Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104012806/fa1065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104012806/fa1065Isup2.hkl |
CCDC reference: 245924
Compound (I) was synthesized starting from equimolar quantities of ethyl coumarin-3-carboxylate (2.12 mmol) and morpholine, refluxed in dry ethyl alcohol (20 ml) for 24 h. The product crystallized from the reaction mixture as a white solid (56% yield; m.p. 488–493 K). Crystals suitable for X-ray analysis were obtained after slow recrystallization from an ethyl alcohol solution. IR (KBr, cm−1): 1764 (C=O), 1606(C=C); 1H NMR (p.p.m., DMSO-d6): 10.3 (b, 1H, OH), 7.94 (s, 1H, H-vinyl), 7.40 (d, 1H, Ho), 7.31 (dd, 1H, Hp), 6.98 (d, 1H, Hm), 6.80 (dd, 1H, Hm), 4.22 (q, 2H, CH2), 3.57–3.41 (m, 4H, CH2O), 3.22–3.11 (m, 4H, CH2N), 1.24 (t, 3H, CH3); 13C NMR (p.p.m., DMSO-d6): 165.5 (COO), 164.9 (NCO), 157.4 (C—OH), 135.2 (C—Ar), 132.9 (Cp), 128.9 (Co), 126.1 (Ci), 120.3 (CCO), 120.0 and 116.6 (Cm), 66.4 and 66.3 (CH2O), 46.9 and 41.9 (CH2N), 16.6 (CH2), 14.8 (CH3).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97 and WinGX2003 (Farrugia, 1999).
C16H19NO5 | Z = 2 |
Mr = 305.32 | F(000) = 324 |
Triclinic, P1 | Dx = 1.332 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.790 (2) Å | Cell parameters from 600 reflections |
b = 9.971 (2) Å | θ = 20–25° |
c = 10.832 (2) Å | µ = 0.10 mm−1 |
α = 72.59 (3)° | T = 293 K |
β = 74.79 (3)° | Block, colourless |
γ = 75.64 (3)° | 0.40 × 0.30 × 0.30 mm |
V = 761.5 (3) Å3 |
Bruker SMART area-detector diffractometer | Rint = 0.025 |
Graphite monochromator | θmax = 26.1°, θmin = 2.0° |
ϕ and ω scans | h = −9→9 |
5151 measured reflections | k = −11→12 |
3003 independent reflections | l = −13→13 |
1669 reflections with I > 2σ(I) |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0361P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3003 reflections | Δρmax = 0.22 e Å−3 |
200 parameters | Δρmin = −0.17 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: 0.027 (3) |
C16H19NO5 | γ = 75.64 (3)° |
Mr = 305.32 | V = 761.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.790 (2) Å | Mo Kα radiation |
b = 9.971 (2) Å | µ = 0.10 mm−1 |
c = 10.832 (2) Å | T = 293 K |
α = 72.59 (3)° | 0.40 × 0.30 × 0.30 mm |
β = 74.79 (3)° |
Bruker SMART area-detector diffractometer | 1669 reflections with I > 2σ(I) |
5151 measured reflections | Rint = 0.025 |
3003 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.22 e Å−3 |
3003 reflections | Δρmin = −0.17 e Å−3 |
200 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O4 | 0.1046 (2) | −0.02996 (18) | 0.29525 (16) | 0.0754 (7) | |
O7 | 0.53751 (18) | 0.22049 (14) | 0.34063 (13) | 0.0530 (5) | |
O15 | 0.31995 (18) | 0.63836 (15) | 0.54654 (13) | 0.0566 (6) | |
O16 | 0.2882 (2) | 0.41502 (16) | 0.09461 (15) | 0.0810 (7) | |
O17 | 0.2584 (2) | 0.62165 (15) | 0.14519 (13) | 0.0619 (6) | |
N1 | 0.2753 (2) | 0.15794 (17) | 0.34815 (16) | 0.0503 (6) | |
C2 | 0.0807 (3) | 0.1906 (2) | 0.3507 (2) | 0.0632 (9) | |
C3 | 0.0394 (3) | 0.1194 (3) | 0.2627 (2) | 0.0738 (10) | |
C5 | 0.2951 (3) | −0.0581 (3) | 0.2839 (2) | 0.0731 (10) | |
C6 | 0.3512 (3) | 0.0049 (2) | 0.3720 (2) | 0.0609 (9) | |
C7 | 0.3745 (3) | 0.2534 (2) | 0.33642 (17) | 0.0435 (7) | |
C8 | 0.2880 (3) | 0.4097 (2) | 0.31390 (18) | 0.0444 (7) | |
C9 | 0.2424 (2) | 0.4822 (2) | 0.40727 (19) | 0.0458 (7) | |
C10 | 0.2420 (2) | 0.4244 (2) | 0.54811 (18) | 0.0432 (7) | |
C11 | 0.1995 (3) | 0.2918 (2) | 0.6204 (2) | 0.0561 (8) | |
C12 | 0.2017 (3) | 0.2416 (3) | 0.7526 (2) | 0.0675 (9) | |
C13 | 0.2456 (3) | 0.3240 (3) | 0.8171 (2) | 0.0711 (10) | |
C14 | 0.2848 (3) | 0.4563 (3) | 0.7501 (2) | 0.0596 (9) | |
C15 | 0.2826 (3) | 0.5076 (2) | 0.6168 (2) | 0.0458 (7) | |
C16 | 0.2767 (3) | 0.4807 (2) | 0.1744 (2) | 0.0530 (8) | |
C18 | 0.2461 (3) | 0.6969 (3) | 0.0102 (2) | 0.0730 (10) | |
C19 | 0.2696 (4) | 0.8439 (3) | −0.0106 (3) | 0.1026 (13) | |
H2A | 0.01527 | 0.15807 | 0.44028 | 0.0758* | |
H2B | 0.04165 | 0.29326 | 0.32193 | 0.0758* | |
H3A | 0.09407 | 0.16022 | 0.17185 | 0.0886* | |
H3B | −0.09056 | 0.13715 | 0.26955 | 0.0886* | |
H5A | 0.33777 | −0.16070 | 0.30558 | 0.0878* | |
H5B | 0.35182 | −0.01953 | 0.19310 | 0.0878* | |
H6A | 0.48220 | −0.00927 | 0.35519 | 0.0731* | |
H6B | 0.30880 | −0.04235 | 0.46360 | 0.0731* | |
H9 | 0.20681 | 0.58073 | 0.37915 | 0.0550* | |
H11 | 0.16884 | 0.23544 | 0.57780 | 0.0673* | |
H12 | 0.17349 | 0.15217 | 0.79847 | 0.0810* | |
H13 | 0.24876 | 0.28978 | 0.90649 | 0.0854* | |
H14 | 0.31304 | 0.51214 | 0.79442 | 0.0715* | |
H15 | 0.36256 | 0.67099 | 0.59053 | 0.0849* | |
H18A | 0.33947 | 0.65029 | −0.05048 | 0.0876* | |
H18B | 0.12914 | 0.69694 | −0.00556 | 0.0876* | |
H19A | 0.26079 | 0.89627 | −0.09951 | 0.1540* | |
H19B | 0.17708 | 0.88888 | 0.05019 | 0.1540* | |
H19C | 0.38637 | 0.84275 | 0.00400 | 0.1540* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O4 | 0.0778 (12) | 0.0706 (12) | 0.0942 (13) | −0.0290 (9) | −0.0244 (10) | −0.0260 (9) |
O7 | 0.0464 (9) | 0.0500 (9) | 0.0696 (10) | −0.0040 (7) | −0.0224 (7) | −0.0200 (7) |
O15 | 0.0642 (10) | 0.0522 (10) | 0.0615 (9) | −0.0131 (7) | −0.0213 (7) | −0.0167 (7) |
O16 | 0.1293 (16) | 0.0638 (11) | 0.0574 (10) | −0.0062 (10) | −0.0356 (10) | −0.0213 (9) |
O17 | 0.0898 (12) | 0.0476 (10) | 0.0463 (9) | −0.0058 (8) | −0.0254 (8) | −0.0046 (7) |
N1 | 0.0461 (10) | 0.0414 (11) | 0.0699 (12) | −0.0054 (8) | −0.0220 (9) | −0.0166 (8) |
C2 | 0.0518 (14) | 0.0601 (15) | 0.0805 (17) | −0.0073 (11) | −0.0193 (12) | −0.0193 (12) |
C3 | 0.0680 (16) | 0.084 (2) | 0.0804 (18) | −0.0191 (14) | −0.0320 (14) | −0.0177 (14) |
C5 | 0.0831 (19) | 0.0606 (16) | 0.0849 (18) | −0.0140 (13) | −0.0213 (15) | −0.0275 (13) |
C6 | 0.0723 (16) | 0.0417 (13) | 0.0725 (16) | −0.0046 (11) | −0.0281 (12) | −0.0132 (11) |
C7 | 0.0487 (13) | 0.0453 (13) | 0.0399 (12) | −0.0055 (10) | −0.0133 (10) | −0.0143 (9) |
C8 | 0.0470 (12) | 0.0411 (12) | 0.0469 (12) | −0.0056 (9) | −0.0151 (10) | −0.0107 (10) |
C9 | 0.0440 (12) | 0.0397 (12) | 0.0542 (13) | −0.0024 (9) | −0.0152 (10) | −0.0124 (10) |
C10 | 0.0413 (12) | 0.0423 (12) | 0.0437 (12) | −0.0011 (9) | −0.0086 (9) | −0.0130 (10) |
C11 | 0.0648 (15) | 0.0492 (14) | 0.0545 (15) | −0.0088 (11) | −0.0116 (12) | −0.0151 (11) |
C12 | 0.0837 (18) | 0.0550 (15) | 0.0522 (15) | −0.0138 (13) | −0.0068 (13) | −0.0017 (12) |
C13 | 0.0839 (18) | 0.0798 (19) | 0.0444 (14) | −0.0116 (15) | −0.0144 (13) | −0.0094 (13) |
C14 | 0.0640 (15) | 0.0700 (17) | 0.0508 (14) | −0.0116 (12) | −0.0144 (11) | −0.0223 (12) |
C15 | 0.0400 (12) | 0.0457 (13) | 0.0493 (13) | −0.0013 (9) | −0.0089 (10) | −0.0141 (10) |
C16 | 0.0597 (14) | 0.0486 (15) | 0.0519 (14) | −0.0026 (11) | −0.0183 (11) | −0.0144 (11) |
C18 | 0.0948 (19) | 0.0692 (18) | 0.0495 (15) | −0.0083 (14) | −0.0256 (13) | −0.0028 (12) |
C19 | 0.180 (3) | 0.0603 (19) | 0.0676 (17) | −0.0293 (19) | −0.0411 (18) | 0.0035 (13) |
O4—C3 | 1.416 (3) | C13—C14 | 1.368 (4) |
O4—C5 | 1.419 (3) | C14—C15 | 1.383 (3) |
O7—C7 | 1.240 (3) | C18—C19 | 1.465 (4) |
O15—C15 | 1.357 (3) | C2—H2A | 0.9699 |
O16—C16 | 1.205 (3) | C2—H2B | 0.9705 |
O17—C16 | 1.324 (3) | C3—H3A | 0.9705 |
O17—C18 | 1.446 (3) | C3—H3B | 0.9702 |
O15—H15 | 0.8200 | C5—H5A | 0.9699 |
N1—C2 | 1.464 (3) | C5—H5B | 0.9697 |
N1—C7 | 1.327 (3) | C6—H6A | 0.9700 |
N1—C6 | 1.463 (3) | C6—H6B | 0.9701 |
C2—C3 | 1.482 (3) | C9—H9 | 0.9300 |
C5—C6 | 1.487 (3) | C11—H11 | 0.9302 |
C7—C8 | 1.510 (3) | C12—H12 | 0.9301 |
C8—C16 | 1.480 (3) | C13—H13 | 0.9302 |
C8—C9 | 1.339 (3) | C14—H14 | 0.9301 |
C9—C10 | 1.460 (3) | C18—H18A | 0.9702 |
C10—C15 | 1.402 (3) | C18—H18B | 0.9699 |
C10—C11 | 1.390 (3) | C19—H19A | 0.9596 |
C11—C12 | 1.372 (3) | C19—H19B | 0.9600 |
C12—C13 | 1.374 (4) | C19—H19C | 0.9601 |
O4···N1 | 2.808 (3) | C8···H11 | 2.9133 |
O7···O15i | 2.688 (2) | C8···H15i | 3.0038 |
O15···C2ii | 3.250 (3) | C9···H15i | 3.0804 |
O15···O7i | 2.688 (2) | C15···H2Bii | 2.8609 |
O15···C15i | 3.356 (3) | C16···H2B | 2.7882 |
O15···C10i | 3.252 (2) | C16···H18Aix | 3.0747 |
O16···N1 | 3.145 (2) | H2A···H11 | 2.5151 |
O16···C2 | 3.323 (3) | H2A···O4iii | 2.7764 |
O4···H2Aiii | 2.7764 | H2A···O15ii | 2.8824 |
O4···H19Biv | 2.8797 | H2B···O16 | 2.8482 |
O7···H6A | 2.3868 | H2B···C8 | 2.4486 |
O7···H15i | 1.8810 | H2B···C16 | 2.7882 |
O7···H3Bv | 2.7742 | H2B···O15ii | 2.8200 |
O7···H6Bvi | 2.6662 | H2B···C15ii | 2.8609 |
O15···H5Avii | 2.7685 | H3A···H5B | 2.3468 |
O15···H2Bii | 2.8200 | H3B···O7x | 2.7742 |
O15···H9 | 2.4714 | H5A···O15iv | 2.7685 |
O15···H2Aii | 2.8824 | H5B···H3A | 2.3468 |
O16···H2B | 2.8482 | H6A···O7 | 2.3868 |
O16···H13viii | 2.8014 | H6B···O7vi | 2.6662 |
O16···H18A | 2.4621 | H9···O15 | 2.4714 |
O16···H18B | 2.7869 | H9···O17 | 2.3830 |
O16···H18Aix | 2.7545 | H11···N1 | 2.6875 |
O17···H9 | 2.3830 | H11···C2 | 2.9016 |
N1···O4 | 2.808 (3) | H11···C7 | 2.6644 |
N1···O16 | 3.145 (2) | H11···C8 | 2.9133 |
N1···C11 | 3.446 (3) | H11···H2A | 2.5151 |
N1···H11 | 2.6875 | H12···H19Axi | 2.4577 |
C2···O16 | 3.323 (3) | H13···O16xii | 2.8014 |
C2···C16 | 3.421 (3) | H14···H15 | 2.3017 |
C2···O15ii | 3.250 (3) | H14···H18Axii | 2.5435 |
C7···C11 | 3.117 (3) | H15···H14 | 2.3017 |
C9···C10ii | 3.593 (3) | H15···O7i | 1.8810 |
C10···O15i | 3.252 (2) | H15···C7i | 2.7136 |
C10···C9ii | 3.593 (3) | H15···C8i | 3.0038 |
C11···C7 | 3.117 (3) | H15···C9i | 3.0804 |
C11···N1 | 3.446 (3) | H18A···O16 | 2.4621 |
C15···O15i | 3.356 (3) | H18A···H14viii | 2.5435 |
C16···C2 | 3.421 (3) | H18A···O16ix | 2.7545 |
C2···H11 | 2.9016 | H18A···C16ix | 3.0747 |
C7···H11 | 2.6644 | H18B···O16 | 2.7869 |
C7···H15i | 2.7136 | H19A···H12xiii | 2.4577 |
C8···H2B | 2.4486 | H19B···O4vii | 2.8797 |
C3—O4—C5 | 110.11 (19) | O4—C3—H3A | 109.25 |
C16—O17—C18 | 116.27 (18) | O4—C3—H3B | 109.28 |
C15—O15—H15 | 109.46 | C2—C3—H3A | 109.25 |
C2—N1—C7 | 124.81 (18) | C2—C3—H3B | 109.26 |
C6—N1—C7 | 121.59 (18) | H3A—C3—H3B | 107.88 |
C2—N1—C6 | 113.39 (17) | O4—C5—H5A | 109.10 |
N1—C2—C3 | 110.20 (18) | O4—C5—H5B | 109.12 |
O4—C3—C2 | 111.84 (19) | C6—C5—H5A | 109.03 |
O4—C5—C6 | 112.6 (2) | C6—C5—H5B | 109.05 |
N1—C6—C5 | 109.79 (19) | H5A—C5—H5B | 107.86 |
O7—C7—C8 | 117.9 (2) | N1—C6—H6A | 109.68 |
N1—C7—C8 | 119.2 (2) | N1—C6—H6B | 109.68 |
O7—C7—N1 | 122.86 (19) | C5—C6—H6A | 109.75 |
C7—C8—C16 | 113.61 (16) | C5—C6—H6B | 109.74 |
C9—C8—C16 | 122.28 (18) | H6A—C6—H6B | 108.19 |
C7—C8—C9 | 123.77 (18) | C8—C9—H9 | 116.24 |
C8—C9—C10 | 127.50 (19) | C10—C9—H9 | 116.26 |
C9—C10—C15 | 118.82 (18) | C10—C11—H11 | 119.01 |
C11—C10—C15 | 117.19 (18) | C12—C11—H11 | 119.06 |
C9—C10—C11 | 123.98 (18) | C11—C12—H12 | 120.15 |
C10—C11—C12 | 121.9 (2) | C13—C12—H12 | 120.10 |
C11—C12—C13 | 119.7 (2) | C12—C13—H13 | 119.98 |
C12—C13—C14 | 120.1 (2) | C14—C13—H13 | 119.89 |
C13—C14—C15 | 120.4 (2) | C13—C14—H14 | 119.82 |
O15—C15—C14 | 122.4 (2) | C15—C14—H14 | 119.79 |
C10—C15—C14 | 120.6 (2) | O17—C18—H18A | 110.11 |
O15—C15—C10 | 117.03 (18) | O17—C18—H18B | 110.14 |
O16—C16—O17 | 123.54 (19) | C19—C18—H18A | 110.08 |
O17—C16—C8 | 113.81 (17) | C19—C18—H18B | 110.09 |
O16—C16—C8 | 122.63 (19) | H18A—C18—H18B | 108.42 |
O17—C18—C19 | 108.0 (2) | C18—C19—H19A | 109.48 |
N1—C2—H2A | 109.62 | C18—C19—H19B | 109.45 |
N1—C2—H2B | 109.59 | C18—C19—H19C | 109.44 |
C3—C2—H2A | 109.64 | H19A—C19—H19B | 109.51 |
C3—C2—H2B | 109.64 | H19A—C19—H19C | 109.49 |
H2A—C2—H2B | 108.11 | H19B—C19—H19C | 109.47 |
C5—O4—C3—C2 | −59.8 (2) | C7—C8—C16—O16 | 19.1 (3) |
C3—O4—C5—C6 | 59.4 (2) | C7—C8—C16—O17 | −159.0 (2) |
C18—O17—C16—C8 | −179.82 (19) | C9—C8—C16—O16 | −167.4 (2) |
C16—O17—C18—C19 | −166.9 (2) | C16—C8—C9—C10 | 177.9 (2) |
C18—O17—C16—O16 | 2.1 (3) | C9—C8—C16—O17 | 14.5 (3) |
C2—N1—C7—C8 | −4.7 (3) | C7—C8—C9—C10 | −9.3 (3) |
C6—N1—C7—C8 | −179.09 (16) | C8—C9—C10—C15 | 147.4 (2) |
C6—N1—C7—O7 | 2.3 (3) | C8—C9—C10—C11 | −34.1 (3) |
C7—N1—C6—C5 | −134.9 (2) | C11—C10—C15—O15 | −178.52 (19) |
C2—N1—C7—O7 | 176.66 (17) | C9—C10—C15—C14 | −179.6 (2) |
C6—N1—C2—C3 | −51.1 (2) | C9—C10—C15—O15 | 0.1 (3) |
C7—N1—C2—C3 | 134.1 (2) | C11—C10—C15—C14 | 1.8 (3) |
C2—N1—C6—C5 | 50.2 (2) | C15—C10—C11—C12 | −1.8 (3) |
N1—C2—C3—O4 | 55.4 (2) | C9—C10—C11—C12 | 179.7 (2) |
O4—C5—C6—N1 | −54.2 (2) | C10—C11—C12—C13 | 0.5 (4) |
O7—C7—C8—C16 | 97.2 (2) | C11—C12—C13—C14 | 0.8 (4) |
O7—C7—C8—C9 | −76.3 (3) | C12—C13—C14—C15 | −0.7 (4) |
N1—C7—C8—C9 | 105.1 (3) | C13—C14—C15—O15 | 179.8 (2) |
N1—C7—C8—C16 | −81.5 (2) | C13—C14—C15—C10 | −0.6 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) x, y−1, z; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) x, y+1, z; (viii) x, y, z−1; (ix) −x+1, −y+1, −z; (x) x−1, y, z; (xi) x, y−1, z+1; (xii) x, y, z+1; (xiii) x, y+1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O15—H15···O7i | 0.82 | 1.88 | 2.688 (2) | 168 |
C6—H6A···O7 | 0.97 | 2.39 | 2.774 (3) | 103 |
C9—H9···O17 | 0.93 | 2.38 | 2.747 (2) | 103 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H19NO5 |
Mr | 305.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.790 (2), 9.971 (2), 10.832 (2) |
α, β, γ (°) | 72.59 (3), 74.79 (3), 75.64 (3) |
V (Å3) | 761.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5151, 3003, 1669 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.104, 1.01 |
No. of reflections | 3003 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.17 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXL97 and WinGX2003 (Farrugia, 1999).
O4—C3 | 1.416 (3) | O17—C18 | 1.446 (3) |
O4—C5 | 1.419 (3) | N1—C2 | 1.464 (3) |
O7—C7 | 1.240 (3) | N1—C7 | 1.327 (3) |
O15—C15 | 1.357 (3) | N1—C6 | 1.463 (3) |
O16—C16 | 1.205 (3) | C8—C9 | 1.339 (3) |
O17—C16 | 1.324 (3) | ||
C3—O4—C5 | 110.11 (19) | N1—C7—C8 | 119.2 (2) |
C16—O17—C18 | 116.27 (18) | O7—C7—N1 | 122.86 (19) |
C2—N1—C7 | 124.81 (18) | O16—C16—O17 | 123.54 (19) |
C6—N1—C7 | 121.59 (18) | O17—C16—C8 | 113.81 (17) |
C2—N1—C6 | 113.39 (17) | O16—C16—C8 | 122.63 (19) |
O7—C7—C8 | 117.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O15—H15···O7i | 0.82 | 1.88 | 2.688 (2) | 168 |
C6—H6A···O7 | 0.97 | 2.39 | 2.774 (3) | 103 |
C9—H9···O17 | 0.93 | 2.38 | 2.747 (2) | 103. |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Lignin-related phenylpropanoids, such as cinnamic acid, are abundant in plant cells and are precursors not only of lignin, the second most abundant carbon compound on earth after cellulose, but also of anthocyanins, phytoalexins and flavonoids (Peng et al., 2003). Many phenylpropanoids are pharmacologically active and thus of pharmaceutical interest (Dixon et al., 1996). The biodegradation of phenylpropanoids is important for the global carbon cycle from an environmental point of view, since these compounds are released from plant wastes as breakdown products from lignin. In view of their importance, augmented further by the potential use of phenylpropanoids as feedstock for bioconversion into valuable molecules (Rosazza et al., 1995), we analyzed the crystal structure of the title compound, (I), which is reported here.
The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. Selected bond lengths and angles are listed in Table 1. The observed bond lengths and angles in the hydroxyphenyl group are in agreement with the average values reported in the literature (Domenicano et al., 1975; Allen et al., 1987). The morpholine ring presents a chair conformation, and its bond lengths and angles are comparable to those reported for a related structure (Decken et al., 2003).
The cinammic derivative (I) has a C8—C9 bond length of 1.339 (3) Å, which confirms its double-bond character. The ester and 2-hydroxyphenyl groups are arranged in opposite positions around the double bond [C16—C8—C9—C10 = 177.9 (2)°], giving it an E configuration. The –OEt group points towards the double bond and is almost coplanar with it [C9—C8—C16—O17 = 14.5 (3)°]. These features support the formation of an S(5) ring motif (Bernstein et al., 1995) through the soft C9(sp2)—H9···O17 intramolecular hydrogen-bonding interaction [C9···O17 = 2.747 (2) Å] (Desiraju, 1995), in spite of the small angle observed for C9—H9···O17 (103°). In the same context, the N-carboxy moiety is almost coplanar with the neighbouring C6 atom of the morpholine ring [C6—N1—C7—O7 = 2.3 (3)°] and the C6—N1—C7 angle [121.59 (18)°] is slightly less open than the C2—N1—C7 angle [124.81 (18)°]. Another plausible soft S(5) hydrogen motif is formed through the C6(sp3)—H6A···O7 interaction [C6···O7 = 2.774 (3) Å and C6—H6A···O7 = 103°; Fig. 2]. The hydrogen-bonding geometry is listed in Table 2. This interaction appears as a consequence of the planarity imposed by electron delocalization in the amide N—C(=O) fragment, as indicated by the short N1—C7 distance of only 1.327 (3) Å; this is even shorter than the value found in N-benzylmorpholine (1.343 Å; Bennet et al., 1991).
The N-carboxymorpholine group is almost perpendicular to the propenoic ester group, with N1—C7—C8—C16 and O7—C7—C8—C16 torsion angles of −81.5 (2) and 97.2 (2)°, respectively. This orthogonal disposition of the two S(5) hydrogen-bonding motifs must be forced by the steric requirements of the morpholine ring, in addition to the restricted rotation of the amide N—C(O) bond (Bennet et al., 1991). The conformation exhibited by (I) in the solid state is similar to that found in solution, as supported by the 13C NMR spectrum, which shows four different signals, at 66.4 and 66.3 p.p.m., and 46.9 and 41.9 p.p.m., for the CH2O and CH2N morpholine ring C atoms, respectively.
Finally, the crystal packing is mediated by a strong (Steiner, 2002) O15—H15···O7i intermolecular interaction [H15···O7i = 1.88 Å, O15···O7i = 2.688 (2) Å and O15—H15···O7i = 168°; symmetry code: (i) 1 − x, 1 − y, 1 − z], leading to dimerization in the ac plane. As a result, a 16-membered ring is formed between molecules whose topological motif corresponds to the first-level graph-set descriptor R22(16) (Fig. 2). No other hydorgen-bonding interactions linking this centrosymmetric dimer are formed.