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The centrosymmetric title compound, C24H34N4O4, has been characterized structurally by 1H NMR and X-ray crystallography. The two benzene rings are parallel to each other. The compound forms intra­molecular hydrogen bonds, where the oxime group acts as a hydrogen-bond donor and the OH group acts as a hydrogen-bond acceptor.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038597/hg2270sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038597/hg2270Isup2.hkl
Contains datablock I

CCDC reference: 652653

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.043
  • wR factor = 0.123
  • Data-to-parameter ratio = 14.4

checkCIF/PLATON results

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Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 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 0 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

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) °).

Related literature top

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).

Experimental top

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.

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).

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I)
5,5'-Bis(diethylamino)-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol top
Crystal data top
C24H34N4O4F(000) = 476
Mr = 442.55Dx = 1.223 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1428 reflections
a = 7.3705 (10) Åθ = 2.2–22.2°
b = 18.386 (2) ŵ = 0.08 mm1
c = 8.9368 (16) ÅT = 298 K
β = 97.063 (2)°Prism, colorless
V = 1201.9 (3) Å30.56 × 0.46 × 0.40 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2114 independent reflections
Radiation source: fine-focus sealed tube1249 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 68
Tmin = 0.954, Tmax = 0.967k = 1921
6175 measured reflectionsl = 1010
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-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 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C24H34N4O4V = 1201.9 (3) Å3
Mr = 442.55Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.3705 (10) ŵ = 0.08 mm1
b = 18.386 (2) ÅT = 298 K
c = 8.9368 (16) Å0.56 × 0.46 × 0.40 mm
β = 97.063 (2)°
Data collection top
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 = 0.967Rint = 0.042
6175 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.05Δρmax = 0.16 e Å3
2114 reflectionsΔρmin = 0.16 e Å3
147 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
N10.7756 (3)0.48722 (11)0.1956 (2)0.0493 (5)
N20.3985 (2)0.32076 (11)0.7116 (2)0.0521 (6)
O10.7825 (2)0.52817 (9)0.06124 (18)0.0582 (5)
O20.8711 (2)0.41916 (11)0.4589 (2)0.0755 (6)
H20.88840.44240.38360.113*
C10.9679 (3)0.53421 (13)0.0339 (3)0.0526 (7)
H1A1.04410.54420.12800.063*
H1B0.98000.57460.03400.063*
C20.6097 (3)0.47704 (12)0.2187 (2)0.0432 (6)
H2A0.51660.49600.15000.052*
C30.5613 (3)0.43738 (12)0.3469 (2)0.0381 (5)
C40.6890 (3)0.40947 (13)0.4609 (3)0.0449 (6)
C50.6359 (3)0.37169 (13)0.5808 (2)0.0452 (6)
H50.72450.35360.65440.054*
C60.4517 (3)0.35996 (12)0.5943 (2)0.0403 (5)
C70.3223 (3)0.38893 (12)0.4812 (2)0.0439 (6)
H70.19810.38250.48660.053*
C80.3788 (3)0.42628 (12)0.3639 (2)0.0433 (6)
H80.29040.44540.29130.052*
C90.5293 (3)0.28426 (14)0.8212 (3)0.0605 (7)
H9A0.63190.26800.77160.073*
H9B0.47190.24160.85850.073*
C100.5996 (4)0.33191 (18)0.9531 (3)0.0809 (9)
H10A0.65900.37380.91740.121*
H10B0.68530.30501.02140.121*
H10C0.49920.34731.00450.121*
C110.2080 (3)0.31521 (14)0.7367 (3)0.0580 (7)
H11A0.14470.35910.69950.070*
H11B0.20160.31240.84430.070*
C120.1107 (4)0.25025 (17)0.6610 (3)0.0808 (9)
H12A0.09870.25650.55360.121*
H12B0.00840.24590.69310.121*
H12C0.18000.20700.68820.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0503 (13)0.0544 (13)0.0452 (11)0.0010 (10)0.0147 (9)0.0087 (10)
N20.0444 (12)0.0628 (14)0.0497 (12)0.0040 (10)0.0083 (9)0.0118 (11)
O10.0512 (10)0.0713 (13)0.0552 (10)0.0023 (8)0.0189 (8)0.0155 (9)
O20.0326 (10)0.1101 (16)0.0841 (13)0.0027 (9)0.0079 (8)0.0416 (12)
C10.0488 (15)0.0563 (17)0.0561 (16)0.0067 (12)0.0205 (12)0.0061 (12)
C20.0396 (13)0.0487 (15)0.0419 (13)0.0039 (11)0.0069 (10)0.0007 (11)
C30.0345 (12)0.0416 (13)0.0391 (13)0.0018 (10)0.0085 (10)0.0012 (10)
C40.0323 (13)0.0485 (15)0.0546 (15)0.0012 (10)0.0090 (11)0.0043 (12)
C50.0369 (13)0.0497 (15)0.0481 (14)0.0034 (10)0.0014 (10)0.0098 (12)
C60.0406 (13)0.0401 (14)0.0412 (13)0.0016 (10)0.0098 (10)0.0010 (10)
C70.0313 (12)0.0518 (15)0.0491 (14)0.0011 (10)0.0071 (10)0.0009 (12)
C80.0373 (13)0.0470 (14)0.0449 (14)0.0035 (10)0.0022 (10)0.0020 (11)
C90.0654 (17)0.0575 (17)0.0587 (16)0.0053 (13)0.0079 (13)0.0175 (14)
C100.087 (2)0.088 (2)0.0627 (18)0.0123 (17)0.0096 (16)0.0095 (17)
C110.0563 (16)0.0679 (19)0.0524 (15)0.0083 (13)0.0167 (12)0.0044 (13)
C120.0655 (19)0.077 (2)0.099 (2)0.0174 (16)0.0063 (16)0.0011 (19)
Geometric parameters (Å, º) top
N1—C21.279 (3)C5—H50.9300
N1—O11.424 (2)C6—C71.407 (3)
N2—C61.369 (3)C7—C81.361 (3)
N2—C91.452 (3)C7—H70.9300
N2—C111.452 (3)C8—H80.9300
O1—C11.422 (2)C9—C101.508 (4)
O2—C41.357 (2)C9—H9A0.9700
O2—H20.8200C9—H9B0.9700
C1—C1i1.498 (4)C10—H10A0.9600
C1—H1A0.9700C10—H10B0.9600
C1—H1B0.9700C10—H10C0.9600
C2—C31.439 (3)C11—C121.510 (4)
C2—H2A0.9300C11—H11A0.9700
C3—C81.387 (3)C11—H11B0.9700
C3—C41.397 (3)C12—H12A0.9600
C4—C51.373 (3)C12—H12B0.9600
C5—C61.394 (3)C12—H12C0.9600
C2—N1—O1110.35 (18)C6—C7—H7120.0
C6—N2—C9122.09 (19)C7—C8—C3123.5 (2)
C6—N2—C11121.92 (19)C7—C8—H8118.3
C9—N2—C11116.0 (2)C3—C8—H8118.3
C1—O1—N1108.75 (17)N2—C9—C10113.2 (2)
C4—O2—H2109.5N2—C9—H9A108.9
O1—C1—C1i111.2 (2)C10—C9—H9A108.9
O1—C1—H1A109.4N2—C9—H9B108.9
C1i—C1—H1A109.4C10—C9—H9B108.9
O1—C1—H1B109.4H9A—C9—H9B107.7
C1i—C1—H1B109.4C9—C10—H10A109.5
H1A—C1—H1B108.0C9—C10—H10B109.5
N1—C2—C3122.5 (2)H10A—C10—H10B109.5
N1—C2—H2A118.7C9—C10—H10C109.5
C3—C2—H2A118.7H10A—C10—H10C109.5
C8—C3—C4116.2 (2)H10B—C10—H10C109.5
C8—C3—C2120.0 (2)N2—C11—C12113.7 (2)
C4—C3—C2123.8 (2)N2—C11—H11A108.8
O2—C4—C5117.0 (2)C12—C11—H11A108.8
O2—C4—C3121.4 (2)N2—C11—H11B108.8
C5—C4—C3121.6 (2)C12—C11—H11B108.8
C4—C5—C6121.3 (2)H11A—C11—H11B107.7
C4—C5—H5119.3C11—C12—H12A109.5
C6—C5—H5119.3C11—C12—H12B109.5
N2—C6—C5121.4 (2)H12A—C12—H12B109.5
N2—C6—C7121.1 (2)C11—C12—H12C109.5
C5—C6—C7117.4 (2)H12A—C12—H12C109.5
C8—C7—C6120.0 (2)H12B—C12—H12C109.5
C8—C7—H7120.0
C2—N1—O1—C1176.15 (19)C9—N2—C6—C7173.7 (2)
N1—O1—C1—C1i78.7 (3)C11—N2—C6—C78.3 (3)
O1—N1—C2—C3179.86 (19)C4—C5—C6—N2178.3 (2)
N1—C2—C3—C8178.2 (2)C4—C5—C6—C70.6 (3)
N1—C2—C3—C43.2 (3)N2—C6—C7—C8178.5 (2)
C8—C3—C4—O2177.8 (2)C5—C6—C7—C80.4 (3)
C2—C3—C4—O20.9 (3)C6—C7—C8—C30.8 (3)
C8—C3—C4—C51.6 (3)C4—C3—C8—C71.8 (3)
C2—C3—C4—C5179.7 (2)C2—C3—C8—C7179.5 (2)
O2—C4—C5—C6178.9 (2)C6—N2—C9—C1088.5 (3)
C3—C4—C5—C60.4 (4)C11—N2—C9—C1089.6 (3)
C9—N2—C6—C55.2 (3)C6—N2—C11—C1291.9 (3)
C11—N2—C6—C5172.8 (2)C9—N2—C11—C1290.0 (3)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.82 (1)1.96 (2)2.68 (2)146 (1)

Experimental details

Crystal data
Chemical formulaC24H34N4O4
Mr442.55
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.3705 (10), 18.386 (2), 8.9368 (16)
β (°) 97.063 (2)
V3)1201.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.56 × 0.46 × 0.40
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.954, 0.967
No. of measured, independent and
observed [I > 2σ(I)] reflections
6175, 2114, 1249
Rint0.042
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.123, 1.05
No. of reflections2114
No. of parameters147
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.16

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.82 (1)1.96 (2)2.68 (2)146.0 (1)
 

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