4,4′,5,5′-Tetra­methyl-2,2′-[1,1′-(propane-1,3-diyldinitrilo)diethyl­idyne]diphenol

Yeap, C.S.; Kia, R.; Fun, H.-K.

doi:10.1107/S1600536808027220

organic compounds

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Volume 64| Part 9| September 2008| Page o1854

doi:10.1107/S1600536808027220

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4,4′,5,5′-Tetramethyl-2,2′-[1,1′-(propane-1,3-diyldinitrilo)diethylidyne]diphenol

Chin Sing Yeap,^a Reza Kia ^a ‡ and Hoong-Kun Fun ^a ^*

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 23 August 2008; accepted 23 August 2008; online 30 August 2008)

The title Schiff base compound, C₂₃H₃₀N₂O₂, has crystallographic twofold rotation symmetry. An intramolecular O—H⋯N hydrogen bond forms a six-membered ring, producing an S(6) ring motif. The imino group is coplanar with the benzene ring. The two benzene rings are almost perpendicular to each other, making a dihedral angle of 87.38 (4)°. In the crystal structure, neighbouring molecules are linked along the c axis by weak intermolecular C—H⋯O hydrogen bonds and are further packed into columns along the b axis, forming sheets which are parallel to the bc plane.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For information on Schiff base ligands and complexes and their applications, see, for example: Fun, Kargar & Kia (2008 ); Fun, Kia & Kargar (2008 ); Fun & Kia (2008a ,b ,c ); Calligaris & Randaccio (1987 ); Casellato & Vigato (1977 ); For a similar structure, see: Fun & Kia (2008a).

Experimental

Crystal data

C₂₃H₃₀N₂O₂
M_r = 366.49
Monoclinic, C 2/c
a = 28.6398 (12) Å
b = 5.1264 (2) Å
c = 13.3856 (5) Å
β = 102.090 (5)°
V = 1921.67 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100.0 (1) K
0.52 × 0.18 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.959, T_max = 0.997
22388 measured reflections
2955 independent reflections
2125 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.163
S = 1.09
2955 reflections
134 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.94 (3)	1.63 (2)	2.5237 (17)	157 (2)
C12—H12C⋯O1ⁱ	0.96	2.57	3.466 (2)	156
Symmetry code: (i) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027220/at2621sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027220/at2621Isup2.hkl

checkCIF report

Comment top

The condensation of primary amines with carbonyl compounds yields Schiff base (Casellato & Vigato, 1977) that are still now regarded as one of the most potential group of chelators for facile preparations of metallo-organic hybrid materials. In the past two decades, the synthesis, structure and properties of Schiff base complexes have stimulated much interest for their noteworthy contributions in single molecule-based magnetism, materials science, catalysis of many reactions like carbonylation, hydroformylation, reduction, oxidation, epoxidation and hydrolysis (Casellato & Vigato, 1977). Only a relatively small number of free Schiff base ligands have been characterized (Calligaris & Randaccio, 1987). As an extension of our work (Fun, Kargar & Kia, 2008; Fun, Kia & Kargar, 2008; Fun & Kia, 2008a,b,c) on the structural characterization of Schiff base ligands and their complexes, the title compound (I), is reported here.

The molecule of the title compound, (I), has a crystallographic twofold rotation symmetry (Fig. 1). The bond lengths and angles are within normal ranges (Allen et al., 1987) and is comparable to its related structure (Fun & Kia 2008c). The asymmetric unit of the compound is composed of one-half of the molecule. An intramolecular O—H···N hydrogen bond forms a six-membered ring, producing a S(6) ring motif (Bernstein et al., 1995). The imino group is coplanar with the benzene ring. The two benzene rings are almost perpendicular to each other with a dihedral angle of 87.38 (4)°. In the crystal structure, neighbouring molecules are linked together along the c-axis by weak intermolecular C—H···O hydrogen bonds and are further packed into columns along the b axis, forming sheets which are parallel to the bc plane(Fig. 2, Fig. 3 and Table 1).

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For information on Schiff base ligands and complexes and their applications, see, for example: Fun, Kargar & Kia (2008); Fun, Kia & Kargar (2008); Fun & Kia (2008a,b,c); Calligaris & Randaccio (1987); Casellato & Vigato (1977); For a similar structure, see, Fun & Kia (2008a).

Experimental top

The synthetic method has been described earlier (Fun & Kia et al., 2008c). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms. The suffix A corresponds to symmetry code (-x + 1, y, -z + 3/2). Intramolecular interactions are shown as dashed lines.
	Fig. 2. The crystal packing of (I), viewed down the b-axis showing chains along the c-axis and stacking of these chains along the b-axis. Intramolecular and intermolecular interactions are shown as dashed lines.
	Fig. 3. The crystal packing of (I), viewed down the c-axis. Intermolecular interaction are shown as dashed lines.

4,4',5,5'-Tetramethyl-2,2'-[1,1'-(propane-1,3- diyldinitrilo)diethylidyne]diphenol top

Crystal data top

C₂₃H₃₀N₂O₂	F(000) = 792
M_r = 366.49	D_x = 1.263 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2732 reflections
a = 28.6398 (12) Å	θ = 3.1–31.1°
b = 5.1264 (2) Å	µ = 0.08 mm⁻¹
c = 13.3856 (5) Å	T = 100 K
β = 102.090 (5)°	Plate, yellow
V = 1921.67 (13) Å³	0.52 × 0.18 × 0.04 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2955 independent reflections
Radiation source: fine-focus sealed tube	2125 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 30.6°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −40→40
T_min = 0.959, T_max = 0.997	k = −6→7
22388 measured reflections	l = −19→19

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0692P)² + 1.4537P] where P = (F_o² + 2F_c²)/3
2955 reflections	(Δ/σ)_max < 0.001
134 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₃H₃₀N₂O₂	V = 1921.67 (13) Å³
M_r = 366.49	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 28.6398 (12) Å	µ = 0.08 mm⁻¹
b = 5.1264 (2) Å	T = 100 K
c = 13.3856 (5) Å	0.52 × 0.18 × 0.04 mm
β = 102.090 (5)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2955 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2125 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.997	R_int = 0.065
22388 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.43 e Å⁻³
2955 reflections	Δρ_min = −0.23 e Å⁻³
134 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.39432 (4)	0.1912 (2)	0.79198 (8)	0.0228 (3)
N1	0.44358 (4)	0.3691 (2)	0.67166 (9)	0.0198 (3)
C1	0.37375 (5)	0.0311 (3)	0.71524 (10)	0.0186 (3)
C2	0.33866 (5)	−0.1421 (3)	0.73211 (11)	0.0202 (3)
H2A	0.3305	−0.1439	0.7958	0.024*
C3	0.31557 (5)	−0.3111 (3)	0.65766 (11)	0.0196 (3)
C4	0.32783 (5)	−0.3098 (3)	0.56081 (11)	0.0201 (3)
C5	0.36250 (5)	−0.1379 (3)	0.54410 (11)	0.0195 (3)
H5A	0.3705	−0.1376	0.4803	0.023*
C6	0.38627 (5)	0.0367 (3)	0.61851 (10)	0.0184 (3)
C7	0.42271 (5)	0.2204 (3)	0.59795 (11)	0.0193 (3)
C8	0.48072 (5)	0.5502 (3)	0.65557 (11)	0.0220 (3)
H8A	0.4677	0.6654	0.5991	0.026*
H8B	0.5067	0.4524	0.6373	0.026*
C9	0.5000	0.7123 (4)	0.7500	0.0228 (4)
C10	0.27787 (5)	−0.4945 (3)	0.67857 (12)	0.0248 (3)
H10A	0.2721	−0.4610	0.7455	0.037*
H10B	0.2885	−0.6712	0.6750	0.037*
H10C	0.2489	−0.4686	0.6285	0.037*
C11	0.30396 (6)	−0.4918 (3)	0.47727 (12)	0.0261 (3)
H11A	0.3177	−0.4684	0.4183	0.039*
H11B	0.2704	−0.4542	0.4597	0.039*
H11C	0.3086	−0.6688	0.5006	0.039*
C12	0.43456 (6)	0.2315 (4)	0.49364 (12)	0.0292 (4)
H12A	0.4686	0.2325	0.5005	0.044*
H12B	0.4213	0.3873	0.4592	0.044*
H12C	0.4213	0.0818	0.4547	0.044*
H1O1	0.4165 (8)	0.284 (5)	0.7632 (17)	0.052 (6)*
H9	0.5269 (6)	0.827 (4)	0.7343 (13)	0.028 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0254 (6)	0.0245 (6)	0.0186 (5)	−0.0057 (4)	0.0047 (4)	−0.0014 (4)
N1	0.0172 (6)	0.0191 (6)	0.0228 (6)	0.0000 (5)	0.0038 (5)	0.0027 (5)
C1	0.0181 (6)	0.0182 (7)	0.0184 (6)	0.0019 (5)	0.0014 (5)	0.0010 (5)
C2	0.0209 (7)	0.0211 (7)	0.0190 (7)	0.0013 (6)	0.0053 (5)	0.0021 (6)
C3	0.0177 (6)	0.0157 (7)	0.0246 (7)	0.0013 (5)	0.0028 (5)	0.0027 (6)
C4	0.0184 (6)	0.0173 (7)	0.0230 (7)	0.0025 (5)	0.0008 (5)	−0.0001 (6)
C5	0.0208 (7)	0.0197 (7)	0.0177 (6)	0.0036 (6)	0.0031 (5)	0.0005 (5)
C6	0.0171 (6)	0.0193 (7)	0.0185 (6)	0.0011 (5)	0.0034 (5)	0.0022 (5)
C7	0.0184 (6)	0.0195 (7)	0.0199 (7)	0.0016 (5)	0.0035 (5)	0.0031 (5)
C8	0.0200 (7)	0.0212 (7)	0.0249 (7)	−0.0008 (6)	0.0050 (6)	0.0037 (6)
C9	0.0192 (10)	0.0193 (11)	0.0297 (11)	0.000	0.0045 (8)	0.000
C10	0.0220 (7)	0.0207 (8)	0.0314 (8)	−0.0012 (6)	0.0050 (6)	0.0022 (6)
C11	0.0266 (8)	0.0222 (8)	0.0271 (8)	0.0004 (6)	−0.0001 (6)	−0.0037 (6)
C12	0.0312 (8)	0.0347 (9)	0.0232 (7)	−0.0063 (7)	0.0094 (6)	−0.0001 (7)

Geometric parameters (Å, º) top

O1—C1	1.3497 (17)	C7—C12	1.505 (2)
O1—H1O1	0.94 (2)	C8—C9	1.5169 (19)
N1—C7	1.2904 (19)	C8—H8A	0.9700
N1—C8	1.4613 (18)	C8—H8B	0.9700
C1—C2	1.395 (2)	C9—C8ⁱ	1.5169 (19)
C1—C6	1.4143 (19)	C9—H9	1.025 (18)
C2—C3	1.380 (2)	C10—H10A	0.9600
C2—H2A	0.9300	C10—H10B	0.9600
C3—C4	1.412 (2)	C10—H10C	0.9600
C3—C10	1.501 (2)	C11—H11A	0.9600
C4—C5	1.380 (2)	C11—H11B	0.9600
C4—C11	1.506 (2)	C11—H11C	0.9600
C5—C6	1.404 (2)	C12—H12A	0.9600
C5—H5A	0.9300	C12—H12B	0.9600
C6—C7	1.474 (2)	C12—H12C	0.9600

C1—O1—H1O1	102.7 (14)	C9—C8—H8A	109.2
C7—N1—C8	119.85 (12)	N1—C8—H8B	109.2
O1—C1—C2	118.58 (12)	C9—C8—H8B	109.2
O1—C1—C6	122.04 (13)	H8A—C8—H8B	107.9
C2—C1—C6	119.38 (13)	C8—C9—C8ⁱ	113.56 (18)
C3—C2—C1	122.37 (13)	C8—C9—H9	107.5 (10)
C3—C2—H2A	118.8	C8ⁱ—C9—H9	109.0 (10)
C1—C2—H2A	118.8	C3—C10—H10A	109.5
C2—C3—C4	119.08 (13)	C3—C10—H10B	109.5
C2—C3—C10	120.86 (13)	H10A—C10—H10B	109.5
C4—C3—C10	120.06 (13)	C3—C10—H10C	109.5
C5—C4—C3	118.52 (13)	H10A—C10—H10C	109.5
C5—C4—C11	120.34 (13)	H10B—C10—H10C	109.5
C3—C4—C11	121.14 (13)	C4—C11—H11A	109.5
C4—C5—C6	123.38 (13)	C4—C11—H11B	109.5
C4—C5—H5A	118.3	H11A—C11—H11B	109.5
C6—C5—H5A	118.3	C4—C11—H11C	109.5
C5—C6—C1	117.27 (13)	H11A—C11—H11C	109.5
C5—C6—C7	122.12 (12)	H11B—C11—H11C	109.5
C1—C6—C7	120.61 (13)	C7—C12—H12A	109.5
N1—C7—C6	117.88 (12)	C7—C12—H12B	109.5
N1—C7—C12	121.89 (13)	H12A—C12—H12B	109.5
C6—C7—C12	120.22 (13)	C7—C12—H12C	109.5
N1—C8—C9	111.98 (11)	H12A—C12—H12C	109.5
N1—C8—H8A	109.2	H12B—C12—H12C	109.5

O1—C1—C2—C3	179.52 (13)	O1—C1—C6—C5	−179.81 (13)
C6—C1—C2—C3	0.3 (2)	C2—C1—C6—C5	−0.6 (2)
C1—C2—C3—C4	0.1 (2)	O1—C1—C6—C7	−0.1 (2)
C1—C2—C3—C10	−179.85 (13)	C2—C1—C6—C7	179.09 (13)
C2—C3—C4—C5	−0.2 (2)	C8—N1—C7—C6	178.61 (12)
C10—C3—C4—C5	179.74 (13)	C8—N1—C7—C12	−1.6 (2)
C2—C3—C4—C11	179.51 (13)	C5—C6—C7—N1	−178.28 (13)
C10—C3—C4—C11	−0.5 (2)	C1—C6—C7—N1	2.0 (2)
C3—C4—C5—C6	−0.1 (2)	C5—C6—C7—C12	1.9 (2)
C11—C4—C5—C6	−179.86 (13)	C1—C6—C7—C12	−177.83 (14)
C4—C5—C6—C1	0.5 (2)	C7—N1—C8—C9	178.56 (13)
C4—C5—C6—C7	−179.19 (13)	N1—C8—C9—C8ⁱ	56.33 (9)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.94 (3)	1.63 (2)	2.5237 (17)	157 (2)
C12—H12C···O1ⁱⁱ	0.96	2.57	3.466 (2)	156

Symmetry code: (ii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₃H₃₀N₂O₂
M_r	366.49
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	28.6398 (12), 5.1264 (2), 13.3856 (5)
β (°)	102.090 (5)
V (Å³)	1921.67 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.52 × 0.18 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.959, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	22388, 2955, 2125
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.717

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.163, 1.09
No. of reflections	2955
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.94 (3)	1.63 (2)	2.5237 (17)	157 (2)
C12—H12C···O1ⁱ	0.9600	2.5700	3.466 (2)	156.00

Symmetry code: (i) x, −y, z−1/2.

Footnotes

‡Additional correspondance author: e-mail: zsrkk@yahoo.com.

Acknowledgements

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund (grant No. 305/PFIZIK/613312). RK thanks Universiti Sains Malaysia for the award of a post-doctoral research fellowship. CSY thanks Universiti Sains Malaysia for the award of a student assistantship.

References

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