N,N′-(Ethane-1,2-diyldi-o-phenyl­ene)bis­(pyridine-2-carboxamide)

Sarkar, S.; Lee, H.-I.

doi:10.1107/S1600536811042309

organic compounds

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Volume 67| Part 11| November 2011| Page o2988

doi:10.1107/S1600536811042309

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N,N′-(Ethane-1,2-diyldi-o-phenylene)bis(pyridine-2-carboxamide)

Shuranjan Sarkar ^a and Hong-In Lee ^a ^*

^aDepartment of Chemistry, Kyungpook National University, Daegu 702-701, Republic of Korea
^*Correspondence e-mail: leehi@knu.ac.kr

(Received 27 September 2011; accepted 13 October 2011; online 22 October 2011)

The title molecule, C₂₆H₂₂N₄O₂, is centrosymmetric and adopts an anti conformation. Two intramolecular hydrogen bonds, viz. amide–pyridine N—H⋯N and phenyl–amide C—H⋯O, stabilize the trans conformation of the (pyridine-2-carboxamido)phenyl group about the amide plane. In the crystal, the presence of weak intermolecular C—H⋯O hydrogen bonds results in the formation of a three-dimensional network.

Related literature

For a related structure, see: Meghdadi et al. (2006 ). For applications of the pyridine-bearing carboxamides, see: Song et al. (2010 ); Piguet et al. (1997 ); Lessmann & Horrocks (2000 ); Singh et al. (2008 ). For the synthesis of the ligand, see: Jain et al. (2004 ).

Experimental

Crystal data

C₂₆H₂₂N₄O₂
M_r = 422.48
Monoclinic, P 2₁ /n
a = 5.9548 (5) Å
b = 11.9548 (10) Å
c = 14.8133 (12) Å
β = 91.429 (2)°
V = 1054.21 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.25 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
7762 measured reflections
2616 independent reflections
1118 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.090
S = 0.84
2616 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H14⋯N1	0.93 (2)	2.11 (3)	2.632 (2)	114.7 (18)
C13—H13⋯O1	0.95	2.33	2.941 (3)	122
C12—H12⋯O1ⁱ	0.95	2.48	3.352 (3)	152
C9—H9B⋯O1ⁱⁱ	0.99	2.61	3.299 (2)	127
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and CrystalMaker (CrystalMaker, 2007 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042309/kp2356sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042309/kp2356Isup2.hkl

checkCIF report

Comment top

Pyridine-bearing carboxamide, a biologically ubiquitous functional group, is an important ligand-construction unit for coordination chemistry (Song et al., 2010). This burgeoning class of ligands can be readily obtained from the condensation reaction between pyridyl carboxylic acid and amine (Jain et al., 2004) and have been used to obtain a wide diversity of consequential structural motifs such as helicates (Piguet et al., 1997; Lessmann & Horrocks, 2000), dinuclear and polynuclear complexes (Singh et al., 2008). In order to explore coordination chemistry of bis(pyridineamide) ligands, we have synthesised the title compound (I) and report here its crystal structure.

The molecule contains two N-phenylene(pyridine-2-carboxiamide) moieties linked by an ethylene bridge. The crystal of (I) adopts an anti conformation (Fig. 1). Only a half of the molecule constitutes the asymmetric unit and the other half is centrosymmetrically related. The bond distances observed in (I) do not deviate significantly from the mean values of those in N,N'-(methylenedi-p-phenylene)bis(pyridine-2-carboxamide) (Meghdadi et al., 2006). The angle between the phenylenyl and pyridyl rings is about 10°. Two intramolecular hydrogen bonds of N_amide—H···N_py and C_ph—H···O_amide stabilise trans conformation of the N-phenylene(pyridine-2-carboxiamide) moiety about the amide plane (Table 1 and Fig. 1). Two relatively weak intermolecular hydrogen bonds of C12—H12···O_amide and C9—H9b···O_amide present to form overall three-dimensional netowork in the crystal (Table 1 and Fig. 2).

Related literature top

For a related structure, see: Meghdadi et al. (2006). For applications of the pyridine-bearing carboxamides, see: Song et al. (2010); Piguet et al. (1997); Lessmann & Horrocks (2000); Singh et al. (2008). For the synthesis of the ligand, see: Jain et al. (2004).

Experimental top

A solution of 2,2'-ethylenedianiline (1.09 g, 5 mmol) in pyridine (5 mL) was added to a solution of pyridine-2-carboxylic acid (1.25 g, 10 mmol) in pyridine (10 mL). After the resulting solution was stirred at 313 K for 10 min, triphenyl phosphate (3.21 g,10 mmol) was added dropwise and the reaction mixture was stirred at 373 K for 4 h. The reaction mixture was cooled to room temperature and stirred for 10 h. The volume of the solution was reduced to 10 mL and kept over night in a hood. The remaining solution was filtered, thoroughly washed four times with 100 mL solvent of water and acetone (1:1), and dried in vacuum. X-ray quality crystals were obtained by slow diffusion of diethyl ether into a dichloromethane solution at room temperature (yield 90%; m.p. about 473 K).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and CrystalMaker (CrystalMaker, 2007); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP drawing of the title compound showing 30% probability displacement ellipsoids and the atomic numbering scheme. Dotted lines represent the intramolecular hydrogen bonds. Atomic-numberings for H atoms are omitted for clarity. Symmetry code to generate the molecule: (i) -x + 1, -y + 2, -z + 1.
	Fig. 2. Perspective view of crystal packing along a axis. Green dotted lines represent the intermolecular hydrogen bonds. C, N, and H atoms are coloured in black, blue, and pink, respectively. All H atoms except for those related to the intermolecular hydrogen bonds are omitted for clarity.

N,N'-(Ethane-1,2-diyldi-o-phenylene)bis(pyridine- 2-carboxamide) top

Crystal data top

C₂₆H₂₂N₄O₂	F(000) = 444
M_r = 422.48	D_x = 1.331 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1330 reflections
a = 5.9548 (5) Å	θ = 2.8–25.8°
b = 11.9548 (10) Å	µ = 0.09 mm⁻¹
c = 14.8133 (12) Å	T = 200 K
β = 91.429 (2)°	Block, colourless
V = 1054.21 (15) Å³	0.25 × 0.16 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1118 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.074
Graphite monochromator	θ_max = 28.3°, θ_min = 2.2°
phi and ω scans	h = −7→7
7762 measured reflections	k = −15→11
2616 independent 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ²(F_o²) + (0.0126P)²] where P = (F_o² + 2F_c²)/3
2616 reflections	(Δ/σ)_max < 0.001
149 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₆H₂₂N₄O₂	V = 1054.21 (15) Å³
M_r = 422.48	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.9548 (5) Å	µ = 0.09 mm⁻¹
b = 11.9548 (10) Å	T = 200 K
c = 14.8133 (12) Å	0.25 × 0.16 × 0.12 mm
β = 91.429 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1118 reflections with I > 2σ(I)
7762 measured reflections	R_int = 0.074
2616 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	Δρ_max = 0.19 e Å⁻³
2616 reflections	Δρ_min = −0.21 e Å⁻³
149 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
N1	0.8708 (3)	0.71472 (14)	0.45440 (12)	0.0405 (5)
C1	0.8708 (4)	0.64611 (19)	0.38332 (15)	0.0499 (7)
H1	0.7466	0.6485	0.3418	0.060*
C2	1.0440 (5)	0.57144 (19)	0.36728 (17)	0.0516 (8)
H2	1.0382	0.5237	0.3160	0.062*
C3	1.2230 (5)	0.5680 (2)	0.42681 (17)	0.0545 (8)
H3	1.3435	0.5176	0.4174	0.065*
C4	1.2270 (4)	0.63841 (18)	0.50077 (15)	0.0452 (7)
H4	1.3501	0.6378	0.5428	0.054*
C5	1.0471 (4)	0.70976 (17)	0.51194 (14)	0.0321 (6)
C6	1.0488 (4)	0.78986 (18)	0.59027 (14)	0.0316 (6)
O1	1.1900 (3)	0.78453 (12)	0.65163 (10)	0.0425 (4)
N2	0.8816 (3)	0.86669 (15)	0.58299 (12)	0.0333 (5)
H14	0.789 (4)	0.8555 (18)	0.5327 (15)	0.073 (9)*
C7	0.8427 (4)	0.96392 (17)	0.63478 (13)	0.0282 (5)
C8	0.6431 (4)	1.02237 (17)	0.61789 (13)	0.0282 (5)
C9	0.4708 (4)	0.98304 (17)	0.54855 (12)	0.0308 (5)
H9A	0.3226	1.0149	0.5632	0.037*
H9B	0.4587	0.9006	0.5518	0.037*
C10	0.6084 (4)	1.12198 (18)	0.66456 (14)	0.0379 (6)
H10	0.4734	1.1627	0.6539	0.046*
C11	0.7673 (4)	1.16257 (18)	0.72620 (15)	0.0425 (7)
H11	0.7412	1.2308	0.7571	0.051*
C12	0.9627 (4)	1.10390 (19)	0.74251 (14)	0.0421 (7)
H12	1.0720	1.1318	0.7845	0.051*
C13	1.0005 (4)	1.00386 (18)	0.69758 (13)	0.0352 (6)
H13	1.1343	0.9627	0.7098	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0473 (15)	0.0353 (12)	0.0385 (12)	0.0060 (10)	−0.0035 (10)	−0.0072 (10)
C1	0.059 (2)	0.0470 (17)	0.0437 (16)	0.0059 (14)	−0.0067 (14)	−0.0121 (13)
C2	0.074 (2)	0.0395 (17)	0.0413 (16)	0.0124 (14)	0.0094 (15)	−0.0059 (13)
C3	0.068 (2)	0.0478 (18)	0.0481 (17)	0.0240 (15)	0.0113 (16)	−0.0006 (14)
C4	0.0487 (19)	0.0428 (16)	0.0442 (16)	0.0168 (13)	0.0035 (13)	0.0024 (13)
C5	0.0394 (16)	0.0260 (13)	0.0314 (13)	0.0055 (10)	0.0068 (11)	0.0065 (10)
C6	0.0353 (16)	0.0290 (14)	0.0306 (13)	0.0010 (11)	0.0038 (11)	0.0084 (11)
O1	0.0430 (12)	0.0442 (10)	0.0399 (10)	0.0075 (8)	−0.0103 (8)	0.0046 (8)
N2	0.0355 (14)	0.0330 (12)	0.0311 (12)	0.0081 (9)	−0.0053 (10)	−0.0056 (9)
C7	0.0318 (15)	0.0292 (13)	0.0239 (12)	−0.0006 (10)	0.0034 (10)	−0.0018 (10)
C8	0.0305 (15)	0.0296 (13)	0.0249 (12)	0.0001 (10)	0.0053 (10)	0.0028 (10)
C9	0.0291 (14)	0.0310 (13)	0.0324 (13)	0.0025 (10)	0.0043 (11)	0.0031 (10)
C10	0.0444 (18)	0.0344 (15)	0.0354 (14)	0.0044 (11)	0.0102 (13)	0.0012 (11)
C11	0.059 (2)	0.0331 (15)	0.0365 (14)	−0.0052 (13)	0.0141 (14)	−0.0064 (11)
C12	0.0527 (19)	0.0460 (17)	0.0278 (13)	−0.0140 (13)	0.0034 (13)	−0.0024 (12)
C13	0.0375 (16)	0.0404 (15)	0.0278 (13)	−0.0035 (11)	0.0026 (11)	0.0015 (11)

Geometric parameters (Å, º) top

N1—C1	1.335 (3)	C7—C13	1.390 (3)
N1—C5	1.337 (3)	C7—C8	1.396 (3)
C1—C2	1.389 (3)	C8—C10	1.395 (3)
C1—H1	0.9500	C8—C9	1.509 (3)
C2—C3	1.367 (3)	C9—C9ⁱ	1.543 (3)
C2—H2	0.9500	C9—H9A	0.9900
C3—C4	1.381 (3)	C9—H9B	0.9900
C3—H3	0.9500	C10—C11	1.386 (3)
C4—C5	1.382 (3)	C10—H10	0.9500
C4—H4	0.9500	C11—C12	1.375 (3)
C5—C6	1.504 (3)	C11—H11	0.9500
C6—O1	1.224 (2)	C12—C13	1.390 (3)
C6—N2	1.357 (3)	C12—H12	0.9500
N2—C7	1.415 (2)	C13—H13	0.9500
N2—H14	0.93 (2)

C1—N1—C5	117.4 (2)	C13—C7—N2	121.9 (2)
N1—C1—C2	123.0 (2)	C8—C7—N2	117.7 (2)
N1—C1—H1	118.5	C10—C8—C7	118.3 (2)
C2—C1—H1	118.5	C10—C8—C9	119.8 (2)
C3—C2—C1	118.6 (2)	C7—C8—C9	121.84 (19)
C3—C2—H2	120.7	C8—C9—C9ⁱ	112.8 (2)
C1—C2—H2	120.7	C8—C9—H9A	109.0
C2—C3—C4	119.4 (2)	C9ⁱ—C9—H9A	109.0
C2—C3—H3	120.3	C8—C9—H9B	109.0
C4—C3—H3	120.3	C9ⁱ—C9—H9B	109.0
C3—C4—C5	118.2 (2)	H9A—C9—H9B	107.8
C3—C4—H4	120.9	C11—C10—C8	121.2 (2)
C5—C4—H4	120.9	C11—C10—H10	119.4
N1—C5—C4	123.3 (2)	C8—C10—H10	119.4
N1—C5—C6	116.96 (19)	C12—C11—C10	119.9 (2)
C4—C5—C6	119.7 (2)	C12—C11—H11	120.1
O1—C6—N2	125.7 (2)	C10—C11—H11	120.1
O1—C6—C5	122.1 (2)	C11—C12—C13	120.1 (2)
N2—C6—C5	112.3 (2)	C11—C12—H12	120.0
C6—N2—C7	130.0 (2)	C13—C12—H12	120.0
C6—N2—H14	112.8 (15)	C12—C13—C7	120.1 (2)
C7—N2—H14	116.9 (15)	C12—C13—H13	120.0
C13—C7—C8	120.4 (2)	C7—C13—H13	120.0

C5—N1—C1—C2	−0.1 (4)	C6—N2—C7—C8	−173.7 (2)
N1—C1—C2—C3	−0.1 (4)	C13—C7—C8—C10	0.9 (3)
C1—C2—C3—C4	−0.1 (4)	N2—C7—C8—C10	−176.24 (18)
C2—C3—C4—C5	0.4 (4)	C13—C7—C8—C9	178.45 (17)
C1—N1—C5—C4	0.5 (3)	N2—C7—C8—C9	1.3 (3)
C1—N1—C5—C6	178.20 (18)	C10—C8—C9—C9ⁱ	96.1 (3)
C3—C4—C5—N1	−0.6 (4)	C7—C8—C9—C9ⁱ	−81.4 (3)
C3—C4—C5—C6	−178.3 (2)	C7—C8—C10—C11	0.1 (3)
N1—C5—C6—O1	172.4 (2)	C9—C8—C10—C11	−177.55 (19)
C4—C5—C6—O1	−9.8 (3)	C8—C10—C11—C12	−0.4 (3)
N1—C5—C6—N2	−8.7 (3)	C10—C11—C12—C13	−0.3 (3)
C4—C5—C6—N2	169.2 (2)	C11—C12—C13—C7	1.2 (3)
O1—C6—N2—C7	8.3 (4)	C8—C7—C13—C12	−1.5 (3)
C5—C6—N2—C7	−170.7 (2)	N2—C7—C13—C12	175.5 (2)
C6—N2—C7—C13	9.2 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H14···N1	0.93 (2)	2.11 (3)	2.632 (2)	114.7 (18)
C13—H13···O1	0.95	2.33	2.941 (3)	122
C12—H12···O1ⁱⁱ	0.95	2.48	3.352 (3)	152
C9—H9B···O1ⁱⁱⁱ	0.99	2.61	3.299 (2)	127

Symmetry codes: (ii) −x+5/2, y+1/2, −z+3/2; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₂N₄O₂
M_r	422.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	5.9548 (5), 11.9548 (10), 14.8133 (12)
β (°)	91.429 (2)
V (Å³)	1054.21 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7762, 2616, 1118
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.090, 0.84
No. of reflections	2616
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and CrystalMaker (CrystalMaker, 2007), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H14···N1	0.93 (2)	2.11 (3)	2.632 (2)	114.7 (18)
C13—H13···O1	0.95	2.33	2.941 (3)	122
C12—H12···O1ⁱ	0.95	2.48	3.352 (3)	152
C9—H9B···O1ⁱⁱ	0.99	2.61	3.299 (2)	127

Symmetry codes: (i) −x+5/2, y+1/2, −z+3/2; (ii) x−1, y, z.

Acknowledgements

This research was supported by the National Research Foundation of Korea Grant funded by the Korean Government (2009–0087304). The authors acknowledge Dr Ha-Jin Lee and the Korea Basic Science Institute for the data collection and refinement.

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