4,4′-[Propane-1,3-diylbis(nitrilo­methyl­idyne)]dibenzonitrile

Fun, H.-K.; Kia, R.; Kargar, H.

doi:10.1107/S1600536808018680

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1335

doi:10.1107/S1600536808018680

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4,4′-[Propane-1,3-diylbis(nitrilomethylidyne)]dibenzonitrile

Hoong-Kun Fun,^a ^* Reza Kia ^a ‡ and Hadi Kargar ^b §

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
^*Correspondence e-mail: hkfun@usm.my

(Received 16 June 2008; accepted 20 June 2008; online 25 June 2008)

The molecule of the title Schiff base compound, C₁₉H₁₆N₄, has crystallographic twofold rotation symmetry. The imino group is coplanar with the aromatic ring. Within the molecule, the planar units are parallel, but extend in opposite directions from the central methylene bridge. The packing of the molecules is controlled by C—H⋯π interactions.

Related literature

For values of bond lengths, see Allen et al. (1987 ). For related structures, see: Li et al. (2005 ); Bomfim et al. (2005 ); Glidewell et al. (2005 , 2006 ); Sun et al. (2004 ); Habibi et al. (2007 ).

Experimental

Crystal data

C₁₉H₁₆N₄
M_r = 300.36
Monoclinic, C 2/c
a = 14.4982 (4) Å
b = 6.9025 (2) Å
c = 16.9842 (6) Å
β = 111.659 (4)°
V = 1579.67 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100.0 (1) K
0.37 × 0.12 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.886, T_max = 0.991
13317 measured reflections
1544 independent reflections
1257 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.081
wR(F²) = 0.127
S = 1.17
1544 reflections
109 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg1ⁱ	0.97	2.85	3.58	133
Symmetry code: (i) $[x, -y, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C1–C6 benzene ring.

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/S1600536808018680/tk2276sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018680/tk2276Isup2.hkl

checkCIF report

Comment top

Schiff bases are one of most prevalent mixed-donor ligands in coordination chemistry. They play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism, and supramolecular architectures. Structures of Schiff bases derived from substituted benzaldehydes and closely related to the title compound, (I), are known (Li et al., 2005; Bomfim et al., 2005; Glidewell et al., 2005, 2006; Sun et al., 2004; Habibi et al., 2007).

The molecule of (I), Fig. 1, has a crystallographic 2-fold symmetry. The bond lengths and angles are within normal ranges (Allen et al., 1987). The group is coplanar with the aromatic ring in each half of the molecule. The planar units are parallel by symmetry, but extend in opposite directions from the central methylene bridge, the C6—C7—N1—C8 torsion angle is 178.9 (3)°. The packing of the molecules, Fig. 2, is controlled by C—H···π interactions, Table 1.

Related literature top

For values of bond lengths, see Allen et al. (1987). For related structures, see: Li et al. (2005); Bomfim et al. (2005); Glidewell et al. (2005, 2006); Sun et al., (2004); Habibi et al. (2007). Cg1 is the centroid of C1–C6 benzene ring.

Experimental top

A solution of 1,3-propanediamine (0.1 mmol, 0.074 g) was slowly added to a solution of 4-cyanobenzaldehyde (0.2 mmol, 0.026 g) in chloroform (30 ml). Recrystallization of the resulting solid from ethanol afforded colourless crystals of (I).

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) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I) showing atom labeling and 50% probability ellipsoids [symmetry code for i: -x, y, 0.5 - z].
	Fig. 2. A view down the b-axis of the unit cell contents for (I), highlighting the parallel arrangement of the molecules.

4,4'-[Propane-1,3-diylbis(nitrilomethylidyne)]dibenzonitrile top

Crystal data top

C₁₉H₁₆N₄	F(000) = 632
M_r = 300.36	D_x = 1.263 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2928 reflections
a = 14.4982 (4) Å	θ = 3.0–30.0°
b = 6.9025 (2) Å	µ = 0.08 mm⁻¹
c = 16.9842 (6) Å	T = 100 K
β = 111.659 (4)°	Needle, colourless
V = 1579.67 (8) Å³	0.37 × 0.12 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1544 independent reflections
Radiation source: fine-focus sealed tube	1257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
T_min = 0.886, T_max = 0.991	k = −8→8
13317 measured reflections	l = −20→20

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0132P)² + 5.0812P] where P = (F_o² + 2F_c²)/3
1544 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₉H₁₆N₄	V = 1579.67 (8) Å³
M_r = 300.36	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.4982 (4) Å	µ = 0.08 mm⁻¹
b = 6.9025 (2) Å	T = 100 K
c = 16.9842 (6) Å	0.37 × 0.12 × 0.12 mm
β = 111.659 (4)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1544 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1257 reflections with I > 2σ(I)
T_min = 0.886, T_max = 0.991	R_int = 0.077
13317 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.18 e Å⁻³
1544 reflections	Δρ_min = −0.37 e Å⁻³
109 parameters

Special details top

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

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
N1	0.14554 (16)	0.8098 (3)	0.29318 (13)	0.0173 (5)
N2	0.5053 (2)	0.1024 (4)	0.59762 (16)	0.0373 (7)
C1	0.29164 (19)	0.6045 (4)	0.43213 (16)	0.0193 (6)
H1A	0.2869	0.7370	0.4397	0.023*
C2	0.3625 (2)	0.4975 (4)	0.49323 (16)	0.0211 (6)
H2A	0.4052	0.5574	0.5422	0.025*
C3	0.3701 (2)	0.2986 (4)	0.48155 (17)	0.0192 (6)
C4	0.3064 (2)	0.2085 (4)	0.40896 (17)	0.0203 (6)
H4A	0.3116	0.0761	0.4012	0.024*
C5	0.23520 (19)	0.3172 (4)	0.34838 (17)	0.0183 (6)
H5A	0.1921	0.2570	0.2997	0.022*
C6	0.22689 (19)	0.5159 (4)	0.35906 (16)	0.0161 (6)
C7	0.15182 (19)	0.6273 (4)	0.29081 (17)	0.0183 (6)
H7A	0.1077	0.5609	0.2446	0.022*
C8	0.06898 (19)	0.9029 (4)	0.22061 (16)	0.0185 (6)
H8A	0.0310	0.8047	0.1811	0.022*
H8B	0.1002	0.9855	0.1915	0.022*
C9	0.0000	1.0233 (6)	0.2500	0.0162 (8)
C10	0.4454 (2)	0.1869 (4)	0.54596 (18)	0.0262 (7)
H9A	0.0367 (18)	1.110 (4)	0.2938 (15)	0.015 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0147 (12)	0.0211 (13)	0.0155 (11)	0.0035 (10)	0.0049 (9)	0.0024 (10)
N2	0.0446 (17)	0.0425 (17)	0.0235 (14)	0.0218 (15)	0.0109 (13)	0.0090 (13)
C1	0.0215 (15)	0.0158 (14)	0.0217 (14)	0.0001 (12)	0.0091 (12)	−0.0019 (12)
C2	0.0220 (15)	0.0242 (16)	0.0142 (13)	0.0027 (12)	0.0034 (12)	−0.0020 (12)
C3	0.0193 (14)	0.0227 (15)	0.0199 (14)	0.0046 (12)	0.0121 (12)	0.0049 (12)
C4	0.0246 (15)	0.0151 (14)	0.0268 (15)	0.0011 (12)	0.0162 (13)	0.0015 (12)
C5	0.0167 (14)	0.0191 (15)	0.0198 (14)	−0.0056 (11)	0.0075 (12)	−0.0058 (11)
C6	0.0150 (14)	0.0202 (15)	0.0165 (13)	0.0008 (11)	0.0097 (11)	0.0004 (11)
C7	0.0135 (14)	0.0229 (16)	0.0177 (14)	−0.0030 (11)	0.0048 (11)	−0.0025 (11)
C8	0.0156 (13)	0.0236 (15)	0.0159 (13)	0.0031 (12)	0.0052 (11)	0.0001 (12)
C9	0.0144 (19)	0.015 (2)	0.0174 (19)	0.000	0.0042 (16)	0.000
C10	0.0330 (17)	0.0270 (17)	0.0206 (15)	0.0072 (14)	0.0123 (14)	0.0013 (13)

Geometric parameters (Å, º) top

N1—C7	1.264 (3)	C4—H4A	0.9300
N1—C8	1.468 (3)	C5—C6	1.395 (4)
N2—C10	1.141 (4)	C5—H5A	0.9300
C1—C2	1.375 (4)	C6—C7	1.479 (4)
C1—C6	1.391 (4)	C7—H7A	0.9300
C1—H1A	0.9300	C8—C9	1.519 (3)
C2—C3	1.398 (4)	C8—H8A	0.9700
C2—H2A	0.9300	C8—H8B	0.9700
C3—C4	1.386 (4)	C9—C8ⁱ	1.519 (3)
C3—C10	1.450 (4)	C9—H9A	0.95 (3)
C4—C5	1.380 (4)

C7—N1—C8	116.8 (2)	C1—C6—C5	119.1 (3)
C2—C1—C6	120.5 (3)	C1—C6—C7	122.0 (2)
C2—C1—H1A	119.7	C5—C6—C7	118.9 (2)
C6—C1—H1A	119.7	N1—C7—C6	122.3 (3)
C1—C2—C3	119.8 (3)	N1—C7—H7A	118.9
C1—C2—H2A	120.1	C6—C7—H7A	118.9
C3—C2—H2A	120.1	N1—C8—C9	110.43 (19)
C4—C3—C2	120.4 (3)	N1—C8—H8A	109.6
C4—C3—C10	120.1 (3)	C9—C8—H8A	109.6
C2—C3—C10	119.5 (3)	N1—C8—H8B	109.6
C5—C4—C3	119.3 (3)	C9—C8—H8B	109.6
C5—C4—H4A	120.4	H8A—C8—H8B	108.1
C3—C4—H4A	120.4	C8—C9—C8ⁱ	113.7 (3)
C4—C5—C6	121.0 (3)	C8—C9—H9A	110.8 (15)
C4—C5—H5A	119.5	C8ⁱ—C9—H9A	109.5 (15)
C6—C5—H5A	119.5	N2—C10—C3	178.6 (4)

C6—C1—C2—C3	0.5 (4)	C4—C5—C6—C7	177.7 (2)
C1—C2—C3—C4	−0.3 (4)	C8—N1—C7—C6	178.9 (2)
C1—C2—C3—C10	179.6 (3)	C1—C6—C7—N1	3.5 (4)
C2—C3—C4—C5	−0.1 (4)	C5—C6—C7—N1	−174.2 (3)
C10—C3—C4—C5	180.0 (3)	C7—N1—C8—C9	123.5 (3)
C3—C4—C5—C6	0.3 (4)	N1—C8—C9—C8ⁱ	−71.64 (19)
C2—C1—C6—C5	−0.4 (4)	C4—C3—C10—N2	−179 (100)
C2—C1—C6—C7	−178.0 (3)	C2—C3—C10—N2	1 (14)
C4—C5—C6—C1	−0.1 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1ⁱⁱ	0.97	2.85	3.58	133

Symmetry code: (ii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₆N₄
M_r	300.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	14.4982 (4), 6.9025 (2), 16.9842 (6)
β (°)	111.659 (4)
V (Å³)	1579.67 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.12 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.886, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	13317, 1544, 1257
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.127, 1.17
No. of reflections	1544
No. of parameters	109
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.37

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1ⁱ	0.97	2.85	3.58	133

Symmetry code: (i) x, −y, z−1/2.

Footnotes

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

§Additional correspondence author, e-mail: hadi_kargar@yahoo.com.

Acknowledgements

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for financial support.

References

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