In the title compound, C
16H
18N
2O
4, the cyclohexene ring adopts a half-chair conformation. In the solid state, intermolecular O—H
N hydrogen bonds link the molecules into dimers. The crystal packing is further stabilized by N—H
O and O—H
O hydrogen bonds and weak C—H
O interactions.
Supporting information
CCDC reference: 298420
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C)= 0.002 Å
- R factor = 0.042
- wR factor = 0.113
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
No errors found in this datablock
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64.05; Farrugia, 1999); software used to prepare material for publication: SHELXL97.
3,t-6-Dihydroxy-t-5-methoxycarbonyl-c-6-methyl-r-4-phenyl-4,5,6,7-tetrahydro-
1
H-indazole
top
Crystal data top
C16H18N2O4 | F(000) = 1280 |
Mr = 302.32 | Dx = 1.342 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9647 reflections |
a = 9.3871 (4) Å | θ = 2.7–27.7° |
b = 14.7295 (6) Å | µ = 0.10 mm−1 |
c = 21.6478 (9) Å | T = 273 K |
V = 2993.2 (2) Å3 | Block, colourless |
Z = 8 | 0.19 × 0.11 × 0.09 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2370 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −11→11 |
26831 measured reflections | k = −17→17 |
2632 independent reflections | l = −25→25 |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0535P)2 + 1.343P] where P = (Fo2 + 2Fc2)/3 |
2632 reflections | (Δ/σ)max < 0.001 |
207 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
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 | |
O31 | 0.33404 (12) | −0.06600 (7) | 0.02235 (6) | 0.0440 (3) | |
H31 | 0.4173 | −0.0720 | 0.0116 | 0.066* | |
O61 | −0.10175 (12) | 0.16306 (8) | 0.03369 (5) | 0.0411 (3) | |
H61 | −0.1707 | 0.1296 | 0.0384 | 0.062* | |
O52 | −0.24705 (14) | 0.03714 (9) | 0.12300 (6) | 0.0532 (3) | |
N1 | 0.32774 (15) | 0.16630 (9) | 0.02600 (7) | 0.0408 (4) | |
H1 | 0.360 (2) | 0.2149 (13) | 0.0144 (8) | 0.042 (5)* | |
N2 | 0.39289 (15) | 0.08665 (9) | 0.00967 (7) | 0.0416 (4) | |
O51 | −0.16175 (18) | 0.06279 (12) | 0.21727 (7) | 0.0743 (5) | |
C3 | 0.30506 (17) | 0.02246 (10) | 0.03013 (7) | 0.0350 (4) | |
C6 | −0.03822 (18) | 0.18171 (10) | 0.09247 (7) | 0.0375 (4) | |
C8 | 0.20413 (16) | 0.15156 (10) | 0.05454 (7) | 0.0344 (4) | |
C13 | 0.09209 (19) | −0.06561 (11) | 0.12926 (7) | 0.0388 (4) | |
C4 | 0.05699 (17) | 0.01710 (10) | 0.09024 (7) | 0.0332 (4) | |
H4 | −0.0109 | −0.0011 | 0.0582 | 0.040* | |
C7 | 0.10587 (17) | 0.22332 (10) | 0.07691 (8) | 0.0396 (4) | |
H7A | 0.0942 | 0.2694 | 0.0453 | 0.048* | |
H7B | 0.1456 | 0.2521 | 0.1134 | 0.048* | |
C5 | −0.01268 (18) | 0.09291 (10) | 0.13008 (7) | 0.0371 (4) | |
H5 | 0.0563 | 0.1081 | 0.1624 | 0.045* | |
C9 | 0.18474 (16) | 0.05924 (10) | 0.05933 (7) | 0.0325 (4) | |
C10 | −0.1459 (2) | 0.06217 (11) | 0.16270 (8) | 0.0441 (4) | |
C14 | 0.1993 (2) | −0.06334 (13) | 0.17275 (8) | 0.0554 (5) | |
H14 | 0.2523 | −0.0106 | 0.1781 | 0.066* | |
C18 | 0.0143 (2) | −0.14464 (12) | 0.12230 (10) | 0.0561 (5) | |
H18 | −0.0587 | −0.1472 | 0.0933 | 0.067* | |
C12 | −0.1275 (2) | 0.24986 (13) | 0.12836 (10) | 0.0568 (5) | |
H12A | −0.1314 | 0.3061 | 0.1060 | 0.085* | |
H12B | −0.0851 | 0.2601 | 0.1681 | 0.085* | |
H12C | −0.2221 | 0.2265 | 0.1336 | 0.085* | |
C15 | 0.2289 (3) | −0.13924 (16) | 0.20871 (9) | 0.0742 (7) | |
H15 | 0.3013 | −0.1371 | 0.2380 | 0.089* | |
C17 | 0.0444 (3) | −0.21982 (14) | 0.15820 (13) | 0.0765 (7) | |
H17 | −0.0086 | −0.2726 | 0.1531 | 0.092* | |
C16 | 0.1511 (3) | −0.21734 (15) | 0.20099 (11) | 0.0783 (8) | |
H16 | 0.1710 | −0.2683 | 0.2248 | 0.094* | |
C11 | −0.3832 (2) | 0.01134 (16) | 0.14978 (12) | 0.0667 (6) | |
H11A | −0.3702 | −0.0402 | 0.1763 | 0.100* | |
H11B | −0.4487 | −0.0040 | 0.1174 | 0.100* | |
H11C | −0.4207 | 0.0612 | 0.1733 | 0.100* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O31 | 0.0356 (6) | 0.0256 (6) | 0.0708 (8) | −0.0005 (5) | 0.0094 (6) | 0.0015 (5) |
O61 | 0.0395 (6) | 0.0341 (6) | 0.0497 (7) | −0.0036 (5) | −0.0043 (5) | 0.0085 (5) |
O52 | 0.0424 (7) | 0.0634 (8) | 0.0539 (8) | −0.0061 (6) | 0.0058 (6) | 0.0072 (6) |
N1 | 0.0400 (8) | 0.0237 (7) | 0.0587 (9) | −0.0038 (6) | 0.0080 (7) | 0.0060 (6) |
N2 | 0.0377 (8) | 0.0274 (7) | 0.0596 (9) | 0.0002 (6) | 0.0081 (7) | 0.0039 (6) |
O51 | 0.0845 (11) | 0.0935 (12) | 0.0450 (8) | −0.0235 (9) | 0.0187 (8) | 0.0017 (7) |
C3 | 0.0351 (8) | 0.0259 (8) | 0.0439 (9) | −0.0014 (6) | 0.0005 (7) | 0.0032 (6) |
C6 | 0.0411 (9) | 0.0307 (8) | 0.0408 (9) | 0.0022 (7) | 0.0032 (7) | 0.0012 (7) |
C8 | 0.0347 (8) | 0.0286 (8) | 0.0399 (8) | −0.0022 (6) | −0.0016 (7) | 0.0031 (6) |
C13 | 0.0478 (9) | 0.0299 (8) | 0.0386 (9) | 0.0022 (7) | 0.0093 (7) | 0.0032 (6) |
C4 | 0.0360 (8) | 0.0292 (8) | 0.0344 (8) | −0.0032 (6) | 0.0007 (7) | 0.0030 (6) |
C7 | 0.0440 (9) | 0.0265 (8) | 0.0484 (9) | −0.0025 (7) | −0.0008 (8) | −0.0009 (7) |
C5 | 0.0422 (9) | 0.0326 (8) | 0.0366 (8) | 0.0004 (7) | 0.0024 (7) | 0.0019 (6) |
C9 | 0.0349 (8) | 0.0265 (8) | 0.0362 (8) | −0.0027 (6) | −0.0016 (6) | 0.0029 (6) |
C10 | 0.0527 (10) | 0.0348 (9) | 0.0449 (10) | 0.0015 (8) | 0.0082 (8) | 0.0038 (7) |
C14 | 0.0790 (14) | 0.0422 (10) | 0.0450 (10) | 0.0092 (10) | −0.0074 (10) | 0.0017 (8) |
C18 | 0.0600 (12) | 0.0357 (9) | 0.0728 (13) | −0.0059 (9) | 0.0145 (10) | 0.0064 (9) |
C12 | 0.0645 (12) | 0.0393 (10) | 0.0666 (13) | 0.0105 (9) | 0.0202 (10) | 0.0019 (9) |
C15 | 0.114 (2) | 0.0662 (15) | 0.0426 (11) | 0.0352 (14) | −0.0032 (12) | 0.0084 (10) |
C17 | 0.0964 (18) | 0.0357 (11) | 0.0975 (18) | −0.0013 (11) | 0.0368 (16) | 0.0186 (11) |
C16 | 0.128 (2) | 0.0465 (13) | 0.0600 (14) | 0.0312 (14) | 0.0363 (15) | 0.0243 (10) |
C11 | 0.0471 (12) | 0.0663 (14) | 0.0868 (16) | −0.0071 (10) | 0.0125 (11) | 0.0084 (12) |
Geometric parameters (Å, º) top
O31—C3 | 1.3417 (18) | C4—C5 | 1.555 (2) |
O31—H31 | 0.8200 | C4—H4 | 0.9800 |
O61—C6 | 1.4319 (19) | C7—H7A | 0.9700 |
O61—H61 | 0.8200 | C7—H7B | 0.9700 |
O52—C10 | 1.333 (2) | C5—C10 | 1.506 (2) |
O52—C11 | 1.454 (2) | C5—H5 | 0.9800 |
N1—C8 | 1.332 (2) | C14—C15 | 1.390 (3) |
N1—N2 | 1.3694 (19) | C14—H14 | 0.9300 |
N1—H1 | 0.82 (2) | C18—C17 | 1.382 (3) |
N2—C3 | 1.330 (2) | C18—H18 | 0.9300 |
O51—C10 | 1.191 (2) | C12—H12A | 0.9600 |
C3—C9 | 1.403 (2) | C12—H12B | 0.9600 |
C6—C12 | 1.521 (2) | C12—H12C | 0.9600 |
C6—C7 | 1.523 (2) | C15—C16 | 1.373 (4) |
C6—C5 | 1.559 (2) | C15—H15 | 0.9300 |
C8—C9 | 1.376 (2) | C17—C16 | 1.364 (4) |
C8—C7 | 1.484 (2) | C17—H17 | 0.9300 |
C13—C14 | 1.379 (3) | C16—H16 | 0.9300 |
C13—C18 | 1.382 (2) | C11—H11A | 0.9600 |
C13—C4 | 1.519 (2) | C11—H11B | 0.9600 |
C4—C9 | 1.507 (2) | C11—H11C | 0.9600 |
| | | |
C3—O31—H31 | 109.5 | C10—C5—H5 | 106.4 |
C6—O61—H61 | 109.5 | C4—C5—H5 | 106.4 |
C10—O52—C11 | 116.22 (15) | C6—C5—H5 | 106.4 |
C8—N1—N2 | 111.65 (13) | C8—C9—C3 | 103.95 (13) |
C8—N1—H1 | 127.5 (13) | C8—C9—C4 | 123.08 (14) |
N2—N1—H1 | 120.4 (13) | C3—C9—C4 | 132.96 (14) |
C3—N2—N1 | 104.26 (13) | O51—C10—O52 | 123.55 (18) |
N2—C3—O31 | 121.52 (14) | O51—C10—C5 | 124.54 (18) |
N2—C3—C9 | 111.98 (14) | O52—C10—C5 | 111.87 (14) |
O31—C3—C9 | 126.50 (14) | C13—C14—C15 | 120.6 (2) |
O61—C6—C12 | 110.56 (14) | C13—C14—H14 | 119.7 |
O61—C6—C7 | 104.52 (13) | C15—C14—H14 | 119.7 |
C12—C6—C7 | 109.67 (14) | C17—C18—C13 | 120.4 (2) |
O61—C6—C5 | 111.54 (12) | C17—C18—H18 | 119.8 |
C12—C6—C5 | 111.81 (13) | C13—C18—H18 | 119.8 |
C7—C6—C5 | 108.45 (13) | C6—C12—H12A | 109.5 |
N1—C8—C9 | 108.13 (14) | C6—C12—H12B | 109.5 |
N1—C8—C7 | 125.21 (14) | H12A—C12—H12B | 109.5 |
C9—C8—C7 | 126.66 (14) | C6—C12—H12C | 109.5 |
C14—C13—C18 | 118.71 (17) | H12A—C12—H12C | 109.5 |
C14—C13—C4 | 121.26 (15) | H12B—C12—H12C | 109.5 |
C18—C13—C4 | 120.03 (16) | C16—C15—C14 | 120.0 (2) |
C9—C4—C13 | 113.87 (13) | C16—C15—H15 | 120.0 |
C9—C4—C5 | 106.56 (12) | C14—C15—H15 | 120.0 |
C13—C4—C5 | 111.03 (12) | C16—C17—C18 | 120.7 (2) |
C9—C4—H4 | 108.4 | C16—C17—H17 | 119.7 |
C13—C4—H4 | 108.4 | C18—C17—H17 | 119.7 |
C5—C4—H4 | 108.4 | C17—C16—C15 | 119.7 (2) |
C8—C7—C6 | 109.73 (13) | C17—C16—H16 | 120.1 |
C8—C7—H7A | 109.7 | C15—C16—H16 | 120.1 |
C6—C7—H7A | 109.7 | O52—C11—H11A | 109.5 |
C8—C7—H7B | 109.7 | O52—C11—H11B | 109.5 |
C6—C7—H7B | 109.7 | H11A—C11—H11B | 109.5 |
H7A—C7—H7B | 108.2 | O52—C11—H11C | 109.5 |
C10—C5—C4 | 113.17 (13) | H11A—C11—H11C | 109.5 |
C10—C5—C6 | 111.69 (13) | H11B—C11—H11C | 109.5 |
C4—C5—C6 | 112.18 (12) | | |
| | | |
C8—N1—N2—C3 | −0.82 (19) | C7—C8—C9—C3 | 178.70 (15) |
N1—N2—C3—O31 | 179.96 (15) | N1—C8—C9—C4 | 178.86 (14) |
N1—N2—C3—C9 | −0.04 (18) | C7—C8—C9—C4 | −1.2 (3) |
N2—N1—C8—C9 | 1.36 (19) | N2—C3—C9—C8 | 0.82 (19) |
N2—N1—C8—C7 | −178.62 (15) | O31—C3—C9—C8 | −179.18 (16) |
C14—C13—C4—C9 | 50.5 (2) | N2—C3—C9—C4 | −179.34 (16) |
C18—C13—C4—C9 | −130.70 (17) | O31—C3—C9—C4 | 0.7 (3) |
C14—C13—C4—C5 | −69.8 (2) | C13—C4—C9—C8 | −139.80 (15) |
C18—C13—C4—C5 | 109.03 (18) | C5—C4—C9—C8 | −17.0 (2) |
N1—C8—C7—C6 | 166.26 (15) | C13—C4—C9—C3 | 40.4 (2) |
C9—C8—C7—C6 | −13.7 (2) | C5—C4—C9—C3 | 163.15 (16) |
O61—C6—C7—C8 | −73.92 (16) | C11—O52—C10—O51 | 1.2 (3) |
C12—C6—C7—C8 | 167.53 (14) | C11—O52—C10—C5 | −176.48 (15) |
C5—C6—C7—C8 | 45.17 (17) | C4—C5—C10—O51 | 120.6 (2) |
C9—C4—C5—C10 | 178.14 (13) | C6—C5—C10—O51 | −111.7 (2) |
C13—C4—C5—C10 | −57.34 (18) | C4—C5—C10—O52 | −61.81 (18) |
C9—C4—C5—C6 | 50.66 (17) | C6—C5—C10—O52 | 65.93 (18) |
C13—C4—C5—C6 | 175.18 (13) | C18—C13—C14—C15 | 0.3 (3) |
O61—C6—C5—C10 | −81.86 (16) | C4—C13—C14—C15 | 179.11 (18) |
C12—C6—C5—C10 | 42.5 (2) | C14—C13—C18—C17 | −0.3 (3) |
C7—C6—C5—C10 | 163.57 (14) | C4—C13—C18—C17 | −179.16 (17) |
O61—C6—C5—C4 | 46.40 (18) | C13—C14—C15—C16 | 0.1 (3) |
C12—C6—C5—C4 | 170.78 (15) | C13—C18—C17—C16 | 0.0 (3) |
C7—C6—C5—C4 | −68.17 (17) | C18—C17—C16—C15 | 0.3 (4) |
N1—C8—C9—C3 | −1.28 (18) | C14—C15—C16—C17 | −0.4 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O61i | 0.82 (2) | 2.11 (2) | 2.9025 (18) | 164.3 (18) |
O31—H31···N2ii | 0.82 | 1.85 | 2.6728 (18) | 178 |
O61—H61···O31iii | 0.82 | 2.23 | 2.8758 (16) | 136 |
C7—H7A···O31iv | 0.97 | 2.57 | 3.3679 (19) | 140 |
O61—H61···O52 | 0.82 | 2.39 | 3.0065 (16) | 132 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1/2, y+1/2, z. |