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The title compound, C18H20N2O4, has been characterized structurally by 1H NMR and X-ray crystallography. The molecule is centrosymmetric. The two benzene rings are parallel to each other with a perpendicular interplanar spacing of ca 1.4 Å. Intra­molecular O—H...N hydrogen bonds are formed between the oxime and hydr­oxy groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047927/hg2302sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047927/hg2302Isup2.hkl
Contains datablock I

CCDC reference: 644785

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.058
  • wR factor = 0.175
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.63 mm PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

(N,N'-bis(salicylidence)ethylenediamine), salen, and its analogues have been extensively investigated for decades (Katsuki, 1995; Atwood & Harvey, 2001). At present, a new class of salen-type bisoxime compounds have been synthesized by using an O-alkyloxime unit (—CH=N—O—(CH)n—O—N=CH—) instead of the (—CH=N—(CH)n—N=CH—) group (Dong & Feng, 2006; Dong, Feng & Yang, 2006; Dong, Duan et al., 2006; Duan et al., 2007) as the large electronegativity of oxygen atoms is expected to affect strongly the electronic properties of N2O2 coordination sphere, which can lead to different and novel properties and structures of the resulting complexes.

Herein, we report on the crystal structure of 2,2'-[ethylenedioxy- bis(nitriloethylidyne)]diphenol (I), shown in Fig. 1. The structure of (I) consists of discrete C18H20N2O4 molecules in which all bond lengths are in normal ranges. The molecule is disposed about a cyrstallographic centre of symmetry with the (—CH=N—O—(CH)2—O—N=CH—) bridge adopting an anti-symmetrized conformation. The two benzene rings of (I) are parallel to each other and separated by ca 1.4 Å. There is an intra-molecular hydrogen bond, O2—H2···N1 (d(O2—H2) = 0.82 Å, d(H2···N1) = 1.85 Å, d(O2···N1) = 2.56 (2) Å, O2—H2···N1 = 145.0°).

Related literature top

For related literature, see: Atwood & Harvey (2001); Dong & Feng (2006); Dong, Feng & Yang (2006); Dong, Duan et al. (2006); Dong et al. (2007); Duan et al. (2007); Katsuki (1995).

Experimental top

2,2'-[ethylenedioxybis(nitriloethylidyne)]diphenol (I) was synthesized according to our previous work (Dong et al., 2007). To an ethanol solution (5 ml) of 2'-hydroxyacetophenone (283.0 mg, 2.00 mmol) was added dropwise an ethanol solution (5 ml) of 1,2-bis(aminooxy)ethane (92.1 mg, 1.00 mmol). The mixture solution was stirred at 328 K for 2 h. After cooling to room temperature, the precipitate was filtered off, and washed successively with ethanol and ethanol-hexane (1:4). The product was dried in vacuo and purified by recrystallization from ethanol to yield 223.1 mg (Yield, 67.9%) of colorless microcrystals; m.p. 387 - 389 K. Anal. Calcd. for C18H20N2O4: C, 65.84; H, 6.14; N, 8.53; Found: C, 65.71; H, 6.24; N, 8.42%. 1H NMR (400 MHz, CDCl3): 2.34 (s, 6H), 4.50 (s, 4H), 6.89 (dd, J = 7.8, 1.4 Hz, 2H), 6.95 (dd, J = 8.4, 1.2 Hz, 2H), 7.25 (dd, J = 6.8, 1.6 Hz, 2H), 7.41 (dd, J = 8.0, 1.6 Hz, 2H), 11.10 (s, 2H).

Single crystals were obtained by slow evaporation from a solution of ethanol of 2,2'-[ethylenedioxybis(nitriloethylidyne)]diphenol at room temperature.

Refinement top

Non-H atoms were refined anisotropically. H atoms were treated as riding atoms with distances C—H = 0.97 (CH2), or 0.93 Å (CH),O—H = 0.82 Å, and Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(O).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I).
2,2'-[1,1'-(Ethylenedioxydinitrilo)diethylidyne]diphenol top
Crystal data top
C18H20N2O4F(000) = 348
Mr = 328.36Dx = 1.289 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1276 reflections
a = 6.9018 (12) Åθ = 2.4–25.1°
b = 17.2184 (18) ŵ = 0.09 mm1
c = 7.3063 (14) ÅT = 298 K
β = 103.003 (2)°Prismatic, colorless
V = 846.0 (2) Å30.63 × 0.58 × 0.45 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1485 independent reflections
Radiation source: fine-focus sealed tube952 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
ϕ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.944, Tmax = 0.960k = 2018
4172 measured reflectionsl = 58
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0801P)2 + 0.199P]
where P = (Fo2 + 2Fc2)/3
1485 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C18H20N2O4V = 846.0 (2) Å3
Mr = 328.36Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.9018 (12) ŵ = 0.09 mm1
b = 17.2184 (18) ÅT = 298 K
c = 7.3063 (14) Å0.63 × 0.58 × 0.45 mm
β = 103.003 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1485 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
952 reflections with I > 2σ(I)
Tmin = 0.944, Tmax = 0.960Rint = 0.065
4172 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.175H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
1485 reflectionsΔρmin = 0.29 e Å3
109 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
xyzUiso*/Ueq
N10.7373 (3)0.04598 (11)0.7165 (3)0.0475 (6)
O10.7376 (2)0.00177 (11)0.8782 (2)0.0579 (6)
O20.8973 (2)0.09878 (10)0.4578 (2)0.0575 (6)
H20.89280.07340.55160.086*
C10.9323 (4)0.03004 (15)0.9451 (4)0.0534 (7)
H1A0.98500.04720.83950.064*
H1B0.92500.07471.02430.064*
C20.3971 (4)0.07355 (16)0.7411 (4)0.0592 (8)
H2A0.43790.04780.86000.089*
H2B0.29320.04420.66130.089*
H2C0.34880.12450.76000.089*
C30.5701 (3)0.08004 (13)0.6508 (3)0.0408 (6)
C40.5586 (3)0.12616 (12)0.4789 (3)0.0406 (6)
C50.7196 (3)0.13387 (13)0.3919 (3)0.0437 (6)
C60.7024 (4)0.17870 (15)0.2319 (4)0.0577 (7)
H60.80990.18320.17530.069*
C70.5280 (5)0.21646 (16)0.1564 (4)0.0698 (9)
H70.51820.24710.04990.084*
C80.3672 (5)0.20922 (16)0.2377 (5)0.0720 (9)
H80.24840.23440.18530.086*
C90.3829 (4)0.16474 (15)0.3962 (4)0.0580 (8)
H90.27340.16020.45000.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0400 (12)0.0603 (13)0.0418 (12)0.0038 (9)0.0084 (9)0.0099 (10)
O10.0428 (10)0.0820 (12)0.0491 (11)0.0102 (8)0.0108 (8)0.0218 (9)
O20.0397 (10)0.0758 (12)0.0591 (12)0.0100 (8)0.0158 (8)0.0167 (10)
C10.0509 (15)0.0637 (16)0.0454 (15)0.0134 (12)0.0108 (12)0.0118 (12)
C20.0444 (15)0.0755 (18)0.0603 (17)0.0048 (13)0.0171 (12)0.0075 (14)
C30.0335 (12)0.0459 (13)0.0423 (14)0.0013 (10)0.0070 (10)0.0045 (11)
C40.0356 (12)0.0392 (12)0.0438 (14)0.0001 (9)0.0022 (10)0.0038 (10)
C50.0383 (13)0.0441 (13)0.0467 (15)0.0016 (10)0.0054 (11)0.0018 (11)
C60.0574 (17)0.0613 (16)0.0559 (17)0.0037 (13)0.0158 (13)0.0097 (13)
C70.073 (2)0.0629 (18)0.070 (2)0.0011 (15)0.0074 (16)0.0243 (15)
C80.0552 (18)0.0686 (19)0.086 (2)0.0131 (14)0.0026 (16)0.0265 (17)
C90.0421 (14)0.0581 (16)0.073 (2)0.0078 (12)0.0111 (13)0.0109 (14)
Geometric parameters (Å, º) top
N1—C31.287 (3)C3—C41.473 (3)
N1—O11.405 (2)C4—C91.396 (3)
O1—C11.432 (3)C4—C51.405 (3)
O2—C51.355 (3)C5—C61.384 (3)
O2—H20.8200C6—C71.370 (4)
C1—C1i1.500 (5)C6—H60.9300
C1—H1A0.9700C7—C81.377 (4)
C1—H1B0.9700C7—H70.9300
C2—C31.493 (3)C8—C91.372 (4)
C2—H2A0.9600C8—H80.9300
C2—H2B0.9600C9—H90.9300
C2—H2C0.9600
C3—N1—O1113.06 (19)C9—C4—C5117.2 (2)
N1—O1—C1108.54 (17)C9—C4—C3120.0 (2)
C5—O2—H2109.5C5—C4—C3122.7 (2)
O1—C1—C1i110.0 (3)O2—C5—C6116.6 (2)
O1—C1—H1A109.7O2—C5—C4122.8 (2)
C1i—C1—H1A109.7C6—C5—C4120.6 (2)
O1—C1—H1B109.7C7—C6—C5120.3 (3)
C1i—C1—H1B109.7C7—C6—H6119.8
H1A—C1—H1B108.2C5—C6—H6119.8
C3—C2—H2A109.5C6—C7—C8120.3 (3)
C3—C2—H2B109.5C6—C7—H7119.9
H2A—C2—H2B109.5C8—C7—H7119.9
C3—C2—H2C109.5C9—C8—C7119.7 (3)
H2A—C2—H2C109.5C9—C8—H8120.1
H2B—C2—H2C109.5C7—C8—H8120.1
N1—C3—C4115.8 (2)C8—C9—C4121.8 (3)
N1—C3—C2122.7 (2)C8—C9—H9119.1
C4—C3—C2121.5 (2)C4—C9—H9119.1
C3—N1—O1—C1176.97 (19)C9—C4—C5—C60.6 (3)
N1—O1—C1—C1i80.3 (3)C3—C4—C5—C6179.1 (2)
O1—N1—C3—C4178.84 (17)O2—C5—C6—C7179.7 (2)
O1—N1—C3—C20.9 (3)C4—C5—C6—C70.2 (4)
N1—C3—C4—C9179.5 (2)C5—C6—C7—C80.9 (4)
C2—C3—C4—C90.3 (3)C6—C7—C8—C90.8 (5)
N1—C3—C4—C50.8 (3)C7—C8—C9—C40.0 (5)
C2—C3—C4—C5179.4 (2)C5—C4—C9—C80.7 (4)
C9—C4—C5—O2179.5 (2)C3—C4—C9—C8179.0 (2)
C3—C4—C5—O20.8 (3)
Symmetry code: (i) x+2, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.852.56 (2)145

Experimental details

Crystal data
Chemical formulaC18H20N2O4
Mr328.36
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)6.9018 (12), 17.2184 (18), 7.3063 (14)
β (°) 103.003 (2)
V3)846.0 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.63 × 0.58 × 0.45
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.944, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
4172, 1485, 952
Rint0.065
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.175, 1.07
No. of reflections1485
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.29

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.852.56 (2)145.0
 

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