Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038597/hg2270sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038597/hg2270Isup2.hkl |
CCDC reference: 652653
5,5'-Di(N,N'-diethylamino)-2,2'-[ethylenedioxybis (nitrilomethylidyne)]diphenol (I) was synthesized according to our previous work (Dong et al., 2007). A solution of 1, 2-bis(aminooxy)ethane (48.5 mg, 0.53 mmol) in ethanol(4 ml) was added to a solution of 4-(N,N-Diethylamino)-2-hydroxybenzaldehyde (204.0 mg, 1.06 mmol) in ethanol(4 ml), and the mixture solution was heated to 328 K under stirring for 4 h. The solution was concentrated to 2 ml in vacuo. After cooling to room temperature, the precipitate was filtered, and washed successively with ethanol-hexane (1:4) and hexane, respectively. The product was dried under reduced pressure, and purified with recrystallization from ethanol to yield colorless crystals. Yield, 68.6%. mp. 398 - 399 K. Anal. Calcd for C24H34N4O4: C, 65.14; H, 7.74; N, 12.66. Found: C, 65.10; H, 7.65; N, 12.68. 1H NMR (400 MHz, CDCl3): 1.17 (t, J= 7.4 Hz, 12H), 3.35 (dd, J= 14.0 Hz, 6.8 Hz, 8H), 4.38 (s, 4H), 6.20 (d, J= 2.8 Hz, 2H), 6.22 (t, J= 2.4 Hz, 2H), 6.94(d, J= 8.8 Hz, 2H), 8.11 (s, 2H), 9.80 (s, 2H). Colorless prismatic single crystals suitable for X-ray diffraction studies were obtained after about one month by slow evaporation at room temperature from an acetone solution of 5,5'-di(N,N'-diethylamino)-2,2'-[ethylenedioxybis (nitrilomethylidyne)]diphenol.
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).
There has been a growing interest in Schiff-base ligands, mainly because of their wide application in the fields of biochemistry, catalysis (Mohand et al., 1995; Campbell & Nguyen, 2001), and synthesis of new ligands and their complexes (Atwood & Harvey, 2001; Morris et al., 2001). A series of N,N'-bis(salicylidence)ethylenediamine (salen) and its analogues have been used as catalysts in various organic reactions (Katsuki, 1995), nonlinear optical materials (Di Bella & Fragala, 2000; Lacroix, 2001), and exhibit interesting magnetic properties (Costes et al., 2000; Bunzli & Piguet, 2002). In addition, in biological and artificial systems allosteric regulation is effective in controlling molecular functions, such as molecular recognition and biological activity (Sun et al., 2004). In context with this background, we report here on the crystal structure of 5,5'-di(N,N'-diethylamino)-2,2'- [ethylenedioxybis(nitrilomethylidyne)]diphenol (I), shown in Fig. 1. The molecule adopts an extended conformation where the two salicylaldoxime moieties are apart from each other. The oxime groups and phenolic groups have the anti-conformation, and there is an intramolecular hydrogen bond, O2—H2···N1(d(O2—H2) = 0.82 (1) Å, d(H2···N1) = 1.96 (2) Å, d(O2···N1) = 2.68 (2) Å, <O2—H2···N1 = 146.0 (1) °).
For related literature, see: Atwood & Harvey (2001); Bunzli & Piguet (2002); Campbell & Nguyen (2001); Costes et al. (2000); Di Bella & Fragala (2000); Dong et al. (2007); Katsuki (1995); Lacroix (2001); Mohand et al. (1995); Morris et al. (2001); Sun et al. (2004).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.
C24H34N4O4 | F(000) = 476 |
Mr = 442.55 | Dx = 1.223 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1428 reflections |
a = 7.3705 (10) Å | θ = 2.2–22.2° |
b = 18.386 (2) Å | µ = 0.08 mm−1 |
c = 8.9368 (16) Å | T = 298 K |
β = 97.063 (2)° | Prism, colorless |
V = 1201.9 (3) Å3 | 0.56 × 0.46 × 0.40 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2114 independent reflections |
Radiation source: fine-focus sealed tube | 1249 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→8 |
Tmin = 0.954, Tmax = 0.967 | k = −19→21 |
6175 measured reflections | l = −10→10 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0358P)2 + 0.4459P] where P = (Fo2 + 2Fc2)/3 |
2114 reflections | (Δ/σ)max < 0.001 |
147 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C24H34N4O4 | V = 1201.9 (3) Å3 |
Mr = 442.55 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3705 (10) Å | µ = 0.08 mm−1 |
b = 18.386 (2) Å | T = 298 K |
c = 8.9368 (16) Å | 0.56 × 0.46 × 0.40 mm |
β = 97.063 (2)° |
Bruker SMART CCD area-detector diffractometer | 2114 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1249 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.967 | Rint = 0.042 |
6175 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.16 e Å−3 |
2114 reflections | Δρmin = −0.16 e Å−3 |
147 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 | 0.7756 (3) | 0.48722 (11) | 0.1956 (2) | 0.0493 (5) | |
N2 | 0.3985 (2) | 0.32076 (11) | 0.7116 (2) | 0.0521 (6) | |
O1 | 0.7825 (2) | 0.52817 (9) | 0.06124 (18) | 0.0582 (5) | |
O2 | 0.8711 (2) | 0.41916 (11) | 0.4589 (2) | 0.0755 (6) | |
H2 | 0.8884 | 0.4424 | 0.3836 | 0.113* | |
C1 | 0.9679 (3) | 0.53421 (13) | 0.0339 (3) | 0.0526 (7) | |
H1A | 1.0441 | 0.5442 | 0.1280 | 0.063* | |
H1B | 0.9800 | 0.5746 | −0.0340 | 0.063* | |
C2 | 0.6097 (3) | 0.47704 (12) | 0.2187 (2) | 0.0432 (6) | |
H2A | 0.5166 | 0.4960 | 0.1500 | 0.052* | |
C3 | 0.5613 (3) | 0.43738 (12) | 0.3469 (2) | 0.0381 (5) | |
C4 | 0.6890 (3) | 0.40947 (13) | 0.4609 (3) | 0.0449 (6) | |
C5 | 0.6359 (3) | 0.37169 (13) | 0.5808 (2) | 0.0452 (6) | |
H5 | 0.7245 | 0.3536 | 0.6544 | 0.054* | |
C6 | 0.4517 (3) | 0.35996 (12) | 0.5943 (2) | 0.0403 (5) | |
C7 | 0.3223 (3) | 0.38893 (12) | 0.4812 (2) | 0.0439 (6) | |
H7 | 0.1981 | 0.3825 | 0.4866 | 0.053* | |
C8 | 0.3788 (3) | 0.42628 (12) | 0.3639 (2) | 0.0433 (6) | |
H8 | 0.2904 | 0.4454 | 0.2913 | 0.052* | |
C9 | 0.5293 (3) | 0.28426 (14) | 0.8212 (3) | 0.0605 (7) | |
H9A | 0.6319 | 0.2680 | 0.7716 | 0.073* | |
H9B | 0.4719 | 0.2416 | 0.8585 | 0.073* | |
C10 | 0.5996 (4) | 0.33191 (18) | 0.9531 (3) | 0.0809 (9) | |
H10A | 0.6590 | 0.3738 | 0.9174 | 0.121* | |
H10B | 0.6853 | 0.3050 | 1.0214 | 0.121* | |
H10C | 0.4992 | 0.3473 | 1.0045 | 0.121* | |
C11 | 0.2080 (3) | 0.31521 (14) | 0.7367 (3) | 0.0580 (7) | |
H11A | 0.1447 | 0.3591 | 0.6995 | 0.070* | |
H11B | 0.2016 | 0.3124 | 0.8443 | 0.070* | |
C12 | 0.1107 (4) | 0.25025 (17) | 0.6610 (3) | 0.0808 (9) | |
H12A | 0.0987 | 0.2565 | 0.5536 | 0.121* | |
H12B | −0.0084 | 0.2459 | 0.6931 | 0.121* | |
H12C | 0.1800 | 0.2070 | 0.6882 | 0.121* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0503 (13) | 0.0544 (13) | 0.0452 (11) | −0.0010 (10) | 0.0147 (9) | 0.0087 (10) |
N2 | 0.0444 (12) | 0.0628 (14) | 0.0497 (12) | −0.0040 (10) | 0.0083 (9) | 0.0118 (11) |
O1 | 0.0512 (10) | 0.0713 (13) | 0.0552 (10) | 0.0023 (8) | 0.0189 (8) | 0.0155 (9) |
O2 | 0.0326 (10) | 0.1101 (16) | 0.0841 (13) | 0.0027 (9) | 0.0079 (8) | 0.0416 (12) |
C1 | 0.0488 (15) | 0.0563 (17) | 0.0561 (16) | −0.0067 (12) | 0.0205 (12) | 0.0061 (12) |
C2 | 0.0396 (13) | 0.0487 (15) | 0.0419 (13) | 0.0039 (11) | 0.0069 (10) | −0.0007 (11) |
C3 | 0.0345 (12) | 0.0416 (13) | 0.0391 (13) | 0.0018 (10) | 0.0085 (10) | −0.0012 (10) |
C4 | 0.0323 (13) | 0.0485 (15) | 0.0546 (15) | 0.0012 (10) | 0.0090 (11) | 0.0043 (12) |
C5 | 0.0369 (13) | 0.0497 (15) | 0.0481 (14) | 0.0034 (10) | 0.0014 (10) | 0.0098 (12) |
C6 | 0.0406 (13) | 0.0401 (14) | 0.0412 (13) | −0.0016 (10) | 0.0098 (10) | −0.0010 (10) |
C7 | 0.0313 (12) | 0.0518 (15) | 0.0491 (14) | −0.0011 (10) | 0.0071 (10) | 0.0009 (12) |
C8 | 0.0373 (13) | 0.0470 (14) | 0.0449 (14) | 0.0035 (10) | 0.0022 (10) | 0.0020 (11) |
C9 | 0.0654 (17) | 0.0575 (17) | 0.0587 (16) | −0.0053 (13) | 0.0079 (13) | 0.0175 (14) |
C10 | 0.087 (2) | 0.088 (2) | 0.0627 (18) | −0.0123 (17) | −0.0096 (16) | 0.0095 (17) |
C11 | 0.0563 (16) | 0.0679 (19) | 0.0524 (15) | −0.0083 (13) | 0.0167 (12) | 0.0044 (13) |
C12 | 0.0655 (19) | 0.077 (2) | 0.099 (2) | −0.0174 (16) | 0.0063 (16) | 0.0011 (19) |
N1—C2 | 1.279 (3) | C5—H5 | 0.9300 |
N1—O1 | 1.424 (2) | C6—C7 | 1.407 (3) |
N2—C6 | 1.369 (3) | C7—C8 | 1.361 (3) |
N2—C9 | 1.452 (3) | C7—H7 | 0.9300 |
N2—C11 | 1.452 (3) | C8—H8 | 0.9300 |
O1—C1 | 1.422 (2) | C9—C10 | 1.508 (4) |
O2—C4 | 1.357 (2) | C9—H9A | 0.9700 |
O2—H2 | 0.8200 | C9—H9B | 0.9700 |
C1—C1i | 1.498 (4) | C10—H10A | 0.9600 |
C1—H1A | 0.9700 | C10—H10B | 0.9600 |
C1—H1B | 0.9700 | C10—H10C | 0.9600 |
C2—C3 | 1.439 (3) | C11—C12 | 1.510 (4) |
C2—H2A | 0.9300 | C11—H11A | 0.9700 |
C3—C8 | 1.387 (3) | C11—H11B | 0.9700 |
C3—C4 | 1.397 (3) | C12—H12A | 0.9600 |
C4—C5 | 1.373 (3) | C12—H12B | 0.9600 |
C5—C6 | 1.394 (3) | C12—H12C | 0.9600 |
C2—N1—O1 | 110.35 (18) | C6—C7—H7 | 120.0 |
C6—N2—C9 | 122.09 (19) | C7—C8—C3 | 123.5 (2) |
C6—N2—C11 | 121.92 (19) | C7—C8—H8 | 118.3 |
C9—N2—C11 | 116.0 (2) | C3—C8—H8 | 118.3 |
C1—O1—N1 | 108.75 (17) | N2—C9—C10 | 113.2 (2) |
C4—O2—H2 | 109.5 | N2—C9—H9A | 108.9 |
O1—C1—C1i | 111.2 (2) | C10—C9—H9A | 108.9 |
O1—C1—H1A | 109.4 | N2—C9—H9B | 108.9 |
C1i—C1—H1A | 109.4 | C10—C9—H9B | 108.9 |
O1—C1—H1B | 109.4 | H9A—C9—H9B | 107.7 |
C1i—C1—H1B | 109.4 | C9—C10—H10A | 109.5 |
H1A—C1—H1B | 108.0 | C9—C10—H10B | 109.5 |
N1—C2—C3 | 122.5 (2) | H10A—C10—H10B | 109.5 |
N1—C2—H2A | 118.7 | C9—C10—H10C | 109.5 |
C3—C2—H2A | 118.7 | H10A—C10—H10C | 109.5 |
C8—C3—C4 | 116.2 (2) | H10B—C10—H10C | 109.5 |
C8—C3—C2 | 120.0 (2) | N2—C11—C12 | 113.7 (2) |
C4—C3—C2 | 123.8 (2) | N2—C11—H11A | 108.8 |
O2—C4—C5 | 117.0 (2) | C12—C11—H11A | 108.8 |
O2—C4—C3 | 121.4 (2) | N2—C11—H11B | 108.8 |
C5—C4—C3 | 121.6 (2) | C12—C11—H11B | 108.8 |
C4—C5—C6 | 121.3 (2) | H11A—C11—H11B | 107.7 |
C4—C5—H5 | 119.3 | C11—C12—H12A | 109.5 |
C6—C5—H5 | 119.3 | C11—C12—H12B | 109.5 |
N2—C6—C5 | 121.4 (2) | H12A—C12—H12B | 109.5 |
N2—C6—C7 | 121.1 (2) | C11—C12—H12C | 109.5 |
C5—C6—C7 | 117.4 (2) | H12A—C12—H12C | 109.5 |
C8—C7—C6 | 120.0 (2) | H12B—C12—H12C | 109.5 |
C8—C7—H7 | 120.0 | ||
C2—N1—O1—C1 | −176.15 (19) | C9—N2—C6—C7 | 173.7 (2) |
N1—O1—C1—C1i | 78.7 (3) | C11—N2—C6—C7 | −8.3 (3) |
O1—N1—C2—C3 | −179.86 (19) | C4—C5—C6—N2 | 178.3 (2) |
N1—C2—C3—C8 | −178.2 (2) | C4—C5—C6—C7 | −0.6 (3) |
N1—C2—C3—C4 | 3.2 (3) | N2—C6—C7—C8 | −178.5 (2) |
C8—C3—C4—O2 | −177.8 (2) | C5—C6—C7—C8 | 0.4 (3) |
C2—C3—C4—O2 | 0.9 (3) | C6—C7—C8—C3 | 0.8 (3) |
C8—C3—C4—C5 | 1.6 (3) | C4—C3—C8—C7 | −1.8 (3) |
C2—C3—C4—C5 | −179.7 (2) | C2—C3—C8—C7 | 179.5 (2) |
O2—C4—C5—C6 | 178.9 (2) | C6—N2—C9—C10 | 88.5 (3) |
C3—C4—C5—C6 | −0.4 (4) | C11—N2—C9—C10 | −89.6 (3) |
C9—N2—C6—C5 | −5.2 (3) | C6—N2—C11—C12 | 91.9 (3) |
C11—N2—C6—C5 | 172.8 (2) | C9—N2—C11—C12 | −90.0 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1 | 0.82 (1) | 1.96 (2) | 2.68 (2) | 146 (1) |
Experimental details
Crystal data | |
Chemical formula | C24H34N4O4 |
Mr | 442.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.3705 (10), 18.386 (2), 8.9368 (16) |
β (°) | 97.063 (2) |
V (Å3) | 1201.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.56 × 0.46 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.954, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6175, 2114, 1249 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.05 |
No. of reflections | 2114 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.16 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1 | 0.82 (1) | 1.96 (2) | 2.68 (2) | 146.0 (1) |
There has been a growing interest in Schiff-base ligands, mainly because of their wide application in the fields of biochemistry, catalysis (Mohand et al., 1995; Campbell & Nguyen, 2001), and synthesis of new ligands and their complexes (Atwood & Harvey, 2001; Morris et al., 2001). A series of N,N'-bis(salicylidence)ethylenediamine (salen) and its analogues have been used as catalysts in various organic reactions (Katsuki, 1995), nonlinear optical materials (Di Bella & Fragala, 2000; Lacroix, 2001), and exhibit interesting magnetic properties (Costes et al., 2000; Bunzli & Piguet, 2002). In addition, in biological and artificial systems allosteric regulation is effective in controlling molecular functions, such as molecular recognition and biological activity (Sun et al., 2004). In context with this background, we report here on the crystal structure of 5,5'-di(N,N'-diethylamino)-2,2'- [ethylenedioxybis(nitrilomethylidyne)]diphenol (I), shown in Fig. 1. The molecule adopts an extended conformation where the two salicylaldoxime moieties are apart from each other. The oxime groups and phenolic groups have the anti-conformation, and there is an intramolecular hydrogen bond, O2—H2···N1(d(O2—H2) = 0.82 (1) Å, d(H2···N1) = 1.96 (2) Å, d(O2···N1) = 2.68 (2) Å, <O2—H2···N1 = 146.0 (1) °).