6,6′-Dihydr­oxy-2,2′-[(propane-1,3-diyl­dioxy)bis­(nitrilo­methyl­idyne)]diphenol

Dong, W.-K.; He, X.-N.; Guan, Y.-H.; Xu, L.; Ren, Z.-L.

doi:10.1107/S1600536808026731

organic compounds

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doi:10.1107/S1600536808026731

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6,6′-Dihydroxy-2,2′-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]diphenol

Wen-Kui Dong,^a ^* Xue-Ni He,^a Yong-Hong Guan,^a Li Xu ^a and Zong-Li Ren ^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 12 August 2008; accepted 19 August 2008; online 23 August 2008)

The molecule of the title compound, C₁₇H₁₈N₂O₆, adopts a V-shaped conformation, the dihedral angle between the two halves of the molecule being 81.31 (4) °. There is one half-molecule in the asymmetric unit, with a crystallographic twofold rotation axis passing through the central C atom. There are strong intramolecular O—H⋯N and O—H⋯O hydrogen bonds involving the hydroxy group and adjacent O and N atoms. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules, forming an infinite three-dimensional supramolecular structure.

Related literature

For related literature, see: Akine et al. (2006 ); Dong & Feng (2006 ); Dong et al. (2008a ,b ,c ); Duan et al. (2007 ); Sharma (2002 ); Sun et al. (2004 ); Venkataramanan et al. (2005 ); Wang et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₈N₂O₆
M_r = 346.33
Monoclinic, C 2/c
a = 27.836 (3) Å
b = 4.5949 (5) Å
c = 13.8081 (10) Å
β = 109.363 (2)°
V = 1666.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 (2) K
0.43 × 0.40 × 0.31 mm

Data collection

Brucker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.956, T_max = 0.968
4032 measured reflections
1476 independent reflections
1025 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.186
S = 1.05
1476 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 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	1.94	2.650 (3)	144
O3—H3⋯O2	0.82	2.25	2.694 (4)	115
O3—H3⋯O1ⁱ	0.82	2.24	2.914 (4)	140
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

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 2, I. DOI: 10.1107/S1600536808026731/pv2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026731/pv2099Isup2.hkl

checkCIF report

Comment top

Salen-type compounds are chelate ligands, which have received great attention during the last decades (Sharma 2002; Akine et al., 2006; Dong et al., 2008a) due to their excellent complexing abilities towards various metal ions, especially in view of their potential use as ligands for preparation of functional complex materials (Venkataramanan et al., 2005). They are widely used in supramolecular chemistry for the construction of some one-dimensional chains, two-dimensional planar or three-dimensional network structural supramolecular complexes. To our interest, some salen-type compounds can be used as elemental building blocks for construction of supramolecular structures via intermolecular hydrogen bonding or short contact interaction (Sun et al., 2004; Akine et al., 2006; Wang et al., 2007). As an extension of our work (Dong & Feng 2006; Dong et al., 2008b; Dong et al., 2008c) on the structural characterization of salen-type bisoxime compounds, we report the structure of the title compound in this paper here.

The molecule of title compound adopts a V-shaped conformation with the dihedral angle between the two halves of the molecule is 81.31 (4) ° (Fig. 1). There is a half molecule in an asymmetric unit with a crystallographic twofold rotation axis passing through the central carbon of the three carbon atoms in the (—CH=N—O—(CH₂)₃—O—N=CH—) bridge. This structure is similar to what was observed in our previously reported salen-type bisoxime compound (Duan et al., 2007). The dihedral angle formed by the two benzene rings in the molecule of the title compound is 82.22 (5) °. There are strong intramolecular O—H···N and O—H···O hydrogen bonds involving the hydroxy group and an adjacent O (or N) atoms (Table 1). In the crystal structure, intermolecular O—H···O hydrogen bonds link each molecule to 2 others into infinite three-dimensional supramolecular structure (Fig. 2), which is not similar to what was observed in our previously reported series salen-type compounds containing two- (Akine et al., 2006) and five-methene (Dong et al., 2008a) bridge.

Related literature top

For related literature, see: Akine et al. (2006); Dong & Feng (2006); Dong et al. (2008a,b,c); Duan et al. (2007); Sharma (2002); Sun et al. (2004); Venkataramanan et al. (2005); Wang et al. (2007).

Experimental top

6,6'-Dihydroxy-2,2'-[(pentane-1,5-diyldioxy)bis(nitrilomethylidyne)]diphenol was synthesized according to an analogous method reported earlier (Dong et al., 2006; Dong et al., 2008a). To an ethanol solution (5 ml) of 2,3-dihydroxybenzaldehyde (276.6 mg, 2.0 mmol) was added an ethanol solution (5 ml) of 1, 3-bis(aminooxy)propane (106.8 mg, 1.0 mmol). After the solution had been stirred at 328 K for 3 h, the mixture was filtered, washed successively with ethanol and ethanol/hexane (1:4), respectively. The product was dried under reduced pressure and purified by recrystallization from ethanol to yield 204.8 mg of pale-brown crystalline solid.

Pale-brown prismatical crystals of the title compound suitable for X-ray crystal analysis were grown up from a tetrahydrofuran-ethanol (3:4) mixed solution by slow evaporation of the solvent at room temperature.

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

	Fig. 1. The molecular structure of the title compound with atom numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level. [Symmetry code: -x + 1,y,-z + 5/2]
	Fig. 2. The packing diagram of the title compound showing intermolecular hydrogen bonds. H atoms are omitted for clarity.

6,6'-Dihydroxy-2,2'-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]diphenol top

Crystal data top

C₁₇H₁₈N₂O₆	F(000) = 728
M_r = 346.33	D_x = 1.381 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1493 reflections
a = 27.836 (3) Å	θ = 2.8–27.7°
b = 4.5949 (5) Å	µ = 0.11 mm⁻¹
c = 13.8081 (10) Å	T = 298 K
β = 109.363 (2)°	Prismatic, pale-brown
V = 1666.2 (3) Å³	0.43 × 0.40 × 0.31 mm
Z = 4

Data collection top

Brucker SMART 1000 CCD area-detector diffractometer	1476 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −32→27
T_min = 0.956, T_max = 0.968	k = −5→5
4032 measured reflections	l = −16→16

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0856P)² + 2.8739P] where P = (F_o² + 2F_c²)/3
1476 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₇H₁₈N₂O₆	V = 1666.2 (3) Å³
M_r = 346.33	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.836 (3) Å	µ = 0.11 mm⁻¹
b = 4.5949 (5) Å	T = 298 K
c = 13.8081 (10) Å	0.43 × 0.40 × 0.31 mm
β = 109.363 (2)°

Data collection top

Brucker SMART 1000 CCD area-detector diffractometer	1476 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1025 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.968	R_int = 0.030
4032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
1476 reflections	Δρ_min = −0.25 e Å⁻³
114 parameters

Special details top

Experimental. Yield, 59.1%, mp. 425–427 K. Anal. Calc. for C₁₇H₁₈N₂O₆: C, 59.96; H, 5.24; N, 8.09. Found: C, 60.17; H, 5.31; N, 7.92.

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)
O1	0.43592 (8)	0.2306 (5)	1.15521 (16)	0.0466 (6)
O2	0.41085 (8)	0.6412 (6)	0.88832 (17)	0.0539 (7)
H2	0.4236	0.5367	0.9385	0.081*
O3	0.36020 (10)	1.0086 (6)	0.73677 (18)	0.0671 (9)
H3	0.3855	0.9080	0.7439	0.101*
N1	0.41732 (9)	0.4035 (6)	1.06706 (18)	0.0413 (7)
C1	0.48064 (12)	0.0823 (7)	1.1531 (2)	0.0456 (8)
H1A	0.5063	0.2214	1.1500	0.055*
H1B	0.4727	−0.0431	1.0933	0.055*
C2	0.5000	−0.0961 (11)	1.2500	0.0529 (13)
H2A	0.4727	−0.2207	1.2545	0.063*	0.50
H2B	0.5273	−0.2207	1.2455	0.063*	0.50
C4	0.37794 (11)	0.5439 (7)	1.0649 (2)	0.0409 (8)
H4	0.3650	0.5210	1.1185	0.049*
C5	0.35228 (11)	0.7400 (7)	0.9813 (2)	0.0372 (7)
C6	0.36954 (11)	0.7802 (7)	0.8979 (2)	0.0387 (8)
C7	0.34391 (12)	0.9687 (7)	0.8197 (2)	0.0446 (8)
C8	0.30183 (13)	1.1161 (8)	0.8225 (3)	0.0499 (9)
H8	0.2850	1.2423	0.7695	0.060*
C9	0.28425 (12)	1.0774 (8)	0.9046 (3)	0.0490 (9)
H9	0.2555	1.1772	0.9066	0.059*
C10	0.30912 (12)	0.8929 (8)	0.9822 (2)	0.0443 (8)
H10	0.2971	0.8682	1.0369	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0425 (12)	0.0521 (15)	0.0435 (13)	0.0042 (11)	0.0119 (10)	0.0151 (11)
O2	0.0523 (14)	0.0655 (16)	0.0510 (14)	0.0138 (12)	0.0267 (11)	0.0107 (12)
O3	0.0821 (19)	0.0788 (19)	0.0470 (15)	0.0177 (15)	0.0303 (13)	0.0176 (13)
N1	0.0411 (15)	0.0424 (16)	0.0377 (14)	−0.0041 (13)	0.0096 (11)	0.0029 (12)
C1	0.0406 (18)	0.044 (2)	0.0480 (19)	0.0026 (15)	0.0094 (15)	−0.0031 (16)
C2	0.049 (3)	0.044 (3)	0.056 (3)	0.000	0.005 (2)	0.000
C4	0.0387 (17)	0.047 (2)	0.0377 (17)	−0.0033 (15)	0.0133 (14)	−0.0002 (15)
C5	0.0364 (16)	0.0367 (18)	0.0360 (16)	−0.0084 (14)	0.0088 (13)	−0.0060 (14)
C6	0.0352 (16)	0.0391 (18)	0.0407 (17)	−0.0009 (14)	0.0110 (13)	−0.0033 (15)
C7	0.051 (2)	0.047 (2)	0.0352 (17)	−0.0083 (16)	0.0123 (15)	−0.0008 (15)
C8	0.0468 (19)	0.048 (2)	0.0446 (19)	0.0064 (17)	0.0017 (15)	0.0040 (16)
C9	0.0396 (18)	0.054 (2)	0.050 (2)	0.0042 (17)	0.0106 (15)	−0.0062 (18)
C10	0.0418 (18)	0.050 (2)	0.0429 (18)	−0.0044 (16)	0.0165 (14)	−0.0055 (16)

Geometric parameters (Å, º) top

O1—N1	1.401 (3)	C2—H2B	0.9700
O1—C1	1.428 (4)	C4—C5	1.452 (4)
O2—C6	1.359 (4)	C4—H4	0.9300
O2—H2	0.8207	C5—C10	1.395 (4)
O3—C7	1.377 (4)	C5—C6	1.400 (4)
O3—H3	0.8195	C6—C7	1.383 (4)
N1—C4	1.264 (4)	C7—C8	1.365 (5)
C1—C2	1.508 (4)	C8—C9	1.387 (5)
C1—H1A	0.9700	C8—H8	0.9300
C1—H1B	0.9700	C9—C10	1.362 (5)
C2—C1ⁱ	1.508 (4)	C9—H9	0.9300
C2—H2A	0.9700	C10—H10	0.9300

N1—O1—C1	109.0 (2)	C10—C5—C6	118.2 (3)
C6—O2—H2	109.7	C10—C5—C4	120.2 (3)
C7—O3—H3	109.3	C6—C5—C4	121.6 (3)
C4—N1—O1	112.2 (2)	O2—C6—C7	116.9 (3)
O1—C1—C2	107.4 (2)	O2—C6—C5	123.4 (3)
O1—C1—H1A	110.2	C7—C6—C5	119.7 (3)
C2—C1—H1A	110.2	C8—C7—O3	118.7 (3)
O1—C1—H1B	110.2	C8—C7—C6	121.0 (3)
C2—C1—H1B	110.2	O3—C7—C6	120.3 (3)
H1A—C1—H1B	108.5	C7—C8—C9	119.9 (3)
C1ⁱ—C2—C1	114.2 (4)	C7—C8—H8	120.1
C1ⁱ—C2—H2A	108.7	C9—C8—H8	120.1
C1—C2—H2A	108.7	C10—C9—C8	119.9 (3)
C1ⁱ—C2—H2B	108.7	C10—C9—H9	120.1
C1—C2—H2B	108.7	C8—C9—H9	120.1
H2A—C2—H2B	107.6	C9—C10—C5	121.4 (3)
N1—C4—C5	122.0 (3)	C9—C10—H10	119.3
N1—C4—H4	119.0	C5—C10—H10	119.3
C5—C4—H4	119.0

C1—O1—N1—C4	−179.2 (3)	O2—C6—C7—C8	179.6 (3)
N1—O1—C1—C2	178.9 (3)	C5—C6—C7—C8	−0.2 (5)
O1—C1—C2—C1ⁱ	−66.8 (2)	O2—C6—C7—O3	0.3 (5)
O1—N1—C4—C5	179.3 (3)	C5—C6—C7—O3	−179.5 (3)
N1—C4—C5—C10	−179.5 (3)	O3—C7—C8—C9	179.3 (3)
N1—C4—C5—C6	0.9 (5)	C6—C7—C8—C9	0.0 (5)
C10—C5—C6—O2	−179.4 (3)	C7—C8—C9—C10	0.1 (5)
C4—C5—C6—O2	0.2 (5)	C8—C9—C10—C5	0.0 (5)
C10—C5—C6—C7	0.3 (4)	C6—C5—C10—C9	−0.2 (5)
C4—C5—C6—C7	179.9 (3)	C4—C5—C10—C9	−179.8 (3)

Symmetry code: (i) −x+1, y, −z+5/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.94	2.650 (3)	144
O3—H3···O2	0.82	2.25	2.694 (4)	115
O3—H3···O1ⁱⁱ	0.82	2.24	2.914 (4)	140

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₂O₆
M_r	346.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	27.836 (3), 4.5949 (5), 13.8081 (10)
β (°)	109.363 (2)
V (Å³)	1666.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.43 × 0.40 × 0.31

Data collection
Diffractometer	Brucker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.956, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	4032, 1476, 1025
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.186, 1.05
No. of reflections	1476
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.25

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	0.821	1.940	2.650 (3)	144.27
O3—H3···O2	0.819	2.246	2.694 (4)	114.80
O3—H3···O1ⁱ	0.819	2.240	2.914 (4)	139.73

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

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

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6,6′-Dihydr­­oxy-2,2′-[(propane-1,3-diyl­di­oxy)bis­­(nitrilo­methyl­­idyne)]diphenol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6,6′-Dihydroxy-2,2′-[(propane-1,3-diyldioxy)bis(nitrilomethylidyne)]diphenol