Ortho­rhom­bic modification of bis­[4-(3-pyridyl­methyl­idene­amino)­phen­yl]methane

Shah, K.; Raza Shah, M.; Khan, I.U.; Ng, S.W.

doi:10.1107/S1600536810032034

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2316

https://doi.org/10.1107/S1600536810032034

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Orthorhombic modification of bis[4-(3-pyridylmethylideneamino)phenyl]methane

Kiramat Shah,^a Muhammad Raza Shah,^a Islam Ullah Khan ^b and Seik Weng Ng ^c ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Chemistry, Government College University, 54000 Lahore, Pakistan, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 5 August 2010; accepted 9 August 2010; online 18 August 2010)

The title compound, C₂₅H₂₀N₄, is a disubstituted methane derivative having two pyridylmethyleneaminophenyl arms, one of which is essentially rigid as all atoms lie on a plane (r.m.s. deviation = 0.074 Å), whereas the other is twisted [dihedral angle between the phenylene and pyridyl rings = 51.1 (4)°]. The angle at the methylene C atom is 113.2 (2)°.

Related literature

For the monoclinic modification, see: Wang et al. (2005 ).

Experimental

Crystal data

C₂₅H₂₀N₄
M_r = 376.45
Orthorhombic, P c a 2₁
a = 11.4213 (4) Å
b = 4.6181 (2) Å
c = 37.3048 (15) Å
V = 1967.63 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker Kappa APEXII diffractometer
9233 measured reflections
1761 independent reflections
1450 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.109
S = 0.92
1761 reflections
262 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032034/nk2051sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032034/nk2051Isup2.hkl

checkCIF report

Comment top

We have synthesized bis[4-(3-pyridylmethyleneamino)phenyl]methane (Scheme I) for use in cocrystallization studies. The compound has previously been reported to belong to the non-centric Pc space group [a = 18.751 (5), b = 4.641 (2), c = 11.387 (1) Å, β = 98.39 (2) °] (Wang et al., 2005). The atoms of one of the two pyridylmethyleneaminophenylarms of the approximately V-shaped molecule all lie on a plane; for the other arm, the two aromatic rings are aligned at 53.9 (2) °]. The present orthorhombic modification (Fig. 1) has one axis that is doubled [c = 37.3048 (15), b = 4.6181 (2), a = 11.4213 (4) Å]. The principal features are similar to those of the reported structure.

Related literature top

For the monoclinic modification, see: Wang et al. (2005).

Experimental top

The compound was synthesized from the condensation of 4,4'-diaminodiphenylmethane and 3-pyridinecarboxaldehyde in ethanol (Wang et al., 2005), and crystals were obtained upon recrystallization from ethyl acetate.

Structure description top

For the monoclinic modification, see: Wang et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: publCIF (Westrip, 2010).

Figures top

Fig. 1. Displacement ellipsoid plot of C₂₅H₂₀N₄ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

N,N'-Bis(3-pyridylmethylidene)-4,4'-methylenedianiline top

Crystal data top

C₂₅H₂₀N₄	F(000) = 792
M_r = 376.45	D_x = 1.271 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1793 reflections
a = 11.4213 (4) Å	θ = 3.3–20.6°
b = 4.6181 (2) Å	µ = 0.08 mm⁻¹
c = 37.3048 (15) Å	T = 293 K
V = 1967.63 (14) Å³	Prism, yellow
Z = 4	0.35 × 0.25 × 0.15 mm

Data collection top

Bruker Kappa APEXII diffractometer	1450 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 25.0°, θ_min = 3.3°
φ and ω scans	h = −13→12
9233 measured reflections	k = −5→5
1761 independent reflections	l = −43→44

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.081P)²] where P = (F_o² + 2F_c²)/3
1761 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₂₅H₂₀N₄	V = 1967.63 (14) Å³
M_r = 376.45	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 11.4213 (4) Å	µ = 0.08 mm⁻¹
b = 4.6181 (2) Å	T = 293 K
c = 37.3048 (15) Å	0.35 × 0.25 × 0.15 mm

Data collection top

Bruker Kappa APEXII diffractometer	1450 reflections with I > 2σ(I)
9233 measured reflections	R_int = 0.039
1761 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.109	H-atom parameters constrained
S = 0.92	Δρ_max = 0.11 e Å⁻³
1761 reflections	Δρ_min = −0.11 e Å⁻³
262 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	−0.0359 (3)	1.7957 (7)	0.50015 (10)	0.0616 (8)
N2	0.1337 (2)	1.1963 (5)	0.43344 (7)	0.0397 (6)
N3	0.4326 (3)	0.9705 (6)	0.20004 (8)	0.0532 (7)
N4	0.7055 (3)	1.3287 (10)	0.11332 (10)	0.0816 (11)
C1	0.1358 (3)	1.5338 (6)	0.48188 (8)	0.0375 (7)
C2	0.1996 (3)	1.6715 (8)	0.50825 (9)	0.0522 (9)
H2	0.2789	1.6316	0.5110	0.063*
C3	0.1457 (4)	1.8681 (8)	0.53055 (9)	0.0576 (10)
H3	0.1874	1.9615	0.5486	0.069*
C4	0.0294 (4)	1.9221 (8)	0.52547 (10)	0.0577 (10)
H4	−0.0067	2.0551	0.5406	0.069*
C5	0.0193 (3)	1.6096 (8)	0.47908 (10)	0.0529 (9)
H5	−0.0240	1.5229	0.4609	0.063*
C6	0.1904 (3)	1.3248 (7)	0.45776 (9)	0.0429 (8)
H6	0.2698	1.2849	0.4604	0.052*
C7	0.1904 (3)	0.9962 (6)	0.41026 (8)	0.0357 (7)
C8	0.3029 (3)	0.8895 (6)	0.41450 (8)	0.0409 (7)
H8	0.3479	0.9497	0.4339	0.049*
C9	0.3488 (3)	0.6942 (6)	0.39020 (9)	0.0415 (8)
H9	0.4241	0.6231	0.3937	0.050*
C10	0.2848 (3)	0.6020 (6)	0.36067 (8)	0.0370 (7)
C11	0.1720 (3)	0.7078 (7)	0.35684 (9)	0.0440 (8)
H11	0.1270	0.6491	0.3374	0.053*
C12	0.1252 (3)	0.8988 (7)	0.38142 (9)	0.0416 (7)
H12	0.0486	0.9630	0.3786	0.050*
C13	0.3353 (3)	0.3988 (7)	0.33309 (9)	0.0459 (8)
H13A	0.2798	0.2439	0.3287	0.055*
H13B	0.4062	0.3125	0.3426	0.055*
C14	0.3636 (3)	0.5460 (6)	0.29792 (9)	0.0419 (7)
C15	0.4547 (3)	0.7423 (7)	0.29520 (9)	0.0452 (8)
H15	0.4998	0.7826	0.3153	0.054*
C16	0.4800 (3)	0.8798 (7)	0.26323 (9)	0.0469 (8)
H16	0.5422	1.0092	0.2621	0.056*
C17	0.4139 (3)	0.8275 (7)	0.23287 (9)	0.0480 (8)
C18	0.3207 (3)	0.6355 (9)	0.23547 (10)	0.0614 (10)
H18	0.2738	0.6004	0.2156	0.074*
C19	0.2972 (3)	0.4961 (8)	0.26751 (10)	0.0572 (9)
H19	0.2353	0.3656	0.2686	0.069*
C20	0.5355 (4)	1.0079 (8)	0.18865 (9)	0.0565 (10)
H20	0.5973	0.9275	0.2015	0.068*
C21	0.5619 (3)	1.1718 (8)	0.15619 (9)	0.0517 (9)
C22	0.6740 (3)	1.1852 (9)	0.14284 (10)	0.0683 (11)
H22	0.7322	1.0870	0.1553	0.082*
C23	0.6200 (4)	1.4715 (11)	0.09659 (12)	0.0764 (13)
H23	0.6391	1.5737	0.0759	0.092*
C24	0.5058 (4)	1.4774 (9)	0.10794 (11)	0.0704 (11)
H24	0.4496	1.5825	0.0954	0.084*
C25	0.4766 (3)	1.3259 (9)	0.13793 (11)	0.0607 (10)
H25	0.3997	1.3257	0.1461	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0476 (17)	0.0680 (19)	0.069 (2)	0.0030 (15)	0.0021 (16)	−0.0211 (17)
N2	0.0379 (14)	0.0420 (14)	0.0392 (15)	0.0028 (11)	0.0002 (13)	−0.0020 (12)
N3	0.0526 (19)	0.0636 (18)	0.0434 (16)	0.0009 (15)	0.0023 (14)	0.0059 (14)
N4	0.059 (2)	0.125 (3)	0.061 (2)	−0.008 (2)	0.0122 (18)	0.011 (2)
C1	0.0387 (17)	0.0362 (15)	0.0375 (16)	−0.0039 (13)	0.0007 (14)	0.0037 (13)
C2	0.048 (2)	0.060 (2)	0.049 (2)	0.0018 (16)	−0.0086 (16)	−0.0053 (17)
C3	0.068 (3)	0.061 (2)	0.044 (2)	−0.0018 (19)	−0.0119 (19)	−0.0096 (17)
C4	0.066 (3)	0.054 (2)	0.053 (2)	0.0022 (19)	0.012 (2)	−0.0063 (17)
C5	0.041 (2)	0.059 (2)	0.058 (2)	−0.0039 (17)	−0.0033 (17)	−0.0148 (18)
C6	0.0354 (17)	0.0451 (16)	0.0483 (19)	0.0002 (14)	−0.0001 (15)	0.0008 (15)
C7	0.0358 (16)	0.0334 (13)	0.0379 (16)	−0.0009 (13)	0.0035 (13)	0.0041 (13)
C8	0.0374 (17)	0.0462 (16)	0.0390 (17)	−0.0015 (14)	−0.0040 (14)	0.0016 (15)
C9	0.0315 (16)	0.0404 (16)	0.053 (2)	0.0017 (13)	0.0014 (15)	0.0081 (15)
C10	0.0391 (17)	0.0310 (14)	0.0410 (18)	−0.0004 (12)	0.0051 (14)	0.0085 (13)
C11	0.0397 (17)	0.0465 (17)	0.0457 (19)	−0.0002 (14)	−0.0029 (15)	−0.0093 (15)
C12	0.0320 (16)	0.0445 (16)	0.0481 (19)	0.0041 (13)	−0.0017 (15)	−0.0021 (15)
C13	0.0472 (19)	0.0360 (15)	0.055 (2)	0.0048 (14)	0.0089 (16)	0.0036 (15)
C14	0.0427 (18)	0.0372 (15)	0.0459 (19)	0.0064 (14)	0.0083 (16)	−0.0029 (15)
C15	0.0485 (19)	0.0443 (16)	0.0427 (18)	0.0014 (14)	−0.0003 (15)	−0.0013 (15)
C16	0.046 (2)	0.0480 (17)	0.0469 (19)	−0.0036 (15)	0.0033 (17)	−0.0009 (15)
C17	0.046 (2)	0.052 (2)	0.0457 (19)	0.0036 (16)	0.0028 (17)	0.0021 (15)
C18	0.057 (2)	0.081 (3)	0.046 (2)	−0.008 (2)	−0.0074 (18)	0.002 (2)
C19	0.050 (2)	0.059 (2)	0.062 (2)	−0.0119 (17)	0.0007 (17)	0.0002 (18)
C20	0.058 (2)	0.065 (2)	0.047 (2)	0.0088 (19)	0.0000 (17)	0.0021 (18)
C21	0.051 (2)	0.062 (2)	0.042 (2)	0.0009 (17)	−0.0007 (17)	−0.0020 (17)
C22	0.054 (2)	0.100 (3)	0.050 (2)	0.003 (2)	0.0016 (19)	0.005 (2)
C23	0.086 (3)	0.096 (3)	0.047 (2)	−0.015 (3)	0.009 (2)	0.010 (2)
C24	0.074 (3)	0.082 (3)	0.055 (2)	0.003 (2)	0.002 (2)	0.016 (2)
C25	0.053 (2)	0.080 (2)	0.048 (2)	−0.0018 (19)	0.0048 (19)	0.0078 (18)

Geometric parameters (Å, º) top

N1—C5	1.325 (5)	C11—C12	1.380 (4)
N1—C4	1.338 (5)	C11—H11	0.9300
N2—C6	1.263 (4)	C12—H12	0.9300
N2—C7	1.422 (4)	C13—C14	1.513 (4)
N3—C20	1.262 (5)	C13—H13A	0.9700
N3—C17	1.408 (4)	C13—H13B	0.9700
N4—C23	1.334 (6)	C14—C15	1.384 (4)
N4—C22	1.335 (5)	C14—C19	1.384 (5)
C1—C5	1.380 (5)	C15—C16	1.382 (5)
C1—C2	1.379 (5)	C15—H15	0.9300
C1—C6	1.459 (4)	C16—C17	1.382 (5)
C2—C3	1.377 (5)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.388 (5)
C3—C4	1.364 (5)	C18—C19	1.384 (5)
C3—H3	0.9300	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.459 (5)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.385 (4)	C21—C22	1.375 (5)
C7—C12	1.384 (4)	C21—C25	1.386 (5)
C8—C9	1.382 (4)	C22—H22	0.9300
C8—H8	0.9300	C23—C24	1.372 (6)
C9—C10	1.389 (4)	C23—H23	0.9300
C9—H9	0.9300	C24—C25	1.361 (5)
C10—C11	1.386 (4)	C24—H24	0.9300
C10—C13	1.507 (4)	C25—H25	0.9300

C5—N1—C4	115.9 (3)	C10—C13—H13A	108.9
C6—N2—C7	120.6 (3)	C14—C13—H13A	108.9
C20—N3—C17	119.9 (3)	C10—C13—H13B	108.9
C23—N4—C22	115.7 (4)	C14—C13—H13B	108.9
C5—C1—C2	116.5 (3)	H13A—C13—H13B	107.8
C5—C1—C6	122.2 (3)	C15—C14—C19	117.4 (3)
C2—C1—C6	121.3 (3)	C15—C14—C13	121.2 (3)
C3—C2—C1	120.0 (3)	C19—C14—C13	121.3 (3)
C3—C2—H2	120.0	C16—C15—C14	121.4 (3)
C1—C2—H2	120.0	C16—C15—H15	119.3
C4—C3—C2	118.1 (3)	C14—C15—H15	119.3
C4—C3—H3	120.9	C15—C16—C17	120.9 (3)
C2—C3—H3	120.9	C15—C16—H16	119.6
N1—C4—C3	124.2 (3)	C17—C16—H16	119.6
N1—C4—H4	117.9	C16—C17—C18	118.2 (3)
C3—C4—H4	117.9	C16—C17—N3	123.2 (3)
N1—C5—C1	125.4 (3)	C18—C17—N3	118.5 (3)
N1—C5—H5	117.3	C19—C18—C17	120.4 (3)
C1—C5—H5	117.3	C19—C18—H18	119.8
N2—C6—C1	122.3 (3)	C17—C18—H18	119.8
N2—C6—H6	118.8	C18—C19—C14	121.6 (3)
C1—C6—H6	118.8	C18—C19—H19	119.2
C8—C7—C12	118.2 (3)	C14—C19—H19	119.2
C8—C7—N2	125.7 (3)	N3—C20—C21	122.9 (3)
C12—C7—N2	116.1 (3)	N3—C20—H20	118.6
C9—C8—C7	120.6 (3)	C21—C20—H20	118.6
C9—C8—H8	119.7	C22—C21—C25	117.0 (3)
C7—C8—H8	119.7	C22—C21—C20	121.1 (4)
C8—C9—C10	121.4 (3)	C25—C21—C20	121.9 (3)
C8—C9—H9	119.3	N4—C22—C21	124.9 (4)
C10—C9—H9	119.3	N4—C22—H22	117.5
C11—C10—C9	117.6 (3)	C21—C22—H22	117.5
C11—C10—C13	120.3 (3)	N4—C23—C24	124.2 (4)
C9—C10—C13	122.1 (3)	N4—C23—H23	117.9
C12—C11—C10	121.1 (3)	C24—C23—H23	117.9
C12—C11—H11	119.4	C25—C24—C23	118.4 (4)
C10—C11—H11	119.4	C25—C24—H24	120.8
C11—C12—C7	121.1 (3)	C23—C24—H24	120.8
C11—C12—H12	119.5	C24—C25—C21	119.7 (4)
C7—C12—H12	119.5	C24—C25—H25	120.1
C10—C13—C14	113.2 (2)	C21—C25—H25	120.1

C5—C1—C2—C3	1.4 (5)	C10—C13—C14—C15	69.5 (4)
C6—C1—C2—C3	179.9 (3)	C10—C13—C14—C19	−108.5 (3)
C1—C2—C3—C4	−0.5 (5)	C19—C14—C15—C16	−1.1 (5)
C5—N1—C4—C3	−0.5 (6)	C13—C14—C15—C16	−179.2 (3)
C2—C3—C4—N1	0.1 (6)	C14—C15—C16—C17	0.7 (5)
C4—N1—C5—C1	1.6 (6)	C15—C16—C17—C18	0.6 (5)
C2—C1—C5—N1	−2.0 (5)	C15—C16—C17—N3	177.2 (3)
C6—C1—C5—N1	179.5 (3)	C20—N3—C17—C16	43.1 (5)
C7—N2—C6—C1	179.4 (3)	C20—N3—C17—C18	−140.4 (4)
C5—C1—C6—N2	−1.6 (5)	C16—C17—C18—C19	−1.5 (5)
C2—C1—C6—N2	180.0 (3)	N3—C17—C18—C19	−178.3 (3)
C6—N2—C7—C8	10.1 (4)	C17—C18—C19—C14	1.1 (6)
C6—N2—C7—C12	−171.1 (3)	C15—C14—C19—C18	0.2 (5)
C12—C7—C8—C9	0.9 (4)	C13—C14—C19—C18	178.3 (3)
N2—C7—C8—C9	179.8 (3)	C17—N3—C20—C21	−175.5 (3)
C7—C8—C9—C10	0.8 (4)	N3—C20—C21—C22	−173.9 (4)
C8—C9—C10—C11	−1.4 (4)	N3—C20—C21—C25	7.6 (6)
C8—C9—C10—C13	177.4 (3)	C23—N4—C22—C21	1.3 (7)
C9—C10—C11—C12	0.3 (4)	C25—C21—C22—N4	−1.8 (6)
C13—C10—C11—C12	−178.6 (3)	C20—C21—C22—N4	179.7 (4)
C10—C11—C12—C7	1.5 (5)	C22—N4—C23—C24	0.0 (7)
C8—C7—C12—C11	−2.1 (4)	N4—C23—C24—C25	−0.8 (7)
N2—C7—C12—C11	178.9 (3)	C23—C24—C25—C21	0.2 (6)
C11—C10—C13—C14	71.8 (4)	C22—C21—C25—C24	0.9 (5)
C9—C10—C13—C14	−107.1 (3)	C20—C21—C25—C24	179.4 (4)

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₄
M_r	376.45
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	11.4213 (4), 4.6181 (2), 37.3048 (15)
V (Å³)	1967.63 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9233, 1761, 1450
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 0.92
No. of reflections	1761
No. of parameters	262
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.11

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the Higher Education Commission of Pakistan, GC University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Q., Pi, X.-D. & Su, C.-Y. (2005). Acta Cryst. C61, o73–o74. Web of Science CSD 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

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