organic compounds
2-[(8-Methoxycarbonyl-4b,8-dimethyl-4b,5,6,7,8,8a,9,10-octahydrophenanthren-3-yl)amino]-3,5-dinitrobenzoic acid ethyl acetate monosolvate
aCollege of Metallurgy and Resources, Anhui University of Technology, Maanshan 243002, People's Republic of China, and bDepartment of Chemistry and Engineering Technology, Guilin Normal College, Guilin 541001, People's Republic of China
*Correspondence e-mail: zhangyexinrudage@126.com
The title compound, C25H27N3O8·C4H8O2, has a diterpene skeleton in which the fused cyclohexane rings exhibit chair and half-chair conformations. An intramolecular C—H⋯O hydrogen bond occurs. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds are observed.
Related literature
For the synthesis of cis-deisopropyldehydroabietate derivatives, see: Fonseca et al. (2001); Baleizao et al. (2004); Feio et al. (1999). For a related structures, see: Wang et al. (2006); Hamodrakas et al. (1978). For uses of dehydroabietic acid (DAA), see: Bhatnagar (1983, 1984). For the geometry of diterpenic compounds, see: Allen et al. (1991);
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812032278/kp2429sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812032278/kp2429Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812032278/kp2429Isup3.cml
The title compound was obtained by refluxing methyl 13-amino- cis-deisopropyldehydroabietate and 2-chloro-3, 5- dinitrobenzoic acid in ethanol in the presence of copper powder and potassium carbonate to give the title compound as a yellow precipitate in 87.7% yield. Recrystallization from ethyl acetate gave orange block-like crystals suitable for an X-ray diffraction experiment. Anal.Calcd. for C29H35N3O10: C, 59.48, H, 6.02, N, 7.18%. Found:C, 58.90, H, 6.56, N, 7.00%.
H atoms were positioned geometrically and refined using a riding model (including
about the ethanol C—C bond), with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) Ueq(C).Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C25H27N3O8·C4H8O2 | F(000) = 620 |
Mr = 585.60 | Dx = 1.325 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3055 reflections |
a = 7.649 (4) Å | θ = 2.8–24.0° |
b = 13.591 (8) Å | µ = 0.10 mm−1 |
c = 14.399 (8) Å | T = 296 K |
β = 101.371 (7)° | Block, orange |
V = 1467.5 (15) Å3 | 0.47 × 0.38 × 0.12 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 5885 independent reflections |
Radiation source: fine-focus sealed tube | 4688 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→9 |
Tmin = 0.954, Tmax = 0.988 | k = −17→14 |
9128 measured reflections | l = −16→18 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.0376P] where P = (Fo2 + 2Fc2)/3 |
5885 reflections | (Δ/σ)max = 0.024 |
385 parameters | Δρmax = 0.13 e Å−3 |
1 restraint | Δρmin = −0.17 e Å−3 |
C25H27N3O8·C4H8O2 | V = 1467.5 (15) Å3 |
Mr = 585.60 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.649 (4) Å | µ = 0.10 mm−1 |
b = 13.591 (8) Å | T = 296 K |
c = 14.399 (8) Å | 0.47 × 0.38 × 0.12 mm |
β = 101.371 (7)° |
Bruker SMART CCD area-detector diffractometer | 5885 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 4688 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.988 | Rint = 0.016 |
9128 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.13 e Å−3 |
5885 reflections | Δρmin = −0.17 e Å−3 |
385 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 | ||
N1 | 0.4541 (2) | 0.20663 (15) | 1.11523 (11) | 0.0506 (4) | |
H1S | 0.4165 | 0.2369 | 1.1599 | 0.061* | |
N2 | 1.1161 (3) | 0.01668 (16) | 1.21945 (16) | 0.0627 (5) | |
N3 | 0.6957 (2) | 0.1904 (2) | 0.98090 (13) | 0.0622 (6) | |
O1 | 0.1533 (2) | −0.19460 (12) | 0.64103 (12) | 0.0619 (4) | |
O2 | 0.2245 (2) | −0.05029 (12) | 0.58598 (11) | 0.0553 (4) | |
O3 | 1.1580 (3) | −0.01462 (18) | 1.30023 (15) | 0.0869 (6) | |
O4 | 1.2085 (3) | 0.00787 (19) | 1.16010 (15) | 0.0920 (7) | |
O5 | 0.6401 (2) | 0.10646 (14) | 1.39061 (11) | 0.0631 (4) | |
H5 | 0.5829 | 0.1229 | 1.4306 | 0.095* | |
O6 | 0.4375 (2) | 0.19827 (14) | 1.29741 (10) | 0.0645 (5) | |
O7 | 0.6592 (3) | 0.27809 (18) | 0.97449 (14) | 0.0812 (6) | |
O8 | 0.7103 (3) | 0.13644 (19) | 0.91429 (12) | 0.0894 (7) | |
O1S | 0.3165 (2) | 0.24418 (17) | 0.61251 (13) | 0.0775 (5) | |
O2S | 0.4987 (2) | 0.16498 (16) | 0.53723 (12) | 0.0749 (6) | |
C1 | 0.8417 (3) | 0.08358 (16) | 1.25915 (15) | 0.0477 (5) | |
H1 | 0.8824 | 0.0633 | 1.3214 | 0.057* | |
C2 | 0.9446 (3) | 0.06669 (17) | 1.19241 (16) | 0.0493 (5) | |
C3 | 0.8917 (3) | 0.09838 (17) | 1.10043 (16) | 0.0513 (5) | |
H3 | 0.9632 | 0.0879 | 1.0561 | 0.062* | |
C4 | 0.7316 (3) | 0.14554 (17) | 1.07577 (13) | 0.0478 (5) | |
C5 | 0.6150 (3) | 0.16232 (16) | 1.13960 (13) | 0.0440 (5) | |
C6 | 0.6781 (3) | 0.13053 (16) | 1.23462 (13) | 0.0441 (4) | |
C7 | 0.5720 (3) | 0.14879 (17) | 1.30933 (14) | 0.0489 (5) | |
C8 | 0.3398 (3) | 0.20904 (16) | 1.02443 (13) | 0.0446 (5) | |
C9 | 0.2480 (3) | 0.29477 (18) | 0.99475 (16) | 0.0523 (5) | |
H9 | 0.2679 | 0.3517 | 1.0311 | 0.063* | |
C10 | 0.1267 (3) | 0.29411 (17) | 0.91050 (16) | 0.0529 (5) | |
H10 | 0.0614 | 0.3509 | 0.8917 | 0.063* | |
C11 | 0.0978 (2) | 0.21138 (16) | 0.85216 (14) | 0.0439 (5) | |
C12 | 0.1923 (2) | 0.12511 (15) | 0.88017 (13) | 0.0396 (4) | |
C13 | 0.3113 (3) | 0.12563 (16) | 0.96844 (13) | 0.0437 (4) | |
H13 | 0.3724 | 0.0682 | 0.9896 | 0.052* | |
C14 | −0.0350 (3) | 0.21756 (17) | 0.76050 (15) | 0.0514 (5) | |
H14A | 0.0206 | 0.2489 | 0.7132 | 0.062* | |
H14B | −0.1345 | 0.2583 | 0.7695 | 0.062* | |
C15 | −0.1040 (3) | 0.11764 (17) | 0.72472 (15) | 0.0480 (5) | |
H15A | −0.1768 | 0.1243 | 0.6618 | 0.058* | |
H15B | −0.1785 | 0.0911 | 0.7660 | 0.058* | |
C16 | 0.0500 (2) | 0.04646 (15) | 0.72138 (13) | 0.0393 (4) | |
H16 | 0.1279 | 0.0787 | 0.6842 | 0.047* | |
C17 | 0.1646 (3) | 0.02907 (14) | 0.82312 (13) | 0.0402 (4) | |
C18 | 0.0684 (3) | −0.04380 (18) | 0.87898 (15) | 0.0540 (5) | |
H18A | 0.1465 | −0.0589 | 0.9389 | 0.065* | |
H18B | −0.0375 | −0.0124 | 0.8927 | 0.065* | |
C19 | 0.0150 (4) | −0.13884 (19) | 0.82600 (18) | 0.0622 (6) | |
H19A | −0.0472 | −0.1808 | 0.8633 | 0.075* | |
H19B | 0.1209 | −0.1733 | 0.8162 | 0.075* | |
C20 | −0.1057 (3) | −0.11764 (19) | 0.73048 (18) | 0.0584 (6) | |
H20A | −0.2146 | −0.0869 | 0.7409 | 0.070* | |
H20B | −0.1377 | −0.1793 | 0.6976 | 0.070* | |
C21 | −0.0177 (3) | −0.05074 (16) | 0.66828 (14) | 0.0444 (4) | |
C22 | −0.1505 (3) | −0.0292 (2) | 0.57444 (17) | 0.0612 (6) | |
H22A | −0.1035 | 0.0220 | 0.5405 | 0.092* | |
H22B | −0.2626 | −0.0086 | 0.5883 | 0.092* | |
H22C | −0.1677 | −0.0878 | 0.5364 | 0.092* | |
C23 | 0.1299 (3) | −0.10728 (17) | 0.63367 (14) | 0.0460 (5) | |
C24 | 0.3485 (3) | −0.01273 (18) | 0.81485 (15) | 0.0499 (5) | |
H24A | 0.4068 | 0.0322 | 0.7794 | 0.075* | |
H24B | 0.3330 | −0.0751 | 0.7829 | 0.075* | |
H24C | 0.4200 | −0.0213 | 0.8770 | 0.075* | |
C25 | 0.3532 (4) | −0.1005 (2) | 0.5418 (2) | 0.0760 (8) | |
H25A | 0.4443 | −0.1289 | 0.5897 | 0.114* | |
H25B | 0.4062 | −0.0545 | 0.5050 | 0.114* | |
H25C | 0.2946 | −0.1517 | 0.5012 | 0.114* | |
C1S | 0.4227 (5) | 0.3569 (3) | 0.7347 (3) | 0.1153 (14) | |
H1S1 | 0.4138 | 0.4133 | 0.6939 | 0.173* | |
H1S2 | 0.5131 | 0.3683 | 0.7901 | 0.173* | |
H1S3 | 0.3103 | 0.3460 | 0.7531 | 0.173* | |
C2S | 0.4685 (4) | 0.2728 (3) | 0.6858 (2) | 0.1023 (12) | |
H2S1 | 0.5012 | 0.2190 | 0.7300 | 0.123* | |
H2S2 | 0.5701 | 0.2878 | 0.6572 | 0.123* | |
C3S | 0.3494 (3) | 0.19013 (19) | 0.54227 (16) | 0.0568 (6) | |
C4S | 0.1866 (4) | 0.1646 (2) | 0.47246 (19) | 0.0685 (7) | |
H4S1 | 0.1995 | 0.1859 | 0.4106 | 0.103* | |
H4S2 | 0.0855 | 0.1966 | 0.4894 | 0.103* | |
H4S3 | 0.1693 | 0.0946 | 0.4721 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0465 (9) | 0.0698 (13) | 0.0344 (8) | 0.0096 (9) | 0.0056 (7) | −0.0083 (8) |
N2 | 0.0529 (11) | 0.0655 (14) | 0.0658 (14) | 0.0085 (9) | 0.0023 (10) | −0.0114 (10) |
N3 | 0.0460 (10) | 0.0995 (19) | 0.0428 (10) | −0.0062 (11) | 0.0133 (8) | −0.0005 (11) |
O1 | 0.0686 (10) | 0.0477 (10) | 0.0715 (11) | 0.0040 (8) | 0.0189 (9) | −0.0004 (8) |
O2 | 0.0591 (9) | 0.0528 (9) | 0.0593 (9) | 0.0054 (7) | 0.0249 (7) | 0.0035 (7) |
O3 | 0.0812 (13) | 0.1000 (15) | 0.0742 (13) | 0.0356 (11) | 0.0025 (10) | 0.0020 (11) |
O4 | 0.0618 (11) | 0.129 (2) | 0.0892 (14) | 0.0323 (11) | 0.0234 (11) | −0.0025 (12) |
O5 | 0.0734 (11) | 0.0769 (12) | 0.0417 (8) | 0.0163 (9) | 0.0178 (8) | 0.0080 (8) |
O6 | 0.0606 (9) | 0.0897 (13) | 0.0448 (8) | 0.0209 (9) | 0.0144 (7) | −0.0002 (8) |
O7 | 0.0831 (13) | 0.0916 (17) | 0.0666 (12) | −0.0033 (11) | 0.0091 (10) | 0.0213 (11) |
O8 | 0.0761 (12) | 0.154 (2) | 0.0423 (9) | 0.0142 (13) | 0.0212 (8) | −0.0121 (11) |
O1S | 0.0567 (10) | 0.1045 (15) | 0.0693 (11) | 0.0140 (10) | 0.0071 (9) | −0.0255 (10) |
O2S | 0.0632 (10) | 0.1121 (17) | 0.0497 (9) | 0.0202 (10) | 0.0117 (8) | −0.0045 (9) |
C1 | 0.0501 (12) | 0.0453 (12) | 0.0436 (11) | −0.0005 (9) | −0.0007 (9) | −0.0074 (9) |
C2 | 0.0429 (11) | 0.0503 (13) | 0.0528 (13) | 0.0018 (9) | 0.0051 (9) | −0.0129 (9) |
C3 | 0.0452 (11) | 0.0621 (14) | 0.0476 (12) | −0.0033 (10) | 0.0115 (9) | −0.0154 (10) |
C4 | 0.0440 (11) | 0.0609 (14) | 0.0374 (10) | −0.0035 (9) | 0.0054 (8) | −0.0080 (9) |
C5 | 0.0428 (10) | 0.0505 (12) | 0.0376 (10) | −0.0016 (9) | 0.0058 (8) | −0.0083 (8) |
C6 | 0.0459 (10) | 0.0475 (12) | 0.0377 (10) | −0.0017 (9) | 0.0057 (8) | −0.0073 (9) |
C7 | 0.0529 (12) | 0.0546 (14) | 0.0384 (11) | 0.0010 (10) | 0.0070 (9) | −0.0061 (9) |
C8 | 0.0405 (10) | 0.0557 (13) | 0.0374 (10) | 0.0030 (9) | 0.0072 (8) | −0.0016 (9) |
C9 | 0.0539 (12) | 0.0534 (14) | 0.0484 (12) | 0.0042 (10) | 0.0075 (10) | −0.0078 (10) |
C10 | 0.0536 (12) | 0.0484 (13) | 0.0542 (13) | 0.0127 (10) | 0.0048 (10) | 0.0010 (10) |
C11 | 0.0396 (10) | 0.0485 (12) | 0.0420 (11) | 0.0067 (9) | 0.0043 (8) | 0.0024 (9) |
C12 | 0.0366 (9) | 0.0459 (11) | 0.0363 (9) | 0.0033 (8) | 0.0072 (7) | 0.0033 (8) |
C13 | 0.0413 (10) | 0.0502 (12) | 0.0387 (10) | 0.0084 (9) | 0.0059 (8) | 0.0029 (9) |
C14 | 0.0490 (12) | 0.0506 (13) | 0.0505 (12) | 0.0127 (10) | −0.0005 (9) | 0.0036 (10) |
C15 | 0.0405 (10) | 0.0548 (13) | 0.0454 (11) | 0.0089 (9) | 0.0007 (9) | 0.0001 (10) |
C16 | 0.0345 (9) | 0.0438 (11) | 0.0392 (10) | 0.0012 (8) | 0.0060 (8) | 0.0031 (8) |
C17 | 0.0411 (10) | 0.0419 (11) | 0.0364 (10) | 0.0053 (8) | 0.0048 (8) | 0.0016 (8) |
C18 | 0.0690 (14) | 0.0514 (13) | 0.0444 (11) | 0.0034 (11) | 0.0177 (10) | 0.0085 (10) |
C19 | 0.0843 (17) | 0.0474 (14) | 0.0618 (15) | −0.0087 (12) | 0.0312 (13) | 0.0079 (11) |
C20 | 0.0551 (13) | 0.0555 (15) | 0.0683 (16) | −0.0136 (11) | 0.0211 (12) | −0.0086 (11) |
C21 | 0.0388 (10) | 0.0475 (12) | 0.0456 (11) | −0.0003 (9) | 0.0055 (8) | −0.0004 (9) |
C22 | 0.0495 (13) | 0.0671 (16) | 0.0598 (14) | 0.0015 (11) | −0.0069 (10) | −0.0117 (12) |
C23 | 0.0441 (11) | 0.0488 (13) | 0.0430 (11) | −0.0010 (9) | 0.0033 (9) | −0.0014 (9) |
C24 | 0.0423 (11) | 0.0553 (13) | 0.0485 (12) | 0.0117 (9) | 0.0004 (9) | −0.0027 (10) |
C25 | 0.0725 (17) | 0.0785 (19) | 0.088 (2) | 0.0140 (14) | 0.0429 (16) | 0.0006 (14) |
C1S | 0.100 (3) | 0.107 (3) | 0.142 (3) | −0.026 (2) | 0.031 (2) | −0.049 (3) |
C2S | 0.077 (2) | 0.136 (3) | 0.083 (2) | 0.019 (2) | −0.0077 (17) | −0.041 (2) |
C3S | 0.0628 (14) | 0.0618 (15) | 0.0457 (12) | 0.0060 (12) | 0.0103 (10) | 0.0077 (11) |
C4S | 0.0693 (16) | 0.0697 (17) | 0.0609 (15) | −0.0036 (12) | −0.0010 (12) | 0.0105 (12) |
N1—C5 | 1.353 (3) | C14—H14B | 0.9700 |
N1—C8 | 1.423 (3) | C15—C16 | 1.532 (3) |
N1—H1S | 0.8600 | C15—H15A | 0.9700 |
N2—O4 | 1.217 (3) | C15—H15B | 0.9700 |
N2—O3 | 1.221 (3) | C16—C21 | 1.562 (3) |
N2—C2 | 1.461 (3) | C16—C17 | 1.570 (3) |
N3—O7 | 1.223 (3) | C16—H16 | 0.9800 |
N3—O8 | 1.230 (3) | C17—C24 | 1.543 (3) |
N3—C4 | 1.472 (3) | C17—C18 | 1.550 (3) |
O1—C23 | 1.202 (3) | C18—C19 | 1.515 (4) |
O2—C23 | 1.338 (3) | C18—H18A | 0.9700 |
O2—C25 | 1.445 (3) | C18—H18B | 0.9700 |
O5—C7 | 1.316 (3) | C19—C20 | 1.525 (4) |
O5—H5 | 0.8200 | C19—H19A | 0.9700 |
O6—C7 | 1.213 (3) | C19—H19B | 0.9700 |
O1S—C3S | 1.314 (3) | C20—C21 | 1.523 (3) |
O1S—C2S | 1.461 (4) | C20—H20A | 0.9700 |
O2S—C3S | 1.209 (3) | C20—H20B | 0.9700 |
C1—C2 | 1.376 (3) | C21—C23 | 1.528 (3) |
C1—C6 | 1.387 (3) | C21—C22 | 1.550 (3) |
C1—H1 | 0.9300 | C22—H22A | 0.9600 |
C2—C3 | 1.376 (3) | C22—H22B | 0.9600 |
C3—C4 | 1.365 (3) | C22—H22C | 0.9600 |
C3—H3 | 0.9300 | C24—H24A | 0.9600 |
C4—C5 | 1.420 (3) | C24—H24B | 0.9600 |
C5—C6 | 1.425 (3) | C24—H24C | 0.9600 |
C6—C7 | 1.491 (3) | C25—H25A | 0.9600 |
C8—C13 | 1.383 (3) | C25—H25B | 0.9600 |
C8—C9 | 1.384 (3) | C25—H25C | 0.9600 |
C9—C10 | 1.374 (3) | C1S—C2S | 1.422 (5) |
C9—H9 | 0.9300 | C1S—H1S1 | 0.9600 |
C10—C11 | 1.395 (3) | C1S—H1S2 | 0.9600 |
C10—H10 | 0.9300 | C1S—H1S3 | 0.9600 |
C11—C12 | 1.394 (3) | C2S—H2S1 | 0.9700 |
C11—C14 | 1.501 (3) | C2S—H2S2 | 0.9700 |
C12—C13 | 1.410 (3) | C3S—C4S | 1.479 (4) |
C12—C17 | 1.534 (3) | C4S—H4S1 | 0.9600 |
C13—H13 | 0.9300 | C4S—H4S2 | 0.9600 |
C14—C15 | 1.510 (3) | C4S—H4S3 | 0.9600 |
C14—H14A | 0.9700 | ||
C5—N1—C8 | 127.69 (16) | C24—C17—C18 | 109.75 (18) |
C5—N1—H1S | 116.2 | C12—C17—C16 | 111.36 (16) |
C8—N1—H1S | 116.2 | C24—C17—C16 | 109.47 (15) |
O4—N2—O3 | 123.7 (2) | C18—C17—C16 | 110.21 (17) |
O4—N2—C2 | 118.3 (2) | C19—C18—C17 | 113.07 (18) |
O3—N2—C2 | 118.0 (2) | C19—C18—H18A | 109.0 |
O7—N3—O8 | 125.2 (2) | C17—C18—H18A | 109.0 |
O7—N3—C4 | 118.2 (2) | C19—C18—H18B | 109.0 |
O8—N3—C4 | 116.6 (3) | C17—C18—H18B | 109.0 |
C23—O2—C25 | 115.90 (19) | H18A—C18—H18B | 107.8 |
C7—O5—H5 | 109.5 | C18—C19—C20 | 110.4 (2) |
C3S—O1S—C2S | 117.3 (2) | C18—C19—H19A | 109.6 |
C2—C1—C6 | 120.7 (2) | C20—C19—H19A | 109.6 |
C2—C1—H1 | 119.7 | C18—C19—H19B | 109.6 |
C6—C1—H1 | 119.7 | C20—C19—H19B | 109.6 |
C1—C2—C3 | 121.4 (2) | H19A—C19—H19B | 108.1 |
C1—C2—N2 | 119.9 (2) | C19—C20—C21 | 112.58 (18) |
C3—C2—N2 | 118.7 (2) | C19—C20—H20A | 109.1 |
C4—C3—C2 | 118.41 (19) | C21—C20—H20A | 109.1 |
C4—C3—H3 | 120.8 | C19—C20—H20B | 109.1 |
C2—C3—H3 | 120.8 | C21—C20—H20B | 109.1 |
C3—C4—C5 | 123.6 (2) | H20A—C20—H20B | 107.8 |
C3—C4—N3 | 115.45 (18) | C20—C21—C23 | 109.39 (18) |
C5—C4—N3 | 120.53 (19) | C20—C21—C22 | 109.59 (19) |
N1—C5—C4 | 124.00 (18) | C23—C21—C22 | 102.13 (17) |
N1—C5—C6 | 120.19 (17) | C20—C21—C16 | 111.04 (17) |
C4—C5—C6 | 115.80 (19) | C23—C21—C16 | 112.97 (16) |
C1—C6—C5 | 120.14 (18) | C22—C21—C16 | 111.35 (18) |
C1—C6—C7 | 119.03 (19) | C21—C22—H22A | 109.5 |
C5—C6—C7 | 120.83 (19) | C21—C22—H22B | 109.5 |
O6—C7—O5 | 122.96 (19) | H22A—C22—H22B | 109.5 |
O6—C7—C6 | 123.90 (19) | C21—C22—H22C | 109.5 |
O5—C7—C6 | 113.13 (19) | H22A—C22—H22C | 109.5 |
C13—C8—C9 | 119.86 (18) | H22B—C22—H22C | 109.5 |
C13—C8—N1 | 120.96 (18) | O1—C23—O2 | 122.0 (2) |
C9—C8—N1 | 119.06 (19) | O1—C23—C21 | 125.1 (2) |
C10—C9—C8 | 118.7 (2) | O2—C23—C21 | 112.64 (19) |
C10—C9—H9 | 120.6 | C17—C24—H24A | 109.5 |
C8—C9—H9 | 120.6 | C17—C24—H24B | 109.5 |
C9—C10—C11 | 122.41 (19) | H24A—C24—H24B | 109.5 |
C9—C10—H10 | 118.8 | C17—C24—H24C | 109.5 |
C11—C10—H10 | 118.8 | H24A—C24—H24C | 109.5 |
C12—C11—C10 | 119.49 (18) | H24B—C24—H24C | 109.5 |
C12—C11—C14 | 121.58 (18) | O2—C25—H25A | 109.5 |
C10—C11—C14 | 118.94 (18) | O2—C25—H25B | 109.5 |
C11—C12—C13 | 117.52 (18) | H25A—C25—H25B | 109.5 |
C11—C12—C17 | 123.47 (16) | O2—C25—H25C | 109.5 |
C13—C12—C17 | 118.90 (16) | H25A—C25—H25C | 109.5 |
C8—C13—C12 | 121.94 (18) | H25B—C25—H25C | 109.5 |
C8—C13—H13 | 119.0 | C2S—C1S—H1S1 | 109.5 |
C12—C13—H13 | 119.0 | C2S—C1S—H1S2 | 109.5 |
C11—C14—C15 | 112.35 (17) | H1S1—C1S—H1S2 | 109.5 |
C11—C14—H14A | 109.1 | C2S—C1S—H1S3 | 109.5 |
C15—C14—H14A | 109.1 | H1S1—C1S—H1S3 | 109.5 |
C11—C14—H14B | 109.1 | H1S2—C1S—H1S3 | 109.5 |
C15—C14—H14B | 109.1 | C1S—C2S—O1S | 109.5 (3) |
H14A—C14—H14B | 107.9 | C1S—C2S—H2S1 | 109.8 |
C14—C15—C16 | 111.05 (18) | O1S—C2S—H2S1 | 109.8 |
C14—C15—H15A | 109.4 | C1S—C2S—H2S2 | 109.8 |
C16—C15—H15A | 109.4 | O1S—C2S—H2S2 | 109.8 |
C14—C15—H15B | 109.4 | H2S1—C2S—H2S2 | 108.2 |
C16—C15—H15B | 109.4 | O2S—C3S—O1S | 122.1 (2) |
H15A—C15—H15B | 108.0 | O2S—C3S—C4S | 124.9 (2) |
C15—C16—C21 | 111.52 (17) | O1S—C3S—C4S | 113.0 (2) |
C15—C16—C17 | 110.93 (16) | C3S—C4S—H4S1 | 109.5 |
C21—C16—C17 | 113.55 (16) | C3S—C4S—H4S2 | 109.5 |
C15—C16—H16 | 106.8 | H4S1—C4S—H4S2 | 109.5 |
C21—C16—H16 | 106.8 | C3S—C4S—H4S3 | 109.5 |
C17—C16—H16 | 106.8 | H4S1—C4S—H4S3 | 109.5 |
C12—C17—C24 | 108.83 (16) | H4S2—C4S—H4S3 | 109.5 |
C12—C17—C18 | 107.17 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1S···O6 | 0.86 | 2.02 | 2.654 (3) | 129 |
O5—H5···O2Si | 0.82 | 1.87 | 2.676 (3) | 168 |
C4S—H4S3···O2 | 0.96 | 2.54 | 3.332 (4) | 139 |
C15—H15B···O8 | 0.97 | 2.53 | 3.326 (4) | 140 |
Symmetry code: (i) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H27N3O8·C4H8O2 |
Mr | 585.60 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 296 |
a, b, c (Å) | 7.649 (4), 13.591 (8), 14.399 (8) |
β (°) | 101.371 (7) |
V (Å3) | 1467.5 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.47 × 0.38 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.954, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9128, 5885, 4688 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.107, 1.03 |
No. of reflections | 5885 |
No. of parameters | 385 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.17 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1S···O6 | 0.86 | 2.02 | 2.654 (3) | 129 |
O5—H5···O2Si | 0.82 | 1.87 | 2.676 (3) | 168 |
C4S—H4S3···O2 | 0.96 | 2.54 | 3.332 (4) | 139 |
C15—H15B···O8 | 0.97 | 2.53 | 3.326 (4) | 140 |
Symmetry code: (i) x, y, z+1. |
Acknowledgements
The authors thank the National Natural Science Foundation of China (No. 50903001) and the Guangxi Department of Education research project (200911MS281, 200911MS282) for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Dehydroabietic acid (DAA) is one of the isomerides in the renewable rosin. It is widely used in the fields such as paint, adhesives, printing ink (Bhatnagar, 1983), papermaking, and rubber food (Bhatnagar, 1983). Like some natural drug, it has an aromatic diterpene structure with three rings. It also has three sterogenic centres but their absolute configuration cannot be determined by this analysis. The compound comprises a reactive carboxy group and DAA molecule might be modified to obtain some multifunctional derivatives which can be used as high added value products like novel fluorescence derivatization reagents and efficient but low toxic medicines through constructing aromatic or heteroaromatic ring on DAA' s skeleton. Methyl cis-deisopropyldehydroabietate can be easily synthesized from DAA (Fonseca et al., 2001). It provides a convenient starting material for the construction of other derivatives. Some of these derivatives lacking the isopropyl group are also antimicrobial agents (Feio et al., 1999). The molecular structure of the title compound (I) (Fig. 1), as typical of diterpenic compounds (Allen et al., 1991), shows a trans junction of rings A (defined by C16, C17, C18, C19, C20, C21) and B (defined by C11, C12, C17, C16, C15, C14) with two methyl groups in axial positions of the six membered rings. The torsion angles show a chair and a half-chair conformation for rings A and B, respectively. The overall geometry of (I) is comparable to that found for methyl dehydroabietate (Hamodrakas et al., 1978), apart from the substituted 2,4,6 - trinitrophenylamino and methylgroups at the benzene ring.