The title compound, C
24H
22N
2O
3, is dimerized
via two intermolecular O—H
O hydrogen bonds contributed by two —COOH groups, resulting in the formation of a planar eight-membered ring. The spiro C atom links two planes that are almost perpendicular to each other.
Supporting information
CCDC reference: 204680
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.046
- wR factor = 0.123
- Data-to-parameter ratio = 12.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The title compound was synthesized as described by Li et al. (1999). The single-crystal was grown by slow evaporation of chloroform–ethanol solution at room temperature.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
3-[3,3-Dimethylspiro[2,3-dihydro-1
H-indole-2,3'-(3'H-naphtho[2,1-
b] [1,4]oxazine)]-1-yl]propionic acid
top
Crystal data top
C24H22N2O3 | F(000) = 816 |
Mr = 386.44 | Dx = 1.328 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 912 reflections |
a = 13.373 (5) Å | θ = 3.2–23.4° |
b = 11.527 (4) Å | µ = 0.09 mm−1 |
c = 13.485 (5) Å | T = 293 K |
β = 111.538 (6)° | Plate, pale_yellow |
V = 1933.5 (11) Å3 | 0.20 × 0.15 × 0.10 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3399 independent reflections |
Radiation source: fine-focus sealed tube | 2000 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→14 |
Tmin = 0.983, Tmax = 1 | k = −13→8 |
7838 measured reflections | l = −14→16 |
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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0562P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3399 reflections | Δρmax = 0.16 e Å−3 |
263 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0055 (11) |
Crystal data top
C24H22N2O3 | V = 1933.5 (11) Å3 |
Mr = 386.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.373 (5) Å | µ = 0.09 mm−1 |
b = 11.527 (4) Å | T = 293 K |
c = 13.485 (5) Å | 0.20 × 0.15 × 0.10 mm |
β = 111.538 (6)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3399 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2000 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 1 | Rint = 0.047 |
7838 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.16 e Å−3 |
3399 reflections | Δρmin = −0.18 e Å−3 |
263 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 | |
O1 | 0.80725 (12) | 0.00877 (12) | 0.12839 (11) | 0.0430 (4) | |
N2 | 0.84053 (15) | 0.17499 (14) | 0.23458 (13) | 0.0395 (5) | |
C11 | 0.72245 (19) | 0.18821 (19) | 0.04688 (18) | 0.0437 (6) | |
H11A | 0.7149 | 0.2674 | 0.0551 | 0.052* | |
O2 | 1.05049 (14) | −0.03606 (15) | 0.14008 (14) | 0.0632 (5) | |
H2 | 1.0431 | −0.0626 | 0.0790 | 0.095* | |
O3 | 0.97452 (14) | 0.12205 (14) | 0.04836 (14) | 0.0568 (5) | |
C1 | 0.71755 (18) | 0.03272 (19) | −0.05998 (18) | 0.0386 (6) | |
C2 | 0.68406 (18) | −0.0158 (2) | −0.16406 (18) | 0.0404 (6) | |
C3 | 0.63130 (19) | 0.0496 (2) | −0.25736 (19) | 0.0495 (6) | |
H3A | 0.6185 | 0.1281 | −0.2517 | 0.059* | |
C4 | 0.5990 (2) | −0.0006 (3) | −0.3552 (2) | 0.0635 (8) | |
H4A | 0.5644 | 0.0439 | −0.4157 | 0.076* | |
C5 | 0.6174 (2) | −0.1187 (3) | −0.3659 (2) | 0.0705 (9) | |
H5A | 0.5938 | −0.1526 | −0.4331 | 0.085* | |
C6 | 0.6694 (2) | −0.1837 (2) | −0.2785 (2) | 0.0596 (7) | |
H6A | 0.6818 | −0.2619 | −0.2863 | 0.072* | |
C7 | 0.70496 (19) | −0.1343 (2) | −0.17560 (19) | 0.0461 (6) | |
C8 | 0.7620 (2) | −0.1993 (2) | −0.0833 (2) | 0.0532 (7) | |
H8A | 0.7769 | −0.2770 | −0.0904 | 0.064* | |
C9 | 0.7958 (2) | −0.1513 (2) | 0.0158 (2) | 0.0504 (7) | |
H9A | 0.8347 | −0.1951 | 0.0755 | 0.061* | |
C10 | 0.77120 (18) | −0.03513 (19) | 0.02675 (18) | 0.0394 (6) | |
N1 | 0.69979 (15) | 0.15171 (16) | −0.04820 (14) | 0.0437 (5) | |
C12 | 0.76019 (17) | 0.11648 (18) | 0.14733 (16) | 0.0381 (6) | |
C13 | 0.67162 (18) | 0.08711 (19) | 0.19386 (18) | 0.0428 (6) | |
C14 | 0.73999 (19) | 0.07577 (18) | 0.31076 (17) | 0.0400 (6) | |
C15 | 0.7180 (2) | 0.0261 (2) | 0.39361 (19) | 0.0502 (7) | |
H15A | 0.6525 | −0.0104 | 0.3812 | 0.060* | |
C16 | 0.7956 (2) | 0.0315 (2) | 0.4962 (2) | 0.0552 (7) | |
H16A | 0.7826 | −0.0031 | 0.5527 | 0.066* | |
C17 | 0.8908 (2) | 0.0875 (2) | 0.5141 (2) | 0.0545 (7) | |
H17A | 0.9412 | 0.0921 | 0.5833 | 0.065* | |
C18 | 0.91385 (19) | 0.1378 (2) | 0.43153 (18) | 0.0468 (6) | |
H18A | 0.9790 | 0.1752 | 0.4443 | 0.056* | |
C19 | 0.83749 (18) | 0.13055 (18) | 0.33018 (17) | 0.0384 (6) | |
C20 | 0.94125 (18) | 0.21569 (19) | 0.22868 (18) | 0.0451 (6) | |
H20A | 0.9729 | 0.2715 | 0.2855 | 0.054* | |
H20B | 0.9252 | 0.2563 | 0.1616 | 0.054* | |
C21 | 1.02480 (19) | 0.1224 (2) | 0.23696 (18) | 0.0505 (7) | |
H21A | 1.0959 | 0.1563 | 0.2685 | 0.061* | |
H21B | 1.0190 | 0.0618 | 0.2845 | 0.061* | |
C22 | 1.01360 (19) | 0.0692 (2) | 0.1328 (2) | 0.0475 (6) | |
C23 | 0.5937 (2) | 0.1893 (2) | 0.1783 (2) | 0.0639 (8) | |
H23A | 0.5402 | 0.1696 | 0.2073 | 0.096* | |
H23B | 0.5594 | 0.2057 | 0.1037 | 0.096* | |
H23C | 0.6328 | 0.2564 | 0.2144 | 0.096* | |
C24 | 0.6085 (2) | −0.0223 (2) | 0.1449 (2) | 0.0616 (8) | |
H24A | 0.5550 | −0.0362 | 0.1754 | 0.092* | |
H24B | 0.6566 | −0.0873 | 0.1594 | 0.092* | |
H24C | 0.5741 | −0.0123 | 0.0693 | 0.092* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0492 (10) | 0.0396 (10) | 0.0398 (10) | 0.0039 (7) | 0.0159 (8) | 0.0005 (7) |
N2 | 0.0388 (12) | 0.0451 (12) | 0.0368 (11) | −0.0063 (9) | 0.0166 (9) | −0.0036 (9) |
C11 | 0.0502 (16) | 0.0344 (14) | 0.0479 (15) | 0.0029 (11) | 0.0195 (12) | 0.0002 (11) |
O2 | 0.0732 (13) | 0.0569 (12) | 0.0658 (12) | 0.0227 (10) | 0.0331 (10) | 0.0055 (9) |
O3 | 0.0727 (13) | 0.0523 (11) | 0.0574 (11) | 0.0136 (9) | 0.0380 (10) | 0.0091 (9) |
C1 | 0.0404 (14) | 0.0349 (14) | 0.0427 (14) | −0.0019 (10) | 0.0177 (11) | −0.0022 (11) |
C2 | 0.0333 (13) | 0.0465 (15) | 0.0459 (15) | −0.0067 (11) | 0.0197 (11) | −0.0053 (11) |
C3 | 0.0444 (15) | 0.0600 (17) | 0.0453 (16) | 0.0033 (12) | 0.0179 (12) | −0.0050 (12) |
C4 | 0.0548 (18) | 0.088 (2) | 0.0429 (16) | 0.0046 (15) | 0.0129 (13) | −0.0085 (14) |
C5 | 0.063 (2) | 0.089 (2) | 0.056 (2) | −0.0054 (17) | 0.0182 (16) | −0.0272 (17) |
C6 | 0.0581 (18) | 0.0563 (18) | 0.067 (2) | −0.0092 (13) | 0.0263 (15) | −0.0232 (15) |
C7 | 0.0435 (15) | 0.0476 (16) | 0.0516 (16) | −0.0091 (12) | 0.0228 (12) | −0.0101 (12) |
C8 | 0.0631 (18) | 0.0368 (15) | 0.0701 (19) | −0.0052 (12) | 0.0366 (15) | −0.0085 (13) |
C9 | 0.0594 (17) | 0.0401 (15) | 0.0579 (17) | 0.0041 (12) | 0.0288 (14) | 0.0034 (12) |
C10 | 0.0400 (14) | 0.0372 (14) | 0.0451 (15) | −0.0034 (11) | 0.0204 (11) | −0.0026 (11) |
N1 | 0.0517 (13) | 0.0422 (12) | 0.0393 (12) | 0.0017 (9) | 0.0190 (9) | 0.0009 (9) |
C12 | 0.0403 (14) | 0.0351 (13) | 0.0397 (14) | 0.0035 (10) | 0.0155 (11) | 0.0007 (10) |
C13 | 0.0362 (14) | 0.0471 (15) | 0.0456 (15) | −0.0003 (11) | 0.0154 (11) | 0.0046 (11) |
C14 | 0.0417 (14) | 0.0405 (14) | 0.0411 (14) | 0.0020 (11) | 0.0189 (11) | 0.0032 (11) |
C15 | 0.0501 (16) | 0.0496 (16) | 0.0580 (17) | 0.0015 (12) | 0.0280 (14) | 0.0057 (12) |
C16 | 0.071 (2) | 0.0566 (17) | 0.0468 (17) | 0.0101 (14) | 0.0313 (15) | 0.0116 (12) |
C17 | 0.0608 (19) | 0.0597 (17) | 0.0405 (15) | 0.0103 (14) | 0.0158 (13) | 0.0034 (12) |
C18 | 0.0439 (15) | 0.0485 (15) | 0.0470 (16) | 0.0000 (12) | 0.0156 (12) | −0.0051 (12) |
C19 | 0.0403 (14) | 0.0395 (14) | 0.0376 (14) | 0.0039 (11) | 0.0169 (11) | −0.0008 (10) |
C20 | 0.0469 (16) | 0.0430 (15) | 0.0511 (15) | −0.0050 (12) | 0.0247 (12) | −0.0053 (11) |
C21 | 0.0458 (15) | 0.0535 (16) | 0.0559 (17) | −0.0037 (12) | 0.0231 (12) | −0.0016 (12) |
C22 | 0.0409 (15) | 0.0519 (17) | 0.0582 (18) | 0.0065 (12) | 0.0283 (12) | 0.0069 (13) |
C23 | 0.0509 (18) | 0.081 (2) | 0.0617 (18) | 0.0177 (14) | 0.0233 (14) | 0.0174 (14) |
C24 | 0.0470 (16) | 0.076 (2) | 0.0602 (18) | −0.0186 (14) | 0.0175 (13) | −0.0005 (14) |
Geometric parameters (Å, º) top
O1—C10 | 1.372 (2) | C9—H9A | 0.9300 |
O1—C12 | 1.456 (2) | C12—C13 | 1.567 (3) |
N2—C19 | 1.402 (3) | C13—C14 | 1.510 (3) |
N2—C12 | 1.437 (3) | C13—C24 | 1.527 (3) |
N2—C20 | 1.456 (3) | C13—C23 | 1.535 (3) |
C11—N1 | 1.276 (3) | C14—C15 | 1.380 (3) |
C11—C12 | 1.507 (3) | C14—C19 | 1.384 (3) |
C11—H11A | 0.9300 | C15—C16 | 1.393 (3) |
O2—C22 | 1.300 (3) | C15—H15A | 0.9300 |
O2—H2 | 0.8501 | C16—C17 | 1.367 (4) |
O3—C22 | 1.226 (3) | C16—H16A | 0.9300 |
C1—C10 | 1.370 (3) | C17—C18 | 1.387 (3) |
C1—N1 | 1.411 (3) | C17—H17A | 0.9300 |
C1—C2 | 1.422 (3) | C18—C19 | 1.376 (3) |
C2—C3 | 1.413 (3) | C18—H18A | 0.9300 |
C2—C7 | 1.414 (3) | C20—C21 | 1.525 (3) |
C3—C4 | 1.358 (3) | C20—H20A | 0.9700 |
C3—H3A | 0.9300 | C20—H20B | 0.9700 |
C4—C5 | 1.400 (4) | C21—C22 | 1.489 (3) |
C4—H4A | 0.9300 | C21—H21A | 0.9700 |
C5—C6 | 1.353 (4) | C21—H21B | 0.9700 |
C5—H5A | 0.9300 | C23—H23A | 0.9600 |
C6—C7 | 1.411 (3) | C23—H23B | 0.9600 |
C6—H6A | 0.9300 | C23—H23C | 0.9600 |
C7—C8 | 1.413 (3) | C24—H24A | 0.9600 |
C8—C9 | 1.361 (3) | C24—H24B | 0.9600 |
C8—H8A | 0.9300 | C24—H24C | 0.9600 |
C9—C10 | 1.399 (3) | | |
| | | |
C10—O1—C12 | 118.28 (16) | C14—C13—C12 | 100.35 (17) |
C19—N2—C12 | 108.43 (17) | C24—C13—C12 | 112.63 (19) |
C19—N2—C20 | 120.52 (18) | C23—C13—C12 | 110.77 (19) |
C12—N2—C20 | 122.35 (17) | C15—C14—C19 | 120.1 (2) |
N1—C11—C12 | 126.9 (2) | C15—C14—C13 | 130.9 (2) |
N1—C11—H11A | 116.6 | C19—C14—C13 | 108.98 (19) |
C12—C11—H11A | 116.6 | C14—C15—C16 | 118.9 (2) |
C22—O2—H2 | 110.9 | C14—C15—H15A | 120.5 |
C10—C1—N1 | 121.05 (19) | C16—C15—H15A | 120.5 |
C10—C1—C2 | 119.6 (2) | C17—C16—C15 | 120.1 (2) |
N1—C1—C2 | 119.3 (2) | C17—C16—H16A | 119.9 |
C3—C2—C7 | 118.1 (2) | C15—C16—H16A | 119.9 |
C3—C2—C1 | 122.8 (2) | C16—C17—C18 | 121.5 (2) |
C7—C2—C1 | 119.0 (2) | C16—C17—H17A | 119.2 |
C4—C3—C2 | 121.0 (2) | C18—C17—H17A | 119.2 |
C4—C3—H3A | 119.5 | C19—C18—C17 | 118.0 (2) |
C2—C3—H3A | 119.5 | C19—C18—H18A | 121.0 |
C3—C4—C5 | 120.6 (3) | C17—C18—H18A | 121.0 |
C3—C4—H4A | 119.7 | C18—C19—C14 | 121.3 (2) |
C5—C4—H4A | 119.7 | C18—C19—N2 | 129.1 (2) |
C6—C5—C4 | 120.2 (3) | C14—C19—N2 | 109.64 (19) |
C6—C5—H5A | 119.9 | N2—C20—C21 | 115.88 (19) |
C4—C5—H5A | 119.9 | N2—C20—H20A | 108.3 |
C5—C6—C7 | 120.8 (3) | C21—C20—H20A | 108.3 |
C5—C6—H6A | 119.6 | N2—C20—H20B | 108.3 |
C7—C6—H6A | 119.6 | C21—C20—H20B | 108.3 |
C6—C7—C8 | 122.1 (2) | H20A—C20—H20B | 107.4 |
C6—C7—C2 | 119.3 (2) | C22—C21—C20 | 113.8 (2) |
C8—C7—C2 | 118.7 (2) | C22—C21—H21A | 108.8 |
C9—C8—C7 | 121.8 (2) | C20—C21—H21A | 108.8 |
C9—C8—H8A | 119.1 | C22—C21—H21B | 108.8 |
C7—C8—H8A | 119.1 | C20—C21—H21B | 108.8 |
C8—C9—C10 | 119.1 (2) | H21A—C21—H21B | 107.7 |
C8—C9—H9A | 120.5 | O3—C22—O2 | 123.7 (2) |
C10—C9—H9A | 120.5 | O3—C22—C21 | 122.2 (2) |
C1—C10—O1 | 121.6 (2) | O2—C22—C21 | 114.2 (2) |
C1—C10—C9 | 121.7 (2) | C13—C23—H23A | 109.5 |
O1—C10—C9 | 116.6 (2) | C13—C23—H23B | 109.5 |
C11—N1—C1 | 116.49 (19) | H23A—C23—H23B | 109.5 |
N2—C12—O1 | 107.60 (16) | C13—C23—H23C | 109.5 |
N2—C12—C11 | 112.42 (18) | H23A—C23—H23C | 109.5 |
O1—C12—C11 | 109.50 (17) | H23B—C23—H23C | 109.5 |
N2—C12—C13 | 102.79 (17) | C13—C24—H24A | 109.5 |
O1—C12—C13 | 108.95 (17) | C13—C24—H24B | 109.5 |
C11—C12—C13 | 115.17 (18) | H24A—C24—H24B | 109.5 |
C14—C13—C24 | 113.99 (19) | C13—C24—H24C | 109.5 |
C14—C13—C23 | 109.22 (19) | H24A—C24—H24C | 109.5 |
C24—C13—C23 | 109.6 (2) | H24B—C24—H24C | 109.5 |
| | | |
C10—C1—C2—C3 | −178.0 (2) | N1—C11—C12—N2 | 141.5 (2) |
N1—C1—C2—C3 | −1.3 (3) | N1—C11—C12—O1 | 22.0 (3) |
C10—C1—C2—C7 | 1.4 (3) | N1—C11—C12—C13 | −101.2 (3) |
N1—C1—C2—C7 | 178.10 (19) | N2—C12—C13—C14 | −29.1 (2) |
C7—C2—C3—C4 | 1.7 (3) | O1—C12—C13—C14 | 84.81 (19) |
C1—C2—C3—C4 | −178.9 (2) | C11—C12—C13—C14 | −151.73 (18) |
C2—C3—C4—C5 | 0.0 (4) | N2—C12—C13—C24 | −150.73 (18) |
C3—C4—C5—C6 | −1.2 (4) | O1—C12—C13—C24 | −36.8 (2) |
C4—C5—C6—C7 | 0.6 (4) | C11—C12—C13—C24 | 86.7 (2) |
C5—C6—C7—C8 | −178.2 (2) | N2—C12—C13—C23 | 86.2 (2) |
C5—C6—C7—C2 | 1.2 (4) | O1—C12—C13—C23 | −159.89 (18) |
C3—C2—C7—C6 | −2.3 (3) | C11—C12—C13—C23 | −36.4 (3) |
C1—C2—C7—C6 | 178.3 (2) | C24—C13—C14—C15 | −42.8 (3) |
C3—C2—C7—C8 | 177.1 (2) | C23—C13—C14—C15 | 80.1 (3) |
C1—C2—C7—C8 | −2.3 (3) | C12—C13—C14—C15 | −163.4 (2) |
C6—C7—C8—C9 | −179.8 (2) | C24—C13—C14—C19 | 139.8 (2) |
C2—C7—C8—C9 | 0.9 (3) | C23—C13—C14—C19 | −97.3 (2) |
C7—C8—C9—C10 | 1.5 (4) | C12—C13—C14—C19 | 19.1 (2) |
N1—C1—C10—O1 | 1.7 (3) | C19—C14—C15—C16 | −0.4 (3) |
C2—C1—C10—O1 | 178.4 (2) | C13—C14—C15—C16 | −177.6 (2) |
N1—C1—C10—C9 | −175.6 (2) | C14—C15—C16—C17 | 1.4 (4) |
C2—C1—C10—C9 | 1.1 (3) | C15—C16—C17—C18 | −1.5 (4) |
C12—O1—C10—C1 | 18.9 (3) | C16—C17—C18—C19 | 0.5 (4) |
C12—O1—C10—C9 | −163.61 (19) | C17—C18—C19—C14 | 0.5 (3) |
C8—C9—C10—C1 | −2.5 (4) | C17—C18—C19—N2 | 179.0 (2) |
C8—C9—C10—O1 | −180.0 (2) | C15—C14—C19—C18 | −0.6 (3) |
C12—C11—N1—C1 | −3.7 (3) | C13—C14—C19—C18 | 177.22 (19) |
C10—C1—N1—C11 | −9.5 (3) | C15—C14—C19—N2 | −179.3 (2) |
C2—C1—N1—C11 | 173.8 (2) | C13—C14—C19—N2 | −1.5 (3) |
C19—N2—C12—O1 | −84.6 (2) | C12—N2—C19—C18 | 162.2 (2) |
C20—N2—C12—O1 | 63.1 (2) | C20—N2—C19—C18 | 13.9 (3) |
C19—N2—C12—C11 | 154.78 (18) | C12—N2—C19—C14 | −19.1 (2) |
C20—N2—C12—C11 | −57.6 (3) | C20—N2—C19—C14 | −167.47 (19) |
C19—N2—C12—C13 | 30.3 (2) | C19—N2—C20—C21 | 68.9 (3) |
C20—N2—C12—C13 | 177.99 (18) | C12—N2—C20—C21 | −75.0 (3) |
C10—O1—C12—N2 | −150.52 (18) | N2—C20—C21—C22 | 87.8 (3) |
C10—O1—C12—C11 | −28.1 (2) | C20—C21—C22—O3 | 27.9 (3) |
C10—O1—C12—C13 | 98.7 (2) | C20—C21—C22—O2 | −153.3 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.85 | 1.78 | 2.632 (3) | 178 |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data |
Chemical formula | C24H22N2O3 |
Mr | 386.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.373 (5), 11.527 (4), 13.485 (5) |
β (°) | 111.538 (6) |
V (Å3) | 1933.5 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.983, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7838, 3399, 2000 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.123, 1.02 |
No. of reflections | 3399 |
No. of parameters | 263 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.18 |
Selected geometric parameters (Å, º) topO1—C12 | 1.456 (2) | C11—N1 | 1.276 (3) |
N2—C19 | 1.402 (3) | C11—C12 | 1.507 (3) |
N2—C12 | 1.437 (3) | O2—H2 | 0.8501 |
N2—C20 | 1.456 (3) | C12—C13 | 1.567 (3) |
| | | |
C10—O1—C12 | 118.28 (16) | O1—C12—C11 | 109.50 (17) |
C19—N2—C12 | 108.43 (17) | N2—C12—C13 | 102.79 (17) |
C19—N2—C20 | 120.52 (18) | O1—C12—C13 | 108.95 (17) |
C12—N2—C20 | 122.35 (17) | C11—C12—C13 | 115.17 (18) |
N1—C11—C12 | 126.9 (2) | C14—C13—C12 | 100.35 (17) |
C22—O2—H2 | 110.9 | C19—C14—C13 | 108.98 (19) |
C10—C1—N1 | 121.05 (19) | C14—C19—N2 | 109.64 (19) |
C1—C10—O1 | 121.6 (2) | O3—C22—O2 | 123.7 (2) |
C11—N1—C1 | 116.49 (19) | O3—C22—C21 | 122.2 (2) |
N2—C12—O1 | 107.60 (16) | O2—C22—C21 | 114.2 (2) |
N2—C12—C11 | 112.42 (18) | | |
| | | |
N1—C1—C10—O1 | 1.7 (3) | N1—C11—C12—N2 | 141.5 (2) |
C2—C1—C10—O1 | 178.4 (2) | N1—C11—C12—O1 | 22.0 (3) |
N1—C1—C10—C9 | −175.6 (2) | N1—C11—C12—C13 | −101.2 (3) |
C12—O1—C10—C1 | 18.9 (3) | N2—C12—C13—C14 | −29.1 (2) |
C12—O1—C10—C9 | −163.61 (19) | O1—C12—C13—C14 | 84.81 (19) |
C12—C11—N1—C1 | −3.7 (3) | C11—C12—C13—C14 | −151.73 (18) |
C10—C1—N1—C11 | −9.5 (3) | C12—C13—C14—C19 | 19.1 (2) |
C19—N2—C12—O1 | −84.6 (2) | C13—C14—C19—C18 | 177.22 (19) |
C19—N2—C12—C11 | 154.78 (18) | C15—C14—C19—N2 | −179.3 (2) |
C19—N2—C12—C13 | 30.3 (2) | C13—C14—C19—N2 | −1.5 (3) |
C10—O1—C12—N2 | −150.52 (18) | C12—N2—C19—C18 | 162.2 (2) |
C10—O1—C12—C11 | −28.1 (2) | C12—N2—C19—C14 | −19.1 (2) |
C10—O1—C12—C13 | 98.7 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.85 | 1.78 | 2.632 (3) | 178 |
Symmetry code: (i) −x+2, −y, −z. |
Spiro-oxazines are novel organic photochromic compounds that are attractive as functional materials for a wide variety of applications, including high-density optical storage devices, optical switches and non-linear optics (Swansburg et al., 2000). Recently, the title compound, (I), was found to exhibit interesting photochemical properties when applied to DNA modifications (Zhang et al., 2001). Thus, the elucidation of the crystal structure of (I) is of importance. To our knowledge, this is the first reported crystal structure determination of dimerized photochromic spiro compound via intermolecular O—H···O hydrogen bonds. The spiro-center C12 in (I) (Fig. 1 and Table 1) is tetrahedral, as expected, with the dihedral angle between the planes O1—C12—C11 and N2—C12—C13 being 89.71 (13)°. The five-membered indoline ring (C12—C13—C14—C19—N2) is non-planar, adopting an flattened envelope conformation. Atom C12 lies 0.4763 (31) Å out of the plane of the other four indoline ring atoms; the torsion angle C13—C14—C19—N2 is −1.5 (3)° and the bending angle along the N2···C13 line is 30.59 (12)°. The N2, C13 and phenyl ring atoms are close to being coplanar [the interplanar angle between the phenyl ring and the plane through C13—C14—C19—N2 is only 1.82 (13)°]. Atom N2 has a pyramidal configuration and lies out of the plane of adjacent atoms by 0.2451 (21) Å with the sum of the bond angles at N2 being 351.30 (52)°. As found for the indoline ring, the oxazine moiety also has an envelope conformation, with C12 0.3335 (31) Å from the plane of the other oxazine atoms. The naphthyl ring, along with N1, C11 and O1, constitutes a roughly planar shape with a maximum deviation of 0.084 (18) Å at C11; the dihedral angle between this plane and C11—C12—O1 is 23.83 (14)°, indicating that spiro-atom C12 lies out of the naphthyl ring.
The main feature of the crystal structure, compared to the report of Osano et al. (1991), is the dimerization in the crystalline state (Fig. 1), which occurs when two molecules approach in a head-to-head fashion with the formation of a centrosymmetric eight-membered ring via hydrogen bonding. The O2···O3i separation is 2.632 (3) Å and the H2···O3i distance is 1.78 Å with an angle of 178°, subtended at H [symmetry code: (i) 2 − x, −y, −z].