N,N′-Bis(4-bromo­phen­yl)pyridine-2,6-dicarboxamide

Waris, G.; Siddiqi, H.M.; Flörke, U.; Hussain, R.; Butt, M.S.

doi:10.1107/S1600536813002705

organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o416

doi:10.1107/S1600536813002705

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N,N′-Bis(4-bromophenyl)pyridine-2,6-dicarboxamide

Ghulam Waris,^a Humaira Masood Siddiqi,^a ^* Ulrich Flörke,^b Rizwan Hussain ^c and M. Saeed Butt ^a

^aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, ^bUniversität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany, and ^cNESCOM, PO Box 2216 Islamabad, Pakistan
^*Correspondence e-mail: humaira_siddiqi@yahoo.com

(Received 22 December 2012; accepted 27 January 2013; online 20 February 2013)

The molecule of the title compound, C₁₉H₁₃Br₂N₃O₂, lies about a twofold rotation axis. The benzene ring makes dihedral angles of 8.9 (2) and 16.4 (2)° with the central pyridine ring and the second benzene ring, respectively. An intramolecular N—H⋯N contact occurs. In the crystal, molecules are connected by pairs of N—H⋯O hydrogen bonds into chains along the c axis.

Related literature

For related structures, see: Malone et al. (1997 ); Qi et al. (2003 ). For imide–amide polymers, see: Sun et al. (2006 ); Zhong et al. (2002 ). For properties of polymers containing heterocyclic groups, see: Diakoumakos & Mikroyannidis (1994 ); Hamciuc et al. (2001 ).

Experimental

Crystal data

C₁₉H₁₃Br₂N₃O₂
M_r = 475.14
Monoclinic, C 2/c
a = 9.550 (2) Å
b = 22.698 (5) Å
c = 8.748 (2) Å
β = 107.511 (5)°
V = 1808.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 4.50 mm⁻¹
T = 130 K
0.21 × 0.12 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.452, T_max = 0.637
8520 measured reflections
2159 independent reflections
1695 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.02
2159 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2	0.88	2.23	2.673 (3)	111
N1—H1A⋯O1ⁱ	0.88	2.32	3.044 (3)	140
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813002705/yk2085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002705/yk2085Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813002705/yk2085Isup3.cml

checkCIF report

Comment top

Aromatic Poly(amide-imide)s are classified as meta aramid family. They are non-flammable, which is a permanent characteristic of their chemical structure. It includes a high proportion of aromatic groups and combined double bonds. The demand for polyamide-imide (PAI) and other high-temperature resistant polymeric materials has grown steadily because of their outstanding mechanical properties, excellent thermal and oxidative stability (Zhong et al., 2002; Sun et al., 2006). Incorporation of heterocylic groups in the polymer backbone is a rational approach which promotes solubility without affecting thermal and mechanical properties to any great extent (Diakoumakos et al., 1994, Hamciuc et al., 2001). As part of our enduring interest in solubility of aromatic poly(amide-imide)s by structural modification, we are reporting a pyridine-based monomer having inbuilt amide functionality. It enhances the solubility of resulting poly(amid-imide)s without worsening the inherent properties of the polymer.

Related literature top

For related structures, see: Malone et al. (1997); Qi et al. (2003). For imide–amide polymers, see: Sun et al. (2006); Zhong et al. (2002). For properties of polymers containing heterocyclic groups, see: Diakoumakos & Mikroyannidis (1994); Hamciuc et al. (2001).

Experimental top

In this preparation, chemicals of reagent grade quality were used without their further purification. In a 100 ml three-necked round-bottomed flask, equipped with a condenser, a nitrogen gas inlet tube, a thermometer and a magnetic stirrer, 0.02 mole (3.44 g) of 4-bromoaniline in 25 mL of dry tetrahydrofuran (THF) were stirred at 273–278 K for 30 minutes and 0.01 mol (2.04 g) of pyridine-2,6-dicarbonyl dichloride in 30 mL of THF was added dropwise by dropping funnel. Stirring was continued for further 1 h at the same conditions. The temperature of reaction mixture was then raised to 308–313 K and stirring was continued for 45 minutes. The flask content was cooled to room temperature, poured into water and left for 24 h. Resulting dark brown precipitate was filtered, washed with hot water and 5% NaOH solution. Finally, product was washed with hot water and methanol, dried under vacuum at 353 K. The crude product was recrystallized from THF-ethylacetate mixture (1:2).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 local programs.

Figures top

	Fig. 1. Molecular structure of the title compound with anisotropic displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) -x+1, y, -z+3/2.
	Fig. 2. Crystal packing viewd along b axis with hydrogen bonds as dotted lines. H-atoms not involved are omitted.

N,N'-Bis(4-bromophenyl)pyridine-2,6-dicarboxamide top

Crystal data top

C₁₉H₁₃Br₂N₃O₂	F(000) = 936
M_r = 475.14	D_x = 1.745 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1650 reflections
a = 9.550 (2) Å	θ = 2.9–23.6°
b = 22.698 (5) Å	µ = 4.50 mm⁻¹
c = 8.748 (2) Å	T = 130 K
β = 107.511 (5)°	Prism, colourless
V = 1808.5 (7) Å³	0.21 × 0.12 × 0.11 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2159 independent reflections
Radiation source: sealed tube	1695 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 27.9°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.452, T_max = 0.637	k = −29→29
8520 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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.105	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0601P)² + 0.9564P] where P = (F_o² + 2F_c²)/3
2159 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₉H₁₃Br₂N₃O₂	V = 1808.5 (7) Å³
M_r = 475.14	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 9.550 (2) Å	µ = 4.50 mm⁻¹
b = 22.698 (5) Å	T = 130 K
c = 8.748 (2) Å	0.21 × 0.12 × 0.11 mm
β = 107.511 (5)°

Data collection top

Bruker SMART APEX diffractometer	2159 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1695 reflections with I > 2σ(I)
T_min = 0.452, T_max = 0.637	R_int = 0.044
8520 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.02	Δρ_max = 0.94 e Å⁻³
2159 reflections	Δρ_min = −0.52 e Å⁻³
119 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Br1	−0.04692 (4)	0.721218 (15)	1.02697 (4)	0.03818 (15)
O1	0.2856 (2)	0.44490 (9)	1.0115 (3)	0.0268 (5)
N1	0.3088 (3)	0.52384 (11)	0.8566 (3)	0.0225 (5)
H1A	0.3497	0.5339	0.7828	0.027*
N2	0.5000	0.46292 (15)	0.7500	0.0199 (7)
C1	0.3308 (3)	0.46760 (13)	0.9081 (4)	0.0214 (6)
C2	0.4206 (3)	0.43212 (13)	0.8256 (4)	0.0210 (6)
C3	0.4179 (3)	0.37121 (13)	0.8303 (4)	0.0243 (6)
H3A	0.3615	0.3510	0.8867	0.029*
C4	0.5000	0.34048 (19)	0.7500	0.0273 (9)
H4A	0.5000	0.2986	0.7500	0.033*
C5	0.2290 (3)	0.56882 (13)	0.9052 (4)	0.0218 (6)
C6	0.2466 (3)	0.62624 (14)	0.8597 (4)	0.0259 (7)
H6A	0.3134	0.6342	0.8008	0.031*
C7	0.1690 (4)	0.67177 (14)	0.8988 (4)	0.0278 (7)
H7A	0.1827	0.7110	0.8685	0.033*
C8	0.0705 (3)	0.65961 (15)	0.9830 (4)	0.0261 (7)
C9	0.0511 (3)	0.60299 (15)	1.0301 (4)	0.0269 (7)
H9A	−0.0168	0.5954	1.0879	0.032*
C10	0.1312 (3)	0.55712 (14)	0.9927 (4)	0.0252 (7)
H10A	0.1198	0.5181	1.0263	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0469 (3)	0.0388 (2)	0.0340 (2)	0.01775 (15)	0.01988 (18)	0.00280 (15)
O1	0.0261 (12)	0.0298 (12)	0.0281 (12)	−0.0035 (9)	0.0136 (10)	0.0022 (9)
N1	0.0198 (13)	0.0268 (13)	0.0233 (13)	0.0011 (10)	0.0100 (11)	0.0006 (10)
N2	0.0142 (17)	0.0228 (17)	0.0212 (18)	0.000	0.0029 (14)	0.000
C1	0.0129 (14)	0.0262 (15)	0.0232 (15)	−0.0029 (11)	0.0024 (11)	−0.0021 (12)
C2	0.0136 (14)	0.0262 (15)	0.0220 (15)	−0.0010 (11)	0.0037 (12)	0.0003 (12)
C3	0.0201 (15)	0.0281 (15)	0.0246 (15)	−0.0032 (12)	0.0068 (12)	0.0011 (13)
C4	0.028 (2)	0.022 (2)	0.029 (2)	0.000	0.0058 (19)	0.000
C5	0.0159 (14)	0.0280 (15)	0.0206 (15)	0.0010 (11)	0.0041 (12)	−0.0008 (12)
C6	0.0253 (16)	0.0305 (16)	0.0245 (16)	0.0020 (13)	0.0115 (13)	0.0039 (13)
C7	0.0332 (18)	0.0262 (15)	0.0250 (16)	0.0058 (13)	0.0100 (14)	0.0054 (13)
C8	0.0198 (15)	0.0341 (17)	0.0219 (16)	0.0094 (12)	0.0027 (12)	−0.0007 (12)
C9	0.0186 (15)	0.0367 (17)	0.0267 (16)	0.0026 (12)	0.0087 (13)	0.0006 (14)
C10	0.0192 (15)	0.0283 (15)	0.0291 (17)	−0.0016 (12)	0.0087 (13)	0.0003 (13)

Geometric parameters (Å, º) top

Br1—C8	1.903 (3)	C4—H4A	0.9500
O1—C1	1.227 (4)	C5—C6	1.387 (4)
N1—C1	1.349 (4)	C5—C10	1.400 (4)
N1—C5	1.414 (4)	C6—C7	1.373 (4)
N1—H1A	0.8800	C6—H6A	0.9500
N2—C2ⁱ	1.343 (3)	C7—C8	1.387 (4)
N2—C2	1.343 (3)	C7—H7A	0.9500
C1—C2	1.509 (4)	C8—C9	1.379 (5)
C2—C3	1.384 (4)	C9—C10	1.388 (4)
C3—C4	1.388 (4)	C9—H9A	0.9500
C3—H3A	0.9500	C10—H10A	0.9500
C4—C3ⁱ	1.388 (4)

C1—N1—C5	128.9 (3)	C6—C5—N1	118.0 (3)
C1—N1—H1A	115.6	C10—C5—N1	122.4 (3)
C5—N1—H1A	115.6	C7—C6—C5	121.0 (3)
C2ⁱ—N2—C2	117.3 (3)	C7—C6—H6A	119.5
O1—C1—N1	126.1 (3)	C5—C6—H6A	119.5
O1—C1—C2	120.3 (3)	C6—C7—C8	119.1 (3)
N1—C1—C2	113.5 (3)	C6—C7—H7A	120.5
N2—C2—C3	123.5 (3)	C8—C7—H7A	120.5
N2—C2—C1	116.4 (3)	C9—C8—C7	121.2 (3)
C3—C2—C1	120.1 (3)	C9—C8—Br1	119.0 (2)
C2—C3—C4	118.0 (3)	C7—C8—Br1	119.8 (2)
C2—C3—H3A	121.0	C8—C9—C10	119.7 (3)
C4—C3—H3A	121.0	C8—C9—H9A	120.2
C3—C4—C3ⁱ	119.7 (4)	C10—C9—H9A	120.2
C3—C4—H4A	120.2	C9—C10—C5	119.5 (3)
C3ⁱ—C4—H4A	120.2	C9—C10—H10A	120.3
C6—C5—C10	119.6 (3)	C5—C10—H10A	120.3

C5—N1—C1—O1	−1.1 (5)	C1—N1—C5—C10	−14.8 (5)
C5—N1—C1—C2	179.0 (3)	C10—C5—C6—C7	−0.3 (5)
C2ⁱ—N2—C2—C3	0.6 (2)	N1—C5—C6—C7	178.0 (3)
C2ⁱ—N2—C2—C1	−179.3 (3)	C5—C6—C7—C8	−0.8 (5)
O1—C1—C2—N2	−161.6 (2)	C6—C7—C8—C9	1.0 (5)
N1—C1—C2—N2	18.3 (4)	C6—C7—C8—Br1	−176.2 (2)
O1—C1—C2—C3	18.5 (4)	C7—C8—C9—C10	−0.1 (5)
N1—C1—C2—C3	−161.6 (3)	Br1—C8—C9—C10	177.1 (2)
N2—C2—C3—C4	−1.1 (4)	C8—C9—C10—C5	−1.1 (5)
C1—C2—C3—C4	178.8 (2)	C6—C5—C10—C9	1.3 (5)
C2—C3—C4—C3ⁱ	0.5 (2)	N1—C5—C10—C9	−177.0 (3)
C1—N1—C5—C6	166.9 (3)

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
N1—H1A···N2	0.88	2.23	2.673 (3)	111
N1—H1A···O1ⁱⁱ	0.88	2.32	3.044 (3)	140

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃Br₂N₃O₂
M_r	475.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	130
a, b, c (Å)	9.550 (2), 22.698 (5), 8.748 (2)
β (°)	107.511 (5)
V (Å³)	1808.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.50
Crystal size (mm)	0.21 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.452, 0.637
No. of measured, independent and observed [I > 2σ(I)] reflections	8520, 2159, 1695
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.02
No. of reflections	2159
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.52

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2	0.88	2.23	2.673 (3)	110.6
N1—H1A···O1ⁱ	0.88	2.32	3.044 (3)	140.2

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

Financial assistance for this project by the Higher Education Commission of Pakistan through the International Research Support Initiative Programe (IRSIP) is acknowledged by the authors.

References

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