In the title compound, C
24H
30N
2O
3·0.5C
3H
8O, the formation of intramolecular O—H
O and N—H
O hydrogen bonds causes considerable changes in the bond lengths within the amidopyridine fragment. This fact probably results in the unusual reactivity of the ether group in this type of compound.
Supporting information
CCDC reference: 165651
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.069
- wR factor = 0.212
- Data-to-parameter ratio = 23.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_701 Alert B Bond Calc 1.562(9), Rep 1.537(5), Dev. 2.78 Sigma
C2S -C1SB 3.567 1.555
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.08
From the CIF: _reflns_number_total 6505
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 6995
Completeness (_total/calc) 92.99%
Alert C: < 95% complete
WEIGH_01 Alert C Extra text has been found in the
_refine_ls_weighting_scheme field. This should be in the
_refine_ls_weighting_details field.
Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.0991P)^2^] wher
Weighting scheme identified as calc
PLAT_202 Alert C Isotropic non-H Atoms in Anion/Solvent = 1
PLAT_302 Alert C Anion/Solvent Disorder ....................... 43.00 Perc.
PLAT_701 Alert C Bond Calc 1.537(17), Rep 1.562(5), Dev. 1.47 Sigma
C2S -C1SA 3.567 1.555
PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ O1SA
O1SA C2S
PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ O1SA
C2S O1SA
PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ O1SA
O1SA C2S C1SB
PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ O1SA
O1SA C2S C1SB
PLAT_712 Alert C ANGLE Unknown or Inconsistent Label ........ O1SA
O1SA C2S C1SA
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.08
From the CIF: _reflns_number_total 6505
From the CIF: _diffrn_reflns_limit_ max hkl 20. 0. 15.
From the CIF: _diffrn_reflns_limit_ min hkl -21. -19. 0.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 21. 19. 17.
Calculated minimum hkl -21. -19. -17.
ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
10 Alert Level C = Please check
Crystals of (I) were grown by slow evaporation from an 2-propanol solution.
Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1991); software used to prepare material for publication: SHELXL97.
N-(1-Adamantyl)-4-hydroxy-2-(2-methylpropyl)-2-oxo-1,2-dihydroquinoline-3- carboxamide
top
Crystal data top
C24H30N2O3·0.5C3H8O | F(000) = 916 |
Mr = 424.55 | Dx = 1.185 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.140 (4) Å | Cell parameters from 24 reflections |
b = 13.655 (3) Å | θ = 10–11° |
c = 12.286 (3) Å | µ = 0.08 mm−1 |
β = 110.51 (3)° | T = 293 K |
V = 2379 (1) Å3 | Needles, colourless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Data collection top
Siemens P3/PC diffractometer | Rint = 0.038 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 2.1° |
Graphite monochromator | h = −21→20 |
θ–2θ scans | k = −19→0 |
6801 measured reflections | l = 0→15 |
6505 independent reflections | 2 standard reflections every 98 reflections |
2175 reflections with I > 2σ(I) | intensity decay: 5% |
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)] = 0.069 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.212 | H-atom parameters constrained |
S = 0.91 | Calculated w = 1/[σ2(Fo2) + (0.0991P)2] where P = (Fo2 + 2Fc2)/3 |
6505 reflections | (Δ/σ)max = 0.042 |
280 parameters | Δρmax = 0.41 e Å−3 |
3 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C24H30N2O3·0.5C3H8O | V = 2379 (1) Å3 |
Mr = 424.55 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.140 (4) Å | µ = 0.08 mm−1 |
b = 13.655 (3) Å | T = 293 K |
c = 12.286 (3) Å | 0.40 × 0.20 × 0.20 mm |
β = 110.51 (3)° | |
Data collection top
Siemens P3/PC diffractometer | Rint = 0.038 |
6801 measured reflections | 2 standard reflections every 98 reflections |
6505 independent reflections | intensity decay: 5% |
2175 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 3 restraints |
wR(F2) = 0.212 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.41 e Å−3 |
6505 reflections | Δρmin = −0.27 e Å−3 |
280 parameters | |
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 | Occ. (<1) |
N1 | −0.14254 (12) | 1.07656 (12) | 1.04873 (16) | 0.0479 (5) | |
N2 | −0.29127 (12) | 0.80550 (14) | 0.92103 (17) | 0.0558 (5) | |
H2N | −0.3186 | 0.8616 | 0.9139 | 0.067* | |
O1 | −0.28282 (10) | 1.00092 (11) | 0.94872 (16) | 0.0654 (5) | |
O2 | −0.15162 (10) | 0.72237 (11) | 1.00499 (13) | 0.0598 (5) | |
O3 | −0.00378 (10) | 0.80816 (11) | 1.12200 (14) | 0.0603 (5) | |
H3O | −0.0398 | 0.7623 | 1.0950 | 0.090* | |
C1 | 0.09968 (15) | 0.97757 (19) | 1.20844 (19) | 0.0561 (6) | |
H1 | 0.1299 | 0.9172 | 1.2252 | 0.067* | |
C2 | 0.15016 (17) | 1.0624 (2) | 1.2483 (2) | 0.0618 (7) | |
H2 | 0.2143 | 1.0595 | 1.2916 | 0.074* | |
C3 | 0.10377 (16) | 1.1536 (2) | 1.2226 (2) | 0.0602 (7) | |
H3 | 0.1378 | 1.2108 | 1.2496 | 0.072* | |
C4 | 0.00752 (16) | 1.15955 (18) | 1.1573 (2) | 0.0550 (6) | |
H4 | −0.0218 | 1.2204 | 1.1410 | 0.066* | |
C5 | −0.04576 (14) | 1.07287 (16) | 1.11575 (18) | 0.0456 (5) | |
C6 | −0.19718 (15) | 0.99120 (16) | 1.00735 (19) | 0.0476 (5) | |
C7 | −0.14824 (14) | 0.89628 (16) | 1.03338 (18) | 0.0459 (5) | |
C8 | −0.05199 (15) | 0.89248 (16) | 1.09774 (17) | 0.0452 (5) | |
C9 | 0.00149 (15) | 0.98192 (17) | 1.14186 (18) | 0.0462 (5) | |
C10 | −0.19022 (16) | 1.17321 (17) | 1.0127 (2) | 0.0558 (6) | |
H10A | −0.2473 | 1.1629 | 0.9462 | 0.067* | |
H10B | −0.1491 | 1.2150 | 0.9878 | 0.067* | |
C11 | −0.21649 (17) | 1.22776 (18) | 1.1074 (2) | 0.0650 (7) | |
H11 | −0.1581 | 1.2445 | 1.1710 | 0.078* | |
C12 | −0.26767 (19) | 1.3245 (2) | 1.0548 (3) | 0.0878 (9) | |
H12A | −0.2283 | 1.3623 | 1.0241 | 0.132* | |
H12B | −0.2803 | 1.3614 | 1.1143 | 0.132* | |
H12C | −0.3260 | 1.3095 | 0.9936 | 0.132* | |
C13 | −0.2777 (2) | 1.1649 (3) | 1.1574 (3) | 0.0903 (9) | |
H13A | −0.2942 | 1.2024 | 1.2135 | 0.135* | |
H13B | −0.2429 | 1.1078 | 1.1941 | 0.135* | |
H13C | −0.3340 | 1.1452 | 1.0957 | 0.135* | |
C14 | −0.19831 (15) | 0.80273 (17) | 0.98503 (18) | 0.0479 (5) | |
C15 | −0.35104 (14) | 0.72114 (16) | 0.86153 (19) | 0.0484 (6) | |
C16 | −0.45272 (15) | 0.76266 (19) | 0.8021 (2) | 0.0643 (7) | |
H16A | −0.4749 | 0.7908 | 0.8603 | 0.077* | |
H16B | −0.4522 | 0.8138 | 0.7476 | 0.077* | |
C17 | −0.51946 (16) | 0.6788 (2) | 0.7374 (2) | 0.0716 (8) | |
H17 | −0.5831 | 0.7053 | 0.7003 | 0.086* | |
C18 | −0.48559 (17) | 0.6358 (2) | 0.6436 (2) | 0.0755 (8) | |
H18A | −0.4850 | 0.6863 | 0.5883 | 0.091* | |
H18B | −0.5281 | 0.5842 | 0.6019 | 0.091* | |
C19 | −0.38528 (17) | 0.5941 (2) | 0.7023 (2) | 0.0655 (7) | |
H19 | −0.3633 | 0.5658 | 0.6430 | 0.079* | |
C20 | −0.31711 (15) | 0.67719 (18) | 0.7672 (2) | 0.0549 (6) | |
H20A | −0.2539 | 0.6512 | 0.8029 | 0.066* | |
H20B | −0.3155 | 0.7278 | 0.7126 | 0.066* | |
C21 | −0.35384 (17) | 0.64023 (18) | 0.9482 (2) | 0.0585 (6) | |
H21A | −0.3749 | 0.6678 | 1.0076 | 0.070* | |
H21B | −0.2911 | 0.6136 | 0.9858 | 0.070* | |
C22 | −0.42213 (18) | 0.55736 (19) | 0.8827 (2) | 0.0661 (7) | |
H22 | −0.4236 | 0.5062 | 0.9380 | 0.079* | |
C23 | −0.38620 (19) | 0.51380 (19) | 0.7910 (3) | 0.0704 (7) | |
H23A | −0.4268 | 0.4603 | 0.7512 | 0.085* | |
H23B | −0.3230 | 0.4881 | 0.8284 | 0.085* | |
C24 | −0.52204 (18) | 0.5996 (2) | 0.8240 (3) | 0.0794 (9) | |
H24A | −0.5650 | 0.5478 | 0.7840 | 0.095* | |
H24B | −0.5444 | 0.6273 | 0.8824 | 0.095* | |
O1S | −0.0781 (5) | 0.4599 (7) | 0.9098 (7) | 0.196 (3)* | 0.50 |
C1SA | 0.0538 (14) | 0.5971 (9) | 1.011 (3) | 0.308 (10)* | 0.50 |
H1S1 | 0.0917 | 0.5949 | 0.9624 | 0.461* | 0.50 |
H1S2 | 0.0938 | 0.6068 | 1.0902 | 0.461* | 0.50 |
H1S3 | 0.0096 | 0.6501 | 0.9865 | 0.461* | 0.50 |
C1SB | −0.0243 (8) | 0.5845 (6) | 0.9085 (8) | 0.160 (4)* | 0.50 |
H1S4 | −0.0915 | 0.5902 | 0.8729 | 0.240* | 0.50 |
H1S5 | 0.0025 | 0.5702 | 0.8500 | 0.240* | 0.50 |
H1S6 | 0.0013 | 0.6450 | 0.9463 | 0.240* | 0.50 |
C2S | 0.0000 | 0.5000 | 1.0000 | 0.204 (4)* | |
H2SB | 0.0384 | 0.4720 | 0.9603 | 0.306* | 0.50 |
H2SA | −0.0384 | 0.5280 | 1.0397 | 0.306* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0475 (11) | 0.0407 (11) | 0.0516 (11) | −0.0010 (8) | 0.0127 (9) | −0.0081 (8) |
N2 | 0.0487 (11) | 0.0405 (11) | 0.0662 (12) | −0.0027 (9) | 0.0052 (9) | −0.0075 (9) |
O1 | 0.0440 (9) | 0.0490 (10) | 0.0880 (13) | 0.0034 (7) | 0.0040 (8) | −0.0133 (9) |
O2 | 0.0555 (9) | 0.0487 (10) | 0.0610 (10) | 0.0015 (8) | 0.0026 (8) | 0.0005 (8) |
O3 | 0.0551 (9) | 0.0472 (10) | 0.0648 (11) | 0.0016 (8) | 0.0038 (8) | 0.0071 (8) |
C1 | 0.0464 (13) | 0.0681 (17) | 0.0427 (12) | −0.0024 (11) | 0.0019 (10) | 0.0017 (11) |
C2 | 0.0481 (13) | 0.084 (2) | 0.0445 (13) | −0.0094 (14) | 0.0053 (11) | −0.0054 (13) |
C3 | 0.0532 (14) | 0.0757 (19) | 0.0536 (14) | −0.0220 (13) | 0.0210 (12) | −0.0156 (13) |
C4 | 0.0584 (14) | 0.0515 (15) | 0.0571 (13) | −0.0087 (11) | 0.0226 (12) | −0.0105 (11) |
C5 | 0.0455 (12) | 0.0541 (14) | 0.0385 (11) | −0.0046 (10) | 0.0164 (10) | −0.0047 (10) |
C6 | 0.0455 (12) | 0.0468 (14) | 0.0466 (12) | −0.0008 (11) | 0.0111 (10) | −0.0104 (10) |
C7 | 0.0470 (12) | 0.0458 (13) | 0.0400 (11) | −0.0065 (10) | 0.0093 (10) | −0.0057 (10) |
C8 | 0.0511 (13) | 0.0466 (14) | 0.0348 (11) | 0.0029 (11) | 0.0115 (10) | 0.0037 (9) |
C9 | 0.0458 (12) | 0.0575 (14) | 0.0335 (11) | −0.0029 (11) | 0.0114 (9) | −0.0016 (10) |
C10 | 0.0554 (13) | 0.0434 (13) | 0.0607 (14) | −0.0032 (11) | 0.0106 (11) | −0.0040 (11) |
C11 | 0.0524 (13) | 0.0592 (16) | 0.0790 (17) | 0.0006 (12) | 0.0176 (12) | −0.0165 (14) |
C12 | 0.0704 (17) | 0.0661 (19) | 0.121 (3) | 0.0171 (15) | 0.0255 (17) | −0.0074 (17) |
C13 | 0.101 (2) | 0.085 (2) | 0.101 (2) | −0.0087 (18) | 0.0553 (19) | −0.0143 (18) |
C14 | 0.0486 (12) | 0.0465 (14) | 0.0417 (12) | −0.0001 (11) | 0.0072 (10) | 0.0006 (10) |
C15 | 0.0438 (11) | 0.0454 (13) | 0.0491 (13) | −0.0064 (10) | 0.0077 (10) | −0.0067 (10) |
C16 | 0.0452 (13) | 0.0629 (16) | 0.0764 (17) | 0.0061 (12) | 0.0108 (12) | −0.0035 (14) |
C17 | 0.0393 (13) | 0.0793 (19) | 0.0813 (19) | −0.0031 (13) | 0.0026 (13) | −0.0074 (16) |
C18 | 0.0621 (16) | 0.0829 (19) | 0.0641 (17) | −0.0255 (14) | 0.0003 (13) | −0.0115 (15) |
C19 | 0.0627 (15) | 0.0713 (18) | 0.0607 (15) | −0.0131 (13) | 0.0193 (12) | −0.0248 (14) |
C20 | 0.0476 (12) | 0.0582 (15) | 0.0538 (13) | −0.0069 (11) | 0.0115 (11) | 0.0018 (11) |
C21 | 0.0613 (15) | 0.0613 (16) | 0.0521 (14) | −0.0027 (12) | 0.0189 (12) | −0.0007 (12) |
C22 | 0.0674 (16) | 0.0617 (16) | 0.0709 (17) | −0.0149 (13) | 0.0267 (13) | 0.0072 (13) |
C23 | 0.0693 (16) | 0.0518 (16) | 0.0872 (19) | −0.0135 (13) | 0.0236 (14) | −0.0119 (14) |
C24 | 0.0580 (16) | 0.085 (2) | 0.098 (2) | −0.0214 (14) | 0.0305 (15) | −0.0124 (18) |
Geometric parameters (Å, º) top
N1—C5 | 1.408 (3) | C11—C12 | 1.553 (4) |
N1—C6 | 1.417 (3) | C15—C21 | 1.545 (3) |
N1—C10 | 1.495 (3) | C15—C20 | 1.544 (3) |
N2—C14 | 1.351 (3) | C15—C16 | 1.561 (3) |
N2—C15 | 1.489 (2) | C16—C17 | 1.549 (3) |
O1—C6 | 1.250 (3) | C17—C24 | 1.528 (4) |
O2—C14 | 1.282 (3) | C17—C18 | 1.534 (4) |
O3—C8 | 1.340 (2) | C18—C19 | 1.544 (4) |
C1—C2 | 1.380 (3) | C19—C23 | 1.550 (4) |
C1—C9 | 1.425 (3) | C19—C20 | 1.553 (3) |
C2—C3 | 1.410 (4) | C21—C22 | 1.554 (4) |
C3—C4 | 1.398 (3) | C22—C23 | 1.532 (4) |
C4—C5 | 1.423 (3) | C22—C24 | 1.541 (4) |
C5—C9 | 1.413 (3) | O1SA—C2S | 1.417 (4) |
C6—C7 | 1.472 (3) | C1SA—C2S | 1.537 (5) |
C7—C8 | 1.394 (3) | C1SB—C2S | 1.562 (5) |
C7—C14 | 1.498 (3) | C2Si—O1SA | 1.417 (5) |
C8—C9 | 1.461 (3) | C2Si—C1SB | 1.537 (5) |
C10—C11 | 1.546 (3) | C2Si—C1SA | 1.562 (5) |
C11—C13 | 1.540 (4) | | |
| | | |
C5—N1—C6 | 122.53 (17) | O2—C14—C7 | 119.07 (18) |
C5—N1—C10 | 120.03 (17) | N2—C14—C7 | 119.09 (19) |
C6—N1—C10 | 117.35 (17) | N2—C15—C21 | 111.95 (18) |
C14—N2—C15 | 126.45 (18) | N2—C15—C20 | 111.37 (18) |
C2—C1—C9 | 120.4 (2) | C21—C15—C20 | 109.62 (19) |
C1—C2—C3 | 119.5 (2) | N2—C15—C16 | 106.19 (17) |
C4—C3—C2 | 121.1 (2) | C21—C15—C16 | 108.74 (18) |
C3—C4—C5 | 120.3 (2) | C20—C15—C16 | 108.85 (19) |
N1—C5—C9 | 120.31 (18) | C17—C16—C15 | 109.31 (19) |
N1—C5—C4 | 121.5 (2) | C24—C17—C18 | 110.4 (2) |
C9—C5—C4 | 118.14 (19) | C24—C17—C16 | 109.7 (2) |
O1—C6—N1 | 118.47 (19) | C18—C17—C16 | 109.8 (2) |
O1—C6—C7 | 124.08 (19) | C17—C18—C19 | 108.9 (2) |
N1—C6—C7 | 117.42 (18) | C18—C19—C23 | 109.9 (2) |
C8—C7—C6 | 120.18 (19) | C18—C19—C20 | 109.8 (2) |
C8—C7—C14 | 118.45 (19) | C23—C19—C20 | 108.9 (2) |
C6—C7—C14 | 121.24 (18) | C15—C20—C19 | 109.48 (18) |
O3—C8—C7 | 122.54 (19) | C15—C21—C22 | 109.8 (2) |
O3—C8—C9 | 116.62 (18) | C23—C22—C24 | 110.1 (2) |
C7—C8—C9 | 120.84 (19) | C23—C22—C21 | 108.7 (2) |
C5—C9—C1 | 120.7 (2) | C24—C22—C21 | 109.6 (2) |
C5—C9—C8 | 118.68 (18) | C22—C23—C19 | 109.6 (2) |
C1—C9—C8 | 120.6 (2) | C17—C24—C22 | 109.28 (19) |
N1—C10—C11 | 115.3 (2) | O1SAi—C2S—C1SB | 101.5 (5) |
C13—C11—C10 | 112.4 (2) | O1SAi—C2S—C1SB | 101.5 (5) |
C13—C11—C12 | 111.0 (2) | C1SBi—C2S—C1SA | 126.2 (10) |
C10—C11—C12 | 108.6 (2) | O1SA—C2S—C1SA | 132.2 (10) |
O2—C14—N2 | 121.84 (19) | C1SBi—C2S—C1SA | 126.2 (10) |
| | | |
C9—C1—C2—C3 | 0.1 (3) | C15—N2—C14—C7 | 176.7 (2) |
C1—C2—C3—C4 | −0.1 (3) | C8—C7—C14—O2 | 0.6 (3) |
C2—C3—C4—C5 | 0.3 (3) | C6—C7—C14—O2 | 176.4 (2) |
C6—N1—C5—C9 | 1.7 (3) | C8—C7—C14—N2 | −179.0 (2) |
C10—N1—C5—C9 | −174.70 (19) | C6—C7—C14—N2 | −3.2 (3) |
C6—N1—C5—C4 | −179.4 (2) | C14—N2—C15—C20 | −62.7 (3) |
C10—N1—C5—C4 | 4.2 (3) | C14—N2—C15—C21 | 60.4 (3) |
C3—C4—C5—N1 | −179.30 (19) | C14—N2—C15—C16 | 178.9 (2) |
C3—C4—C5—C9 | −0.3 (3) | N2—C15—C16—C17 | 179.7 (2) |
C5—N1—C6—O1 | 179.74 (19) | C20—C15—C16—C17 | 59.7 (3) |
C10—N1—C6—O1 | −3.8 (3) | C21—C15—C16—C17 | −59.7 (3) |
C5—N1—C6—C7 | −2.1 (3) | C15—C16—C17—C24 | 60.8 (3) |
C10—N1—C6—C7 | 174.33 (19) | C15—C16—C17—C18 | −60.7 (3) |
O1—C6—C7—C8 | 178.8 (2) | C24—C17—C18—C19 | −60.4 (3) |
N1—C6—C7—C8 | 0.8 (3) | C16—C17—C18—C19 | 60.7 (3) |
O1—C6—C7—C14 | 3.1 (3) | C17—C18—C19—C23 | 59.2 (3) |
N1—C6—C7—C14 | −174.91 (19) | C17—C18—C19—C20 | −60.5 (3) |
C6—C7—C8—O3 | −178.76 (19) | N2—C15—C20—C19 | −176.31 (18) |
C14—C7—C8—O3 | −2.9 (3) | C21—C15—C20—C19 | 59.3 (2) |
C6—C7—C8—C9 | 1.0 (3) | C16—C15—C20—C19 | −59.6 (2) |
C14—C7—C8—C9 | 176.79 (19) | C18—C19—C20—C15 | 60.5 (3) |
N1—C5—C9—C1 | 179.23 (19) | C23—C19—C20—C15 | −59.8 (3) |
C4—C5—C9—C1 | 0.3 (3) | N2—C15—C21—C22 | 176.34 (19) |
N1—C5—C9—C8 | 0.2 (3) | C20—C15—C21—C22 | −59.6 (2) |
C4—C5—C9—C8 | −178.81 (19) | C16—C15—C21—C22 | 59.3 (2) |
C2—C1—C9—C5 | −0.1 (3) | C15—C21—C22—C23 | 60.5 (3) |
C2—C1—C9—C8 | 178.9 (2) | C15—C21—C22—C24 | −60.0 (3) |
O3—C8—C9—C5 | 178.27 (19) | C24—C22—C23—C19 | 58.7 (3) |
C7—C8—C9—C5 | −1.5 (3) | C21—C22—C23—C19 | −61.4 (3) |
O3—C8—C9—C1 | −0.8 (3) | C18—C19—C23—C22 | −58.9 (3) |
C7—C8—C9—C1 | 179.46 (19) | C20—C19—C23—C22 | 61.4 (3) |
C5—N1—C10—C11 | −79.1 (2) | C18—C17—C24—C22 | 60.3 (3) |
C6—N1—C10—C11 | 104.3 (2) | C16—C17—C24—C22 | −60.9 (3) |
N1—C10—C11—C13 | −55.2 (3) | C23—C22—C24—C17 | −59.3 (3) |
N1—C10—C11—C12 | −178.3 (2) | C21—C22—C24—C17 | 60.3 (3) |
C15—N2—C14—O2 | −2.9 (4) | | |
Symmetry code: (i) −x, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1 | 0.86 | 1.98 | 2.687 (2) | 138 |
O3—H3O···O2 | 0.82 | 1.75 | 2.489 (2) | 148 |
Experimental details
Crystal data |
Chemical formula | C24H30N2O3·0.5C3H8O |
Mr | 424.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.140 (4), 13.655 (3), 12.286 (3) |
β (°) | 110.51 (3) |
V (Å3) | 2379 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Siemens P3/PC diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6801, 6505, 2175 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.705 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.212, 0.91 |
No. of reflections | 6505 |
No. of parameters | 280 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.27 |
Selected bond lengths (Å) topN1—C5 | 1.408 (3) | O2—C14 | 1.282 (3) |
N1—C6 | 1.417 (3) | O3—C8 | 1.340 (2) |
N1—C10 | 1.495 (3) | C6—C7 | 1.472 (3) |
N2—C14 | 1.351 (3) | C7—C8 | 1.394 (3) |
N2—C15 | 1.489 (2) | C7—C14 | 1.498 (3) |
O1—C6 | 1.250 (3) | C8—C9 | 1.461 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1 | 0.86 | 1.98 | 2.687 (2) | 138.3 |
O3—H3O···O2 | 0.82 | 1.75 | 2.489 (2) | 148.3 |
Earlier, we demonstrated that intramolecular hydrogen bonds in the ethyl ethers of 1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid results in the marked lengthening of the C═O bond of the 3-carboethoxy group (Ukrainets et al., 2000). This fact, probably, determines an unusual reactivity of these compounds. A similar situation is observed for heteryl (Shishkina et al., 2000) and arylalkyl (Ukrainets et al., 2000) amides of this acid. In this paper, we report results of the X-ray diffraction study of the adamantyl-1-amide of 1-isobutyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid, (I).
The quinolone fragment and the C10, O1, O3, C14, O2, N2 and C15 atoms are coplanar within 0.04 Å. The isopropyl group of the alkyl substituent at the N1 atom is arranged nearly orthogonal with respect to the pyridone ring [the C5—N1—C10—C11 torsion angle is -79.1 (2)°] and has an +ac orientation relatively to the N1—C10 bond (the N1—C10—C11—H11 torsion angle is 64.3°). It should be noted some difference between values of the C—C bonds within isopropyl group. The C11—C12 bond [1.553 (4) Å] is longer than the C11—C13 bond [1.540 (4) Å].
The adamantane fragment is arranged with respect to the amide group in such a way that the C14—N2 and C16—C15 bonds have an ap orientation [the C14—N2—C15—C16 torsion angle is 178.9 (2)°]. Repulsion between the bulky adamantane substituent and the carbonyl group, probably, causes some elongation of the N2—C15 bond [1.489 (3) Å] with respect to its mean value 1.469 Å (Burgi & Dunitz, 1994).
The formation of the N2—H2N···O1 and O3—H3O···O2 intramolecular hydrogen bonds (H2N···O1 1.98 Å, N2—H2N···O1 138°; H3O···O2 1.75 Å and O3—H3O···O2 148°) results in an elongation of the O1—C6, O2—C14, C7—C8 and C7—C14 bonds (Table 1) compared with their mean values of 1.210, 1.330 and 1.465 Å (Burgi & Dunitz, 1994), respectively.
The presence of shortened intramolecular contacts O1···H10A = 2.29 Å (the van der Waals radii sum is 2.45 Å; Zefirov & Zorky, 1995), H10B···C4 = 2.66 Å (2.87 Å), H10B···H4 = 2.17 Å (2.32 Å), H11.·C4 = 2.82 Å, H11···H4 = 2.25 Å, probably causes the elongation of the N1—C5, N1—C6 and N1—C10 bonds (mean values are 1.371, 1.355 and 1.469 Å, respectively).
In the crystal phase, compound (I) exists as the solvate with 2-propanol in a 2:1 ratio. The molecules of the solvent are disordered over two positions with equal populations with respect to the centre of symmetry.