Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013653/ln1145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013653/ln1145Isup2.hkl |
CCDC reference: 195628
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).
The position of the amine H atom was determined from a difference Fourier map and refined freely, with its isotropic displacement parameter constrained to Uiso(H) = 1.2Ueq(N). The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(C). Examination of the crystal structure with PLATON (Spek, 1995) showed that there are no solvent-accessible voids in the crystal lattice.
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.
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) Å3 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.156 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.1001P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0043 (8) |
C21H37NO2 | γ = 99.93 (9)° |
Mr = 335.52 | V = 1069.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.4778 (6) Å | Cu Kα radiation |
b = 9.8774 (10) Å | µ = 0.50 mm−1 |
c = 20.4090 (16) Å | T = 293 K |
α = 98.79 (7)° | 0.49 × 0.37 × 0.31 mm |
β = 94.06 (8)° |
Enraf-Nonius CAD-4 diffractometer | 2953 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.812, Tmax = 0.984 | 3 standard reflections every 180 min |
8228 measured reflections | intensity decay: 4% |
4238 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.156 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.17 e Å−3 |
4238 reflections | Δρmin = −0.18 e Å−3 |
225 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.875 (19) | 1.996 (19) | 2.850 (3) | 164.9 (18) |
C6—H6A···Cgii | 0.97 | 3.18 | 4.119 (2) | 164 |
C8—H8C···Cgiii | 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. |
Experimental details
Crystal data | |
Chemical formula | C21H37NO2 |
Mr | 335.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.4778 (6), 9.8774 (10), 20.4090 (16) |
α, β, γ (°) | 98.79 (7), 94.06 (8), 99.93 (9) |
V (Å3) | 1069.6 (5) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.49 × 0.37 × 0.31 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.812, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8228, 4238, 2953 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.156, 1.14 |
No. of reflections | 4238 |
No. of parameters | 225 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
N1—C4 | 1.356 (2) | C2—C3 | 1.414 (2) |
N1—C1 | 1.374 (2) | C3—C4 | 1.385 (3) |
C1—C2 | 1.385 (3) | ||
N1—C1—C5 | 117.84 (16) | C3—C4—C9 | 131.27 (16) |
C1—C2—C8 | 127.29 (17) | O2—C5—O1 | 122.00 (16) |
C3—C2—C8 | 125.87 (17) | O1—C6—C7 | 107.22 (19) |
N1—C4—C9 | 120.97 (16) | ||
N1—C1—C2—C3 | −0.10 (17) | N1—C1—C5—O1 | 179.02 (14) |
N1—C1—C2—C8 | 179.87 (15) | C5—O1—C6—C7 | −178.67 (16) |
C1—N1—C4—C9 | −179.84 (15) | C10—C11—C12—C13 | 167.42 (18) |
C2—C3—C4—C9 | 179.74 (17) | C11—C12—C13—C14 | −171.63 (18) |
C10—C3—C4—C9 | 1.3 (3) | C12—C13—C14—C15 | 172.76 (18) |
N1—C1—C5—O2 | −1.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.875 (19) | 1.996 (19) | 2.850 (3) | 164.9 (18) |
C6—H6A···Cgii | 0.97 | 3.18 | 4.119 (2) | 164 |
C8—H8C···Cgiii | 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. |
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 C2v 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···πarene interactions have been shown previously to have a profound effect on the molecular packing patterns of macrocycles (Ferguson et al., 1996).