	0.0449	0.9152	0.031*
C13	0.3295 (2)	0.10119 (7)	0.92866 (14)	0.0234 (4)
C14	0.2873 (2)	0.15742 (7)	0.91831 (14)	0.0257 (4)
H14	0.1686	0.1702	0.9358	0.031*
C15	0.4167 (2)	0.19500 (7)	0.88274 (15)	0.0258 (4)
H15	0.3874	0.2333	0.8761	0.031*
C16	0.1912 (2)	0.05846 (6)	0.95898 (14)	0.0249 (4)
O17	0.21751 (17)	0.00909 (5)	0.93557 (12)	0.0358 (3)
N18	0.0402 (2)	0.07550 (6)	1.00793 (14)	0.0297 (4)
H18A	−0.042 (3)	0.0479 (8)	1.0285 (16)	0.036*
H18B	0.026 (3)	0.1111 (8)	1.0283 (16)	0.036*
C20	0.8457 (2)	0.29263 (7)	0.76501 (14)	0.0233 (4)
C21	1.0063 (2)	0.26650 (7)	0.71928 (14)	0.0236 (4)
O21	1.02365 (16)	0.21421 (5)	0.72299 (11)	0.0305 (3)
C22	1.1446 (2)	0.30173 (7)	0.67047 (14)	0.0245 (4)
C23	1.1245 (2)	0.35767 (7)	0.67620 (14)	0.0250 (4)
H23	1.2189	0.3802	0.6481	0.030*
C24	0.9696 (2)	0.38480 (7)	0.72198 (14)	0.0252 (4)
C25	0.9566 (3)	0.44295 (7)	0.72281 (15)	0.0315 (4)
H25	1.0538	0.4647	0.6957	0.038*
C26	0.8045 (3)	0.46865 (7)	0.76242 (16)	0.0346 (4)
H26	0.7971	0.5080	0.7634	0.042*
C27	0.6608 (3)	0.43667 (7)	0.80128 (16)	0.0342 (4)
H27	0.5546	0.4545	0.8271	0.041*
C28	0.6707 (2)	0.37968 (7)	0.80278 (15)	0.0296 (4)
H28	0.5722	0.3586	0.8303	0.035*
C29	0.8258 (2)	0.35248 (7)	0.76388 (14)	0.0247 (4)
O30	1.42644 (16)	0.31045 (5)	0.57583 (11)	0.0315 (3)
C31	1.3109 (2)	0.27915 (7)	0.61400 (14)	0.0242 (4)
N32	1.3190 (2)	0.22321 (6)	0.60724 (12)	0.0269 (3)
H32	1.228 (3)	0.2058 (8)	0.6389 (16)	0.032*
C33	1.4588 (2)	0.18879 (7)	0.56802 (14)	0.0265 (4)
C34	1.6272 (2)	0.20672 (8)	0.53259 (15)	0.0305 (4)
H34	1.6537	0.2453	0.5299	0.037*
C35	1.7574 (3)	0.16828 (8)	0.50092 (16)	0.0374 (5)
H35	1.8735	0.1807	0.4779	0.045*
C36	1.7193 (3)	0.11237 (8)	0.50274 (17)	0.0416 (5)
H36	1.8086	0.0864	0.4803	0.050*
C37	1.5502 (3)	0.09372 (8)	0.53736 (16)	0.0373 (5)
H37	1.5240	0.0551	0.5385	0.045*
C38	1.4208 (2)	0.13150 (7)	0.57008 (15)	0.0304 (4)
O39	1.25075 (18)	0.11823 (5)	0.60622 (11)	0.0383 (3)
C40	1.2120 (3)	0.06142 (7)	0.62649 (19)	0.0444 (5)
H40A	1.2100	0.0410	0.5532	0.067*
H40B	1.0914	0.0582	0.6589	0.067*
H40C	1.3080	0.0460	0.6813	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0201 (7)	0.0196 (7)	0.0333 (8)	−0.0004 (6)	0.0111 (6)	0.0035 (6)
N2	0.0244 (7)	0.0211 (7)	0.0275 (7)	−0.0015 (6)	0.0050 (6)	0.0013 (5)
C10	0.0207 (8)	0.0236 (8)	0.0246 (8)	−0.0022 (7)	0.0051 (7)	0.0018 (6)
C11	0.0182 (8)	0.0234 (8)	0.0361 (9)	0.0019 (7)	0.0089 (7)	−0.0001 (7)
C12	0.0248 (9)	0.0171 (8)	0.0378 (10)	0.0017 (7)	0.0100 (8)	0.0008 (7)
C13	0.0228 (8)	0.0211 (8)	0.0271 (8)	−0.0016 (7)	0.0067 (7)	0.0013 (6)
C14	0.0193 (8)	0.0237 (8)	0.0354 (9)	0.0025 (7)	0.0111 (7)	0.0017 (7)
C15	0.0247 (9)	0.0193 (8)	0.0344 (9)	0.0025 (7)	0.0090 (7)	0.0040 (7)
C16	0.0224 (9)	0.0181 (8)	0.0350 (9)	−0.0002 (7)	0.0081 (7)	0.0018 (7)
O17	0.0286 (7)	0.0190 (6)	0.0628 (9)	−0.0016 (5)	0.0228 (6)	−0.0010 (6)
N18	0.0241 (8)	0.0179 (7)	0.0490 (9)	−0.0022 (6)	0.0159 (7)	0.0006 (7)
C20	0.0209 (8)	0.0236 (8)	0.0259 (8)	−0.0029 (7)	0.0042 (7)	0.0016 (7)
C21	0.0210 (8)	0.0227 (8)	0.0272 (8)	−0.0015 (7)	0.0027 (7)	0.0022 (6)
O21	0.0242 (6)	0.0198 (6)	0.0493 (8)	0.0003 (5)	0.0143 (5)	0.0043 (5)
C22	0.0230 (9)	0.0236 (8)	0.0275 (9)	−0.0020 (7)	0.0052 (7)	0.0016 (6)
C23	0.0224 (8)	0.0257 (9)	0.0278 (9)	−0.0061 (7)	0.0073 (7)	0.0031 (7)
C24	0.0272 (9)	0.0225 (8)	0.0267 (8)	−0.0031 (7)	0.0068 (7)	0.0005 (7)
C25	0.0332 (10)	0.0238 (9)	0.0387 (10)	−0.0066 (8)	0.0115 (8)	0.0001 (7)
C26	0.0418 (11)	0.0204 (9)	0.0432 (11)	−0.0006 (8)	0.0141 (9)	0.0010 (7)
C27	0.0358 (10)	0.0264 (9)	0.0424 (11)	0.0040 (8)	0.0155 (9)	−0.0001 (8)
C28	0.0277 (9)	0.0276 (9)	0.0348 (9)	−0.0031 (7)	0.0125 (8)	0.0027 (7)
C29	0.0256 (9)	0.0236 (8)	0.0254 (8)	−0.0019 (7)	0.0058 (7)	0.0012 (6)
O30	0.0253 (7)	0.0248 (6)	0.0463 (8)	−0.0032 (5)	0.0150 (6)	0.0037 (5)
C31	0.0205 (8)	0.0256 (9)	0.0270 (8)	−0.0020 (7)	0.0041 (7)	0.0028 (7)
N32	0.0237 (8)	0.0237 (8)	0.0346 (8)	−0.0009 (6)	0.0122 (6)	0.0028 (6)
C33	0.0255 (9)	0.0294 (9)	0.0252 (9)	0.0033 (7)	0.0056 (7)	0.0007 (7)
C34	0.0287 (9)	0.0310 (9)	0.0328 (9)	0.0012 (8)	0.0087 (8)	−0.0001 (7)
C35	0.0296 (10)	0.0445 (12)	0.0394 (10)	0.0050 (9)	0.0116 (8)	−0.0021 (9)
C36	0.0390 (11)	0.0425 (11)	0.0443 (11)	0.0132 (9)	0.0107 (9)	−0.0053 (9)
C37	0.0446 (12)	0.0267 (9)	0.0413 (11)	0.0062 (8)	0.0083 (9)	−0.0022 (8)
C38	0.0315 (10)	0.0289 (9)	0.0315 (9)	0.0002 (8)	0.0073 (8)	0.0012 (7)
O39	0.0388 (8)	0.0232 (6)	0.0551 (8)	−0.0031 (6)	0.0179 (6)	−0.0002 (6)
C40	0.0532 (13)	0.0257 (10)	0.0554 (13)	−0.0072 (9)	0.0114 (11)	0.0032 (9)

Geometric parameters (Å, º)

N1—N2	1.3012 (19)	C24—C29	1.416 (2)
N1—C10	1.400 (2)	C25—C26	1.373 (3)
N1—H1	0.85 (2)	C25—H25	0.9500
N2—C20	1.346 (2)	C26—C27	1.397 (3)
C10—C15	1.390 (2)	C26—H26	0.9500
C10—C11	1.392 (2)	C27—C28	1.376 (2)
C11—C12	1.377 (2)	C27—H27	0.9500
C11—H11	0.9500	C28—C29	1.404 (2)
C12—C13	1.394 (2)	C28—H28	0.9500
C12—H12	0.9500	O30—C31	1.2332 (19)
C13—C14	1.393 (2)	C31—N32	1.353 (2)
C13—C16	1.497 (2)	N32—C33	1.411 (2)
C14—C15	1.389 (2)	N32—H32	0.89 (2)
C14—H14	0.9500	C33—C34	1.385 (2)
C15—H15	0.9500	C33—C38	1.409 (2)
C16—O17	1.2388 (19)	C34—C35	1.392 (3)
C16—N18	1.334 (2)	C34—H34	0.9500
N18—H18A	0.94 (2)	C35—C36	1.377 (3)
N18—H18B	0.90 (2)	C35—H35	0.9500
C20—C29	1.450 (2)	C36—C37	1.392 (3)
C20—C21	1.458 (2)	C36—H36	0.9500
C21—O21	1.268 (2)	C37—C38	1.381 (3)
C21—C22	1.460 (2)	C37—H37	0.9500
C22—C23	1.359 (2)	C38—O39	1.369 (2)
C22—C31	1.515 (2)	O39—C40	1.421 (2)
C23—C24	1.434 (2)	C40—H40A	0.9800
C23—H23	0.9500	C40—H40B	0.9800
C24—C25	1.406 (2)	C40—H40C	0.9800
N2—N1—C10	122.76 (14)	C24—C25—H25	119.7
N2—N1—H1	112.9 (13)	C25—C26—C27	119.65 (16)
C10—N1—H1	124.3 (13)	C25—C26—H26	120.2
N1—N2—C20	117.75 (14)	C27—C26—H26	120.2
C15—C10—C11	120.57 (15)	C28—C27—C26	121.05 (17)
C15—C10—N1	123.12 (15)	C28—C27—H27	119.5
C11—C10—N1	116.30 (15)	C26—C27—H27	119.5
C12—C11—C10	119.89 (15)	C27—C28—C29	120.30 (16)
C12—C11—H11	120.1	C27—C28—H28	119.8
C10—C11—H11	120.1	C29—C28—H28	119.8
C11—C12—C13	120.43 (15)	C28—C29—C24	118.71 (15)
C11—C12—H12	119.8	C28—C29—C20	122.91 (15)
C13—C12—H12	119.8	C24—C29—C20	118.38 (15)
C14—C13—C12	119.22 (15)	O30—C31—N32	123.78 (15)
C14—C13—C16	122.91 (15)	O30—C31—C22	121.20 (14)
C12—C13—C16	117.83 (14)	N32—C31—C22	115.01 (14)
C15—C14—C13	120.78 (15)	C31—N32—C33	129.84 (15)
C15—C14—H14	119.6	C31—N32—H32	114.3 (12)
C13—C14—H14	119.6	C33—N32—H32	115.6 (12)
C14—C15—C10	119.07 (15)	C34—C33—C38	119.27 (16)
C14—C15—H15	120.5	C34—C33—N32	125.55 (16)
C10—C15—H15	120.5	C38—C33—N32	115.15 (15)
O17—C16—N18	122.20 (15)	C33—C34—C35	120.01 (17)
O17—C16—C13	119.58 (15)	C33—C34—H34	120.0
N18—C16—C13	118.19 (14)	C35—C34—H34	120.0
C16—N18—H18A	116.5 (12)	C36—C35—C34	120.48 (19)
C16—N18—H18B	121.4 (13)	C36—C35—H35	119.8
H18A—N18—H18B	121.6 (17)	C34—C35—H35	119.8
N2—C20—C29	116.23 (14)	C35—C36—C37	120.19 (18)
N2—C20—C21	123.19 (15)	C35—C36—H36	119.9
C29—C20—C21	120.58 (14)	C37—C36—H36	119.9
O21—C21—C20	119.87 (14)	C38—C37—C36	119.78 (18)
O21—C21—C22	121.50 (15)	C38—C37—H37	120.1
C20—C21—C22	118.62 (14)	C36—C37—H37	120.1
C23—C22—C21	118.66 (15)	O39—C38—C37	125.13 (16)
C23—C22—C31	118.01 (14)	O39—C38—C33	114.60 (15)
C21—C22—C31	123.33 (14)	C37—C38—C33	120.27 (17)
C22—C23—C24	124.09 (15)	C38—O39—C40	117.98 (15)
C22—C23—H23	118.0	O39—C40—H40A	109.5
C24—C23—H23	118.0	O39—C40—H40B	109.5
C25—C24—C29	119.66 (16)	H40A—C40—H40B	109.5
C25—C24—C23	120.83 (15)	O39—C40—H40C	109.5
C29—C24—C23	119.48 (15)	H40A—C40—H40C	109.5
C26—C25—C24	120.60 (16)	H40B—C40—H40C	109.5
C26—C25—H25	119.7
C10—N1—N2—C20	−177.33 (14)	C25—C26—C27—C28	1.4 (3)
N2—N1—C10—C15	7.2 (2)	C26—C27—C28—C29	−0.7 (3)
N2—N1—C10—C11	−173.73 (15)	C27—C28—C29—C24	−0.8 (3)
C15—C10—C11—C12	1.1 (3)	C27—C28—C29—C20	178.99 (16)
N1—C10—C11—C12	−178.00 (15)	C25—C24—C29—C28	1.5 (2)
C10—C11—C12—C13	0.9 (3)	C23—C24—C29—C28	−176.72 (15)
C11—C12—C13—C14	−2.2 (3)	C25—C24—C29—C20	−178.26 (15)
C11—C12—C13—C16	175.38 (15)	C23—C24—C29—C20	3.5 (2)
C12—C13—C14—C15	1.6 (3)	N2—C20—C29—C28	−2.5 (2)
C16—C13—C14—C15	−175.83 (15)	C21—C20—C29—C28	177.54 (15)
C13—C14—C15—C10	0.3 (3)	N2—C20—C29—C24	177.26 (14)
C11—C10—C15—C14	−1.6 (2)	C21—C20—C29—C24	−2.7 (2)
N1—C10—C15—C14	177.37 (15)	C23—C22—C31—O30	1.1 (2)
C14—C13—C16—O17	159.68 (16)	C21—C22—C31—O30	−178.60 (15)
C12—C13—C16—O17	−17.8 (2)	C23—C22—C31—N32	−177.64 (15)
C14—C13—C16—N18	−18.5 (2)	C21—C22—C31—N32	2.7 (2)
C12—C13—C16—N18	163.99 (16)	O30—C31—N32—C33	6.2 (3)
N1—N2—C20—C29	−177.69 (14)	C22—C31—N32—C33	−175.08 (15)
N1—N2—C20—C21	2.2 (2)	C31—N32—C33—C34	3.6 (3)
N2—C20—C21—O21	−1.4 (2)	C31—N32—C33—C38	−178.57 (16)
C29—C20—C21—O21	178.57 (15)	C38—C33—C34—C35	−0.8 (3)
N2—C20—C21—C22	178.96 (15)	N32—C33—C34—C35	176.93 (16)
C29—C20—C21—C22	−1.1 (2)	C33—C34—C35—C36	1.0 (3)
O21—C21—C22—C23	−175.55 (15)	C34—C35—C36—C37	−0.6 (3)
C20—C21—C22—C23	4.1 (2)	C35—C36—C37—C38	−0.1 (3)
O21—C21—C22—C31	4.1 (2)	C36—C37—C38—O39	−179.64 (17)
C20—C21—C22—C31	−176.20 (14)	C36—C37—C38—C33	0.3 (3)
C21—C22—C23—C24	−3.5 (2)	C34—C33—C38—O39	−179.91 (15)
C31—C22—C23—C24	176.84 (15)	N32—C33—C38—O39	2.1 (2)
C22—C23—C24—C25	−178.65 (17)	C34—C33—C38—C37	0.1 (3)
C22—C23—C24—C29	−0.4 (2)	N32—C33—C38—C37	−177.81 (16)
C29—C24—C25—C26	−0.9 (3)	C37—C38—O39—C40	8.7 (3)
C23—C24—C25—C26	177.37 (17)	C33—C38—O39—C40	−171.23 (16)
C24—C25—C26—C27	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.85 (2)	1.73 (2)	2.4845 (18)	147.4 (18)
N18—H18A···O17^i	0.94 (2)	1.94 (2)	2.8747 (19)	177.4 (17)
N18—H18B···O30^ii	0.90 (2)	2.11 (2)	2.9929 (19)	166.7 (18)
N32—H32···O21	0.89 (2)	1.84 (2)	2.6178 (18)	145.2 (17)
N32—H32···O39	0.89 (2)	2.155 (19)	2.5796 (18)	108.8 (15)
C11—H11···N18^iii	0.95	2.75	3.419 (2)	128
C12—H12···O17^iv	0.95	2.72	3.434 (2)	133
C14—H14···O30^ii	0.95	2.52	3.387 (2)	152

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