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A salicylideneaniline (SA) derivative, (6Z)-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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768111052608/ry5040sup1.cif
Contains datablocks I, global, publication_text

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768111052608/ry5040Isup2.hkl
Contains datablock I

CCDC reference: 866774

Computing details top

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).

(6Z)-6-({[2-(hydroxymethyl)phenyl]amino}methylidene) -3,5-dimethoxycyclohexa-2,4-dien-1-one monohydrate top
Crystal data top
C16H17NO4·H2OZ = 2
Mr = 305.32F(000) = 324
Triclinic, P1Dx = 1.336 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.0816 (6) ÅCell parameters from 17629 reflections
b = 11.0087 (12) Åθ = 1.5–27.7°
c = 14.5301 (16) ŵ = 0.10 mm1
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 tubeRint = 0.050
Graphite monochromatorθmax = 26.0°, θmin = 1.5°
Detector resolution: 6.67 pixels mm-1h = 66
ω–scank = 1313
12593 measured reflectionsl = 1717
2989 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158All 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 parametersΔρmax = 0.16 e Å3
3 restraintsΔρmin = 0.16 e Å3
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
xyzUiso*/Ueq
O5W0.7597 (6)0.0611 (3)0.5138 (2)0.0825 (8)
N10.5087 (4)0.2983 (2)0.25145 (15)0.0477 (6)
O30.3605 (4)0.68493 (18)0.21785 (13)0.0654 (6)
O10.3468 (4)0.50820 (17)0.36107 (12)0.0559 (5)
C40.2042 (6)0.4969 (3)0.12552 (19)0.0551 (7)
C130.6909 (5)0.2041 (2)0.24413 (17)0.0456 (6)
C60.1580 (5)0.4032 (2)0.19478 (17)0.0448 (6)
C20.0000 (5)0.6035 (3)0.29541 (19)0.0497 (7)
C70.3269 (5)0.3061 (2)0.18177 (18)0.0472 (6)
C111.0602 (6)0.1277 (3)0.3198 (2)0.0578 (7)
C120.8772 (5)0.2188 (2)0.32696 (17)0.0441 (6)
C30.1827 (5)0.5967 (2)0.21705 (18)0.0476 (6)
C10.1770 (5)0.5060 (2)0.28775 (17)0.0443 (6)
C50.0388 (6)0.4024 (2)0.11492 (17)0.0503 (7)
O20.6682 (4)0.29633 (17)0.46902 (13)0.0533 (5)
O50.0430 (5)0.30067 (19)0.03069 (13)0.0731 (7)
C80.6900 (6)0.1021 (3)0.1585 (2)0.0617 (8)
C140.8808 (6)0.3265 (3)0.42238 (18)0.0480 (6)
C101.0597 (7)0.0257 (3)0.2346 (2)0.0685 (9)
C310.3635 (9)0.7875 (3)0.3087 (2)0.0700 (10)
C90.8739 (7)0.0132 (3)0.1534 (2)0.0679 (9)
C510.2462 (9)0.2908 (4)0.0502 (2)0.0818 (12)
H10.506 (5)0.357 (3)0.305 (2)0.045 (7)*
H70.309 (5)0.239 (3)0.119 (2)0.052 (7)*
H210.670 (7)0.364 (3)0.523 (2)0.075 (10)*
H6W0.730 (8)0.126 (3)0.501 (3)0.092 (13)*
H5W0.678 (9)0.003 (4)0.475 (5)0.29 (5)*
H80.571 (6)0.093 (2)0.105 (2)0.049 (7)*
H111.187 (6)0.134 (3)0.374 (2)0.063 (8)*
H90.875 (6)0.054 (3)0.094 (2)0.074 (9)*
H101.180 (7)0.038 (3)0.229 (2)0.076 (9)*
H14A0.859 (5)0.409 (3)0.4104 (19)0.055 (8)*
H14B1.071 (7)0.333 (3)0.462 (2)0.072 (9)*
H20.015 (5)0.669 (3)0.355 (2)0.052 (7)*
H40.336 (6)0.495 (2)0.079 (2)0.049 (7)*
H51A0.219 (8)0.218 (4)0.098 (3)0.108 (13)*
H51B0.228 (8)0.367 (4)0.077 (3)0.095 (12)*
H51C0.431 (9)0.291 (4)0.027 (3)0.099 (13)*
H31A0.503 (8)0.831 (3)0.296 (2)0.083 (10)*
H31B0.192 (8)0.841 (3)0.326 (3)0.080 (11)*
H31C0.389 (7)0.744 (3)0.364 (3)0.084 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O5W0.0846 (18)0.0619 (14)0.1055 (19)0.0129 (13)0.0215 (15)0.0306 (14)
N10.0540 (14)0.0431 (11)0.0383 (11)0.0152 (10)0.0010 (10)0.0036 (9)
O30.0707 (14)0.0643 (12)0.0524 (11)0.0339 (10)0.0055 (10)0.0084 (9)
O10.0584 (12)0.0574 (11)0.0411 (9)0.0218 (9)0.0072 (8)0.0045 (8)
C40.0581 (18)0.0613 (16)0.0409 (13)0.0183 (14)0.0074 (13)0.0136 (12)
C130.0454 (15)0.0433 (13)0.0452 (13)0.0127 (11)0.0046 (11)0.0103 (10)
C60.0479 (15)0.0456 (13)0.0398 (12)0.0076 (11)0.0051 (11)0.0128 (10)
C20.0516 (16)0.0510 (14)0.0397 (13)0.0141 (12)0.0029 (12)0.0060 (11)
C70.0524 (16)0.0469 (13)0.0363 (12)0.0093 (11)0.0014 (11)0.0069 (11)
C110.0520 (18)0.0611 (17)0.0578 (16)0.0142 (13)0.0027 (14)0.0190 (13)
C120.0413 (14)0.0424 (13)0.0452 (13)0.0034 (10)0.0032 (11)0.0111 (10)
C30.0473 (15)0.0516 (14)0.0442 (13)0.0156 (12)0.0053 (11)0.0154 (11)
C10.0439 (15)0.0481 (13)0.0393 (12)0.0107 (11)0.0029 (11)0.0127 (10)
C50.0589 (17)0.0509 (14)0.0363 (12)0.0157 (13)0.0013 (11)0.0085 (11)
O20.0596 (12)0.0486 (10)0.0428 (10)0.0057 (9)0.0070 (9)0.0034 (8)
O50.0960 (17)0.0657 (12)0.0392 (9)0.0383 (11)0.0139 (10)0.0037 (8)
C80.0629 (19)0.0619 (17)0.0464 (15)0.0213 (14)0.0064 (14)0.0019 (12)
C140.0485 (17)0.0454 (14)0.0438 (13)0.0031 (11)0.0001 (12)0.0092 (11)
C100.069 (2)0.0590 (17)0.0700 (19)0.0322 (16)0.0052 (15)0.0096 (14)
C310.074 (2)0.0616 (19)0.0626 (19)0.0341 (19)0.0019 (17)0.0049 (15)
C90.073 (2)0.0592 (17)0.0570 (17)0.0269 (15)0.0037 (15)0.0010 (14)
C510.098 (3)0.082 (2)0.0435 (16)0.035 (2)0.0184 (17)0.0020 (16)
Geometric parameters (Å, º) top
O5W—H6W0.81 (3)C11—C121.393 (4)
O5W—H5W0.80 (3)C11—H110.93 (3)
N1—C71.312 (3)C12—C141.501 (3)
N1—C131.414 (3)C5—O51.361 (3)
N1—H10.84 (3)O2—C141.423 (3)
O3—C31.360 (3)O2—H210.89 (3)
O3—C311.434 (3)O5—C511.437 (4)
O1—C11.279 (3)C8—C91.380 (4)
C4—C51.355 (4)C8—H80.90 (3)
C4—C31.411 (4)C14—H14A0.99 (3)
C4—H40.89 (3)C14—H14B1.05 (3)
C13—C81.379 (3)C10—C91.382 (4)
C13—C121.396 (3)C10—H100.95 (3)
C6—C71.386 (3)C31—H31A0.91 (4)
C6—C51.433 (3)C31—H31B0.98 (4)
C6—C11.442 (3)C31—H31C1.08 (4)
C2—C31.357 (3)C9—H90.94 (3)
C2—C11.422 (3)C51—H51A0.90 (4)
C2—H20.93 (3)C51—H51B1.05 (4)
C7—H70.96 (3)C51—H51C1.03 (4)
C11—C101.374 (4)
H6W—O5W—H5W113 (6)C4—C5—O5124.4 (2)
C7—N1—C13127.4 (2)C4—C5—C6121.0 (2)
C7—N1—H1112.2 (17)O5—C5—C6114.6 (2)
C13—N1—H1120.4 (17)C14—O2—H21106 (2)
C3—O3—C31117.7 (2)C5—O5—C51117.1 (2)
C5—C4—C3119.2 (2)C13—C8—C9120.5 (3)
C5—C4—H4122.3 (16)C13—C8—H8120.1 (16)
C3—C4—H4118.3 (16)C9—C8—H8119.4 (16)
C8—C13—C12120.5 (2)O2—C14—C12108.2 (2)
C8—C13—N1122.0 (2)O2—C14—H14A110.1 (16)
C12—C13—N1117.5 (2)C12—C14—H14A110.5 (15)
C7—C6—C5119.9 (2)O2—C14—H14B114.4 (17)
C7—C6—C1121.1 (2)C12—C14—H14B105.4 (17)
C5—C6—C1119.0 (2)H14A—C14—H14B108 (2)
C3—C2—C1120.0 (2)C11—C10—C9119.4 (3)
C3—C2—H2122.7 (16)C11—C10—H10123.2 (19)
C1—C2—H2117.3 (16)C9—C10—H10117.4 (19)
N1—C7—C6123.8 (2)O3—C31—H31A104 (2)
N1—C7—H7117.4 (16)O3—C31—H31B109 (2)
C6—C7—H7118.8 (16)H31A—C31—H31B113 (3)
C10—C11—C12121.9 (3)O3—C31—H31C107.7 (18)
C10—C11—H11118.1 (18)H31A—C31—H31C113 (3)
C12—C11—H11120.1 (18)H31B—C31—H31C110 (3)
C11—C12—C13117.8 (2)C8—C9—C10120.0 (3)
C11—C12—C14119.9 (2)C8—C9—H9119.5 (19)
C13—C12—C14122.2 (2)C10—C9—H9120.4 (19)
O3—C3—C2124.0 (2)O5—C51—H51A104 (3)
O3—C3—C4113.2 (2)O5—C51—H51B113 (2)
C2—C3—C4122.8 (2)H51A—C51—H51B108 (3)
O1—C1—C2121.4 (2)O5—C51—H51C109 (2)
O1—C1—C6120.6 (2)H51A—C51—H51C115 (3)
C2—C1—C6118.0 (2)H51B—C51—H51C107 (3)
C7—N1—C13—C82.3 (5)C7—C6—C1—O11.6 (4)
C7—N1—C13—C12176.7 (3)C5—C6—C1—O1178.6 (3)
C13—N1—C7—C6179.0 (3)C7—C6—C1—C2179.1 (3)
C5—C6—C7—N1178.6 (3)C5—C6—C1—C20.8 (4)
C1—C6—C7—N11.5 (4)C3—C4—C5—O5179.3 (3)
C10—C11—C12—C130.2 (5)C3—C4—C5—C60.6 (5)
C10—C11—C12—C14178.3 (3)C7—C6—C5—C4179.3 (3)
C8—C13—C12—C110.1 (4)C1—C6—C5—C40.5 (4)
N1—C13—C12—C11178.9 (2)C7—C6—C5—O50.9 (4)
C8—C13—C12—C14178.4 (3)C1—C6—C5—O5179.3 (2)
N1—C13—C12—C142.6 (4)C4—C5—O5—C513.3 (5)
C31—O3—C3—C23.3 (4)C6—C5—O5—C51176.6 (3)
C31—O3—C3—C4177.3 (3)C12—C13—C8—C90.2 (5)
C1—C2—C3—O3179.6 (3)N1—C13—C8—C9178.8 (3)
C1—C2—C3—C41.1 (5)C11—C12—C14—O2102.7 (3)
C5—C4—C3—O3179.8 (3)C13—C12—C14—O275.8 (3)
C5—C4—C3—C20.9 (5)C12—C11—C10—C90.4 (5)
C3—C2—C1—O1178.3 (3)C13—C8—C9—C100.3 (6)
C3—C2—C1—C61.1 (4)C11—C10—C9—C80.4 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.84 (3)1.88 (3)2.587 (3)142 (2)
O5W—H6W···O20.81 (3)2.10 (3)2.915 (3)178 (4)
O2—H21···O1i0.89 (3)1.82 (4)2.710 (2)174 (3)
O5W—H5W···O5Wii0.80 (3)2.32 (3)2.819 (6)121 (3)
C51—H51B···O3iii1.05 (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) x1, y+1, z.
 

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