4,4′,6,6′-Tetra-tert-butyl-2,2′-[butane-1,4-diylbis(nitrilo­methanylyl­idene)]diphenol

Tee, J.T.; Abdullah, N.; Khaledi, H.

doi:10.1107/S1600536811041614

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2954

doi:10.1107/S1600536811041614

Open

access

4,4′,6,6′-Tetra-tert-butyl-2,2′-[butane-1,4-diylbis(nitrilomethanylylidene)]diphenol

Jia Ti Tee,^a Norbani Abdullah ^a and Hamid Khaledi ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 7 October 2011; accepted 10 October 2011; online 12 October 2011)

The title compound, C₃₄H₅₂N₂O₂, is centrosymmetric, the mid-point of the central C—C bond being located on an inversion centre. Intramolecular O—H⋯N and weak C—H⋯O hydrogen bonds are observed, but no significant intermolecular interactions occur in the crystal structure.

Related literature

For structures of some metal complexes of the title Schiff base, see: Doyle et al. (2007 ); Keizer et al. (2002a ,b ).

Experimental

Crystal data

C₃₄H₅₂N₂O₂
M_r = 520.78
Monoclinic, P 2₁ /c
a = 19.1255 (4) Å
b = 9.5702 (2) Å
c = 8.6312 (1) Å
β = 90.383 (1)°
V = 1579.78 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.26 × 0.15 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.983, T_max = 0.996
14602 measured reflections
3631 independent reflections
3039 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.114
S = 1.03
3631 reflections
181 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.927 (16)	1.735 (17)	2.5840 (13)	150.8 (14)
C8—H8B⋯O1	0.98	2.29	2.9546 (16)	125
C9—H9A⋯O1	0.98	2.44	3.0720 (15)	122

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811041614/xu5350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041614/xu5350Isup2.hkl

checkCIF report

Comment top

The title Schiff base has been displayed ambidentate ligation behavior towards metal ions (Doyle et al., 2007; Keizer et al., 2002a,b). Herein, wish to report the crystal structure of the free ligand, obtained through the condensation reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 1,4-diaminobutane. The molecule lies across a crystallographic inversion centre. The imino group is almost coplanar with the phenyl ring [dihedral angle = 3.00 (13)] and adopts an E configuration. The hydroxyl group is engaged in an intramolecular O—H···N hydrogen bond with the imine group. Moreover, it acts as an acceptor in two intramolecular C—H···O hydrogen bonds (Table 1). The structure does not display any significant intermolecular interactions.

Related literature top

For structures of some metal complexes of the title Schiff base, see: Doyle et al. (2007); Keizer et al. (2002a,b).

Experimental top

3,5-Di-tert-butyl-2-hydroxybenzaldehyde (5.86 g, 25 mmol) was dissolved in methanol (50 ml) in a round-bottomed flask fitted with a reflux condenser. The solution was heated, followed by portionwise addition of 1,4-diaminobutane (1.10 g; 12.5 mmol). The pale yellow solution formed was then gently refluxed for 3 h. The product obtained on cooling was recrystallized from ethanol at room temperature to give X-ray quality crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

4,4',6,6'-Tetra-tert-butyl-2,2'-[butane-1,4- diylbis(nitrilomethanylylidene)]diphenol top

Crystal data top

C₃₄H₅₂N₂O₂	F(000) = 572
M_r = 520.78	D_x = 1.095 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4857 reflections
a = 19.1255 (4) Å	θ = 2.4–30.3°
b = 9.5702 (2) Å	µ = 0.07 mm⁻¹
c = 8.6312 (1) Å	T = 100 K
β = 90.383 (1)°	Plate, yellow
V = 1579.78 (5) Å³	0.26 × 0.15 × 0.06 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3631 independent reflections
Radiation source: fine-focus sealed tube	3039 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
T_min = 0.983, T_max = 0.996	k = −12→12
14602 measured reflections	l = −11→11

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0533P)² + 0.5079P] where P = (F_o² + 2F_c²)/3
3631 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₃₄H₅₂N₂O₂	V = 1579.78 (5) Å³
M_r = 520.78	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 19.1255 (4) Å	µ = 0.07 mm⁻¹
b = 9.5702 (2) Å	T = 100 K
c = 8.6312 (1) Å	0.26 × 0.15 × 0.06 mm
β = 90.383 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3631 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3039 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.996	R_int = 0.024
14602 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.30 e Å⁻³
3631 reflections	Δρ_min = −0.16 e Å⁻³
181 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
O1	0.38365 (4)	0.98230 (9)	0.47339 (10)	0.0267 (2)
H1	0.4145 (8)	0.9488 (17)	0.3998 (19)	0.040*
N1	0.43079 (5)	0.86964 (11)	0.22286 (12)	0.0276 (2)
C1	0.31824 (6)	0.96886 (11)	0.41401 (12)	0.0198 (2)
C2	0.26044 (6)	1.01998 (11)	0.49629 (12)	0.0193 (2)
C3	0.19476 (6)	1.00283 (11)	0.42796 (12)	0.0203 (2)
H3	0.1553	1.0373	0.4824	0.024*
C4	0.18292 (6)	0.93820 (12)	0.28429 (12)	0.0197 (2)
C5	0.24129 (6)	0.88907 (11)	0.20702 (12)	0.0196 (2)
H5	0.2353	0.8443	0.1096	0.024*
C6	0.30834 (6)	0.90361 (11)	0.26843 (12)	0.0194 (2)
C7	0.26927 (7)	1.09122 (12)	0.65518 (12)	0.0230 (3)
C8	0.31935 (8)	1.21639 (13)	0.64423 (15)	0.0348 (3)
H8A	0.3004	1.2849	0.5707	0.052*
H8B	0.3651	1.1842	0.6085	0.052*
H8C	0.3244	1.2599	0.7465	0.052*
C9	0.29756 (7)	0.98400 (12)	0.77258 (13)	0.0254 (3)
H9A	0.3430	0.9492	0.7377	0.038*
H9B	0.2647	0.9058	0.7807	0.038*
H9C	0.3030	1.0286	0.8741	0.038*
C10	0.19963 (7)	1.14567 (14)	0.71697 (14)	0.0323 (3)
H10A	0.2074	1.1915	0.8172	0.049*
H10B	0.1672	1.0674	0.7300	0.049*
H10C	0.1797	1.2130	0.6434	0.049*
C11	0.10988 (6)	0.92199 (13)	0.21236 (13)	0.0246 (3)
C12	0.09358 (7)	0.76642 (15)	0.19055 (17)	0.0357 (3)
H12A	0.0932	0.7200	0.2918	0.053*
H12B	0.1294	0.7237	0.1252	0.053*
H12C	0.0477	0.7560	0.1407	0.053*
C13	0.10838 (7)	0.99276 (15)	0.05301 (15)	0.0339 (3)
H13A	0.0630	0.9757	0.0029	0.051*
H13B	0.1457	0.9542	−0.0114	0.051*
H13C	0.1154	1.0936	0.0656	0.051*
C14	0.05296 (7)	0.9870 (2)	0.31222 (17)	0.0449 (4)
H14A	0.0526	0.9413	0.4138	0.067*
H14B	0.0074	0.9745	0.2615	0.067*
H14C	0.0623	1.0870	0.3255	0.067*
C15	0.36766 (6)	0.85464 (12)	0.17746 (13)	0.0225 (2)
H15	0.3589	0.8100	0.0810	0.027*
C16	0.48707 (6)	0.82786 (14)	0.11850 (16)	0.0312 (3)
H16A	0.4676	0.7714	0.0324	0.037*
H16B	0.5214	0.7697	0.1755	0.037*
C17	0.52336 (6)	0.95676 (14)	0.05349 (15)	0.0294 (3)
H17A	0.5653	0.9268	−0.0045	0.035*
H17B	0.5393	1.0163	0.1407	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0244 (4)	0.0311 (5)	0.0246 (4)	−0.0036 (4)	−0.0030 (3)	−0.0032 (3)
N1	0.0240 (5)	0.0289 (6)	0.0299 (5)	−0.0012 (4)	0.0047 (4)	−0.0003 (4)
C1	0.0244 (6)	0.0152 (5)	0.0196 (5)	−0.0026 (4)	−0.0019 (4)	0.0027 (4)
C2	0.0299 (6)	0.0126 (5)	0.0155 (5)	0.0009 (4)	−0.0011 (4)	0.0015 (4)
C3	0.0273 (6)	0.0173 (5)	0.0163 (5)	0.0051 (4)	0.0019 (4)	0.0010 (4)
C4	0.0241 (6)	0.0183 (5)	0.0167 (5)	0.0011 (4)	−0.0012 (4)	0.0022 (4)
C5	0.0271 (6)	0.0169 (5)	0.0149 (5)	−0.0014 (4)	0.0005 (4)	−0.0011 (4)
C6	0.0245 (6)	0.0150 (5)	0.0188 (5)	−0.0013 (4)	0.0023 (4)	0.0014 (4)
C7	0.0365 (7)	0.0163 (5)	0.0163 (5)	0.0007 (5)	−0.0025 (4)	−0.0011 (4)
C8	0.0597 (9)	0.0205 (6)	0.0241 (6)	−0.0090 (6)	−0.0021 (6)	−0.0033 (5)
C9	0.0379 (7)	0.0204 (6)	0.0178 (5)	0.0002 (5)	−0.0058 (5)	−0.0004 (4)
C10	0.0474 (8)	0.0301 (7)	0.0195 (5)	0.0118 (6)	−0.0011 (5)	−0.0064 (5)
C11	0.0242 (6)	0.0301 (6)	0.0194 (5)	0.0025 (5)	−0.0021 (4)	−0.0005 (4)
C12	0.0289 (7)	0.0346 (7)	0.0434 (8)	−0.0081 (6)	−0.0053 (6)	0.0044 (6)
C13	0.0378 (7)	0.0374 (7)	0.0263 (6)	−0.0042 (6)	−0.0118 (5)	0.0057 (5)
C14	0.0272 (7)	0.0746 (12)	0.0327 (7)	0.0171 (7)	−0.0063 (6)	−0.0116 (7)
C15	0.0276 (6)	0.0184 (5)	0.0215 (5)	−0.0020 (4)	0.0035 (4)	−0.0001 (4)
C16	0.0245 (6)	0.0314 (7)	0.0377 (7)	0.0021 (5)	0.0075 (5)	−0.0009 (5)
C17	0.0192 (6)	0.0355 (7)	0.0334 (6)	−0.0014 (5)	0.0037 (5)	−0.0032 (5)

Geometric parameters (Å, º) top

O1—C1	1.3549 (14)	C9—H9C	0.9800
O1—H1	0.927 (16)	C10—H10A	0.9800
N1—C15	1.2749 (15)	C10—H10B	0.9800
N1—C16	1.4638 (15)	C10—H10C	0.9800
C1—C2	1.4058 (16)	C11—C14	1.5257 (18)
C1—C6	1.4147 (15)	C11—C12	1.5325 (18)
C2—C3	1.3939 (16)	C11—C13	1.5332 (16)
C2—C7	1.5398 (14)	C12—H12A	0.9800
C3—C4	1.4028 (15)	C12—H12B	0.9800
C3—H3	0.9500	C12—H12C	0.9800
C4—C5	1.3863 (15)	C13—H13A	0.9800
C4—C11	1.5328 (16)	C13—H13B	0.9800
C5—C6	1.3914 (16)	C13—H13C	0.9800
C5—H5	0.9500	C14—H14A	0.9800
C6—C15	1.4613 (15)	C14—H14B	0.9800
C7—C10	1.5295 (17)	C14—H14C	0.9800
C7—C8	1.5371 (17)	C15—H15	0.9500
C7—C9	1.5380 (15)	C16—C17	1.5244 (18)
C8—H8A	0.9800	C16—H16A	0.9900
C8—H8B	0.9800	C16—H16B	0.9900
C8—H8C	0.9800	C17—C17ⁱ	1.525 (3)
C9—H9A	0.9800	C17—H17A	0.9900
C9—H9B	0.9800	C17—H17B	0.9900

C1—O1—H1	107.4 (10)	H10A—C10—H10C	109.5
C15—N1—C16	118.61 (11)	H10B—C10—H10C	109.5
O1—C1—C2	120.20 (10)	C14—C11—C12	108.67 (12)
O1—C1—C6	119.71 (10)	C14—C11—C4	112.44 (10)
C2—C1—C6	120.09 (10)	C12—C11—C4	109.40 (10)
C3—C2—C1	117.05 (10)	C14—C11—C13	108.51 (11)
C3—C2—C7	121.48 (10)	C12—C11—C13	108.45 (10)
C1—C2—C7	121.47 (10)	C4—C11—C13	109.28 (10)
C2—C3—C4	124.44 (10)	C11—C12—H12A	109.5
C2—C3—H3	117.8	C11—C12—H12B	109.5
C4—C3—H3	117.8	H12A—C12—H12B	109.5
C5—C4—C3	116.69 (10)	C11—C12—H12C	109.5
C5—C4—C11	120.36 (10)	H12A—C12—H12C	109.5
C3—C4—C11	122.95 (10)	H12B—C12—H12C	109.5
C4—C5—C6	121.73 (10)	C11—C13—H13A	109.5
C4—C5—H5	119.1	C11—C13—H13B	109.5
C6—C5—H5	119.1	H13A—C13—H13B	109.5
C5—C6—C1	120.00 (10)	C11—C13—H13C	109.5
C5—C6—C15	118.70 (10)	H13A—C13—H13C	109.5
C1—C6—C15	121.27 (10)	H13B—C13—H13C	109.5
C10—C7—C8	107.48 (10)	C11—C14—H14A	109.5
C10—C7—C9	107.51 (10)	C11—C14—H14B	109.5
C8—C7—C9	110.11 (10)	H14A—C14—H14B	109.5
C10—C7—C2	111.77 (10)	C11—C14—H14C	109.5
C8—C7—C2	110.79 (9)	H14A—C14—H14C	109.5
C9—C7—C2	109.11 (9)	H14B—C14—H14C	109.5
C7—C8—H8A	109.5	N1—C15—C6	122.40 (10)
C7—C8—H8B	109.5	N1—C15—H15	118.8
H8A—C8—H8B	109.5	C6—C15—H15	118.8
C7—C8—H8C	109.5	N1—C16—C17	110.12 (11)
H8A—C8—H8C	109.5	N1—C16—H16A	109.6
H8B—C8—H8C	109.5	C17—C16—H16A	109.6
C7—C9—H9A	109.5	N1—C16—H16B	109.6
C7—C9—H9B	109.5	C17—C16—H16B	109.6
H9A—C9—H9B	109.5	H16A—C16—H16B	108.1
C7—C9—H9C	109.5	C16—C17—C17ⁱ	113.31 (13)
H9A—C9—H9C	109.5	C16—C17—H17A	108.9
H9B—C9—H9C	109.5	C17ⁱ—C17—H17A	108.9
C7—C10—H10A	109.5	C16—C17—H17B	108.9
C7—C10—H10B	109.5	C17ⁱ—C17—H17B	108.9
H10A—C10—H10B	109.5	H17A—C17—H17B	107.7
C7—C10—H10C	109.5

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.927 (16)	1.735 (17)	2.5840 (13)	150.8 (14)
C8—H8B···O1	0.98	2.29	2.9546 (16)	125
C9—H9A···O1	0.98	2.44	3.0720 (15)	122

Experimental details

Crystal data
Chemical formula	C₃₄H₅₂N₂O₂
M_r	520.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	19.1255 (4), 9.5702 (2), 8.6312 (1)
β (°)	90.383 (1)
V (Å³)	1579.78 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.26 × 0.15 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.983, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	14602, 3631, 3039
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.03
No. of reflections	3631
No. of parameters	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.16

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.927 (16)	1.735 (17)	2.5840 (13)	150.8 (14)
C8—H8B···O1	0.98	2.29	2.9546 (16)	124.6
C9—H9A···O1	0.98	2.44	3.0720 (15)	122.2

Acknowledgements

Financial support from the University of Malaya is highly appreciated (PPP grant No. PS342/2009 C)

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Doyle, D. J., Gibson, V. C. & White, A. J. P. (2007). Dalton Trans. pp. 358–363. Web of Science CSD CrossRef Google Scholar
Keizer, T. S., De Pue, L. J., Parkin, S. & Atwood, D. A. (2002a). J. Cluster Sci. 13, 609–620. Web of Science CSD CrossRef CAS Google Scholar
Keizer, T. S., De Pue, L. J., Parkin, S. & Atwood, D. A. (2002b). J. Am. Chem. Soc. 124, 1864–1865. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2954

doi:10.1107/S1600536811041614

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

4,4′,6,6′-Tetra-tert-butyl-2,2′-[butane-1,4-diylbis(nitrilo­methanylyl­­idene)]diphenol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,4′,6,6′-Tetra-tert-butyl-2,2′-[butane-1,4-diylbis(nitrilomethanylylidene)]diphenol