A salicylideneaniline (SA) derivative, (6
Z)-6-({[2-(hydroxymethyl)phenyl]amino}methylidene)-3,5-dimethoxycyclohexa-2,4-dien-1-one monohydrate, has an increased aromaticity within its hydrogen-bridged chelate ring owing to its NH character. In the reported crystal structure, nonconventional π-stacking interactions, which are referred to as
hybrid π-stacking interactions, are observed between a quasiaromatic chelate ring, formed as a result of the resonance-assisted intramolecular hydrogen bond and ordinary aromatic rings. Besides, π-stacking interactions are also seen between two hydrogen-bridged quasiaromatic chelate rings, which are referred to as
pure π-stacking interactions. A CSD search has revealed that both kinds of interactions are frequently observed in molecular crystals of SA derivatives in fully or partially NH tautomeric form, and aromaticity levels of certain fragments of SA derivatives have dramatic effects on their stacking arrangements. These interactions are distinguished from the usual π
π interactions by their formation character,
i.e. both σ- and π-deficient and σ-deficient character of pure interactions is more pronounced than that of the hybrid ones.
Supporting information
CCDC reference: 866774
Data collection: STOE X-AREA (Stoe & Cie, 2002); cell refinement: STOE X-AREA (Stoe & Cie, 2002); data reduction: STOE X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003), ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), enCIFer (Allen et al., 2004b)
and publCIF (Westrip, 2010).
(6
Z)-6-({[2-(hydroxymethyl)phenyl]amino}methylidene)
-3,5-dimethoxycyclohexa-2,4-dien-1-one monohydrate
top
Crystal data top
C16H17NO4·H2O | Z = 2 |
Mr = 305.32 | F(000) = 324 |
Triclinic, P1 | Dx = 1.336 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.0816 (6) Å | Cell parameters from 17629 reflections |
b = 11.0087 (12) Å | θ = 1.5–27.7° |
c = 14.5301 (16) Å | µ = 0.10 mm−1 |
α = 108.935 (8)° | T = 296 K |
β = 97.042 (9)° | Plate, yellow |
γ = 93.092 (9)° | 0.65 × 0.31 × 0.06 mm |
V = 759.24 (15) Å3 | |
Data collection top
STOE IPDS 2 diffractometer | 1913 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 26.0°, θmin = 1.5° |
Detector resolution: 6.67 pixels mm-1 | h = −6→6 |
ω–scan | k = −13→13 |
12593 measured reflections | l = −17→17 |
2989 independent reflections | |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | All H-atom parameters refined |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0898P)2 + 0.0419P] where P = (Fo2 + 2Fc2)/3 |
2989 reflections | (Δ/σ)max = 0.002 |
275 parameters | Δρmax = 0.16 e Å−3 |
3 restraints | Δρmin = −0.16 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 | |
O5W | 0.7597 (6) | 0.0611 (3) | 0.5138 (2) | 0.0825 (8) | |
N1 | 0.5087 (4) | 0.2983 (2) | 0.25145 (15) | 0.0477 (6) | |
O3 | −0.3605 (4) | 0.68493 (18) | 0.21785 (13) | 0.0654 (6) | |
O1 | 0.3468 (4) | 0.50820 (17) | 0.36107 (12) | 0.0559 (5) | |
C4 | −0.2042 (6) | 0.4969 (3) | 0.12552 (19) | 0.0551 (7) | |
C13 | 0.6909 (5) | 0.2041 (2) | 0.24413 (17) | 0.0456 (6) | |
C6 | 0.1580 (5) | 0.4032 (2) | 0.19478 (17) | 0.0448 (6) | |
C2 | 0.0000 (5) | 0.6035 (3) | 0.29541 (19) | 0.0497 (7) | |
C7 | 0.3269 (5) | 0.3061 (2) | 0.18177 (18) | 0.0472 (6) | |
C11 | 1.0602 (6) | 0.1277 (3) | 0.3198 (2) | 0.0578 (7) | |
C12 | 0.8772 (5) | 0.2188 (2) | 0.32696 (17) | 0.0441 (6) | |
C3 | −0.1827 (5) | 0.5967 (2) | 0.21705 (18) | 0.0476 (6) | |
C1 | 0.1770 (5) | 0.5060 (2) | 0.28775 (17) | 0.0443 (6) | |
C5 | −0.0388 (6) | 0.4024 (2) | 0.11492 (17) | 0.0503 (7) | |
O2 | 0.6682 (4) | 0.29633 (17) | 0.46902 (13) | 0.0533 (5) | |
O5 | −0.0430 (5) | 0.30067 (19) | 0.03069 (13) | 0.0731 (7) | |
C8 | 0.6900 (6) | 0.1021 (3) | 0.1585 (2) | 0.0617 (8) | |
C14 | 0.8808 (6) | 0.3265 (3) | 0.42238 (18) | 0.0480 (6) | |
C10 | 1.0597 (7) | 0.0257 (3) | 0.2346 (2) | 0.0685 (9) | |
C31 | −0.3635 (9) | 0.7875 (3) | 0.3087 (2) | 0.0700 (10) | |
C9 | 0.8739 (7) | 0.0132 (3) | 0.1534 (2) | 0.0679 (9) | |
C51 | −0.2462 (9) | 0.2908 (4) | −0.0502 (2) | 0.0818 (12) | |
H1 | 0.506 (5) | 0.357 (3) | 0.305 (2) | 0.045 (7)* | |
H7 | 0.309 (5) | 0.239 (3) | 0.119 (2) | 0.052 (7)* | |
H21 | 0.670 (7) | 0.364 (3) | 0.523 (2) | 0.075 (10)* | |
H6W | 0.730 (8) | 0.126 (3) | 0.501 (3) | 0.092 (13)* | |
H5W | 0.678 (9) | −0.003 (4) | 0.475 (5) | 0.29 (5)* | |
H8 | 0.571 (6) | 0.093 (2) | 0.105 (2) | 0.049 (7)* | |
H11 | 1.187 (6) | 0.134 (3) | 0.374 (2) | 0.063 (8)* | |
H9 | 0.875 (6) | −0.054 (3) | 0.094 (2) | 0.074 (9)* | |
H10 | 1.180 (7) | −0.038 (3) | 0.229 (2) | 0.076 (9)* | |
H14A | 0.859 (5) | 0.409 (3) | 0.4104 (19) | 0.055 (8)* | |
H14B | 1.071 (7) | 0.333 (3) | 0.462 (2) | 0.072 (9)* | |
H2 | 0.015 (5) | 0.669 (3) | 0.355 (2) | 0.052 (7)* | |
H4 | −0.336 (6) | 0.495 (2) | 0.079 (2) | 0.049 (7)* | |
H51A | −0.219 (8) | 0.218 (4) | −0.098 (3) | 0.108 (13)* | |
H51B | −0.228 (8) | 0.367 (4) | −0.077 (3) | 0.095 (12)* | |
H51C | −0.431 (9) | 0.291 (4) | −0.027 (3) | 0.099 (13)* | |
H31A | −0.503 (8) | 0.831 (3) | 0.296 (2) | 0.083 (10)* | |
H31B | −0.192 (8) | 0.841 (3) | 0.326 (3) | 0.080 (11)* | |
H31C | −0.389 (7) | 0.744 (3) | 0.364 (3) | 0.084 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O5W | 0.0846 (18) | 0.0619 (14) | 0.1055 (19) | 0.0129 (13) | 0.0215 (15) | 0.0306 (14) |
N1 | 0.0540 (14) | 0.0431 (11) | 0.0383 (11) | 0.0152 (10) | 0.0010 (10) | 0.0036 (9) |
O3 | 0.0707 (14) | 0.0643 (12) | 0.0524 (11) | 0.0339 (10) | −0.0055 (10) | 0.0084 (9) |
O1 | 0.0584 (12) | 0.0574 (11) | 0.0411 (9) | 0.0218 (9) | −0.0072 (8) | 0.0045 (8) |
C4 | 0.0581 (18) | 0.0613 (16) | 0.0409 (13) | 0.0183 (14) | −0.0074 (13) | 0.0136 (12) |
C13 | 0.0454 (15) | 0.0433 (13) | 0.0452 (13) | 0.0127 (11) | 0.0046 (11) | 0.0103 (10) |
C6 | 0.0479 (15) | 0.0456 (13) | 0.0398 (12) | 0.0076 (11) | 0.0051 (11) | 0.0128 (10) |
C2 | 0.0516 (16) | 0.0510 (14) | 0.0397 (13) | 0.0141 (12) | 0.0029 (12) | 0.0060 (11) |
C7 | 0.0524 (16) | 0.0469 (13) | 0.0363 (12) | 0.0093 (11) | 0.0014 (11) | 0.0069 (11) |
C11 | 0.0520 (18) | 0.0611 (17) | 0.0578 (16) | 0.0142 (13) | −0.0027 (14) | 0.0190 (13) |
C12 | 0.0413 (14) | 0.0424 (13) | 0.0452 (13) | 0.0034 (10) | 0.0032 (11) | 0.0111 (10) |
C3 | 0.0473 (15) | 0.0516 (14) | 0.0442 (13) | 0.0156 (12) | 0.0053 (11) | 0.0154 (11) |
C1 | 0.0439 (15) | 0.0481 (13) | 0.0393 (12) | 0.0107 (11) | 0.0029 (11) | 0.0127 (10) |
C5 | 0.0589 (17) | 0.0509 (14) | 0.0363 (12) | 0.0157 (13) | 0.0013 (11) | 0.0085 (11) |
O2 | 0.0596 (12) | 0.0486 (10) | 0.0428 (10) | 0.0057 (9) | 0.0070 (9) | 0.0034 (8) |
O5 | 0.0960 (17) | 0.0657 (12) | 0.0392 (9) | 0.0383 (11) | −0.0139 (10) | −0.0037 (8) |
C8 | 0.0629 (19) | 0.0619 (17) | 0.0464 (15) | 0.0213 (14) | −0.0064 (14) | 0.0019 (12) |
C14 | 0.0485 (17) | 0.0454 (14) | 0.0438 (13) | 0.0031 (11) | −0.0001 (12) | 0.0092 (11) |
C10 | 0.069 (2) | 0.0590 (17) | 0.0700 (19) | 0.0322 (16) | 0.0052 (15) | 0.0096 (14) |
C31 | 0.074 (2) | 0.0616 (19) | 0.0626 (19) | 0.0341 (19) | −0.0019 (17) | 0.0049 (15) |
C9 | 0.073 (2) | 0.0592 (17) | 0.0570 (17) | 0.0269 (15) | 0.0037 (15) | −0.0010 (14) |
C51 | 0.098 (3) | 0.082 (2) | 0.0435 (16) | 0.035 (2) | −0.0184 (17) | −0.0020 (16) |
Geometric parameters (Å, º) top
O5W—H6W | 0.81 (3) | C11—C12 | 1.393 (4) |
O5W—H5W | 0.80 (3) | C11—H11 | 0.93 (3) |
N1—C7 | 1.312 (3) | C12—C14 | 1.501 (3) |
N1—C13 | 1.414 (3) | C5—O5 | 1.361 (3) |
N1—H1 | 0.84 (3) | O2—C14 | 1.423 (3) |
O3—C3 | 1.360 (3) | O2—H21 | 0.89 (3) |
O3—C31 | 1.434 (3) | O5—C51 | 1.437 (4) |
O1—C1 | 1.279 (3) | C8—C9 | 1.380 (4) |
C4—C5 | 1.355 (4) | C8—H8 | 0.90 (3) |
C4—C3 | 1.411 (4) | C14—H14A | 0.99 (3) |
C4—H4 | 0.89 (3) | C14—H14B | 1.05 (3) |
C13—C8 | 1.379 (3) | C10—C9 | 1.382 (4) |
C13—C12 | 1.396 (3) | C10—H10 | 0.95 (3) |
C6—C7 | 1.386 (3) | C31—H31A | 0.91 (4) |
C6—C5 | 1.433 (3) | C31—H31B | 0.98 (4) |
C6—C1 | 1.442 (3) | C31—H31C | 1.08 (4) |
C2—C3 | 1.357 (3) | C9—H9 | 0.94 (3) |
C2—C1 | 1.422 (3) | C51—H51A | 0.90 (4) |
C2—H2 | 0.93 (3) | C51—H51B | 1.05 (4) |
C7—H7 | 0.96 (3) | C51—H51C | 1.03 (4) |
C11—C10 | 1.374 (4) | | |
| | | |
H6W—O5W—H5W | 113 (6) | C4—C5—O5 | 124.4 (2) |
C7—N1—C13 | 127.4 (2) | C4—C5—C6 | 121.0 (2) |
C7—N1—H1 | 112.2 (17) | O5—C5—C6 | 114.6 (2) |
C13—N1—H1 | 120.4 (17) | C14—O2—H21 | 106 (2) |
C3—O3—C31 | 117.7 (2) | C5—O5—C51 | 117.1 (2) |
C5—C4—C3 | 119.2 (2) | C13—C8—C9 | 120.5 (3) |
C5—C4—H4 | 122.3 (16) | C13—C8—H8 | 120.1 (16) |
C3—C4—H4 | 118.3 (16) | C9—C8—H8 | 119.4 (16) |
C8—C13—C12 | 120.5 (2) | O2—C14—C12 | 108.2 (2) |
C8—C13—N1 | 122.0 (2) | O2—C14—H14A | 110.1 (16) |
C12—C13—N1 | 117.5 (2) | C12—C14—H14A | 110.5 (15) |
C7—C6—C5 | 119.9 (2) | O2—C14—H14B | 114.4 (17) |
C7—C6—C1 | 121.1 (2) | C12—C14—H14B | 105.4 (17) |
C5—C6—C1 | 119.0 (2) | H14A—C14—H14B | 108 (2) |
C3—C2—C1 | 120.0 (2) | C11—C10—C9 | 119.4 (3) |
C3—C2—H2 | 122.7 (16) | C11—C10—H10 | 123.2 (19) |
C1—C2—H2 | 117.3 (16) | C9—C10—H10 | 117.4 (19) |
N1—C7—C6 | 123.8 (2) | O3—C31—H31A | 104 (2) |
N1—C7—H7 | 117.4 (16) | O3—C31—H31B | 109 (2) |
C6—C7—H7 | 118.8 (16) | H31A—C31—H31B | 113 (3) |
C10—C11—C12 | 121.9 (3) | O3—C31—H31C | 107.7 (18) |
C10—C11—H11 | 118.1 (18) | H31A—C31—H31C | 113 (3) |
C12—C11—H11 | 120.1 (18) | H31B—C31—H31C | 110 (3) |
C11—C12—C13 | 117.8 (2) | C8—C9—C10 | 120.0 (3) |
C11—C12—C14 | 119.9 (2) | C8—C9—H9 | 119.5 (19) |
C13—C12—C14 | 122.2 (2) | C10—C9—H9 | 120.4 (19) |
O3—C3—C2 | 124.0 (2) | O5—C51—H51A | 104 (3) |
O3—C3—C4 | 113.2 (2) | O5—C51—H51B | 113 (2) |
C2—C3—C4 | 122.8 (2) | H51A—C51—H51B | 108 (3) |
O1—C1—C2 | 121.4 (2) | O5—C51—H51C | 109 (2) |
O1—C1—C6 | 120.6 (2) | H51A—C51—H51C | 115 (3) |
C2—C1—C6 | 118.0 (2) | H51B—C51—H51C | 107 (3) |
| | | |
C7—N1—C13—C8 | −2.3 (5) | C7—C6—C1—O1 | −1.6 (4) |
C7—N1—C13—C12 | 176.7 (3) | C5—C6—C1—O1 | 178.6 (3) |
C13—N1—C7—C6 | −179.0 (3) | C7—C6—C1—C2 | 179.1 (3) |
C5—C6—C7—N1 | −178.6 (3) | C5—C6—C1—C2 | −0.8 (4) |
C1—C6—C7—N1 | 1.5 (4) | C3—C4—C5—O5 | 179.3 (3) |
C10—C11—C12—C13 | −0.2 (5) | C3—C4—C5—C6 | −0.6 (5) |
C10—C11—C12—C14 | 178.3 (3) | C7—C6—C5—C4 | −179.3 (3) |
C8—C13—C12—C11 | 0.1 (4) | C1—C6—C5—C4 | 0.5 (4) |
N1—C13—C12—C11 | −178.9 (2) | C7—C6—C5—O5 | 0.9 (4) |
C8—C13—C12—C14 | −178.4 (3) | C1—C6—C5—O5 | −179.3 (2) |
N1—C13—C12—C14 | 2.6 (4) | C4—C5—O5—C51 | −3.3 (5) |
C31—O3—C3—C2 | −3.3 (4) | C6—C5—O5—C51 | 176.6 (3) |
C31—O3—C3—C4 | 177.3 (3) | C12—C13—C8—C9 | −0.2 (5) |
C1—C2—C3—O3 | 179.6 (3) | N1—C13—C8—C9 | 178.8 (3) |
C1—C2—C3—C4 | −1.1 (5) | C11—C12—C14—O2 | −102.7 (3) |
C5—C4—C3—O3 | −179.8 (3) | C13—C12—C14—O2 | 75.8 (3) |
C5—C4—C3—C2 | 0.9 (5) | C12—C11—C10—C9 | 0.4 (5) |
C3—C2—C1—O1 | −178.3 (3) | C13—C8—C9—C10 | 0.3 (6) |
C3—C2—C1—C6 | 1.1 (4) | C11—C10—C9—C8 | −0.4 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.84 (3) | 1.88 (3) | 2.587 (3) | 142 (2) |
O5W—H6W···O2 | 0.81 (3) | 2.10 (3) | 2.915 (3) | 178 (4) |
O2—H21···O1i | 0.89 (3) | 1.82 (4) | 2.710 (2) | 174 (3) |
O5W—H5W···O5Wii | 0.80 (3) | 2.32 (3) | 2.819 (6) | 121 (3) |
C51—H51B···O3iii | 1.05 (4) | 2.63 (4) | 3.048 (4) | 103 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x−1, −y+1, −z. |