organic compounds
Pheophorbide b ethyl ester from a chlorella vulgaris dietary supplement
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
In the title compound, C37H38N4O6, four five-membered nitrogen-bearing rings are nearly coplanar. Two N atoms in two these five-membered rings have attached H atoms, which contribute to the formation of intramolecular N—H⋯N hydrogen bonds [N⋯N = 2.713 (5)–3.033 (6) Å].
Related literature
For the a methyl ester, see: Fischer et al. (1972). For another example of a chlorin, see: Senge & Smith (1997).
of pheophorbideExperimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
Supporting information
10.1107/S160053680802970X/cv2447sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053680802970X/cv2447Isup2.hkl
A sample of the dietary supplement Chlorenergy (C'est Si Bon Co., USA) (20 g) was dissolved in 100 ml e thanol and 10 ml dilute sulfuric acid (10%, v/v). The mixture was heated at 323 K for 2 h. The solution was cooled and then stirred at room temperature for 3 days under normal day light (light intensity not measured), during which the solution turned green yellowish. The solvent was evaporated to dryness at reduced pressure. The crude product was purified by HPLC on an RP18e semi-preparative column (Merck Chromolith 100–10 mm) with acetonitrile-water (90:10, v/v) as the
Pheophorbide b ethyl ester was isolated as brownish plates. Single crystals were grown by slow evaporation of a mixture of acetone and chloroform solution.C-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the
in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The amino H-atoms were located on a difference Fourier map, and were isotropically refined with a distance restraint N–H=0.88 (2) Å). In the absence of heavy scatterers, 3452 Friedel pairs were merged in the refinement.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).Fig. 1. The molecular structure of the title compound showing the atomic numbering and 70% probability displacement ellipsoids. |
C37H38N4O6 | F(000) = 672 |
Mr = 634.71 | Dx = 1.352 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3714 reflections |
a = 7.0222 (2) Å | θ = 2.7–28.4° |
b = 30.5501 (7) Å | µ = 0.09 mm−1 |
c = 7.8539 (2) Å | T = 100 K |
β = 112.300 (2)° | Plate, brown |
V = 1558.87 (7) Å3 | 0.35 × 0.20 × 0.01 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 3100 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 27.5°, θmin = 1.3° |
ω scans | h = −9→9 |
14310 measured reflections | k = −39→39 |
3633 independent reflections | l = −9→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.177 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0986P)2 + 0.882P] where P = (Fo2 + 2Fc2)/3 |
3633 reflections | (Δ/σ)max = 0.001 |
438 parameters | Δρmax = 0.55 e Å−3 |
3 restraints | Δρmin = −0.38 e Å−3 |
C37H38N4O6 | V = 1558.87 (7) Å3 |
Mr = 634.71 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.0222 (2) Å | µ = 0.09 mm−1 |
b = 30.5501 (7) Å | T = 100 K |
c = 7.8539 (2) Å | 0.35 × 0.20 × 0.01 mm |
β = 112.300 (2)° |
Bruker SMART APEX diffractometer | 3100 reflections with I > 2σ(I) |
14310 measured reflections | Rint = 0.054 |
3633 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 3 restraints |
wR(F2) = 0.177 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.55 e Å−3 |
3633 reflections | Δρmin = −0.38 e Å−3 |
438 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.4731 (6) | 0.50000 (12) | 0.2630 (5) | 0.0208 (8) | |
O2 | 0.2600 (6) | 0.49420 (13) | 0.4146 (6) | 0.0291 (9) | |
O3 | −0.0879 (6) | 0.43359 (11) | 0.0419 (5) | 0.0197 (8) | |
O4 | −0.2243 (5) | 0.39650 (12) | 0.2153 (5) | 0.0194 (7) | |
O5 | −0.1704 (5) | 0.33907 (12) | −0.1938 (4) | 0.0185 (7) | |
O6 | 0.2153 (7) | 0.07387 (13) | 0.9416 (5) | 0.0317 (9) | |
N1 | 0.3166 (7) | 0.25068 (14) | 0.8896 (6) | 0.0151 (8) | |
H1N | 0.236 (11) | 0.251 (3) | 0.772 (3) | 0.06 (3)* | |
N2 | 0.2567 (6) | 0.32123 (13) | 0.6242 (5) | 0.0144 (8) | |
N3 | 0.0540 (6) | 0.25217 (13) | 0.3274 (5) | 0.0132 (8) | |
H3N | 0.101 (8) | 0.2426 (19) | 0.441 (3) | 0.019 (15)* | |
N4 | 0.1148 (6) | 0.18688 (13) | 0.5768 (5) | 0.0145 (8) | |
C1 | 0.3315 (7) | 0.21173 (16) | 0.9824 (6) | 0.0136 (9) | |
C2 | 0.4415 (7) | 0.22289 (17) | 1.1778 (6) | 0.0147 (9) | |
C3 | 0.4902 (9) | 0.19315 (19) | 1.3358 (7) | 0.0270 (12) | |
H3 | 0.5425 | 0.2079 | 1.4508 | 0.032* | |
C4 | 0.4778 (11) | 0.1527 (2) | 1.3517 (8) | 0.0388 (16) | |
H4A | 0.4273 | 0.1348 | 1.2451 | 0.047* | |
H4B | 0.5187 | 0.1399 | 1.4704 | 0.047* | |
C5 | 0.4844 (7) | 0.26621 (16) | 1.1902 (6) | 0.0149 (9) | |
C6 | 0.6018 (8) | 0.29141 (17) | 1.3629 (6) | 0.0173 (10) | |
H6A | 0.7268 | 0.2753 | 1.4360 | 0.026* | |
H6B | 0.5155 | 0.2952 | 1.4349 | 0.026* | |
H6C | 0.6395 | 0.3202 | 1.3303 | 0.026* | |
C7 | 0.4064 (7) | 0.28444 (16) | 1.0051 (6) | 0.0135 (9) | |
C8 | 0.4182 (7) | 0.32710 (16) | 0.9564 (6) | 0.0129 (9) | |
H8 | 0.4804 | 0.3471 | 1.0545 | 0.016* | |
C9 | 0.3481 (7) | 0.34462 (16) | 0.7770 (6) | 0.0142 (9) | |
C10 | 0.3693 (7) | 0.39297 (15) | 0.7423 (6) | 0.0132 (9) | |
H10 | 0.5172 | 0.4018 | 0.8000 | 0.016* | |
C11 | 0.2387 (9) | 0.42253 (16) | 0.8135 (7) | 0.0200 (10) | |
H11A | 0.2931 | 0.4215 | 0.9482 | 0.030* | |
H11B | 0.0959 | 0.4122 | 0.7647 | 0.030* | |
H11C | 0.2439 | 0.4527 | 0.7729 | 0.030* | |
C12 | 0.2977 (7) | 0.39420 (16) | 0.5286 (6) | 0.0137 (9) | |
H12 | 0.1865 | 0.4165 | 0.4753 | 0.016* | |
C13 | 0.4771 (7) | 0.40329 (15) | 0.4667 (6) | 0.0151 (9) | |
H13A | 0.5884 | 0.3820 | 0.5277 | 0.018* | |
H13B | 0.4289 | 0.3983 | 0.3324 | 0.018* | |
C14 | 0.5668 (8) | 0.44977 (16) | 0.5091 (7) | 0.0187 (10) | |
H14A | 0.6030 | 0.4562 | 0.6413 | 0.022* | |
H14B | 0.6944 | 0.4514 | 0.4839 | 0.022* | |
C15 | 0.4162 (8) | 0.48372 (16) | 0.3950 (7) | 0.0180 (10) | |
C16 | 0.3316 (9) | 0.53099 (19) | 0.1365 (7) | 0.0243 (11) | |
H16A | 0.1884 | 0.5210 | 0.1061 | 0.029* | |
H16B | 0.3571 | 0.5320 | 0.0209 | 0.029* | |
C17 | 0.3570 (9) | 0.5764 (2) | 0.2186 (9) | 0.0294 (12) | |
H17A | 0.2695 | 0.5970 | 0.1262 | 0.044* | |
H17B | 0.5011 | 0.5855 | 0.2576 | 0.044* | |
H17C | 0.3167 | 0.5762 | 0.3252 | 0.044* | |
C18 | 0.2128 (7) | 0.34861 (15) | 0.4764 (6) | 0.0137 (9) | |
C19 | 0.1041 (7) | 0.33397 (15) | 0.3001 (6) | 0.0139 (9) | |
C20 | 0.0327 (7) | 0.36154 (15) | 0.1264 (6) | 0.0131 (9) | |
H20 | 0.1544 | 0.3737 | 0.1058 | 0.016* | |
C21 | −0.1089 (7) | 0.39854 (15) | 0.1341 (6) | 0.0135 (9) | |
C22 | −0.2130 (8) | 0.47095 (16) | 0.0499 (7) | 0.0200 (10) | |
H22A | −0.1934 | 0.4948 | −0.0251 | 0.030* | |
H22B | −0.1714 | 0.4807 | 0.1777 | 0.030* | |
H22C | −0.3583 | 0.4624 | 0.0024 | 0.030* | |
C23 | −0.0867 (7) | 0.32839 (16) | −0.0327 (7) | 0.0158 (9) | |
C24 | −0.0692 (7) | 0.28555 (15) | 0.0547 (6) | 0.0128 (9) | |
C25 | 0.0404 (7) | 0.29118 (16) | 0.2478 (7) | 0.0147 (9) | |
C26 | −0.1222 (7) | 0.24197 (16) | 0.0190 (6) | 0.0139 (9) | |
C27 | −0.2368 (8) | 0.22101 (17) | −0.1630 (7) | 0.0191 (10) | |
H27A | −0.3305 | 0.2424 | −0.2461 | 0.029* | |
H27B | −0.3163 | 0.1961 | −0.1465 | 0.029* | |
H27C | −0.1389 | 0.2107 | −0.2158 | 0.029* | |
C28 | −0.0448 (7) | 0.22063 (16) | 0.1955 (6) | 0.0145 (9) | |
C29 | −0.0575 (7) | 0.17779 (16) | 0.2429 (7) | 0.0143 (9) | |
H29 | −0.1221 | 0.1577 | 0.1458 | 0.017* | |
C30 | 0.0173 (7) | 0.16128 (16) | 0.4234 (7) | 0.0157 (9) | |
C31 | 0.0040 (7) | 0.11672 (16) | 0.4739 (7) | 0.0180 (10) | |
C32 | −0.0871 (8) | 0.07875 (17) | 0.3481 (7) | 0.0217 (10) | |
H32A | −0.1830 | 0.0899 | 0.2278 | 0.026* | |
H32B | −0.1672 | 0.0605 | 0.4011 | 0.026* | |
C33 | 0.0764 (9) | 0.0507 (2) | 0.3185 (9) | 0.0298 (12) | |
H33A | 0.0127 | 0.0240 | 0.2519 | 0.045* | |
H33B | 0.1821 | 0.0428 | 0.4380 | 0.045* | |
H33C | 0.1397 | 0.0671 | 0.2465 | 0.045* | |
C34 | 0.0948 (8) | 0.11562 (17) | 0.6626 (7) | 0.0207 (11) | |
C35 | 0.1192 (9) | 0.07653 (17) | 0.7743 (7) | 0.0216 (10) | |
H35 | 0.0550 | 0.0506 | 0.7124 | 0.026* | |
C36 | 0.1628 (8) | 0.15993 (17) | 0.7220 (7) | 0.0177 (10) | |
C37 | 0.2647 (8) | 0.17179 (16) | 0.9098 (7) | 0.0194 (10) | |
H37 | 0.2893 | 0.1486 | 0.9960 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0238 (18) | 0.0243 (19) | 0.0161 (17) | 0.0037 (15) | 0.0096 (14) | 0.0056 (14) |
O2 | 0.027 (2) | 0.025 (2) | 0.041 (2) | 0.0052 (16) | 0.0194 (18) | 0.0084 (17) |
O3 | 0.0251 (19) | 0.0137 (17) | 0.0232 (19) | 0.0047 (14) | 0.0125 (15) | 0.0038 (14) |
O4 | 0.0182 (16) | 0.0191 (18) | 0.0251 (18) | 0.0012 (14) | 0.0130 (14) | 0.0029 (14) |
O5 | 0.0202 (17) | 0.0240 (19) | 0.0094 (16) | 0.0010 (14) | 0.0034 (13) | 0.0023 (13) |
O6 | 0.052 (3) | 0.021 (2) | 0.023 (2) | −0.0026 (18) | 0.0138 (18) | 0.0042 (16) |
N1 | 0.0177 (19) | 0.0155 (19) | 0.0128 (19) | 0.0002 (15) | 0.0068 (16) | 0.0017 (15) |
N2 | 0.017 (2) | 0.012 (2) | 0.014 (2) | −0.0004 (15) | 0.0055 (16) | 0.0021 (15) |
N3 | 0.0161 (19) | 0.0112 (19) | 0.0125 (19) | 0.0002 (15) | 0.0058 (16) | 0.0006 (15) |
N4 | 0.0158 (19) | 0.016 (2) | 0.0136 (19) | −0.0003 (15) | 0.0080 (16) | 0.0009 (15) |
C1 | 0.014 (2) | 0.018 (2) | 0.012 (2) | 0.0036 (18) | 0.0081 (17) | 0.0018 (17) |
C2 | 0.014 (2) | 0.021 (2) | 0.012 (2) | 0.0024 (18) | 0.0078 (18) | 0.0013 (18) |
C3 | 0.041 (3) | 0.024 (3) | 0.012 (2) | 0.000 (2) | 0.006 (2) | 0.002 (2) |
C4 | 0.053 (4) | 0.032 (3) | 0.018 (3) | −0.008 (3) | −0.002 (3) | 0.006 (2) |
C5 | 0.015 (2) | 0.020 (2) | 0.010 (2) | 0.0031 (18) | 0.0055 (18) | 0.0038 (17) |
C6 | 0.016 (2) | 0.026 (3) | 0.010 (2) | 0.0034 (19) | 0.0058 (18) | −0.0005 (18) |
C7 | 0.011 (2) | 0.016 (2) | 0.014 (2) | 0.0004 (17) | 0.0057 (17) | −0.0003 (17) |
C8 | 0.011 (2) | 0.018 (2) | 0.009 (2) | −0.0013 (17) | 0.0034 (16) | 0.0002 (17) |
C9 | 0.013 (2) | 0.018 (2) | 0.011 (2) | 0.0022 (18) | 0.0044 (17) | 0.0031 (17) |
C10 | 0.017 (2) | 0.013 (2) | 0.009 (2) | −0.0014 (18) | 0.0048 (17) | −0.0019 (17) |
C11 | 0.032 (3) | 0.014 (2) | 0.018 (2) | 0.002 (2) | 0.014 (2) | 0.0001 (18) |
C12 | 0.016 (2) | 0.013 (2) | 0.014 (2) | 0.0024 (17) | 0.0089 (17) | 0.0027 (17) |
C13 | 0.017 (2) | 0.015 (2) | 0.016 (2) | 0.0011 (18) | 0.0088 (18) | 0.0022 (17) |
C14 | 0.023 (3) | 0.018 (2) | 0.013 (2) | −0.0040 (19) | 0.0049 (19) | 0.0009 (18) |
C15 | 0.018 (2) | 0.015 (2) | 0.023 (2) | −0.0048 (18) | 0.0096 (19) | −0.0008 (19) |
C16 | 0.024 (3) | 0.027 (3) | 0.020 (3) | 0.007 (2) | 0.007 (2) | 0.007 (2) |
C17 | 0.027 (3) | 0.026 (3) | 0.037 (3) | 0.004 (2) | 0.015 (2) | 0.003 (2) |
C18 | 0.014 (2) | 0.014 (2) | 0.014 (2) | 0.0047 (17) | 0.0060 (18) | 0.0012 (17) |
C19 | 0.015 (2) | 0.015 (2) | 0.013 (2) | 0.0012 (17) | 0.0065 (17) | 0.0039 (17) |
C20 | 0.015 (2) | 0.015 (2) | 0.010 (2) | 0.0020 (18) | 0.0054 (17) | 0.0009 (16) |
C21 | 0.016 (2) | 0.009 (2) | 0.016 (2) | −0.0018 (17) | 0.0053 (17) | −0.0015 (17) |
C22 | 0.022 (2) | 0.010 (2) | 0.028 (3) | 0.0020 (18) | 0.010 (2) | −0.0006 (19) |
C23 | 0.014 (2) | 0.018 (2) | 0.016 (2) | 0.0022 (18) | 0.0062 (18) | −0.0001 (18) |
C24 | 0.009 (2) | 0.019 (2) | 0.012 (2) | 0.0030 (17) | 0.0056 (17) | 0.0004 (17) |
C25 | 0.009 (2) | 0.021 (2) | 0.015 (2) | 0.0041 (18) | 0.0054 (17) | 0.0026 (18) |
C26 | 0.011 (2) | 0.019 (2) | 0.013 (2) | 0.0066 (18) | 0.0072 (18) | 0.0017 (18) |
C27 | 0.019 (2) | 0.021 (3) | 0.016 (2) | −0.002 (2) | 0.0052 (19) | −0.0046 (19) |
C28 | 0.009 (2) | 0.019 (2) | 0.015 (2) | 0.0037 (17) | 0.0051 (17) | −0.0012 (18) |
C29 | 0.013 (2) | 0.013 (2) | 0.018 (2) | −0.0019 (17) | 0.0075 (18) | −0.0042 (18) |
C30 | 0.014 (2) | 0.014 (2) | 0.022 (2) | −0.0014 (17) | 0.0100 (19) | −0.0038 (18) |
C31 | 0.012 (2) | 0.019 (2) | 0.024 (3) | −0.0003 (18) | 0.0080 (19) | 0.001 (2) |
C32 | 0.021 (2) | 0.018 (3) | 0.022 (3) | −0.001 (2) | 0.004 (2) | 0.000 (2) |
C33 | 0.032 (3) | 0.026 (3) | 0.031 (3) | 0.002 (2) | 0.011 (2) | −0.007 (2) |
C34 | 0.027 (3) | 0.017 (3) | 0.021 (2) | 0.000 (2) | 0.011 (2) | 0.0016 (19) |
C35 | 0.033 (3) | 0.014 (2) | 0.022 (2) | −0.005 (2) | 0.015 (2) | 0.0004 (19) |
C36 | 0.016 (2) | 0.016 (2) | 0.023 (2) | 0.0008 (18) | 0.0107 (19) | −0.0003 (19) |
C37 | 0.030 (3) | 0.012 (2) | 0.018 (2) | 0.003 (2) | 0.011 (2) | 0.0032 (18) |
O1—C15 | 1.340 (6) | C13—H13A | 0.9900 |
O1—C16 | 1.456 (6) | C13—H13B | 0.9900 |
O2—C15 | 1.207 (6) | C14—C15 | 1.509 (7) |
O3—C21 | 1.332 (6) | C14—H14A | 0.9900 |
O3—C22 | 1.456 (6) | C14—H14B | 0.9900 |
O4—C21 | 1.208 (6) | C16—C17 | 1.511 (8) |
O5—C23 | 1.220 (6) | C16—H16A | 0.9900 |
O6—C35 | 1.231 (7) | C16—H16B | 0.9900 |
N1—C7 | 1.360 (6) | C17—H17A | 0.9800 |
N1—C1 | 1.379 (6) | C17—H17B | 0.9800 |
N1—H1N | 0.88 (3) | C17—H17C | 0.9800 |
N2—C9 | 1.333 (6) | C18—C19 | 1.378 (6) |
N2—C18 | 1.368 (6) | C19—C25 | 1.392 (7) |
N3—C25 | 1.332 (6) | C19—C20 | 1.518 (6) |
N3—C28 | 1.392 (6) | C20—C21 | 1.522 (6) |
N3—H3N | 0.88 (3) | C20—C23 | 1.579 (6) |
N4—C36 | 1.342 (6) | C20—H20 | 1.0000 |
N4—C30 | 1.380 (6) | C22—H22A | 0.9800 |
C1—C37 | 1.353 (7) | C22—H22B | 0.9800 |
C1—C2 | 1.472 (6) | C22—H22C | 0.9800 |
C2—C5 | 1.352 (7) | C23—C24 | 1.461 (7) |
C2—C3 | 1.470 (7) | C24—C26 | 1.382 (7) |
C3—C4 | 1.248 (9) | C24—C25 | 1.427 (6) |
C3—H3 | 0.9500 | C26—C28 | 1.439 (6) |
C4—H4A | 0.9500 | C26—C27 | 1.493 (7) |
C4—H4B | 0.9500 | C27—H27A | 0.9800 |
C5—C7 | 1.456 (6) | C27—H27B | 0.9800 |
C5—C6 | 1.505 (7) | C27—H27C | 0.9800 |
C6—H6A | 0.9800 | C28—C29 | 1.373 (7) |
C6—H6B | 0.9800 | C29—C30 | 1.405 (7) |
C6—H6C | 0.9800 | C29—H29 | 0.9500 |
C7—C8 | 1.370 (7) | C30—C31 | 1.431 (7) |
C8—C9 | 1.410 (6) | C31—C34 | 1.373 (7) |
C8—H8 | 0.9500 | C31—C32 | 1.500 (7) |
C9—C10 | 1.519 (7) | C32—C33 | 1.520 (8) |
C10—C11 | 1.535 (7) | C32—H32A | 0.9900 |
C10—C12 | 1.559 (6) | C32—H32B | 0.9900 |
C10—H10 | 1.0000 | C33—H33A | 0.9800 |
C11—H11A | 0.9800 | C33—H33B | 0.9800 |
C11—H11B | 0.9800 | C33—H33C | 0.9800 |
C11—H11C | 0.9800 | C34—C36 | 1.452 (7) |
C12—C18 | 1.509 (7) | C34—C35 | 1.453 (7) |
C12—C13 | 1.538 (6) | C35—H35 | 0.9500 |
C12—H12 | 1.0000 | C36—C37 | 1.420 (7) |
C13—C14 | 1.538 (7) | C37—H37 | 0.9500 |
C15—O1—C16 | 116.3 (4) | C16—C17—H17B | 109.5 |
C21—O3—C22 | 114.4 (4) | H17A—C17—H17B | 109.5 |
C7—N1—C1 | 112.2 (4) | C16—C17—H17C | 109.5 |
C7—N1—H1N | 131 (6) | H17A—C17—H17C | 109.5 |
C1—N1—H1N | 116 (6) | H17B—C17—H17C | 109.5 |
C9—N2—C18 | 108.2 (4) | N2—C18—C19 | 121.0 (4) |
C25—N3—C28 | 110.1 (4) | N2—C18—C12 | 113.3 (4) |
C25—N3—H3N | 135 (4) | C19—C18—C12 | 125.7 (4) |
C28—N3—H3N | 115 (4) | C18—C19—C25 | 126.5 (4) |
C36—N4—C30 | 106.0 (4) | C18—C19—C20 | 126.3 (4) |
C37—C1—N1 | 127.6 (4) | C25—C19—C20 | 107.2 (4) |
C37—C1—C2 | 127.5 (4) | C19—C20—C21 | 112.0 (4) |
N1—C1—C2 | 104.8 (4) | C19—C20—C23 | 104.5 (4) |
C5—C2—C3 | 124.8 (5) | C21—C20—C23 | 110.4 (4) |
C5—C2—C1 | 108.4 (4) | C19—C20—H20 | 109.9 |
C3—C2—C1 | 126.8 (5) | C21—C20—H20 | 109.9 |
C4—C3—C2 | 133.9 (5) | C23—C20—H20 | 109.9 |
C4—C3—H3 | 113.0 | O4—C21—O3 | 124.3 (4) |
C2—C3—H3 | 113.0 | O4—C21—C20 | 124.2 (4) |
C3—C4—H4A | 120.0 | O3—C21—C20 | 111.5 (4) |
C3—C4—H4B | 120.0 | O3—C22—H22A | 109.5 |
H4A—C4—H4B | 120.0 | O3—C22—H22B | 109.5 |
C2—C5—C7 | 108.3 (4) | H22A—C22—H22B | 109.5 |
C2—C5—C6 | 126.6 (4) | O3—C22—H22C | 109.5 |
C7—C5—C6 | 125.1 (4) | H22A—C22—H22C | 109.5 |
C5—C6—H6A | 109.5 | H22B—C22—H22C | 109.5 |
C5—C6—H6B | 109.5 | O5—C23—C24 | 130.4 (5) |
H6A—C6—H6B | 109.5 | O5—C23—C20 | 123.4 (4) |
C5—C6—H6C | 109.5 | C24—C23—C20 | 106.1 (4) |
H6A—C6—H6C | 109.5 | C26—C24—C25 | 109.1 (4) |
H6B—C6—H6C | 109.5 | C26—C24—C23 | 143.1 (4) |
N1—C7—C8 | 126.7 (4) | C25—C24—C23 | 107.8 (4) |
N1—C7—C5 | 106.2 (4) | N3—C25—C19 | 138.0 (5) |
C8—C7—C5 | 127.1 (4) | N3—C25—C24 | 107.7 (4) |
C7—C8—C9 | 127.2 (4) | C19—C25—C24 | 114.2 (4) |
C7—C8—H8 | 116.4 | C24—C26—C28 | 105.5 (4) |
C9—C8—H8 | 116.4 | C24—C26—C27 | 127.8 (4) |
N2—C9—C8 | 124.2 (4) | C28—C26—C27 | 126.7 (4) |
N2—C9—C10 | 114.0 (4) | C26—C27—H27A | 109.5 |
C8—C9—C10 | 121.8 (4) | C26—C27—H27B | 109.5 |
C9—C10—C11 | 113.2 (4) | H27A—C27—H27B | 109.5 |
C9—C10—C12 | 101.7 (4) | C26—C27—H27C | 109.5 |
C11—C10—C12 | 112.6 (4) | H27A—C27—H27C | 109.5 |
C9—C10—H10 | 109.7 | H27B—C27—H27C | 109.5 |
C11—C10—H10 | 109.7 | C29—C28—N3 | 121.6 (4) |
C12—C10—H10 | 109.7 | C29—C28—C26 | 130.8 (4) |
C10—C11—H11A | 109.5 | N3—C28—C26 | 107.6 (4) |
C10—C11—H11B | 109.5 | C28—C29—C30 | 125.3 (4) |
H11A—C11—H11B | 109.5 | C28—C29—H29 | 117.3 |
C10—C11—H11C | 109.5 | C30—C29—H29 | 117.3 |
H11A—C11—H11C | 109.5 | N4—C30—C29 | 123.3 (4) |
H11B—C11—H11C | 109.5 | N4—C30—C31 | 111.1 (4) |
C18—C12—C13 | 111.6 (4) | C29—C30—C31 | 125.6 (4) |
C18—C12—C10 | 101.7 (4) | C34—C31—C30 | 105.7 (4) |
C13—C12—C10 | 112.1 (4) | C34—C31—C32 | 126.8 (5) |
C18—C12—H12 | 110.4 | C30—C31—C32 | 127.5 (5) |
C13—C12—H12 | 110.4 | C31—C32—C33 | 112.3 (4) |
C10—C12—H12 | 110.4 | C31—C32—H32A | 109.1 |
C14—C13—C12 | 114.6 (4) | C33—C32—H32A | 109.1 |
C14—C13—H13A | 108.6 | C31—C32—H32B | 109.1 |
C12—C13—H13A | 108.6 | C33—C32—H32B | 109.1 |
C14—C13—H13B | 108.6 | H32A—C32—H32B | 107.9 |
C12—C13—H13B | 108.6 | C32—C33—H33A | 109.5 |
H13A—C13—H13B | 107.6 | C32—C33—H33B | 109.5 |
C15—C14—C13 | 111.7 (4) | H33A—C33—H33B | 109.5 |
C15—C14—H14A | 109.3 | C32—C33—H33C | 109.5 |
C13—C14—H14A | 109.3 | H33A—C33—H33C | 109.5 |
C15—C14—H14B | 109.3 | H33B—C33—H33C | 109.5 |
C13—C14—H14B | 109.3 | C31—C34—C36 | 106.6 (4) |
H14A—C14—H14B | 107.9 | C31—C34—C35 | 124.9 (5) |
O2—C15—O1 | 123.5 (5) | C36—C34—C35 | 128.5 (5) |
O2—C15—C14 | 124.9 (5) | O6—C35—C34 | 126.2 (5) |
O1—C15—C14 | 111.5 (4) | O6—C35—H35 | 116.9 |
O1—C16—C17 | 111.5 (5) | C34—C35—H35 | 116.9 |
O1—C16—H16A | 109.3 | N4—C36—C37 | 126.2 (5) |
C17—C16—H16A | 109.3 | N4—C36—C34 | 110.6 (4) |
O1—C16—H16B | 109.3 | C37—C36—C34 | 123.1 (5) |
C17—C16—H16B | 109.3 | C1—C37—C36 | 128.7 (5) |
H16A—C16—H16B | 108.0 | C1—C37—H37 | 115.7 |
C16—C17—H17A | 109.5 | C36—C37—H37 | 115.7 |
C7—N1—C1—C37 | −177.9 (5) | C19—C20—C21—O3 | 147.9 (4) |
C7—N1—C1—C2 | 0.6 (5) | C23—C20—C21—O3 | −96.1 (4) |
C37—C1—C2—C5 | 178.4 (5) | C19—C20—C23—O5 | 178.5 (4) |
N1—C1—C2—C5 | 0.0 (5) | C21—C20—C23—O5 | 58.0 (6) |
C37—C1—C2—C3 | −4.1 (8) | C19—C20—C23—C24 | −2.4 (4) |
N1—C1—C2—C3 | 177.5 (5) | C21—C20—C23—C24 | −122.9 (4) |
C5—C2—C3—C4 | −173.5 (7) | O5—C23—C24—C26 | 0.1 (10) |
C1—C2—C3—C4 | 9.4 (11) | C20—C23—C24—C26 | −178.9 (6) |
C3—C2—C5—C7 | −178.1 (4) | O5—C23—C24—C25 | −178.6 (5) |
C1—C2—C5—C7 | −0.5 (5) | C20—C23—C24—C25 | 2.3 (5) |
C3—C2—C5—C6 | 4.8 (8) | C28—N3—C25—C19 | −179.8 (5) |
C1—C2—C5—C6 | −177.7 (4) | C28—N3—C25—C24 | −0.9 (5) |
C1—N1—C7—C8 | 179.9 (4) | C18—C19—C25—N3 | −0.8 (9) |
C1—N1—C7—C5 | −0.9 (5) | C20—C19—C25—N3 | 178.8 (5) |
C2—C5—C7—N1 | 0.9 (5) | C18—C19—C25—C24 | −179.7 (4) |
C6—C5—C7—N1 | 178.1 (4) | C20—C19—C25—C24 | −0.1 (5) |
C2—C5—C7—C8 | −179.9 (4) | C26—C24—C25—N3 | 0.1 (5) |
C6—C5—C7—C8 | −2.7 (8) | C23—C24—C25—N3 | 179.3 (4) |
N1—C7—C8—C9 | −3.0 (8) | C26—C24—C25—C19 | 179.3 (4) |
C5—C7—C8—C9 | 178.0 (4) | C23—C24—C25—C19 | −1.5 (5) |
C18—N2—C9—C8 | −179.1 (4) | C25—C24—C26—C28 | 0.7 (5) |
C18—N2—C9—C10 | 1.7 (5) | C23—C24—C26—C28 | −178.1 (6) |
C7—C8—C9—N2 | 0.3 (8) | C25—C24—C26—C27 | −179.8 (4) |
C7—C8—C9—C10 | 179.4 (4) | C23—C24—C26—C27 | 1.5 (9) |
N2—C9—C10—C11 | 113.3 (4) | C25—N3—C28—C29 | −178.2 (4) |
C8—C9—C10—C11 | −65.9 (6) | C25—N3—C28—C26 | 1.3 (5) |
N2—C9—C10—C12 | −7.8 (5) | C24—C26—C28—C29 | 178.3 (5) |
C8—C9—C10—C12 | 173.0 (4) | C27—C26—C28—C29 | −1.3 (8) |
C9—C10—C12—C18 | 9.8 (4) | C24—C26—C28—N3 | −1.2 (5) |
C11—C10—C12—C18 | −111.7 (4) | C27—C26—C28—N3 | 179.2 (4) |
C9—C10—C12—C13 | −109.5 (4) | N3—C28—C29—C30 | 2.5 (7) |
C11—C10—C12—C13 | 129.0 (4) | C26—C28—C29—C30 | −176.9 (4) |
C18—C12—C13—C14 | 177.9 (4) | C36—N4—C30—C29 | 179.8 (4) |
C10—C12—C13—C14 | −68.7 (5) | C36—N4—C30—C31 | −0.2 (5) |
C12—C13—C14—C15 | −68.1 (5) | C28—C29—C30—N4 | −0.2 (7) |
C16—O1—C15—O2 | −1.7 (7) | C28—C29—C30—C31 | 179.8 (5) |
C16—O1—C15—C14 | 176.1 (4) | N4—C30—C31—C34 | 0.4 (6) |
C13—C14—C15—O2 | 70.4 (7) | C29—C30—C31—C34 | −179.6 (5) |
C13—C14—C15—O1 | −107.3 (5) | N4—C30—C31—C32 | −178.9 (5) |
C15—O1—C16—C17 | 81.0 (6) | C29—C30—C31—C32 | 1.1 (8) |
C9—N2—C18—C19 | −175.3 (4) | C34—C31—C32—C33 | −78.8 (7) |
C9—N2—C18—C12 | 5.7 (5) | C30—C31—C32—C33 | 100.3 (6) |
C13—C12—C18—N2 | 109.5 (4) | C30—C31—C34—C36 | −0.4 (5) |
C10—C12—C18—N2 | −10.2 (5) | C32—C31—C34—C36 | 178.8 (5) |
C13—C12—C18—C19 | −69.4 (6) | C30—C31—C34—C35 | −178.9 (5) |
C10—C12—C18—C19 | 170.9 (4) | C32—C31—C34—C35 | 0.3 (9) |
N2—C18—C19—C25 | −5.0 (7) | C31—C34—C35—O6 | 173.3 (6) |
C12—C18—C19—C25 | 173.9 (4) | C36—C34—C35—O6 | −4.9 (9) |
N2—C18—C19—C20 | 175.5 (4) | C30—N4—C36—C37 | −179.8 (5) |
C12—C18—C19—C20 | −5.6 (7) | C30—N4—C36—C34 | −0.1 (5) |
C18—C19—C20—C21 | −59.4 (6) | C31—C34—C36—N4 | 0.3 (6) |
C25—C19—C20—C21 | 121.0 (4) | C35—C34—C36—N4 | 178.8 (5) |
C18—C19—C20—C23 | −178.9 (4) | C31—C34—C36—C37 | −180.0 (5) |
C25—C19—C20—C23 | 1.5 (5) | C35—C34—C36—C37 | −1.5 (8) |
C22—O3—C21—O4 | 1.7 (7) | N1—C1—C37—C36 | −0.3 (9) |
C22—O3—C21—C20 | −177.6 (4) | C2—C1—C37—C36 | −178.4 (5) |
C19—C20—C21—O4 | −31.4 (6) | N4—C36—C37—C1 | 1.1 (9) |
C23—C20—C21—O4 | 84.6 (5) | C34—C36—C37—C1 | −178.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.88 (3) | 2.48 (9) | 2.915 (6) | 111 (7) |
N1—H1N···N4 | 0.88 (3) | 2.42 (8) | 3.033 (6) | 127 (8) |
N3—H3N···N4 | 0.88 (3) | 1.99 (4) | 2.713 (5) | 139 (5) |
Experimental details
Crystal data | |
Chemical formula | C37H38N4O6 |
Mr | 634.71 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 7.0222 (2), 30.5501 (7), 7.8539 (2) |
β (°) | 112.300 (2) |
V (Å3) | 1558.87 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.20 × 0.01 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14310, 3633, 3100 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.177, 1.17 |
No. of reflections | 3633 |
No. of parameters | 438 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.38 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.88 (3) | 2.48 (9) | 2.915 (6) | 111 (7) |
N1—H1N···N4 | 0.88 (3) | 2.42 (8) | 3.033 (6) | 127 (8) |
N3—H3N···N4 | 0.88 (3) | 1.99 (4) | 2.713 (5) | 139 (5) |
Acknowledgements
We thank the University of Malaya (grant No. PS149/2007B) for supporting this study.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fischer, M. S., Templeton, D. H., Zalkin, A. & Calvin, M. (1972). J. Am. Chem. Soc. 94, 3613–3619. CSD CrossRef CAS Web of Science Google Scholar
Senge, M. O. & Smith, K. M. (1997). Acta Cryst. C53, 1314–1318. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
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