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Acta Cryst. (2008). E64, o659    [ doi:10.1107/S1600536808004352 ]

5,5'-Bis(diethylamino)-2,2'-[butane-1,4-diyldioxybis(nitrilomethylidyne)]diphenol

G.-L. Liu, X. Chen, X.-N. He and W.-K. Dong

Abstract top

The title complex, C26H38N4O4, was synthesized by the reaction of 4-diethylamino-2-hydroxybenzaldehyde with 1,4-bis(aminooxy)butane in ethanol. It crystallizes as discrete centrosymmetric molecules adopting an extended conformation where the two salicylaldoxime groups are separated from each other. Intramolecular O-H...N hydrogen bonding is observed between the hydroxy groups and oxime N atoms. Intermolecular [pi]-[pi] stacking interactions [3.979 (2) Å] between aromatic rings are apparent in the crystal structure. Each ethyl group is disordered over two positions; in one the site occupancy factors are 0.55 and 0.45, in the other 0.53 and 0.47.

Comment top

A great deal of attention has recently been attracted to the study of salen and its derivatives (Boghaei et al., 2006; Abu-Surrah et al., 1999) due to the ease of formation of metal complexes which model reaction centers of metalloenzymes. These compounds also have excellent magnetic properties (Costes et al., 2000) and form nonlinear optical materials (Lacroix, 2001). Recently, we have reported some salen-type bisoxime derivatives (Dong, Duan et al., 2007; Dong, He et al., 2007; Zhang et al., 2007), Now, the title compound, (I) was synthesized and its crystal structure determined. (Fig. 1). The molecule of (I) is disposed about a crystallographic centre of symmetry, and adopts an extended conformation with the two salicylaldoxime groups separated from each other.

The oxime groups and phenolic groups adopt a trans conformation about the C?N bond, and there is a strong O—H···N intramolecular hydrogen bond, O2—H2···N1 (d(O2—H2) = 0.820 Å, d(H2···N1) = 1.913 Å, d(O2···N1) = 2.639 (2) Å, <O2—H2···N1 = 147.01°). The carbon atoms of N,N'-diethylamino of the ligands (C10, C11, C12, C13 and C10', C11', C12', C13') are disordered over two different positions, which were allowed for during refinement.

Related literature top

For related literature, see: Abu-Surrah et al. (1999); Boghaei et al. (2006); Costes et al. (2000); Dong, Duan et al. (2007); Dong, He et al. (2007); Lacroix (2001); Zhang et al. (2007).

Experimental top

5,5'-di(N,N'-diethylamino)-2,2'-[(1,4-butylene) dioxybis(nitrilomethylidyne)]diphenol was synthesized according to an method reported earlier (Zhang et al., 2007). To an ethanol solution (5 ml) of 4-(N,N-diethylamino)-2-hydroxybenzaldehyde (398.07 mg, 2.06 mmol) was added an ethanol (3 ml) solution of 1,4-bis(aminooxy)butane (121.66 mg, 1.03 mmol). The solution was stirred at 328 K for 4 h. then concentrated to about 2 ml under reduced pressure, and washed successively with ethanol and hexane, respectively. The product was dried under vacuum and purified with recrystallization from ethanol to yield 436.26 mg of the title compound. Yield, 45%. mp. 397–398 K. Anal. Calc. for C26H38N4O4: C, 66.36; H, 8.14; N, 11.91%. Found: C, 66.25; H, 8.08; N, 12.07%. Colorless prismatic single crystals suitable for X-ray diffraction studies were obtained after about two weeks by slow evaporation of (I) at room temperature from an acetone/chloroform solution

Refinement top

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). The hydroxyl protons were located directly from a Fourier difference map. Each ethyl group is disordered over two positions; in one the site occupancy factors are 0.55 and 0.45, in the other 0.53 and 0.47.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecule structure of (I) with atom labelling and displacement ellipsoids at the 30% probability level for non-hydrogen atoms.
5,5'-Bis(diethylamino)-2,2'-[butane-1,4- diyldioxybis(nitrilomethylidyne)]diphenol top
Crystal data top
C26H38N4O4F000 = 508
Mr = 470.60Dx = 1.190 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1484 reflections
a = 7.6888 (9) Åθ = 3.0–23.4º
b = 13.777 (2) ŵ = 0.08 mm−1
c = 12.6547 (19) ÅT = 298 (2) K
β = 101.627 (2)ºBlock, colourless
V = 1313.0 (3) Å30.45 × 0.43 × 0.37 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		2303 independent reflections
Radiation source: fine-focus sealed tube1176 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→8
Tmin = 0.965, Tmax = 0.971k = −16→16
6450 measured reflectionsl = −15→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.152  w = 1/[σ2(Fo2) + (0.0421P)2 + 0.5356P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2303 reflectionsΔρmax = 0.12 e Å−3
196 parametersΔρmin = −0.15 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C26H38N4O4V = 1313.0 (3) Å3
Mr = 470.60Z = 2
Monoclinic, P21/cMo Kα
a = 7.6888 (9) ŵ = 0.08 mm−1
b = 13.777 (2) ÅT = 298 (2) K
c = 12.6547 (19) Å0.45 × 0.43 × 0.37 mm
β = 101.627 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2303 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1176 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.971Rint = 0.034
6450 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051196 parameters
wR(F2) = 0.152H-atom parameters constrained
S = 1.06Δρmax = 0.12 e Å−3
2303 reflectionsΔρmin = −0.15 e Å−3
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*/UeqOcc. (<1)
N10.4824 (3)0.15042 (16)0.05037 (19)0.0661 (6)
N21.2014 (4)0.3925 (2)0.0621 (2)0.1031 (10)
O10.3420 (3)0.10682 (14)0.08908 (15)0.0762 (6)
O20.6803 (3)0.21500 (17)−0.08246 (16)0.1077 (9)
H20.59620.1874−0.06470.162*
C10.2185 (4)0.0666 (2)0.0010 (2)0.0731 (8)
H1A0.27630.0180−0.03540.088*
H1B0.17250.1171−0.05050.088*
C20.0702 (3)0.0215 (2)0.0445 (2)0.0721 (8)
H2A0.01620.07030.08280.086*
H2B0.1178−0.02910.09540.086*
C30.5929 (4)0.1909 (2)0.1266 (2)0.0640 (8)
H30.57270.18770.19650.077*
C40.7474 (3)0.24132 (19)0.1074 (2)0.0578 (7)
C50.7878 (4)0.2523 (2)0.0062 (2)0.0638 (7)
C60.9367 (4)0.3015 (2)−0.0082 (2)0.0736 (9)
H60.95850.3077−0.07760.088*
C71.0547 (4)0.3419 (2)0.0766 (2)0.0765 (9)
C81.0136 (4)0.3313 (3)0.1787 (2)0.1091 (14)
H81.08930.35720.23870.131*
C90.8640 (4)0.2835 (3)0.1913 (2)0.0949 (11)
H90.83970.27920.26020.114*
C101.2063 (14)0.4298 (8)−0.0475 (9)0.086 (3)0.546 (16)
H10A1.27050.4908−0.04040.104*0.546 (16)
H10B1.08570.4428−0.08520.104*0.546 (16)
C111.2923 (12)0.3612 (8)−0.1148 (11)0.117 (4)0.546 (16)
H11A1.41150.3474−0.07790.175*0.546 (16)
H11B1.29460.3908−0.18320.175*0.546 (16)
H11C1.22540.3020−0.12610.175*0.546 (16)
C121.3562 (12)0.3955 (8)0.1481 (10)0.094 (4)0.525 (13)
H12A1.46520.39430.12050.112*0.525 (13)
H12B1.35690.34250.19860.112*0.525 (13)
C131.3294 (17)0.4919 (10)0.1982 (10)0.094 (4)0.525 (13)
H13A1.31610.54170.14410.141*0.525 (13)
H13B1.43040.50630.25420.141*0.525 (13)
H13C1.22450.48940.22840.141*0.525 (13)
C10'1.2900 (15)0.3771 (9)−0.0279 (11)0.086 (4)0.454 (16)
H10C1.27140.3111−0.05420.104*0.454 (16)
H10D1.41670.3880−0.00510.104*0.454 (16)
C11'1.2124 (14)0.4477 (10)−0.1155 (12)0.105 (4)0.454 (16)
H11D1.08560.4408−0.13220.158*0.454 (16)
H11E1.25940.4346−0.17880.158*0.454 (16)
H11F1.24270.5127−0.09130.158*0.454 (16)
C12'1.298 (2)0.4652 (12)0.1485 (10)0.083 (4)0.475 (13)
H12C1.35260.51580.11280.100*0.475 (13)
H12D1.21130.49560.18380.100*0.475 (13)
C13'1.4401 (12)0.4176 (7)0.2334 (9)0.091 (4)0.475 (13)
H13D1.38990.36320.26400.136*0.475 (13)
H13E1.48460.46370.28910.136*0.475 (13)
H13F1.53550.39570.20070.136*0.475 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0676 (15)0.0703 (15)0.0680 (15)0.0002 (13)0.0315 (13)0.0105 (13)
N20.080 (2)0.156 (3)0.0764 (19)−0.036 (2)0.0222 (17)0.008 (2)
O10.0714 (13)0.0932 (15)0.0707 (13)−0.0087 (11)0.0302 (11)0.0124 (11)
O20.135 (2)0.137 (2)0.0643 (14)−0.0630 (17)0.0500 (13)−0.0323 (13)
C10.070 (2)0.082 (2)0.0717 (19)−0.0014 (17)0.0248 (16)0.0077 (16)
C20.0660 (19)0.081 (2)0.0742 (19)0.0035 (16)0.0250 (14)0.0138 (16)
C30.0654 (19)0.077 (2)0.0546 (16)0.0103 (16)0.0241 (15)0.0148 (15)
C40.0542 (16)0.0727 (18)0.0495 (15)0.0095 (14)0.0179 (13)0.0136 (13)
C50.0772 (19)0.0689 (18)0.0508 (16)−0.0059 (16)0.0262 (15)−0.0074 (14)
C60.087 (2)0.086 (2)0.0577 (17)−0.0134 (18)0.0392 (17)−0.0018 (15)
C70.064 (2)0.105 (2)0.0617 (19)−0.0059 (18)0.0168 (16)0.0116 (17)
C80.069 (2)0.203 (4)0.0511 (18)−0.034 (2)0.0026 (15)0.017 (2)
C90.069 (2)0.172 (3)0.0444 (17)−0.015 (2)0.0130 (15)0.0235 (19)
C100.078 (6)0.103 (7)0.082 (7)−0.016 (5)0.024 (5)0.006 (6)
C110.118 (6)0.125 (8)0.124 (10)0.000 (6)0.063 (6)0.014 (6)
C120.074 (6)0.095 (7)0.115 (10)0.007 (5)0.027 (7)−0.001 (6)
C130.083 (7)0.086 (7)0.106 (9)−0.006 (6)0.003 (7)−0.012 (7)
C10'0.067 (6)0.105 (8)0.089 (9)−0.004 (5)0.020 (5)0.012 (6)
C11'0.099 (7)0.119 (10)0.096 (8)0.006 (6)0.016 (6)0.022 (7)
C12'0.068 (7)0.102 (11)0.079 (8)−0.021 (7)0.011 (7)0.002 (7)
C13'0.070 (6)0.111 (7)0.083 (7)0.003 (5)−0.004 (5)−0.016 (5)
Geometric parameters (Å, °) top
N1—C31.278 (3)C9—H90.9300
N1—O11.407 (2)C10—C111.51 (2)
N2—C71.370 (4)C10—H10A0.9700
N2—C121.442 (12)C10—H10B0.9700
N2—C10'1.456 (14)C11—H11A0.9600
N2—C101.486 (12)C11—H11B0.9600
N2—C12'1.557 (13)C11—H11C0.9600
O1—C11.422 (3)C12—C131.50 (2)
O2—C51.353 (3)C12—H12A0.9700
O2—H20.8200C12—H12B0.9700
C1—C21.497 (3)C13—H13A0.9600
C1—H1A0.9700C13—H13B0.9600
C1—H1B0.9700C13—H13C0.9600
C2—C2i1.515 (5)C10'—C11'1.50 (3)
C2—H2A0.9700C10'—H10C0.9700
C2—H2B0.9700C10'—H10D0.9700
C3—C41.438 (3)C11'—H11D0.9600
C3—H30.9300C11'—H11E0.9600
C4—C91.372 (4)C11'—H11F0.9600
C4—C51.386 (3)C12'—C13'1.52 (2)
C5—C61.374 (4)C12'—H12C0.9700
C6—C71.376 (4)C12'—H12D0.9700
C6—H60.9300C13'—H13D0.9600
C7—C81.398 (4)C13'—H13E0.9600
C8—C91.363 (4)C13'—H13F0.9600
C8—H80.9300
C3—N1—O1111.3 (2)C9—C8—H8119.6
C7—N2—C12119.3 (4)C7—C8—H8119.6
C7—N2—C10'124.0 (5)C8—C9—C4123.4 (3)
C12—N2—C10'98.6 (6)C8—C9—H9118.3
C7—N2—C10118.5 (4)C4—C9—H9118.3
C12—N2—C10121.4 (5)N2—C10—C11114.0 (12)
C10'—N2—C1038.4 (4)N2—C10—H10A108.7
C7—N2—C12'121.5 (5)C11—C10—H10A108.7
C12—N2—C12'41.1 (6)N2—C10—H10B108.7
C10'—N2—C12'114.2 (6)C11—C10—H10B108.7
C10—N2—C12'109.6 (6)H10A—C10—H10B107.6
N1—O1—C1109.36 (19)N2—C12—C13100.4 (9)
C5—O2—H2109.5N2—C12—H12A111.7
O1—C1—C2108.2 (2)C13—C12—H12A111.7
O1—C1—H1A110.1N2—C12—H12B111.7
C2—C1—H1A110.1C13—C12—H12B111.7
O1—C1—H1B110.1H12A—C12—H12B109.5
C2—C1—H1B110.1N2—C10'—C11'107.7 (13)
H1A—C1—H1B108.4N2—C10'—H10C110.2
C1—C2—C2i111.8 (3)C11'—C10'—H10C110.2
C1—C2—H2A109.3N2—C10'—H10D110.2
C2i—C2—H2A109.3C11'—C10'—H10D110.2
C1—C2—H2B109.3H10C—C10'—H10D108.5
C2i—C2—H2B109.3C10'—C11'—H11D109.5
H2A—C2—H2B107.9C10'—C11'—H11E109.5
N1—C3—C4122.0 (2)H11D—C11'—H11E109.5
N1—C3—H3119.0C10'—C11'—H11F109.5
C4—C3—H3119.0H11D—C11'—H11F109.5
C9—C4—C5115.8 (2)H11E—C11'—H11F109.5
C9—C4—C3120.5 (2)C13'—C12'—N2113.2 (13)
C5—C4—C3123.7 (3)C13'—C12'—H12C108.9
O2—C5—C6117.6 (2)N2—C12'—H12C108.9
O2—C5—C4120.8 (2)C13'—C12'—H12D108.9
C6—C5—C4121.6 (3)N2—C12'—H12D108.9
C5—C6—C7122.1 (3)H12C—C12'—H12D107.8
C5—C6—H6118.9C12'—C13'—H13D109.5
C7—C6—H6118.9C12'—C13'—H13E109.5
N2—C7—C6122.1 (3)H13D—C13'—H13E109.5
N2—C7—C8121.5 (3)C12'—C13'—H13F109.5
C6—C7—C8116.3 (3)H13D—C13'—H13F109.5
C9—C8—C7120.8 (3)H13E—C13'—H13F109.5
C3—N1—O1—C1177.3 (2)N2—C7—C8—C9177.8 (4)
N1—O1—C1—C2−179.6 (2)C6—C7—C8—C9−0.1 (5)
O1—C1—C2—C2i178.8 (3)C7—C8—C9—C41.4 (6)
O1—N1—C3—C4−179.4 (2)C5—C4—C9—C8−1.7 (5)
N1—C3—C4—C9−179.6 (3)C3—C4—C9—C8179.3 (3)
N1—C3—C4—C51.5 (4)C7—N2—C10—C11−92.1 (8)
C9—C4—C5—O2−178.9 (3)C12—N2—C10—C1178.4 (9)
C3—C4—C5—O20.1 (4)C10'—N2—C10—C1117.7 (8)
C9—C4—C5—C60.7 (4)C12'—N2—C10—C11122.3 (9)
C3—C4—C5—C6179.7 (3)C7—N2—C12—C13−97.9 (8)
O2—C5—C6—C7−179.8 (3)C10'—N2—C12—C13125.0 (8)
C4—C5—C6—C70.6 (5)C10—N2—C12—C1391.8 (9)
C12—N2—C7—C6−152.3 (6)C12'—N2—C12—C137.7 (11)
C10'—N2—C7—C6−26.5 (8)C7—N2—C10'—C11'93.2 (9)
C10—N2—C7—C618.3 (7)C12—N2—C10'—C11'−132.5 (8)
C12'—N2—C7—C6159.7 (8)C10—N2—C10'—C11'−1.3 (8)
C12—N2—C7—C829.9 (7)C12'—N2—C10'—C11'−92.7 (10)
C10'—N2—C7—C8155.7 (7)C7—N2—C12'—C13'88.0 (10)
C10—N2—C7—C8−159.5 (6)C12—N2—C12'—C13'−11.8 (7)
C12'—N2—C7—C8−18.1 (9)C10'—N2—C12'—C13'−86.3 (10)
C5—C6—C7—N2−178.7 (3)C10—N2—C12'—C13'−127.6 (9)
C5—C6—C7—C8−0.8 (5)
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.912.639 (2)147
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.912.639 (2)147
Acknowledgements top

This work was supported by the Foundation of the Education Department of Gansu Province (grant No. 0604–01) and the Qing Lan Talent Engineering Fund of Lanzhou Jiaotong University (grant No. QL-03–01 A), which are gratefully acknowledged.

references
References top

Abu-Surrah, A. S., Thewalt, U. & Rieger, B. (1999). J. Organomet. Chem. 587, 58–66.

Boghaei, D. M., Bezaatpour, A. & Behzad, M. (2006). J. Mol. Catal. A Chem. 245, 12–16.

Costes, J. P., Dahan, F. & Dupuis, A. (2000). Inorg. Chem. 39, 165–168.

Dong, W. K., Duan, J. G., Dong, C. M., Ren, Z. L. & Shi, J. Y. (2007). Z. Kristallogr. New Cryst. Struct. 222, 327–328.

Dong, W. K., He, X. N., Dong, C. M., Wang, L., Zhong, J. K., Chen, X. & Yu, T. Z. (2007). Z. Kristallogr. New Cryst. Struct. 222, 289–290.

Lacroix, P. G. (2001). Eur. J. Inorg. Chem. pp. 339–348.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Zhang, Y.-P., Chen, X., Shi, J.-Y., Xu, L. & Dong, W.-K. (2007). Acta Cryst. E63, o3852–?.