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organic compounds
3,3,3′,3′-Tetramethyl-6,6′-bis[(pyridin-4-yl)methoxy]-1,1′-spirobiindane monohydrate
aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
*Correspondence e-mail: dyh@mail.cnu.edu.cn
The 33H34N2O2·H2O, consists of a V-shaped molecule and a water molecule to which it is hydrogen bonded. The angle between the mean planes of the two spiro-connected indane groups is 77.06 (5)°. The two five-membered rings of the indane groups have envelope conformations with the methylene atoms adjacent to the spiro C atom forming the flaps. They have deviations from the mean plane of the other four atoms in the rings of 0.374 (4) and 0.362 (4) Å. In the crystal, molecules are linked to form inversion dimers via O—H⋯N hydrogen bonds involving the pyridine N atoms and the solvent water molecule. The dimers are linked into a chain along the b axis by π–π stacking interactions between a pyridine ring and its centrosymmetrically related ring in an adjacent dimer. The centroid–centroid distance between the planes is 3.7756 (17) Å, the perpendicular distance is 3.4478 (11) Å and the offset is 1.539 Å.
in the title compound, CRelated literature
For the use of spirane derivatives in ligand design, see: Chan et al. (1997); Cottam & Steel (2009
); Ding et al. (2009
); Srivastava et al. (1992
). For 1,1′-spirobiindane and its analogues, see: Cottam & Steel (2009
); Birman et al. (1999
); Brewster & Prudence (1973
). For the experimental procedure, see: Cottam & Steel (2009
); Kendhale et al. (2008
); Yao et al. (2010
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2007); cell APEX2 and SAINT (Bruker, 2007
); data reduction: APEX2 and SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: DIAMOND (Brandenburg, 2001
); software used to prepare material for publication: SHELXTL (Sheldrick, 2008
).
Supporting information
10.1107/S1600536812021289/go2055sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812021289/go2055Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812021289/go2055Isup3.cml
The starting material compound, 6,6'-dihydroxy-3,3,3',3'-tetramethyl- 1,1'-spirobiindane, was synthesized by the literature method (Kendhale et al., 2008). The title compound was prepared following the literature procedure (Cottam & Steel, 2009). A mixture of 6,6'-dihydroxy-3,3,3',3'- tetramethyl-1,1'-spirobiindane, 4-chloromethylpyridine and sodium hydroxide (mole ratio: 1:2:4) was refluxed in dry acetone solvent for 3 days under an N2 atmosphere. The solid crude product was obtained by removal of the solvent and further purified by
on silica gel (hexane/EtOAc = 8:2 v.v), yield 50%. Colourless crystals were obtained by slow evaporation from a solution of hexane.The hydrogen atoms were placed in idealized positions and allowed to ride on the relevant atoms, with C—H = 0.93 and 0.97 Å for aryl and methylene H atoms, respectively, Uiso(H)=1.2Ueq(C), O—H = 0.89 Å with Uiso(H)=1.2Ueq(O). The positions of the methyl and water H atoms were checked on a final difference Fourier.
Data collection: APEX2 (Bruker, 2007); cell
APEX2 and SAINT (Bruker, 2007); data reduction: APEX2 and SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C33H34N2O2·H2O | Z = 2 |
Mr = 508.64 | F(000) = 544 |
Triclinic, P1 | Dx = 1.225 Mg m−3 |
a = 6.0101 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.724 (2) Å | Cell parameters from 3702 reflections |
c = 22.156 (4) Å | θ = 1.9–25.3° |
α = 81.92 (3)° | µ = 0.08 mm−1 |
β = 87.17 (3)° | T = 173 K |
γ = 77.22 (3)° | Block, colourless |
V = 1378.6 (5) Å3 | 0.49 × 0.25 × 0.21 mm |
Bruker APEXII CCD diffractometer | 4988 independent reflections |
Radiation source: fine-focus sealed tube | 4253 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 25.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −7→7 |
Tmin = 0.963, Tmax = 0.984 | k = −12→12 |
10554 measured reflections | l = −24→26 |
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: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.7601P] where P = (Fo2 + 2Fc2)/3 |
4988 reflections | (Δ/σ)max < 0.001 |
347 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C33H34N2O2·H2O | γ = 77.22 (3)° |
Mr = 508.64 | V = 1378.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.0101 (12) Å | Mo Kα radiation |
b = 10.724 (2) Å | µ = 0.08 mm−1 |
c = 22.156 (4) Å | T = 173 K |
α = 81.92 (3)° | 0.49 × 0.25 × 0.21 mm |
β = 87.17 (3)° |
Bruker APEXII CCD diffractometer | 4988 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 4253 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.984 | Rint = 0.034 |
10554 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.24 e Å−3 |
4988 reflections | Δρmin = −0.17 e Å−3 |
347 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 | ||
O1 | 1.1312 (3) | 0.04027 (16) | 0.33047 (7) | 0.0397 (4) | |
O2 | 0.1540 (3) | 0.43323 (16) | 0.23137 (8) | 0.0427 (4) | |
N1 | 1.5601 (4) | 0.2248 (2) | 0.46452 (11) | 0.0507 (6) | |
N2 | −0.4528 (4) | 0.5560 (2) | 0.38411 (11) | 0.0528 (6) | |
C1 | 0.6971 (4) | 0.0684 (2) | 0.14537 (10) | 0.0306 (5) | |
C2 | 0.5655 (4) | 0.2053 (2) | 0.14847 (10) | 0.0292 (5) | |
C3 | 0.4135 (4) | 0.2482 (2) | 0.19451 (10) | 0.0314 (5) | |
H3 | 0.3835 | 0.1900 | 0.2288 | 0.038* | |
C4 | 0.3069 (4) | 0.3778 (2) | 0.18911 (11) | 0.0336 (5) | |
C5 | 0.3525 (4) | 0.4625 (2) | 0.13868 (11) | 0.0395 (6) | |
H5 | 0.2780 | 0.5511 | 0.1353 | 0.047* | |
C6 | 0.5050 (4) | 0.4188 (2) | 0.09374 (11) | 0.0381 (6) | |
H6 | 0.5361 | 0.4771 | 0.0596 | 0.046* | |
C7 | 0.6129 (4) | 0.2894 (2) | 0.09859 (10) | 0.0313 (5) | |
C8 | 0.7834 (4) | 0.2204 (2) | 0.05474 (11) | 0.0351 (6) | |
C9 | 0.8772 (4) | 0.0906 (2) | 0.09442 (11) | 0.0386 (6) | |
H9A | 1.0229 | 0.0928 | 0.1128 | 0.046* | |
H9B | 0.9059 | 0.0194 | 0.0691 | 0.046* | |
C10 | 0.8030 (4) | 0.0020 (2) | 0.20557 (10) | 0.0286 (5) | |
C11 | 0.9276 (4) | 0.0530 (2) | 0.24253 (10) | 0.0313 (5) | |
H11 | 0.9555 | 0.1370 | 0.2312 | 0.038* | |
C12 | 1.0119 (4) | −0.0205 (2) | 0.29660 (10) | 0.0318 (5) | |
C13 | 0.9705 (4) | −0.1428 (2) | 0.31379 (10) | 0.0345 (6) | |
H13 | 1.0265 | −0.1919 | 0.3512 | 0.041* | |
C14 | 0.8451 (4) | −0.1929 (2) | 0.27528 (11) | 0.0350 (5) | |
H14 | 0.8170 | −0.2770 | 0.2864 | 0.042* | |
C15 | 0.7615 (4) | −0.1208 (2) | 0.22100 (10) | 0.0291 (5) | |
C16 | 0.6323 (4) | −0.1574 (2) | 0.17100 (11) | 0.0315 (5) | |
C17 | 0.5423 (4) | −0.0241 (2) | 0.13356 (11) | 0.0373 (6) | |
H17A | 0.3828 | 0.0110 | 0.1460 | 0.045* | |
H17B | 0.5455 | −0.0327 | 0.0896 | 0.045* | |
C18 | 0.6609 (4) | 0.2012 (3) | −0.00128 (11) | 0.0429 (6) | |
H18A | 0.5397 | 0.1550 | 0.0119 | 0.064* | |
H18B | 0.7705 | 0.1510 | −0.0277 | 0.064* | |
H18C | 0.5941 | 0.2855 | −0.0239 | 0.064* | |
C19 | 0.9733 (4) | 0.2922 (3) | 0.03409 (13) | 0.0521 (7) | |
H19A | 0.9085 | 0.3739 | 0.0091 | 0.078* | |
H19B | 1.0881 | 0.2390 | 0.0100 | 0.078* | |
H19C | 1.0449 | 0.3095 | 0.0699 | 0.078* | |
C20 | 0.4349 (4) | −0.2201 (3) | 0.19443 (13) | 0.0433 (6) | |
H20A | 0.4950 | −0.3051 | 0.2172 | 0.065* | |
H20B | 0.3473 | −0.2297 | 0.1599 | 0.065* | |
H20C | 0.3354 | −0.1656 | 0.2213 | 0.065* | |
C21 | 0.7993 (4) | −0.2496 (2) | 0.13409 (12) | 0.0405 (6) | |
H21A | 0.9238 | −0.2087 | 0.1176 | 0.061* | |
H21B | 0.7186 | −0.2695 | 0.1005 | 0.061* | |
H21C | 0.8619 | −0.3295 | 0.1607 | 0.061* | |
C22 | 0.1231 (4) | 0.3548 (2) | 0.28763 (12) | 0.0405 (6) | |
H22A | 0.2627 | 0.3366 | 0.3122 | 0.049* | |
H22B | 0.0926 | 0.2717 | 0.2796 | 0.049* | |
C23 | −0.0741 (4) | 0.4264 (2) | 0.32137 (11) | 0.0361 (6) | |
C24 | −0.0538 (5) | 0.4563 (2) | 0.37921 (12) | 0.0445 (6) | |
H24 | 0.0898 | 0.4334 | 0.3986 | 0.053* | |
C25 | −0.2440 (5) | 0.5196 (3) | 0.40854 (13) | 0.0533 (8) | |
H25 | −0.2268 | 0.5388 | 0.4484 | 0.064* | |
C26 | −0.4693 (5) | 0.5269 (3) | 0.32831 (13) | 0.0479 (7) | |
H26 | −0.6144 | 0.5520 | 0.3098 | 0.057* | |
C27 | −0.2893 (4) | 0.4629 (2) | 0.29563 (12) | 0.0410 (6) | |
H27 | −0.3119 | 0.4439 | 0.2561 | 0.049* | |
C28 | 1.2225 (4) | −0.0277 (2) | 0.38685 (11) | 0.0400 (6) | |
H28A | 1.3343 | −0.1076 | 0.3800 | 0.048* | |
H28B | 1.0993 | −0.0513 | 0.4144 | 0.048* | |
C29 | 1.3368 (4) | 0.0620 (2) | 0.41402 (10) | 0.0336 (5) | |
C30 | 1.2521 (4) | 0.1158 (2) | 0.46561 (11) | 0.0388 (6) | |
H30 | 1.1150 | 0.0987 | 0.4847 | 0.047* | |
C31 | 1.3682 (5) | 0.1949 (3) | 0.48926 (12) | 0.0473 (7) | |
H31 | 1.3082 | 0.2300 | 0.5252 | 0.057* | |
C32 | 1.6353 (4) | 0.1750 (3) | 0.41367 (13) | 0.0463 (7) | |
H32 | 1.7691 | 0.1965 | 0.3944 | 0.056* | |
C33 | 1.5327 (4) | 0.0949 (3) | 0.38721 (11) | 0.0404 (6) | |
H33 | 1.5951 | 0.0623 | 0.3509 | 0.048* | |
O3 | −0.8355 (3) | 0.67390 (19) | 0.45596 (8) | 0.0520 (5) | |
H3A | −0.7253 | 0.6347 | 0.4324 | 0.078* | |
H3B | −0.7606 | 0.7035 | 0.4826 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0548 (11) | 0.0366 (10) | 0.0309 (9) | −0.0167 (8) | −0.0149 (8) | −0.0001 (7) |
O2 | 0.0518 (11) | 0.0325 (10) | 0.0368 (10) | 0.0030 (8) | 0.0097 (8) | −0.0040 (8) |
N1 | 0.0622 (15) | 0.0435 (14) | 0.0499 (15) | −0.0175 (11) | −0.0158 (12) | −0.0026 (11) |
N2 | 0.0571 (15) | 0.0490 (15) | 0.0481 (15) | −0.0058 (12) | 0.0146 (12) | −0.0065 (11) |
C1 | 0.0310 (12) | 0.0293 (12) | 0.0299 (12) | −0.0006 (9) | −0.0058 (10) | −0.0058 (10) |
C2 | 0.0268 (11) | 0.0292 (12) | 0.0311 (12) | −0.0030 (9) | −0.0053 (9) | −0.0060 (10) |
C3 | 0.0330 (12) | 0.0294 (12) | 0.0307 (13) | −0.0053 (10) | −0.0019 (10) | −0.0024 (10) |
C4 | 0.0308 (12) | 0.0335 (13) | 0.0355 (13) | −0.0022 (10) | 0.0014 (10) | −0.0092 (10) |
C5 | 0.0460 (15) | 0.0266 (13) | 0.0422 (15) | −0.0014 (11) | −0.0023 (12) | −0.0015 (11) |
C6 | 0.0452 (14) | 0.0313 (13) | 0.0353 (14) | −0.0066 (11) | 0.0014 (11) | 0.0003 (11) |
C7 | 0.0313 (12) | 0.0330 (13) | 0.0286 (12) | −0.0037 (10) | −0.0051 (10) | −0.0042 (10) |
C8 | 0.0330 (13) | 0.0406 (14) | 0.0286 (13) | −0.0023 (10) | −0.0023 (10) | −0.0022 (10) |
C9 | 0.0325 (13) | 0.0450 (15) | 0.0321 (13) | 0.0044 (11) | −0.0018 (10) | −0.0046 (11) |
C10 | 0.0261 (11) | 0.0300 (12) | 0.0269 (12) | 0.0005 (9) | −0.0015 (9) | −0.0042 (9) |
C11 | 0.0332 (12) | 0.0293 (12) | 0.0315 (13) | −0.0060 (10) | −0.0040 (10) | −0.0044 (10) |
C12 | 0.0343 (12) | 0.0332 (13) | 0.0294 (13) | −0.0078 (10) | −0.0020 (10) | −0.0085 (10) |
C13 | 0.0404 (14) | 0.0376 (14) | 0.0238 (12) | −0.0065 (11) | −0.0035 (10) | −0.0004 (10) |
C14 | 0.0386 (13) | 0.0309 (13) | 0.0359 (14) | −0.0091 (10) | −0.0003 (11) | −0.0035 (10) |
C15 | 0.0252 (11) | 0.0293 (12) | 0.0316 (12) | −0.0009 (9) | 0.0002 (9) | −0.0080 (10) |
C16 | 0.0304 (12) | 0.0293 (13) | 0.0350 (13) | −0.0027 (10) | −0.0040 (10) | −0.0092 (10) |
C17 | 0.0380 (13) | 0.0334 (14) | 0.0405 (14) | −0.0015 (10) | −0.0132 (11) | −0.0109 (11) |
C18 | 0.0453 (15) | 0.0482 (16) | 0.0295 (13) | 0.0035 (12) | −0.0064 (11) | −0.0058 (11) |
C19 | 0.0449 (16) | 0.065 (2) | 0.0454 (17) | −0.0152 (14) | 0.0060 (13) | −0.0031 (14) |
C20 | 0.0371 (14) | 0.0431 (16) | 0.0535 (17) | −0.0118 (11) | −0.0017 (12) | −0.0139 (13) |
C21 | 0.0406 (14) | 0.0403 (15) | 0.0397 (15) | −0.0005 (11) | −0.0045 (11) | −0.0136 (12) |
C22 | 0.0463 (15) | 0.0314 (14) | 0.0422 (15) | −0.0057 (11) | 0.0005 (12) | −0.0039 (11) |
C23 | 0.0449 (14) | 0.0287 (13) | 0.0369 (14) | −0.0123 (11) | 0.0015 (11) | −0.0054 (10) |
C24 | 0.0543 (16) | 0.0398 (15) | 0.0398 (15) | −0.0104 (12) | −0.0047 (12) | −0.0053 (12) |
C25 | 0.078 (2) | 0.0466 (17) | 0.0330 (15) | −0.0080 (15) | 0.0076 (14) | −0.0106 (13) |
C26 | 0.0449 (15) | 0.0467 (16) | 0.0514 (17) | −0.0113 (13) | 0.0031 (13) | −0.0035 (13) |
C27 | 0.0460 (15) | 0.0413 (15) | 0.0387 (15) | −0.0145 (12) | 0.0022 (12) | −0.0087 (12) |
C28 | 0.0528 (16) | 0.0402 (15) | 0.0281 (13) | −0.0147 (12) | −0.0095 (11) | 0.0019 (11) |
C29 | 0.0383 (13) | 0.0319 (13) | 0.0292 (13) | −0.0058 (10) | −0.0085 (10) | 0.0011 (10) |
C30 | 0.0358 (13) | 0.0449 (15) | 0.0344 (14) | −0.0066 (11) | −0.0011 (11) | −0.0041 (11) |
C31 | 0.0596 (18) | 0.0447 (16) | 0.0379 (15) | −0.0071 (13) | −0.0071 (13) | −0.0114 (12) |
C32 | 0.0420 (15) | 0.0523 (17) | 0.0459 (16) | −0.0182 (13) | −0.0060 (12) | 0.0042 (13) |
C33 | 0.0430 (14) | 0.0449 (15) | 0.0329 (14) | −0.0086 (12) | 0.0000 (11) | −0.0055 (11) |
O3 | 0.0498 (11) | 0.0609 (13) | 0.0485 (12) | −0.0123 (9) | −0.0020 (9) | −0.0167 (10) |
O1—C12 | 1.378 (3) | C16—C17 | 1.547 (3) |
O1—C28 | 1.424 (3) | C17—H17A | 0.9900 |
O2—C4 | 1.380 (3) | C17—H17B | 0.9900 |
O2—C22 | 1.431 (3) | C18—H18A | 0.9800 |
N1—C32 | 1.331 (3) | C18—H18B | 0.9800 |
N1—C31 | 1.336 (4) | C18—H18C | 0.9800 |
N2—C26 | 1.330 (4) | C19—H19A | 0.9800 |
N2—C25 | 1.345 (4) | C19—H19B | 0.9800 |
C1—C2 | 1.515 (3) | C19—H19C | 0.9800 |
C1—C10 | 1.519 (3) | C20—H20A | 0.9800 |
C1—C9 | 1.556 (3) | C20—H20B | 0.9800 |
C1—C17 | 1.556 (3) | C20—H20C | 0.9800 |
C2—C7 | 1.385 (3) | C21—H21A | 0.9800 |
C2—C3 | 1.393 (3) | C21—H21B | 0.9800 |
C3—C4 | 1.387 (3) | C21—H21C | 0.9800 |
C3—H3 | 0.9500 | C22—C23 | 1.491 (3) |
C4—C5 | 1.394 (3) | C22—H22A | 0.9900 |
C5—C6 | 1.379 (3) | C22—H22B | 0.9900 |
C5—H5 | 0.9500 | C23—C24 | 1.381 (3) |
C6—C7 | 1.388 (3) | C23—C27 | 1.392 (4) |
C6—H6 | 0.9500 | C24—C25 | 1.378 (4) |
C7—C8 | 1.520 (3) | C24—H24 | 0.9500 |
C8—C19 | 1.531 (3) | C25—H25 | 0.9500 |
C8—C18 | 1.534 (3) | C26—C27 | 1.378 (4) |
C8—C9 | 1.545 (3) | C26—H26 | 0.9500 |
C9—H9A | 0.9900 | C27—H27 | 0.9500 |
C9—H9B | 0.9900 | C28—C29 | 1.502 (3) |
C10—C11 | 1.378 (3) | C28—H28A | 0.9900 |
C10—C15 | 1.387 (3) | C28—H28B | 0.9900 |
C11—C12 | 1.389 (3) | C29—C30 | 1.377 (3) |
C11—H11 | 0.9500 | C29—C33 | 1.386 (3) |
C12—C13 | 1.387 (3) | C30—C31 | 1.379 (4) |
C13—C14 | 1.399 (3) | C30—H30 | 0.9500 |
C13—H13 | 0.9500 | C31—H31 | 0.9500 |
C14—C15 | 1.387 (3) | C32—C33 | 1.368 (4) |
C14—H14 | 0.9500 | C32—H32 | 0.9500 |
C15—C16 | 1.525 (3) | C33—H33 | 0.9500 |
C16—C20 | 1.524 (3) | O3—H3A | 0.8906 |
C16—C21 | 1.536 (3) | O3—H3B | 0.8904 |
C12—O1—C28 | 118.01 (18) | H17A—C17—H17B | 108.4 |
C4—O2—C22 | 117.53 (18) | C8—C18—H18A | 109.5 |
C32—N1—C31 | 115.9 (2) | C8—C18—H18B | 109.5 |
C26—N2—C25 | 116.0 (2) | H18A—C18—H18B | 109.5 |
C2—C1—C10 | 113.22 (19) | C8—C18—H18C | 109.5 |
C2—C1—C9 | 101.17 (19) | H18A—C18—H18C | 109.5 |
C10—C1—C9 | 113.16 (18) | H18B—C18—H18C | 109.5 |
C2—C1—C17 | 113.07 (18) | C8—C19—H19A | 109.5 |
C10—C1—C17 | 101.16 (19) | C8—C19—H19B | 109.5 |
C9—C1—C17 | 115.6 (2) | H19A—C19—H19B | 109.5 |
C7—C2—C3 | 121.4 (2) | C8—C19—H19C | 109.5 |
C7—C2—C1 | 111.9 (2) | H19A—C19—H19C | 109.5 |
C3—C2—C1 | 126.7 (2) | H19B—C19—H19C | 109.5 |
C4—C3—C2 | 118.5 (2) | C16—C20—H20A | 109.5 |
C4—C3—H3 | 120.8 | C16—C20—H20B | 109.5 |
C2—C3—H3 | 120.8 | H20A—C20—H20B | 109.5 |
O2—C4—C3 | 124.5 (2) | C16—C20—H20C | 109.5 |
O2—C4—C5 | 115.1 (2) | H20A—C20—H20C | 109.5 |
C3—C4—C5 | 120.4 (2) | H20B—C20—H20C | 109.5 |
C6—C5—C4 | 120.5 (2) | C16—C21—H21A | 109.5 |
C6—C5—H5 | 119.8 | C16—C21—H21B | 109.5 |
C4—C5—H5 | 119.8 | H21A—C21—H21B | 109.5 |
C5—C6—C7 | 119.7 (2) | C16—C21—H21C | 109.5 |
C5—C6—H6 | 120.1 | H21A—C21—H21C | 109.5 |
C7—C6—H6 | 120.1 | H21B—C21—H21C | 109.5 |
C2—C7—C6 | 119.6 (2) | O2—C22—C23 | 108.06 (19) |
C2—C7—C8 | 111.7 (2) | O2—C22—H22A | 110.1 |
C6—C7—C8 | 128.7 (2) | C23—C22—H22A | 110.1 |
C7—C8—C19 | 112.7 (2) | O2—C22—H22B | 110.1 |
C7—C8—C18 | 110.23 (19) | C23—C22—H22B | 110.1 |
C19—C8—C18 | 109.5 (2) | H22A—C22—H22B | 108.4 |
C7—C8—C9 | 101.34 (18) | C24—C23—C27 | 117.4 (2) |
C19—C8—C9 | 111.4 (2) | C24—C23—C22 | 122.2 (2) |
C18—C8—C9 | 111.5 (2) | C27—C23—C22 | 120.4 (2) |
C8—C9—C1 | 108.22 (18) | C25—C24—C23 | 119.3 (3) |
C8—C9—H9A | 110.1 | C25—C24—H24 | 120.3 |
C1—C9—H9A | 110.1 | C23—C24—H24 | 120.3 |
C8—C9—H9B | 110.1 | N2—C25—C24 | 123.9 (3) |
C1—C9—H9B | 110.1 | N2—C25—H25 | 118.0 |
H9A—C9—H9B | 108.4 | C24—C25—H25 | 118.0 |
C11—C10—C15 | 121.5 (2) | N2—C26—C27 | 124.2 (3) |
C11—C10—C1 | 126.1 (2) | N2—C26—H26 | 117.9 |
C15—C10—C1 | 112.4 (2) | C27—C26—H26 | 117.9 |
C10—C11—C12 | 118.9 (2) | C26—C27—C23 | 119.1 (3) |
C10—C11—H11 | 120.5 | C26—C27—H27 | 120.4 |
C12—C11—H11 | 120.5 | C23—C27—H27 | 120.4 |
O1—C12—C13 | 124.8 (2) | O1—C28—C29 | 106.27 (19) |
O1—C12—C11 | 114.2 (2) | O1—C28—H28A | 110.5 |
C13—C12—C11 | 121.0 (2) | C29—C28—H28A | 110.5 |
C12—C13—C14 | 119.0 (2) | O1—C28—H28B | 110.5 |
C12—C13—H13 | 120.5 | C29—C28—H28B | 110.5 |
C14—C13—H13 | 120.5 | H28A—C28—H28B | 108.7 |
C15—C14—C13 | 120.5 (2) | C30—C29—C33 | 117.3 (2) |
C15—C14—H14 | 119.7 | C30—C29—C28 | 122.1 (2) |
C13—C14—H14 | 119.7 | C33—C29—C28 | 120.6 (2) |
C14—C15—C10 | 119.0 (2) | C29—C30—C31 | 119.4 (2) |
C14—C15—C16 | 129.7 (2) | C29—C30—H30 | 120.3 |
C10—C15—C16 | 111.2 (2) | C31—C30—H30 | 120.3 |
C20—C16—C15 | 114.1 (2) | N1—C31—C30 | 123.8 (3) |
C20—C16—C21 | 109.0 (2) | N1—C31—H31 | 118.1 |
C15—C16—C21 | 109.26 (18) | C30—C31—H31 | 118.1 |
C20—C16—C17 | 110.53 (19) | N1—C32—C33 | 124.4 (3) |
C15—C16—C17 | 101.35 (18) | N1—C32—H32 | 117.8 |
C21—C16—C17 | 112.5 (2) | C33—C32—H32 | 117.8 |
C16—C17—C1 | 108.51 (18) | C32—C33—C29 | 119.2 (2) |
C16—C17—H17A | 110.0 | C32—C33—H33 | 120.4 |
C1—C17—H17A | 110.0 | C29—C33—H33 | 120.4 |
C16—C17—H17B | 110.0 | H3A—O3—H3B | 103.8 |
C1—C17—H17B | 110.0 | ||
C10—C1—C2—C7 | 135.5 (2) | C10—C11—C12—C13 | −0.6 (3) |
C9—C1—C2—C7 | 14.1 (2) | O1—C12—C13—C14 | 179.5 (2) |
C17—C1—C2—C7 | −110.2 (2) | C11—C12—C13—C14 | 1.1 (3) |
C10—C1—C2—C3 | −44.3 (3) | C12—C13—C14—C15 | −0.6 (3) |
C9—C1—C2—C3 | −165.7 (2) | C13—C14—C15—C10 | −0.3 (3) |
C17—C1—C2—C3 | 70.0 (3) | C13—C14—C15—C16 | 176.7 (2) |
C7—C2—C3—C4 | 0.8 (3) | C11—C10—C15—C14 | 0.9 (3) |
C1—C2—C3—C4 | −179.4 (2) | C1—C10—C15—C14 | −179.16 (19) |
C22—O2—C4—C3 | 7.4 (3) | C11—C10—C15—C16 | −176.65 (19) |
C22—O2—C4—C5 | −172.1 (2) | C1—C10—C15—C16 | 3.3 (3) |
C2—C3—C4—O2 | −179.6 (2) | C14—C15—C16—C20 | 47.7 (3) |
C2—C3—C4—C5 | −0.2 (3) | C10—C15—C16—C20 | −135.1 (2) |
O2—C4—C5—C6 | 179.1 (2) | C14—C15—C16—C21 | −74.5 (3) |
C3—C4—C5—C6 | −0.4 (4) | C10—C15—C16—C21 | 102.7 (2) |
C4—C5—C6—C7 | 0.4 (4) | C14—C15—C16—C17 | 166.5 (2) |
C3—C2—C7—C6 | −0.8 (3) | C10—C15—C16—C17 | −16.3 (2) |
C1—C2—C7—C6 | 179.4 (2) | C20—C16—C17—C1 | 144.4 (2) |
C3—C2—C7—C8 | 179.9 (2) | C15—C16—C17—C1 | 23.1 (2) |
C1—C2—C7—C8 | 0.1 (3) | C21—C16—C17—C1 | −93.5 (2) |
C5—C6—C7—C2 | 0.2 (4) | C2—C1—C17—C16 | −142.7 (2) |
C5—C6—C7—C8 | 179.4 (2) | C10—C1—C17—C16 | −21.3 (2) |
C2—C7—C8—C19 | −133.6 (2) | C9—C1—C17—C16 | 101.4 (2) |
C6—C7—C8—C19 | 47.2 (3) | C4—O2—C22—C23 | −170.9 (2) |
C2—C7—C8—C18 | 103.8 (2) | O2—C22—C23—C24 | −122.1 (3) |
C6—C7—C8—C18 | −75.4 (3) | O2—C22—C23—C27 | 59.6 (3) |
C2—C7—C8—C9 | −14.3 (3) | C27—C23—C24—C25 | 0.1 (4) |
C6—C7—C8—C9 | 166.5 (2) | C22—C23—C24—C25 | −178.3 (2) |
C7—C8—C9—C1 | 22.9 (2) | C26—N2—C25—C24 | 0.1 (4) |
C19—C8—C9—C1 | 143.0 (2) | C23—C24—C25—N2 | −0.4 (4) |
C18—C8—C9—C1 | −94.3 (2) | C25—N2—C26—C27 | 0.5 (4) |
C2—C1—C9—C8 | −22.9 (2) | N2—C26—C27—C23 | −0.8 (4) |
C10—C1—C9—C8 | −144.3 (2) | C24—C23—C27—C26 | 0.5 (4) |
C17—C1—C9—C8 | 99.6 (2) | C22—C23—C27—C26 | 178.9 (2) |
C2—C1—C10—C11 | −47.6 (3) | C12—O1—C28—C29 | −178.67 (19) |
C9—C1—C10—C11 | 66.8 (3) | O1—C28—C29—C30 | 111.0 (2) |
C17—C1—C10—C11 | −168.9 (2) | O1—C28—C29—C33 | −68.3 (3) |
C2—C1—C10—C15 | 132.4 (2) | C33—C29—C30—C31 | −2.3 (3) |
C9—C1—C10—C15 | −113.2 (2) | C28—C29—C30—C31 | 178.3 (2) |
C17—C1—C10—C15 | 11.2 (2) | C32—N1—C31—C30 | 1.1 (4) |
C15—C10—C11—C12 | −0.4 (3) | C29—C30—C31—N1 | 0.9 (4) |
C1—C10—C11—C12 | 179.6 (2) | C31—N1—C32—C33 | −1.7 (4) |
C28—O1—C12—C13 | 1.1 (3) | N1—C32—C33—C29 | 0.2 (4) |
C28—O1—C12—C11 | 179.6 (2) | C30—C29—C33—C32 | 1.8 (4) |
C10—C11—C12—O1 | −179.12 (19) | C28—C29—C33—C32 | −178.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2 | 0.89 | 2.00 | 2.888 (3) | 173 |
O3—H3B···N1i | 0.89 | 2.05 | 2.940 (3) | 173 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C33H34N2O2·H2O |
Mr | 508.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.0101 (12), 10.724 (2), 22.156 (4) |
α, β, γ (°) | 81.92 (3), 87.17 (3), 77.22 (3) |
V (Å3) | 1378.6 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.49 × 0.25 × 0.21 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.963, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10554, 4988, 4253 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.137, 1.16 |
No. of reflections | 4988 |
No. of parameters | 347 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.17 |
Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2 | 0.89 | 2.00 | 2.888 (3) | 173 |
O3—H3B···N1i | 0.89 | 2.05 | 2.940 (3) | 173 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant No. 20971091), the Beijing Municipal Natural Science Foundation (grant No. 2102011) and the Scientific Research Common Program of Beijing Municipal Commission of Education (grant No. KM201010028008).
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.
Spirane derivatives, which are typical molecules with axial chirality, have been mainly employed in ligand design and asymmetric synthesis (Srivastava et al., 1992; Chan et al., 1997; Ding et al., 2009; Cottam & Steel, 2009). Among them, 1,1'-spirobiindane and its analogs have also attracted much attention for their featuring C2-symmetric chiral property (Birman et al., 1999; Brewster & Prudence, 1973; Cottam & Steel, 2009). Following our previous work(Yao et al., 2010), we report the structure of a bidentate flexible nitrogen ligand by coupling 1,1,-spirobiindane with nitrogen-containing heterocycles.
The molecule of C33H34N2O2.H2O, is V-shaped, Figure 1. The angle between the mean planes of the two spiro connected indane groups is 77.06 (5)°.
The two five membered rings of the indane groups have an envelope pucker with the methylene atoms, C9 and C17, adjacent to the spiro carbon atom forming the flaps. They have deviations from mean plane of other 4 atoms in the rings of 0.374 (4) Å and 0.362 (4) Å, respectively.
Two molecules are linked to form a centrosymmetric dimer via hydrogen bonds between the pyridinyl nitrogen atoms and the solvent water, O3—H3A···N2 (within the asymmetric unit) and O3—H3B···N1 (1 - x,1 - y,1 - z), Table 1 and Figure 2.
The dimers are linked to form a one-dimensional chain structure by π—π stacking interactions between the pyridinyl ring (C29—C30—N1—C31—C32—C33) and its centrosymmetrically related ring at (3 - x,-y,1 - z+). The centroid-centroid distance between the planes is 3.7756 (17) Å, the perpendicular distance is 3.4478 (11) Å and the offset is 1.539 Å, Figure 2.