Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047927/hg2302sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047927/hg2302Isup2.hkl |
CCDC reference: 644785
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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).
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.
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).
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).
C18H20N2O4 | F(000) = 348 |
Mr = 328.36 | Dx = 1.289 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1276 reflections |
a = 6.9018 (12) Å | θ = 2.4–25.1° |
b = 17.2184 (18) Å | µ = 0.09 mm−1 |
c = 7.3063 (14) Å | T = 298 K |
β = 103.003 (2)° | Prismatic, colorless |
V = 846.0 (2) Å3 | 0.63 × 0.58 × 0.45 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1485 independent reflections |
Radiation source: fine-focus sealed tube | 952 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.944, Tmax = 0.960 | k = −20→18 |
4172 measured reflections | l = −5→8 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.175 | H-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 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C18H20N2O4 | V = 846.0 (2) Å3 |
Mr = 328.36 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9018 (12) Å | µ = 0.09 mm−1 |
b = 17.2184 (18) Å | T = 298 K |
c = 7.3063 (14) Å | 0.63 × 0.58 × 0.45 mm |
β = 103.003 (2)° |
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 = 0.960 | Rint = 0.065 |
4172 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.25 e Å−3 |
1485 reflections | Δρmin = −0.29 e Å−3 |
109 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 | ||
N1 | 0.7373 (3) | 0.04598 (11) | 0.7165 (3) | 0.0475 (6) | |
O1 | 0.7376 (2) | 0.00177 (11) | 0.8782 (2) | 0.0579 (6) | |
O2 | 0.8973 (2) | 0.09878 (10) | 0.4578 (2) | 0.0575 (6) | |
H2 | 0.8928 | 0.0734 | 0.5516 | 0.086* | |
C1 | 0.9323 (4) | −0.03004 (15) | 0.9451 (4) | 0.0534 (7) | |
H1A | 0.9850 | −0.0472 | 0.8395 | 0.064* | |
H1B | 0.9250 | −0.0747 | 1.0243 | 0.064* | |
C2 | 0.3971 (4) | 0.07355 (16) | 0.7411 (4) | 0.0592 (8) | |
H2A | 0.4379 | 0.0478 | 0.8600 | 0.089* | |
H2B | 0.2932 | 0.0442 | 0.6613 | 0.089* | |
H2C | 0.3488 | 0.1245 | 0.7600 | 0.089* | |
C3 | 0.5701 (3) | 0.08004 (13) | 0.6508 (3) | 0.0408 (6) | |
C4 | 0.5586 (3) | 0.12616 (12) | 0.4789 (3) | 0.0406 (6) | |
C5 | 0.7196 (3) | 0.13387 (13) | 0.3919 (3) | 0.0437 (6) | |
C6 | 0.7024 (4) | 0.17870 (15) | 0.2319 (4) | 0.0577 (7) | |
H6 | 0.8099 | 0.1832 | 0.1753 | 0.069* | |
C7 | 0.5280 (5) | 0.21646 (16) | 0.1564 (4) | 0.0698 (9) | |
H7 | 0.5182 | 0.2471 | 0.0499 | 0.084* | |
C8 | 0.3672 (5) | 0.20922 (16) | 0.2377 (5) | 0.0720 (9) | |
H8 | 0.2484 | 0.2344 | 0.1853 | 0.086* | |
C9 | 0.3829 (4) | 0.16474 (15) | 0.3962 (4) | 0.0580 (8) | |
H9 | 0.2734 | 0.1602 | 0.4500 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0400 (12) | 0.0603 (13) | 0.0418 (12) | 0.0038 (9) | 0.0084 (9) | 0.0099 (10) |
O1 | 0.0428 (10) | 0.0820 (12) | 0.0491 (11) | 0.0102 (8) | 0.0108 (8) | 0.0218 (9) |
O2 | 0.0397 (10) | 0.0758 (12) | 0.0591 (12) | 0.0100 (8) | 0.0158 (8) | 0.0167 (10) |
C1 | 0.0509 (15) | 0.0637 (16) | 0.0454 (15) | 0.0134 (12) | 0.0108 (12) | 0.0118 (12) |
C2 | 0.0444 (15) | 0.0755 (18) | 0.0603 (17) | 0.0048 (13) | 0.0171 (12) | 0.0075 (14) |
C3 | 0.0335 (12) | 0.0459 (13) | 0.0423 (14) | −0.0013 (10) | 0.0070 (10) | −0.0045 (11) |
C4 | 0.0356 (12) | 0.0392 (12) | 0.0438 (14) | −0.0001 (9) | 0.0022 (10) | −0.0038 (10) |
C5 | 0.0383 (13) | 0.0441 (13) | 0.0467 (15) | −0.0016 (10) | 0.0054 (11) | −0.0018 (11) |
C6 | 0.0574 (17) | 0.0613 (16) | 0.0559 (17) | −0.0037 (13) | 0.0158 (13) | 0.0097 (13) |
C7 | 0.073 (2) | 0.0629 (18) | 0.070 (2) | 0.0011 (15) | 0.0074 (16) | 0.0243 (15) |
C8 | 0.0552 (18) | 0.0686 (19) | 0.086 (2) | 0.0131 (14) | 0.0026 (16) | 0.0265 (17) |
C9 | 0.0421 (14) | 0.0581 (16) | 0.073 (2) | 0.0078 (12) | 0.0111 (13) | 0.0109 (14) |
N1—C3 | 1.287 (3) | C3—C4 | 1.473 (3) |
N1—O1 | 1.405 (2) | C4—C9 | 1.396 (3) |
O1—C1 | 1.432 (3) | C4—C5 | 1.405 (3) |
O2—C5 | 1.355 (3) | C5—C6 | 1.384 (3) |
O2—H2 | 0.8200 | C6—C7 | 1.370 (4) |
C1—C1i | 1.500 (5) | C6—H6 | 0.9300 |
C1—H1A | 0.9700 | C7—C8 | 1.377 (4) |
C1—H1B | 0.9700 | C7—H7 | 0.9300 |
C2—C3 | 1.493 (3) | C8—C9 | 1.372 (4) |
C2—H2A | 0.9600 | C8—H8 | 0.9300 |
C2—H2B | 0.9600 | C9—H9 | 0.9300 |
C2—H2C | 0.9600 | ||
C3—N1—O1 | 113.06 (19) | C9—C4—C5 | 117.2 (2) |
N1—O1—C1 | 108.54 (17) | C9—C4—C3 | 120.0 (2) |
C5—O2—H2 | 109.5 | C5—C4—C3 | 122.7 (2) |
O1—C1—C1i | 110.0 (3) | O2—C5—C6 | 116.6 (2) |
O1—C1—H1A | 109.7 | O2—C5—C4 | 122.8 (2) |
C1i—C1—H1A | 109.7 | C6—C5—C4 | 120.6 (2) |
O1—C1—H1B | 109.7 | C7—C6—C5 | 120.3 (3) |
C1i—C1—H1B | 109.7 | C7—C6—H6 | 119.8 |
H1A—C1—H1B | 108.2 | C5—C6—H6 | 119.8 |
C3—C2—H2A | 109.5 | C6—C7—C8 | 120.3 (3) |
C3—C2—H2B | 109.5 | C6—C7—H7 | 119.9 |
H2A—C2—H2B | 109.5 | C8—C7—H7 | 119.9 |
C3—C2—H2C | 109.5 | C9—C8—C7 | 119.7 (3) |
H2A—C2—H2C | 109.5 | C9—C8—H8 | 120.1 |
H2B—C2—H2C | 109.5 | C7—C8—H8 | 120.1 |
N1—C3—C4 | 115.8 (2) | C8—C9—C4 | 121.8 (3) |
N1—C3—C2 | 122.7 (2) | C8—C9—H9 | 119.1 |
C4—C3—C2 | 121.5 (2) | C4—C9—H9 | 119.1 |
C3—N1—O1—C1 | −176.97 (19) | C9—C4—C5—C6 | 0.6 (3) |
N1—O1—C1—C1i | 80.3 (3) | C3—C4—C5—C6 | −179.1 (2) |
O1—N1—C3—C4 | −178.84 (17) | O2—C5—C6—C7 | −179.7 (2) |
O1—N1—C3—C2 | 0.9 (3) | C4—C5—C6—C7 | 0.2 (4) |
N1—C3—C4—C9 | 179.5 (2) | C5—C6—C7—C8 | −0.9 (4) |
C2—C3—C4—C9 | −0.3 (3) | C6—C7—C8—C9 | 0.8 (5) |
N1—C3—C4—C5 | −0.8 (3) | C7—C8—C9—C4 | 0.0 (5) |
C2—C3—C4—C5 | 179.4 (2) | C5—C4—C9—C8 | −0.7 (4) |
C9—C4—C5—O2 | −179.5 (2) | C3—C4—C9—C8 | 179.0 (2) |
C3—C4—C5—O2 | 0.8 (3) |
Symmetry code: (i) −x+2, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C18H20N2O4 |
Mr | 328.36 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 6.9018 (12), 17.2184 (18), 7.3063 (14) |
β (°) | 103.003 (2) |
V (Å3) | 846.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.63 × 0.58 × 0.45 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.944, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4172, 1485, 952 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.175, 1.07 |
No. of reflections | 1485 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.29 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
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(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°).