The title compound, C
18H
21BrN
2O
6, exhibits weak intermolecular C—H
Br and C—H
O hydrogen bonds, which stabilize the structure. The title compound represents a new derivative of dehydroabietic acid.
Supporting information
CCDC reference: 283908
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.004 Å
- R factor = 0.030
- wR factor = 0.064
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B .. BR1 .. 3.03 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14A .. O5 .. 2.67 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A .. O5 .. 2.63 Ang.
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.34
From the CIF: _reflns_number_total 3438
Count of symmetry unique reflns 1980
Completeness (_total/calc) 173.64%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1458
Fraction of Friedel pairs measured 0.736
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
4 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
Methyl 12-bromo-13,14-dinitrodeisopropyldehydroabietate
top
Crystal data top
C18H21BrN2O6 | F(000) = 904 |
Mr = 441.28 | Dx = 1.556 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8056 reflections |
a = 10.215 (5) Å | θ = 3.1–25.3° |
b = 11.003 (5) Å | µ = 2.22 mm−1 |
c = 16.761 (7) Å | T = 193 K |
V = 1883.9 (14) Å3 | Block, colorless |
Z = 4 | 0.35 × 0.21 × 0.19 mm |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 3438 independent reflections |
Radiation source: fine-focus sealed tube | 3178 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.3°, θmin = 3.1° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −12→13 |
Tmin = 0.495, Tmax = 0.658 | l = −18→20 |
18829 measured reflections | |
Refinement top
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.026P)2 + 0.2102P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3438 reflections | Δρmax = 0.27 e Å−3 |
248 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Absolute structure: (Flack, 1983), 1458 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.004 (8) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.86973 (4) | 0.61704 (3) | 0.784092 (15) | 0.04822 (11) | |
O1 | 0.7154 (2) | 0.3829 (2) | 0.72328 (13) | 0.0586 (6) | |
O2 | 0.8731 (2) | 0.32048 (18) | 0.64671 (14) | 0.0574 (6) | |
O3 | 0.6745 (2) | 0.3486 (2) | 0.51612 (15) | 0.0572 (6) | |
O4 | 0.8529 (2) | 0.39271 (18) | 0.45426 (12) | 0.0490 (5) | |
O5 | 0.8105 (3) | 1.0215 (2) | 0.24200 (12) | 0.0619 (7) | |
O6 | 0.93364 (18) | 0.87737 (19) | 0.29632 (10) | 0.0395 (4) | |
N1 | 0.7968 (3) | 0.3968 (2) | 0.67042 (14) | 0.0393 (6) | |
N2 | 0.7683 (2) | 0.4129 (2) | 0.50345 (14) | 0.0338 (6) | |
C1 | 0.8094 (3) | 0.7332 (2) | 0.63862 (14) | 0.0276 (6) | |
H1A | 0.8213 | 0.8051 | 0.6692 | 0.033* | |
C2 | 0.8193 (3) | 0.6215 (3) | 0.67593 (14) | 0.0302 (6) | |
C3 | 0.7996 (3) | 0.5168 (2) | 0.63195 (16) | 0.0293 (6) | |
C4 | 0.7803 (3) | 0.5263 (2) | 0.55073 (16) | 0.0268 (6) | |
C5 | 0.7698 (2) | 0.6373 (2) | 0.51116 (14) | 0.0235 (5) | |
C6 | 0.7825 (2) | 0.7433 (2) | 0.55686 (15) | 0.0240 (6) | |
C7 | 0.7445 (3) | 0.6401 (2) | 0.42165 (14) | 0.0285 (6) | |
H7A | 0.8261 | 0.6180 | 0.3932 | 0.034* | |
H7B | 0.6774 | 0.5785 | 0.4083 | 0.034* | |
C8 | 0.6986 (3) | 0.7637 (2) | 0.39290 (14) | 0.0269 (6) | |
H8A | 0.6065 | 0.7772 | 0.4090 | 0.032* | |
H8B | 0.7037 | 0.7678 | 0.3340 | 0.032* | |
C9 | 0.7865 (2) | 0.8613 (2) | 0.42995 (13) | 0.0234 (5) | |
H9 | 0.8776 | 0.8291 | 0.4245 | 0.028* | |
C10 | 0.7625 (2) | 0.8705 (2) | 0.52153 (13) | 0.0233 (5) | |
C11 | 0.7866 (3) | 0.9829 (2) | 0.38350 (15) | 0.0302 (6) | |
C12 | 0.8833 (3) | 1.0712 (2) | 0.42432 (15) | 0.0359 (6) | |
H12A | 0.9738 | 1.0415 | 0.4159 | 0.043* | |
H12B | 0.8760 | 1.1521 | 0.3988 | 0.043* | |
C13 | 0.8585 (3) | 1.0843 (2) | 0.51363 (15) | 0.0336 (6) | |
H13A | 0.7718 | 1.1223 | 0.5222 | 0.040* | |
H13B | 0.9257 | 1.1385 | 0.5370 | 0.040* | |
C14 | 0.8624 (3) | 0.9615 (2) | 0.55595 (14) | 0.0282 (6) | |
H14A | 0.8441 | 0.9737 | 0.6134 | 0.034* | |
H14B | 0.9515 | 0.9268 | 0.5511 | 0.034* | |
C15 | 0.6222 (3) | 0.9072 (2) | 0.54703 (14) | 0.0323 (6) | |
H15A | 0.6128 | 0.8971 | 0.6048 | 0.049* | |
H15B | 0.5584 | 0.8553 | 0.5196 | 0.049* | |
H15C | 0.6064 | 0.9923 | 0.5327 | 0.049* | |
C16 | 0.8412 (3) | 0.9628 (2) | 0.29960 (15) | 0.0348 (7) | |
C17 | 0.9924 (3) | 0.8579 (3) | 0.21846 (17) | 0.0549 (9) | |
H17A | 0.9236 | 0.8402 | 0.1794 | 0.082* | |
H17B | 1.0533 | 0.7893 | 0.2212 | 0.082* | |
H17C | 1.0399 | 0.9312 | 0.2022 | 0.082* | |
C18 | 0.6511 (3) | 1.0419 (3) | 0.37398 (17) | 0.0409 (7) | |
H18A | 0.6220 | 1.0739 | 0.4256 | 0.061* | |
H18B | 0.5884 | 0.9809 | 0.3551 | 0.061* | |
H18C | 0.6565 | 1.1084 | 0.3352 | 0.061* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0817 (2) | 0.03998 (16) | 0.02296 (13) | −0.00616 (18) | −0.01090 (16) | 0.00622 (13) |
O1 | 0.0878 (16) | 0.0454 (12) | 0.0427 (12) | −0.0111 (13) | 0.0107 (13) | 0.0159 (12) |
O2 | 0.0664 (14) | 0.0289 (11) | 0.0770 (16) | 0.0097 (13) | −0.0044 (14) | 0.0092 (11) |
O3 | 0.0434 (13) | 0.0359 (13) | 0.0923 (18) | −0.0076 (11) | −0.0017 (12) | −0.0202 (12) |
O4 | 0.0720 (15) | 0.0322 (10) | 0.0429 (11) | 0.0035 (13) | 0.0174 (12) | −0.0083 (9) |
O5 | 0.0912 (18) | 0.0667 (15) | 0.0276 (11) | 0.0215 (14) | 0.0050 (12) | 0.0186 (11) |
O6 | 0.0529 (11) | 0.0410 (11) | 0.0245 (9) | 0.0079 (11) | 0.0130 (9) | 0.0016 (10) |
N1 | 0.0565 (15) | 0.0246 (13) | 0.0367 (14) | −0.0056 (13) | −0.0067 (12) | 0.0063 (11) |
N2 | 0.0420 (14) | 0.0226 (13) | 0.0369 (14) | 0.0025 (11) | −0.0073 (12) | −0.0013 (10) |
C1 | 0.0396 (15) | 0.0231 (13) | 0.0203 (13) | 0.0007 (12) | 0.0011 (12) | −0.0039 (10) |
C2 | 0.0406 (14) | 0.0303 (14) | 0.0196 (12) | −0.0017 (14) | −0.0021 (11) | 0.0020 (12) |
C3 | 0.0338 (15) | 0.0227 (13) | 0.0315 (15) | 0.0012 (12) | 0.0004 (12) | 0.0065 (11) |
C4 | 0.0306 (14) | 0.0213 (14) | 0.0286 (14) | −0.0001 (11) | −0.0002 (12) | −0.0054 (11) |
C5 | 0.0274 (12) | 0.0226 (14) | 0.0204 (12) | 0.0009 (11) | 0.0025 (10) | 0.0005 (10) |
C6 | 0.0282 (14) | 0.0236 (13) | 0.0201 (13) | 0.0000 (11) | 0.0035 (11) | −0.0006 (10) |
C7 | 0.0370 (14) | 0.0276 (15) | 0.0209 (12) | 0.0002 (13) | −0.0002 (11) | −0.0044 (11) |
C8 | 0.0350 (14) | 0.0293 (14) | 0.0163 (13) | −0.0002 (12) | −0.0015 (11) | −0.0006 (10) |
C9 | 0.0289 (13) | 0.0237 (14) | 0.0177 (12) | 0.0022 (11) | 0.0003 (10) | 0.0021 (10) |
C10 | 0.0314 (13) | 0.0201 (13) | 0.0183 (12) | 0.0033 (12) | 0.0006 (10) | 0.0000 (10) |
C11 | 0.0406 (16) | 0.0237 (13) | 0.0264 (14) | 0.0040 (12) | 0.0000 (12) | 0.0042 (11) |
C12 | 0.0522 (17) | 0.0251 (13) | 0.0304 (14) | −0.0035 (14) | 0.0035 (15) | 0.0043 (11) |
C13 | 0.0474 (16) | 0.0217 (13) | 0.0318 (14) | −0.0034 (13) | −0.0006 (14) | −0.0028 (10) |
C14 | 0.0418 (15) | 0.0217 (12) | 0.0211 (12) | −0.0008 (14) | −0.0009 (13) | −0.0025 (9) |
C15 | 0.0364 (14) | 0.0353 (15) | 0.0253 (13) | 0.0098 (14) | 0.0064 (13) | −0.0010 (11) |
C16 | 0.0468 (17) | 0.0317 (15) | 0.0259 (15) | −0.0055 (13) | −0.0008 (13) | 0.0053 (11) |
C17 | 0.068 (2) | 0.067 (2) | 0.0303 (15) | −0.0013 (18) | 0.0222 (18) | −0.0013 (18) |
C18 | 0.0490 (18) | 0.0352 (15) | 0.0384 (16) | 0.0155 (15) | −0.0034 (15) | 0.0097 (12) |
Geometric parameters (Å, º) top
Br1—C2 | 1.885 (2) | C9—C11 | 1.548 (3) |
O1—N1 | 1.225 (3) | C9—C10 | 1.558 (3) |
O2—N1 | 1.213 (3) | C9—H9 | 1.0000 |
O3—N2 | 1.210 (3) | C10—C14 | 1.542 (4) |
O4—N2 | 1.215 (3) | C10—C15 | 1.549 (4) |
O5—C16 | 1.203 (3) | C11—C16 | 1.529 (4) |
O6—C16 | 1.333 (3) | C11—C18 | 1.537 (4) |
O6—C17 | 1.452 (3) | C11—C12 | 1.546 (4) |
N1—C3 | 1.469 (3) | C12—C13 | 1.525 (3) |
N2—C4 | 1.483 (3) | C12—H12A | 0.9900 |
C1—C2 | 1.383 (4) | C12—H12B | 0.9900 |
C1—C6 | 1.402 (4) | C13—C14 | 1.526 (3) |
C1—H1A | 0.9500 | C13—H13A | 0.9900 |
C2—C3 | 1.383 (4) | C13—H13B | 0.9900 |
C3—C4 | 1.380 (4) | C14—H14A | 0.9900 |
C4—C5 | 1.394 (4) | C14—H14B | 0.9900 |
C5—C6 | 1.402 (3) | C15—H15A | 0.9800 |
C5—C7 | 1.523 (3) | C15—H15B | 0.9800 |
C6—C10 | 1.533 (4) | C15—H15C | 0.9800 |
C7—C8 | 1.517 (4) | C17—H17A | 0.9800 |
C7—H7A | 0.9900 | C17—H17B | 0.9800 |
C7—H7B | 0.9900 | C17—H17C | 0.9800 |
C8—C9 | 1.531 (3) | C18—H18A | 0.9800 |
C8—H8A | 0.9900 | C18—H18B | 0.9800 |
C8—H8B | 0.9900 | C18—H18C | 0.9800 |
| | | |
C16—O6—C17 | 115.7 (2) | C14—C10—C9 | 107.83 (19) |
O2—N1—O1 | 126.0 (3) | C15—C10—C9 | 115.7 (2) |
O2—N1—C3 | 117.7 (2) | C16—C11—C18 | 107.1 (2) |
O1—N1—C3 | 116.3 (3) | C16—C11—C12 | 105.4 (2) |
O3—N2—O4 | 125.1 (2) | C18—C11—C12 | 110.9 (2) |
O3—N2—C4 | 117.6 (2) | C16—C11—C9 | 109.7 (2) |
O4—N2—C4 | 117.2 (2) | C18—C11—C9 | 114.6 (2) |
C2—C1—C6 | 121.8 (2) | C12—C11—C9 | 108.7 (2) |
C2—C1—H1A | 119.1 | C13—C12—C11 | 112.8 (2) |
C6—C1—H1A | 119.1 | C13—C12—H12A | 109.0 |
C1—C2—C3 | 119.3 (2) | C11—C12—H12A | 109.0 |
C1—C2—Br1 | 118.6 (2) | C13—C12—H12B | 109.0 |
C3—C2—Br1 | 122.0 (2) | C11—C12—H12B | 109.0 |
C4—C3—C2 | 118.9 (2) | H12A—C12—H12B | 107.8 |
C4—C3—N1 | 119.9 (2) | C12—C13—C14 | 111.6 (2) |
C2—C3—N1 | 121.2 (2) | C12—C13—H13A | 109.3 |
C3—C4—C5 | 123.2 (2) | C14—C13—H13A | 109.3 |
C3—C4—N2 | 118.4 (2) | C12—C13—H13B | 109.3 |
C5—C4—N2 | 118.5 (2) | C14—C13—H13B | 109.3 |
C4—C5—C6 | 117.5 (2) | H13A—C13—H13B | 108.0 |
C4—C5—C7 | 120.0 (2) | C13—C14—C10 | 112.6 (2) |
C6—C5—C7 | 122.5 (2) | C13—C14—H14A | 109.1 |
C5—C6—C1 | 119.1 (2) | C10—C14—H14A | 109.1 |
C5—C6—C10 | 122.4 (2) | C13—C14—H14B | 109.1 |
C1—C6—C10 | 118.4 (2) | C10—C14—H14B | 109.1 |
C8—C7—C5 | 112.56 (19) | H14A—C14—H14B | 107.8 |
C8—C7—H7A | 109.1 | C10—C15—H15A | 109.5 |
C5—C7—H7A | 109.1 | C10—C15—H15B | 109.5 |
C8—C7—H7B | 109.1 | H15A—C15—H15B | 109.5 |
C5—C7—H7B | 109.1 | C10—C15—H15C | 109.5 |
H7A—C7—H7B | 107.8 | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 108.6 (2) | H15B—C15—H15C | 109.5 |
C7—C8—H8A | 110.0 | O5—C16—O6 | 122.0 (3) |
C9—C8—H8A | 110.0 | O5—C16—C11 | 124.4 (3) |
C7—C8—H8B | 110.0 | O6—C16—C11 | 113.5 (2) |
C9—C8—H8B | 110.0 | O6—C17—H17A | 109.5 |
H8A—C8—H8B | 108.4 | O6—C17—H17B | 109.5 |
C8—C9—C11 | 113.7 (2) | H17A—C17—H17B | 109.5 |
C8—C9—C10 | 110.64 (19) | O6—C17—H17C | 109.5 |
C11—C9—C10 | 116.1 (2) | H17A—C17—H17C | 109.5 |
C8—C9—H9 | 105.0 | H17B—C17—H17C | 109.5 |
C11—C9—H9 | 105.0 | C11—C18—H18A | 109.5 |
C10—C9—H9 | 105.0 | C11—C18—H18B | 109.5 |
C6—C10—C14 | 111.1 (2) | H18A—C18—H18B | 109.5 |
C6—C10—C15 | 104.8 (2) | C11—C18—H18C | 109.5 |
C14—C10—C15 | 109.9 (2) | H18A—C18—H18C | 109.5 |
C6—C10—C9 | 107.50 (19) | H18B—C18—H18C | 109.5 |
| | | |
C6—C1—C2—C3 | −1.3 (4) | C1—C6—C10—C14 | 41.4 (3) |
C6—C1—C2—Br1 | 174.9 (2) | C5—C6—C10—C15 | 100.3 (3) |
C1—C2—C3—C4 | 4.8 (4) | C1—C6—C10—C15 | −77.2 (3) |
Br1—C2—C3—C4 | −171.3 (2) | C5—C6—C10—C9 | −23.4 (3) |
C1—C2—C3—N1 | −174.2 (3) | C1—C6—C10—C9 | 159.2 (2) |
Br1—C2—C3—N1 | 9.8 (4) | C8—C9—C10—C6 | 55.1 (3) |
O2—N1—C3—C4 | 57.6 (4) | C11—C9—C10—C6 | −173.4 (2) |
O1—N1—C3—C4 | −121.5 (3) | C8—C9—C10—C14 | 174.9 (2) |
O2—N1—C3—C2 | −123.4 (3) | C11—C9—C10—C14 | −53.5 (3) |
O1—N1—C3—C2 | 57.5 (4) | C8—C9—C10—C15 | −61.6 (3) |
C2—C3—C4—C5 | −5.0 (4) | C11—C9—C10—C15 | 70.0 (3) |
N1—C3—C4—C5 | 174.0 (2) | C8—C9—C11—C16 | −62.6 (3) |
C2—C3—C4—N2 | 175.9 (2) | C10—C9—C11—C16 | 167.3 (2) |
N1—C3—C4—N2 | −5.1 (4) | C8—C9—C11—C18 | 57.9 (3) |
O3—N2—C4—C3 | 65.4 (3) | C10—C9—C11—C18 | −72.2 (3) |
O4—N2—C4—C3 | −115.5 (3) | C8—C9—C11—C12 | −177.4 (2) |
O3—N2—C4—C5 | −113.8 (3) | C10—C9—C11—C12 | 52.5 (3) |
O4—N2—C4—C5 | 65.4 (3) | C16—C11—C12—C13 | −169.7 (2) |
C3—C4—C5—C6 | 1.4 (4) | C18—C11—C12—C13 | 74.8 (3) |
N2—C4—C5—C6 | −179.5 (2) | C9—C11—C12—C13 | −52.1 (3) |
C3—C4—C5—C7 | −178.2 (2) | C11—C12—C13—C14 | 56.2 (3) |
N2—C4—C5—C7 | 0.9 (4) | C12—C13—C14—C10 | −57.6 (3) |
C4—C5—C6—C1 | 2.2 (4) | C6—C10—C14—C13 | 171.8 (2) |
C7—C5—C6—C1 | −178.2 (2) | C15—C10—C14—C13 | −72.8 (3) |
C4—C5—C6—C10 | −175.2 (2) | C9—C10—C14—C13 | 54.2 (3) |
C7—C5—C6—C10 | 4.4 (4) | C17—O6—C16—O5 | −1.4 (4) |
C2—C1—C6—C5 | −2.3 (4) | C17—O6—C16—C11 | −177.7 (2) |
C2—C1—C6—C10 | 175.2 (2) | C18—C11—C16—O5 | 25.6 (4) |
C4—C5—C7—C8 | 163.9 (2) | C12—C11—C16—O5 | −92.5 (3) |
C6—C5—C7—C8 | −15.7 (3) | C9—C11—C16—O5 | 150.6 (3) |
C5—C7—C8—C9 | 46.1 (3) | C18—C11—C16—O6 | −158.2 (2) |
C7—C8—C9—C11 | 158.3 (2) | C12—C11—C16—O6 | 83.7 (3) |
C7—C8—C9—C10 | −68.9 (3) | C9—C11—C16—O6 | −33.2 (3) |
C5—C6—C10—C14 | −141.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7B···Br1i | 0.99 | 3.03 | 3.832 (3) | 139 |
C14—H14A···O5ii | 0.98 | 2.67 | 3.589 (4) | 154 |
C15—H15A···O5ii | 0.98 | 2.59 | 3.430 (4) | 144 |
C1—H1A···O5ii | 0.95 | 2.63 | 3.433 (4) | 142 |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) −x+3/2, −y+2, z+1/2. |