2,2′-{1,1′-[Pentane-1,5-diyl­bis(oxy­nitrilo)]­diethyl­idyne}diphenol

Dong, W.-K.; Lv, Z.-W.; He, X.-N.; Guan, Y.-H.; Tong, J.-F.

doi:10.1107/S160053680803136X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2059

doi:10.1107/S160053680803136X

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2,2′-{1,1′-[Pentane-1,5-diylbis(oxynitrilo)]diethylidyne}diphenol

Wen-Kui Dong,^a ^* Zhong-Wu Lv,^a Xue-Ni He,^a Yong-Hong Guan ^a and Jun-Feng Tong ^a

^aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: dongwk@mail.lzjtu.cn

(Received 28 July 2008; accepted 28 September 2008; online 4 October 2008)

In the title compound, C₂₁H₂₆N₂O₄, there is half a molecule in the asymmetric unit with a crystallographic twofold rotation axis passing through the central C atom of the –CH=N—O—(CH₂)₅—O—N=CH– bridge. The dihedral angle formed by the two benzene rings is 80.85 (2)°. Strong intramolecular O—H⋯N and C—H⋯O hydrogen bonds help to establish the molecular conformation. There are also weak intermolecular π–π stacking interactions between neighbouring benzene rings [centroid–centroid separation = 3.502 (3) Å].

Related literature

For general background, see: Bhadbhade & Srinivas (1993 ). For related structures, see: Dong et al. (2007 , 2008 ); Wang et al. (2007 ); Xu et al. (2007 ).

Experimental

Crystal data

C₂₁H₂₆N₂O₄
M_r = 370.44
Monoclinic, C 2
a = 12.9691 (13) Å
b = 4.601 (1) Å
c = 16.3639 (16) Å
β = 91.621 (1)°
V = 976.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.48 × 0.40 × 0.32 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.959, T_max = 0.973
2421 measured reflections
972 independent reflections
646 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.123
S = 1.04
972 reflections
123 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.84	2.553 (4)	144
C4—H4A⋯O1	0.96	2.16	2.631 (5)	109

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803136X/gw2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803136X/gw2048Isup2.hkl

checkCIF report

Comment top

salen-type compounds containing strong donor sites such as oxygen and imine nitrogen atoms and their metal complexes have been the subject of extensive investigation (Bhadbhade & Srinivas, 1993). Structures of salen-type compounds derived from O-alkyl oxime moiety (–CH═N—O-(CH₂)_n-O—N═CH–) instead of the imine moiety and closely related to the title compound (Wang et al., 2007; Dong et al., 2008; Dong et al., 2007), are known. In this research, we report the synthesis and crystal structure of the title compound, and shown in Fig. 1.

The single-crystal structure of the title compound is built up by discrete C₂₁H₂₆N₂O₄ molecules, within all bond lengths are in normal ranges. There is 1/2 molecule per asymmetric unit with a crystallographic twofold rotation axis passing through the central carbon (symmetry code: -x, y, -z) of the five carbon atoms in the (—CH═N—O—(CH₂)₅—O—N═CH—) bridge. The dihedral angle formed by the two benzene rings in the molecule of the title compound is 80.85 (2)°. The strong intramolecular O2—H2···N1 and C4—H4A···O1 hydrogen bonds play an important role in the stability of the crystal structure in the title compound. The five carbon atoms in the C1—C2—C3—C2A—C1A bridge are almost in the same plane with slight deviation of 0.015 and 0.029 Å below for C1, C2A, 0.015 and 0.029 Å above the plane for C2 and C1A (symmetry code A: -x, y, -z + 1), respectively. In the crystal structure, there is weak intermolecular π–π stacking interaction between the neighbouring benzene rings, and the inter-molecular plane-to-plane distance is 3.502 (3) Å along b axis. This structure is not similar to what was observed in our previously reported series of salen-type compound containing two- (Wang et al., 2007), three- (Dong et al., 2008) and four-methene (Dong et al., 2007) bridge.

Related literature top

For related literature, see: Bhadbhade & Srinivas (1993); Dong et al. (2007, 2008); Wang et al. (2007); Xu et al. (2007). [From the Section Editors: It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···." etc. Please revise this section as indicated.]

Experimental top

2,2'-[1,1'-(Pentane-1,5-diyldioxydinitrilo)diethylidyne]diphenol was synthesized according to an analogous method reported earlier (Wang et al., 2007; Xu et al., 2007). To an ethanol solution (5 ml) of 2'-hydroxyacetophenone (516.2 mg, 4.00 mmol) was added an ethanol solution (3 ml) of 1,5-bis(aminooxy)pentane (268.4 mg, 2.00 mmol). The reaction mixture was stirred at 328 K for 4 h. The formed precipitate was separated by filtration, and washed successively with ethanol and ethanol–hexane (1:4), respectively. The product was dried under vacuum to yield 410.9 mg of the title compound. Yield, 55.5%. mp. 344–345 K. Anal. Calc. for C₁₇H₁₆Cl₂N₂O₂: C, 68.09; H, 7.07; N, 7.56. Found: C, 68.19; H, 7.21; N, 7.42.

Colorless block-like single crystals suitable for X-ray diffraction studies were obtained after two weeks by slow evaporation from a diethyl-ether solution of the title compound.

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, 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

Fig. 1. The molecular structure of the title compound with atom numbering scheme [Symmetry codes: A: -x, y, -z + 1]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.

2,2'-{1,1'-[Pentane-1,5-diylbis(oxynitrilo)]diethylidyne}diphenol top

Crystal data top

C₂₁H₂₆N₂O₄	F(000) = 396
M_r = 370.44	D_x = 1.260 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 813 reflections
a = 12.9691 (13) Å	θ = 2.5–23.2°
b = 4.601 (1) Å	µ = 0.09 mm⁻¹
c = 16.3639 (16) Å	T = 298 K
β = 91.621 (1)°	Needle-like, colourless
V = 976.1 (3) Å³	0.48 × 0.40 × 0.32 mm
Z = 2

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	972 independent reflections
Radiation source: fine-focus sealed tube	646 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.959, T_max = 0.973	k = −5→5
2421 measured reflections	l = −19→10

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0568P)² + 0.2844P] where P = (F_o² + 2F_c²)/3
972 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.15 e Å⁻³
2 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₂₁H₂₆N₂O₄	V = 976.1 (3) Å³
M_r = 370.44	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 12.9691 (13) Å	µ = 0.09 mm⁻¹
b = 4.601 (1) Å	T = 298 K
c = 16.3639 (16) Å	0.48 × 0.40 × 0.32 mm
β = 91.621 (1)°

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	972 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	646 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.973	R_int = 0.038
2421 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.15 e Å⁻³
972 reflections	Δρ_min = −0.12 e Å⁻³
123 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.1857 (2)	0.7552 (7)	0.30501 (17)	0.0533 (8)
O1	0.23002 (19)	0.6005 (8)	0.37063 (14)	0.0656 (7)
O2	0.0337 (2)	0.9262 (9)	0.21462 (17)	0.0796 (9)
H2	0.0629	0.8223	0.2488	0.119*
C1	0.1512 (3)	0.4342 (11)	0.4082 (2)	0.0607 (10)
H1A	0.1834	0.2927	0.4447	0.073*
H1B	0.1126	0.3286	0.3662	0.073*
C2	0.0778 (3)	0.6170 (10)	0.4558 (2)	0.0551 (9)
H2A	0.1169	0.7333	0.4952	0.066*
H2B	0.0418	0.7489	0.4186	0.066*
C3	0.0000	0.4391 (13)	0.5000	0.0526 (12)
H3A	0.0361	0.3147	0.5392	0.063*	0.50
H3B	−0.0361	0.3147	0.4608	0.063*	0.50
C4	0.3610 (3)	0.9300 (15)	0.2926 (2)	0.0836 (14)
H4A	0.3736	0.8041	0.3386	0.125*
H4B	0.3787	1.1259	0.3074	0.125*
H4C	0.4023	0.8688	0.2479	0.125*
C5	0.2494 (3)	0.9162 (9)	0.2673 (2)	0.0494 (9)
C6	0.2084 (3)	1.0860 (9)	0.1985 (2)	0.0485 (9)
C7	0.1043 (3)	1.0870 (11)	0.1759 (2)	0.0573 (9)
C8	0.0682 (3)	1.2544 (12)	0.1116 (2)	0.0745 (12)
H8	−0.0017	1.2535	0.0971	0.089*
C9	0.1348 (4)	1.4212 (13)	0.0693 (2)	0.0773 (13)
H9	0.1099	1.5343	0.0260	0.093*
C10	0.2363 (4)	1.4250 (12)	0.0892 (2)	0.0735 (12)
H10	0.2812	1.5389	0.0595	0.088*
C11	0.2732 (3)	1.2605 (10)	0.1533 (2)	0.0610 (11)
H11	0.3433	1.2656	0.1670	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0547 (18)	0.0514 (18)	0.0545 (16)	0.0036 (18)	0.0125 (14)	−0.0018 (17)
O1	0.0574 (15)	0.0702 (16)	0.0701 (15)	0.0067 (17)	0.0167 (12)	0.0136 (17)
O2	0.0532 (16)	0.0868 (19)	0.099 (2)	−0.006 (2)	0.0049 (14)	0.018 (2)
C1	0.065 (2)	0.053 (2)	0.066 (2)	0.011 (3)	0.0173 (19)	0.009 (2)
C2	0.062 (2)	0.045 (2)	0.059 (2)	−0.001 (2)	0.0143 (17)	−0.002 (2)
C3	0.062 (3)	0.041 (3)	0.054 (3)	0.000	0.009 (2)	0.000
C4	0.055 (2)	0.107 (4)	0.089 (3)	−0.014 (3)	0.004 (2)	0.015 (4)
C5	0.0469 (19)	0.048 (2)	0.0541 (19)	−0.003 (2)	0.0155 (17)	−0.010 (2)
C6	0.053 (2)	0.0447 (19)	0.0478 (18)	−0.011 (2)	0.0105 (16)	−0.010 (2)
C7	0.056 (2)	0.055 (2)	0.062 (2)	−0.004 (3)	0.0132 (18)	−0.005 (3)
C8	0.071 (3)	0.078 (3)	0.074 (3)	−0.001 (3)	−0.004 (2)	0.005 (3)
C9	0.106 (4)	0.067 (3)	0.058 (2)	0.001 (3)	0.000 (2)	0.001 (3)
C10	0.098 (4)	0.066 (3)	0.058 (2)	−0.023 (3)	0.014 (2)	−0.004 (3)
C11	0.063 (2)	0.062 (3)	0.059 (2)	−0.014 (3)	0.013 (2)	−0.012 (3)

Geometric parameters (Å, º) top

N1—C5	1.282 (4)	C4—H4A	0.9600
N1—O1	1.398 (4)	C4—H4B	0.9600
O1—C1	1.430 (5)	C4—H4C	0.9600
O2—C7	1.349 (5)	C5—C6	1.459 (5)
O2—H2	0.8200	C6—C7	1.389 (5)
C1—C2	1.504 (5)	C6—C11	1.390 (5)
C1—H1A	0.9700	C7—C8	1.375 (5)
C1—H1B	0.9700	C8—C9	1.360 (6)
C2—C3	1.501 (5)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.348 (6)
C2—H2B	0.9700	C9—H9	0.9300
C3—C2ⁱ	1.501 (5)	C10—C11	1.370 (6)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—H11	0.9300
C4—C5	1.495 (5)

C5—N1—O1	114.0 (3)	C5—C4—H4C	109.5
N1—O1—C1	108.6 (3)	H4A—C4—H4C	109.5
C7—O2—H2	109.5	H4B—C4—H4C	109.5
O1—C1—C2	113.2 (4)	N1—C5—C6	117.0 (3)
O1—C1—H1A	108.9	N1—C5—C4	121.6 (4)
C2—C1—H1A	108.9	C6—C5—C4	121.3 (4)
O1—C1—H1B	108.9	C7—C6—C11	117.0 (4)
C2—C1—H1B	108.9	C7—C6—C5	122.5 (3)
H1A—C1—H1B	107.7	C11—C6—C5	120.4 (3)
C3—C2—C1	112.9 (3)	O2—C7—C8	116.4 (4)
C3—C2—H2A	109.0	O2—C7—C6	122.7 (4)
C1—C2—H2A	109.0	C8—C7—C6	120.8 (4)
C3—C2—H2B	109.0	C9—C8—C7	119.9 (4)
C1—C2—H2B	109.0	C9—C8—H8	120.1
H2A—C2—H2B	107.8	C7—C8—H8	120.1
C2—C3—C2ⁱ	113.9 (5)	C10—C9—C8	121.0 (5)
C2—C3—H3A	108.8	C10—C9—H9	119.5
C2ⁱ—C3—H3A	108.8	C8—C9—H9	119.5
C2—C3—H3B	108.8	C9—C10—C11	119.7 (4)
C2ⁱ—C3—H3B	108.8	C9—C10—H10	120.2
H3A—C3—H3B	107.7	C11—C10—H10	120.2
C5—C4—H4A	109.5	C10—C11—C6	121.6 (4)
C5—C4—H4B	109.5	C10—C11—H11	119.2
H4A—C4—H4B	109.5	C6—C11—H11	119.2

C5—N1—O1—C1	179.0 (3)	C5—C6—C7—O2	−1.6 (6)
N1—O1—C1—C2	−72.2 (4)	C11—C6—C7—C8	0.0 (6)
O1—C1—C2—C3	−175.9 (3)	C5—C6—C7—C8	178.7 (4)
C1—C2—C3—C2ⁱ	−176.9 (4)	O2—C7—C8—C9	−179.6 (4)
O1—N1—C5—C6	−179.5 (3)	C6—C7—C8—C9	0.1 (6)
O1—N1—C5—C4	0.5 (5)	C7—C8—C9—C10	0.2 (7)
N1—C5—C6—C7	2.9 (5)	C8—C9—C10—C11	−0.5 (8)
C4—C5—C6—C7	−177.1 (4)	C9—C10—C11—C6	0.6 (7)
N1—C5—C6—C11	−178.5 (3)	C7—C6—C11—C10	−0.3 (6)
C4—C5—C6—C11	1.5 (6)	C5—C6—C11—C10	−179.1 (4)
C11—C6—C7—O2	179.7 (4)

Symmetry code: (i) −x, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.84	2.553 (4)	144
C4—H4A···O1	0.96	2.16	2.631 (5)	109

Experimental details

Crystal data
Chemical formula	C₂₁H₂₆N₂O₄
M_r	370.44
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	12.9691 (13), 4.601 (1), 16.3639 (16)
β (°)	91.621 (1)
V (Å³)	976.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.40 × 0.32

Data collection
Diffractometer	Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.959, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	2421, 972, 646
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.123, 1.04
No. of reflections	972
No. of parameters	123
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.12

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.820	1.840	2.553 (4)	144.3
C4—H4A···O1	0.960	2.160	2.631 (5)	108.8

Acknowledgements

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

References

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