Ethyl 4-do­decyl-3,5-di­methyl-1H-pyrrole-2-carboxyl­ate: intermolecular interactions in an amphiphilic pyrrole

The title compound, C₂₁H₃₇NO₂, is a new amphiphilic pyrrole with a long hydro­carbon chain, which will be used as a precursor for the synthesis of Langmuir–Blodgett films of porphyrins. Molecules related by an inversion centre are joined head-to-head into dimers by strong N—H...O hydrogen bonds. The dimers pack in the structure with their carbon chains parallel to one another, thereby forming alternating layers of carbon chains and pyrrole heads. The structure is further stabilized by two weak C—H...π intermolecular interactions, thereby saturating the hydrogen-bonding capability of the aromatic π-electron clouds.

S1. Comment

Pyrroles are important as pharmaceutical agents, monomers for polymer chemistry, and precursors of porphyrins and related macrocycles, and have been studied intensely over recent decades (Baltazzi & Krimen, 1963; Chadwick, 1990). The porphyrin core is a system of four pyrrole rings. This ring system plays an important role in the chemistry of living organisms, appearing in chlorophylls, hemoglobin and myoglobin proteins. New and exciting research in porphyrin materials seeks to design novel polymers with the potential to behave as electrical conductors and semiconductors (Reimers et al., 1996, 1999). Studies in the areas of molecular switching devices, molecular shift-registers and non-linear optics (Hush et al., 1998, Kadish et al., 2002) are also flourishing. For instance, the possibility of using redox-active organic monolayers as molecular-scale information storage systems is being considered (Crossley et al. 1995), where the information is stored in the oxidation state. For many of these applications, molecular films of porphyrins are required. Assembling highly ordered molecular films is easiest with the Langmuir–Blodgett technique, which involves transferring monolayers of molecules with an amphiphylic tail, floating on a water surface, to a solid substrate (Pitt & Walpita, 1980; Vincent & Roberts, 1980; Ruaudel-Teixier et al., 1983; Ohtake et al., 1992; Palto et al., 1992). Porphyrins substituted with long hydrocarbon chains have already been shown to form stable films (Hudson et al., 1993). Following previous structural studies on pyrrole chemistry (Ramos Silva et al., 2000a) and on the deposition of porphyrins in Langmuir–Blodgett films (Richardson et al., 1998), the title compound, (I), was synthesized with the intention of using it as a precursor of new amphiphylic porphyrins, and its structure is now reported.

The pyrrolic ring in (I) is almost planar and all intra-ring torsion angles are less than 0.1 (2)°. The intra-ring bond angles range from 106.83 (16) to 109.95 (15)°, which indicates that the ring is slightly distorted from C_2v symmetry. The non-H atoms of the two methyl and ethoxy carbonyl substituents share the pyrrole plane, with a maximum deviation of 0.038 (3) Å (for O1) from the least-squares plane of the pyrrole ring. Atom C10 of the dodecylic chain is also only 0.032 (3) Å from this plane. Although rotation around the C5—C1 bond is possible, the conformation adopted by the ethoxycarbonyl group is the one usually found in similar compounds (Bonnet et al., 1972, Yamamoto et al., 1986), with the ethyl group trans to atom N1.

The conformation of the dodecylic chain is that most often found for larger alkanes, i.e. staggered with the largest substituents at any C—C bond anti to each other. The largest deviation from the ideal 180° torsion angle is 12.58 (18)° for C10—C11—C12—C13. The average C—C bond length in the chain is 1.500 (9) Å and the average valence angle is 116 (1)°. These values are similar to those found in related compounds already studied by us [1.516 (3) Å and 113.8 (8)° for 9-(n-dodecylaminomethyl)anthracene (Ramos Silva et al., 2000b), and 1.511 (6) Å and 114.3 (4)° for N-n-dodecylbis(9-anthrylmethyl)amine (Matos Beja et al., 2001)]. The carbon backbone zigzag dodecyl skeleton is less planar than in the above-mentioned compounds, being bent towards atom C9. Atom C13 is a transition atom between the two planar parts of the chain, deviating by 0.295 (4) Å from the plane defined by atoms C10, C11 and C12, and by 0.224(3 Å from the least-squares plane defined by atoms C14–C21. The mean deviation of atoms C14–C21 from their least-squares plane is 0.021 (2) Å [maximum deviation 0.047 (2) Å for C19]. The angle between the planar sections of the chain is 20.5 (3)°.

A strong intermolecular hydrogen bond exists between atoms N1 and O2ⁱ [symmetry code: (i) -x + 1, -y, -z; Table 2]. This joins the molecules head-to-head across crystallographic inversion centres to give dimers. The molecular packing is such that the hydrocarbon chains lie side-by-side, thereby forming alternating layers of carbon chains and pyrrolic heads. The structure is stabilized by two C—H···π intermolecular interactions, thereby saturating the hydrogen-bonding capability of the aromatic π-electron clouds. One of the bonds belongs to a geometric type-II interaction, according to the classification of Malone et al. (1997), with the C6—H6A bond pointing in the direction of the ring centre (α ≈ 164° and θ ≈ 60°). The other has a type-III interaction, with the H atom above the centre of the pyrrole ring and the C8—H8C bond pointing towards a ring atom. Both C—H···π bonds have a slightly large H···Cg distance (Cg is the ring centroid), compared with the limit of 3.05 Å, which is based on the sum of the van der Waals radii of the atoms concerned (Malone et al., 1997). C—H···π_arene interactions have been shown previously to have a profound effect on the molecular packing patterns of macrocycles (Ferguson et al., 1996).

S2. Experimental

The title compound was prepared through a Knorr-type reaction (Paine, 1978) in a 22% yield. Small single crystals were grown from a solution of dichloromethane–hexane (1:1) (m.p. 303–308 K). IR (cm^-1; group): (1697, νC═O), (2854, νC—H), (3313, νN—H); MS (FAB+): M⁺ m/z 335. 1H NMR (CDCl₃, δ, p.p.m.): 0.88 [t, 3H, CH₃-(CH₂)₁₀, J = 6.69 Hz], 1.25 [m, 20H, CH₃-(CH₂)₁₀-C], 2.13 (s, 3H, ring⁵-CH₃), 2.26 (s, 3H, ring³-CH₃), 2.35 (t, 3H, CH₃—CH₂O, J = 7.11 Hz), 3.61 [t, 2H, ring-CH₂-(CH₂)₁₀CH₃], 4.28 (q, 2H, O—CH₂—CH₃, J = 7.11 Hz), 8.7 (m, 1H, NH).

S3. Refinement

The position of the amine H atom was determined from a difference Fourier map and refined freely, with its isotropic displacement parameter constrained to U_iso(H) = 1.2U_eq(N). The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.97 Å) and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). Examination of the crystal structure with PLATON (Spek, 1995) showed that there are no solvent-accessible voids in the crystal lattice.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the unit-cell packing, with the hydrogen-bonding scheme shown as dashed lines. H atoms not partipating in hydrogen bonding have been omitted for clarity.

Ethyl 4-dodecyl-3,5-dimethyl-1H-pyrrole-2-carboxylate

Crystal data

C21H37NO2	Z = 2
Mr = 335.52	F(000) = 372
Triclinic, P1	Dx = 1.042 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.5418 Å
a = 5.4778 (6) Å	Cell parameters from 25 reflections
b = 9.8774 (10) Å	θ = 21.7–29.2°
c = 20.4090 (16) Å	µ = 0.50 mm^−1
α = 98.79 (7)°	T = 293 K
β = 94.06 (8)°	Block, translucent light yellow
γ = 99.93 (9)°	0.49 × 0.37 × 0.31 mm
V = 1069.6 (5) Å^3

Data collection

Enraf-Nonius CAD-4 diffractometer	2953 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 72.4°, θmin = 4.4°
ω–2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.812, Tmax = 0.984	l = −25→25
8228 measured reflections	3 standard reflections every 180 min
4238 independent reflections	intensity decay: 4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0647P)^2 + 0.1001P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.013
4238 reflections	Δρmax = 0.17 e Å^−3
225 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0043 (8)

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	1.0100 (2)	−0.14476 (12)	0.08837 (6)	0.0788 (4)
O2	0.6962 (3)	−0.12250 (13)	0.01766 (6)	0.0896 (4)
N1	0.6976 (3)	0.14459 (14)	0.08465 (7)	0.0689 (4)
H1	0.578 (3)	0.1216 (19)	0.0519 (10)	0.083*
C1	0.8588 (3)	0.06328 (17)	0.10478 (8)	0.0665 (4)
C2	1.0068 (3)	0.13898 (17)	0.16073 (8)	0.0674 (4)
C3	0.9304 (3)	0.26928 (17)	0.17390 (8)	0.0677 (4)
C4	0.7386 (3)	0.26943 (16)	0.12589 (8)	0.0676 (4)
C5	0.8446 (3)	−0.07390 (17)	0.06595 (8)	0.0694 (4)
C6	0.9986 (4)	−0.28412 (19)	0.05197 (10)	0.0864 (5)
H6A	1.0303	−0.2803	0.0061	0.104*
H6B	0.8350	−0.3403	0.0523	0.104*
C7	1.1922 (5)	−0.3456 (2)	0.08564 (14)	0.1121 (8)
H7A	1.3536	−0.2909	0.0837	0.168*
H7B	1.1863	−0.4394	0.0636	0.168*
H7C	1.1617	−0.3461	0.1314	0.168*
C8	1.2096 (3)	0.0935 (2)	0.20041 (10)	0.0858 (5)
H8A	1.1370	0.0268	0.2265	0.129*
H8B	1.3073	0.1729	0.2295	0.129*
H8C	1.3142	0.0516	0.1707	0.129*
C9	0.5878 (4)	0.37766 (19)	0.11528 (10)	0.0843 (5)
H9A	0.5813	0.3891	0.0694	0.127*
H9B	0.6629	0.4645	0.1429	0.127*
H9C	0.4219	0.3490	0.1267	0.127*
C10	1.0316 (3)	0.38638 (19)	0.23060 (9)	0.0769 (5)
H10A	1.0354	0.4743	0.2147	0.092*
H10B	1.2018	0.3802	0.2445	0.092*
C11	0.8836 (3)	0.3869 (2)	0.29048 (9)	0.0803 (5)
H11A	0.8898	0.3020	0.3085	0.096*
H11B	0.7109	0.3866	0.2762	0.096*
C12	0.9780 (3)	0.5112 (2)	0.34502 (9)	0.0824 (5)
H12A	1.1366	0.5001	0.3657	0.099*
H12B	1.0076	0.5944	0.3248	0.099*
C13	0.8075 (3)	0.5328 (2)	0.39818 (9)	0.0806 (5)
H13A	0.7975	0.4556	0.4227	0.097*
H13B	0.6421	0.5298	0.3769	0.097*
C14	0.8810 (3)	0.6665 (2)	0.44707 (9)	0.0839 (5)
H14A	1.0367	0.6640	0.4722	0.101*
H14B	0.9121	0.7428	0.4222	0.101*
C15	0.6970 (4)	0.6979 (2)	0.49536 (10)	0.0911 (6)
H15A	0.5364	0.6898	0.4703	0.109*
H15B	0.6802	0.6270	0.5236	0.109*
C16	0.7559 (4)	0.8371 (2)	0.53899 (10)	0.0910 (6)
H16A	0.7830	0.9078	0.5108	0.109*
H16B	0.9115	0.8429	0.5660	0.109*
C17	0.5643 (4)	0.8721 (2)	0.58458 (11)	0.0942 (6)
H17A	0.4063	0.8611	0.5578	0.113*
H17B	0.5442	0.8046	0.6146	0.113*
C18	0.6178 (4)	1.0149 (2)	0.62554 (10)	0.0870 (5)
H18A	0.6370	1.0824	0.5955	0.104*
H18B	0.7762	1.0260	0.6521	0.104*
C19	0.4271 (3)	1.0498 (2)	0.67136 (10)	0.0839 (5)
H19A	0.2706	1.0432	0.6446	0.101*
H19B	0.4020	0.9799	0.7001	0.101*
C20	0.4885 (4)	1.1908 (2)	0.71444 (11)	0.0944 (6)
H20A	0.6489	1.1993	0.7397	0.113*
H20B	0.5051	1.2611	0.6858	0.113*
C21	0.3023 (5)	1.2212 (3)	0.76213 (14)	0.1170 (8)
H21A	0.1426	1.2135	0.7379	0.175*
H21B	0.3540	1.3140	0.7867	0.175*
H21C	0.2909	1.1555	0.7925	0.175*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0927 (8)	0.0680 (7)	0.0761 (7)	0.0233 (6)	0.0007 (6)	0.0072 (6)
O2	0.1149 (10)	0.0777 (8)	0.0718 (8)	0.0297 (7)	−0.0142 (7)	−0.0042 (6)
N1	0.0832 (9)	0.0651 (8)	0.0559 (7)	0.0153 (7)	0.0019 (6)	0.0033 (6)
C1	0.0786 (10)	0.0630 (9)	0.0585 (8)	0.0149 (7)	0.0082 (7)	0.0095 (7)
C2	0.0702 (9)	0.0701 (10)	0.0598 (8)	0.0069 (7)	0.0095 (7)	0.0103 (7)
C3	0.0722 (9)	0.0659 (9)	0.0602 (8)	0.0027 (7)	0.0120 (7)	0.0044 (7)
C4	0.0795 (10)	0.0599 (9)	0.0619 (9)	0.0110 (7)	0.0135 (8)	0.0050 (7)
C5	0.0852 (11)	0.0655 (10)	0.0585 (9)	0.0163 (8)	0.0079 (8)	0.0104 (7)
C6	0.1074 (14)	0.0682 (11)	0.0862 (12)	0.0265 (10)	0.0139 (11)	0.0081 (9)
C7	0.1125 (17)	0.0904 (15)	0.138 (2)	0.0387 (13)	0.0037 (15)	0.0164 (14)
C8	0.0805 (11)	0.0902 (13)	0.0814 (12)	0.0100 (9)	−0.0056 (9)	0.0113 (10)
C9	0.1004 (13)	0.0701 (11)	0.0822 (12)	0.0218 (10)	0.0112 (10)	0.0042 (9)
C10	0.0770 (10)	0.0745 (11)	0.0707 (10)	0.0001 (8)	0.0126 (8)	−0.0004 (8)
C11	0.0768 (11)	0.0842 (12)	0.0685 (10)	−0.0038 (9)	0.0110 (8)	−0.0032 (9)
C12	0.0696 (10)	0.0945 (13)	0.0704 (10)	−0.0020 (9)	0.0081 (8)	−0.0069 (9)
C13	0.0745 (10)	0.0851 (12)	0.0732 (11)	0.0024 (9)	0.0096 (8)	−0.0015 (9)
C14	0.0710 (10)	0.0974 (13)	0.0712 (10)	0.0006 (9)	0.0085 (8)	−0.0070 (10)
C15	0.0766 (11)	0.0956 (13)	0.0887 (13)	0.0018 (10)	0.0148 (10)	−0.0102 (11)
C16	0.0770 (11)	0.0997 (14)	0.0829 (12)	0.0006 (10)	0.0129 (9)	−0.0111 (11)
C17	0.0782 (12)	0.0967 (14)	0.0939 (14)	0.0034 (10)	0.0133 (10)	−0.0148 (11)
C18	0.0792 (11)	0.0904 (13)	0.0818 (12)	0.0045 (9)	0.0066 (9)	−0.0020 (10)
C19	0.0677 (10)	0.0876 (12)	0.0885 (12)	0.0103 (9)	0.0022 (9)	−0.0029 (10)
C20	0.0878 (13)	0.0868 (13)	0.0995 (14)	0.0085 (10)	0.0058 (11)	−0.0019 (11)
C21	0.1020 (16)	0.1111 (17)	0.1258 (19)	0.0202 (13)	0.0167 (14)	−0.0209 (15)

Geometric parameters (Å, º)

O1—C5	1.334 (2)	C12—C13	1.495 (3)
O1—C6	1.450 (2)	C12—H12A	0.9700
O2—C5	1.212 (2)	C12—H12B	0.9700
N1—C4	1.356 (2)	C13—C14	1.503 (3)
N1—C1	1.374 (2)	C13—H13A	0.9700
N1—H1	0.875 (19)	C13—H13B	0.9700
C1—C2	1.385 (3)	C14—C15	1.496 (3)
C1—C5	1.448 (2)	C14—H14A	0.9700
C2—C3	1.414 (2)	C14—H14B	0.9700
C2—C8	1.499 (3)	C15—C16	1.489 (3)
C3—C4	1.385 (3)	C15—H15A	0.9700
C3—C10	1.504 (3)	C15—H15B	0.9700
C4—C9	1.491 (3)	C16—C17	1.501 (3)
C6—C7	1.487 (3)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700
C6—H6B	0.9700	C17—C18	1.495 (3)
C7—H7A	0.9600	C17—H17A	0.9700
C7—H7B	0.9600	C17—H17B	0.9700
C7—H7C	0.9600	C18—C19	1.499 (3)
C8—H8A	0.9600	C18—H18A	0.9700
C8—H8B	0.9600	C18—H18B	0.9700
C8—H8C	0.9600	C19—C20	1.499 (3)
C9—H9A	0.9600	C19—H19A	0.9700
C9—H9B	0.9600	C19—H19B	0.9700
C9—H9C	0.9600	C20—C21	1.495 (3)
C10—C11	1.513 (2)	C20—H20A	0.9700
C10—H10A	0.9700	C20—H20B	0.9700
C10—H10B	0.9700	C21—H21A	0.9600
C11—C12	1.515 (3)	C21—H21B	0.9600
C11—H11A	0.9700	C21—H21C	0.9600
C11—H11B	0.9700
C5—O1—C6	115.78 (15)	C13—C12—H12B	108.5
C4—N1—C1	109.95 (15)	C11—C12—H12B	108.5
C4—N1—H1	122.5 (13)	H12A—C12—H12B	107.5
C1—N1—H1	127.5 (12)	C12—C13—C14	115.56 (16)
N1—C1—C2	107.78 (15)	C12—C13—H13A	108.4
N1—C1—C5	117.84 (16)	C14—C13—H13A	108.4
C2—C1—C5	134.38 (17)	C12—C13—H13B	108.4
C1—C2—C3	106.83 (16)	C14—C13—H13B	108.4
C1—C2—C8	127.29 (17)	H13A—C13—H13B	107.5
C3—C2—C8	125.87 (17)	C15—C14—C13	116.19 (17)
C4—C3—C2	107.68 (16)	C15—C14—H14A	108.2
C4—C3—C10	125.42 (17)	C13—C14—H14A	108.2
C2—C3—C10	126.89 (17)	C15—C14—H14B	108.2
N1—C4—C3	107.76 (16)	C13—C14—H14B	108.2
N1—C4—C9	120.97 (16)	H14A—C14—H14B	107.4
C3—C4—C9	131.27 (16)	C16—C15—C14	116.44 (17)
O2—C5—O1	122.00 (16)	C16—C15—H15A	108.2
O2—C5—C1	124.14 (18)	C14—C15—H15A	108.2
O1—C5—C1	113.85 (16)	C16—C15—H15B	108.2
O1—C6—C7	107.22 (19)	C14—C15—H15B	108.2
O1—C6—H6A	110.3	H15A—C15—H15B	107.3
C7—C6—H6A	110.3	C15—C16—C17	116.48 (18)
O1—C6—H6B	110.3	C15—C16—H16A	108.2
C7—C6—H6B	110.3	C17—C16—H16A	108.2
H6A—C6—H6B	108.5	C15—C16—H16B	108.2
C6—C7—H7A	109.5	C17—C16—H16B	108.2
C6—C7—H7B	109.5	H16A—C16—H16B	107.3
H7A—C7—H7B	109.5	C18—C17—C16	116.28 (18)
C6—C7—H7C	109.5	C18—C17—H17A	108.2
H7A—C7—H7C	109.5	C16—C17—H17A	108.2
H7B—C7—H7C	109.5	C18—C17—H17B	108.2
C2—C8—H8A	109.5	C16—C17—H17B	108.2
C2—C8—H8B	109.5	H17A—C17—H17B	107.4
H8A—C8—H8B	109.5	C17—C18—C19	116.35 (18)
C2—C8—H8C	109.5	C17—C18—H18A	108.2
H8A—C8—H8C	109.5	C19—C18—H18A	108.2
H8B—C8—H8C	109.5	C17—C18—H18B	108.2
C4—C9—H9A	109.5	C19—C18—H18B	108.2
C4—C9—H9B	109.5	H18A—C18—H18B	107.4
H9A—C9—H9B	109.5	C20—C19—C18	115.83 (18)
C4—C9—H9C	109.5	C20—C19—H19A	108.3
H9A—C9—H9C	109.5	C18—C19—H19A	108.3
H9B—C9—H9C	109.5	C20—C19—H19B	108.3
C3—C10—C11	114.20 (15)	C18—C19—H19B	108.3
C3—C10—H10A	108.7	H19A—C19—H19B	107.4
C11—C10—H10A	108.7	C21—C20—C19	115.10 (19)
C3—C10—H10B	108.7	C21—C20—H20A	108.5
C11—C10—H10B	108.7	C19—C20—H20A	108.5
H10A—C10—H10B	107.6	C21—C20—H20B	108.5
C10—C11—C12	113.31 (15)	C19—C20—H20B	108.5
C10—C11—H11A	108.9	H20A—C20—H20B	107.5
C12—C11—H11A	108.9	C20—C21—H21A	109.5
C10—C11—H11B	108.9	C20—C21—H21B	109.5
C12—C11—H11B	108.9	H21A—C21—H21B	109.5
H11A—C11—H11B	107.7	C20—C21—H21C	109.5
C13—C12—C11	115.06 (16)	H21A—C21—H21C	109.5
C13—C12—H12A	108.5	H21B—C21—H21C	109.5
C11—C12—H12A	108.5
C4—N1—C1—C2	0.10 (18)	N1—C1—C5—O2	−1.6 (3)
C4—N1—C1—C5	−179.21 (13)	C2—C1—C5—O2	179.36 (17)
N1—C1—C2—C3	−0.10 (17)	N1—C1—C5—O1	179.02 (14)
C5—C1—C2—C3	179.05 (17)	C2—C1—C5—O1	−0.1 (3)
N1—C1—C2—C8	179.87 (15)	C5—O1—C6—C7	−178.67 (16)
C5—C1—C2—C8	−1.0 (3)	C4—C3—C10—C11	83.1 (2)
C1—C2—C3—C4	0.07 (17)	C2—C3—C10—C11	−95.1 (2)
C8—C2—C3—C4	−179.90 (15)	C3—C10—C11—C12	−175.98 (17)
C1—C2—C3—C10	178.49 (15)	C10—C11—C12—C13	167.42 (18)
C8—C2—C3—C10	−1.5 (3)	C11—C12—C13—C14	−171.63 (18)
C1—N1—C4—C3	−0.05 (18)	C12—C13—C14—C15	172.76 (18)
C1—N1—C4—C9	−179.84 (15)	C13—C14—C15—C16	−173.58 (19)
C2—C3—C4—N1	−0.01 (18)	C14—C15—C16—C17	176.47 (19)
C10—C3—C4—N1	−178.46 (14)	C15—C16—C17—C18	−176.7 (2)
C2—C3—C4—C9	179.74 (17)	C16—C17—C18—C19	−179.71 (19)
C10—C3—C4—C9	1.3 (3)	C17—C18—C19—C20	177.30 (19)
C6—O1—C5—O2	−0.9 (2)	C18—C19—C20—C21	−177.2 (2)
C6—O1—C5—C1	178.55 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.875 (19)	1.996 (19)	2.850 (3)	164.9 (18)
C6—H6A···Cg^ii	0.97	3.18	4.119 (2)	164
C8—H8C···Cg^iii	0.96	3.18	3.872 (2)	130

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