A monoclinic polymorph of 1,3-bis­(2-pyridylamino­meth­yl)benzene

Zhu, L.-N.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536807063878

organic compounds

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Volume 64| Part 1| January 2008| Page o252

https://doi.org/10.1107/S1600536807063878

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A monoclinic polymorph of 1,3-bis(2-pyridylaminomethyl)benzene

Li-Na Zhu,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^aSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 16 November 2007; accepted 27 November 2007; online 12 December 2007)

The molecules of the title compound, C₁₈H₁₈N₄, are linked by two different N—H⋯N_pyridyl hydrogen bonds into a linear chain.

Related literature

In the orthorhombic polymorph, the molecule lies on a twofold rotation axis; adjacent molecules are hydrogen-bonded into a linear chain, see: Zhu et al. (2007 ).

Experimental

Crystal data

C₁₈H₁₈N₄
M_r = 290.36
Monoclinic, C 2/c
a = 35.647 (2) Å
b = 5.7899 (4) Å
c = 14.9019 (9) Å
β = 94.074 (2)°
V = 3067.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 (2) K
0.32 × 0.28 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.589, T_max = 0.982
13991 measured reflections
3512 independent reflections
1833 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.150
S = 1.02
3512 reflections
208 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N1ⁱ	0.86 (1)	2.19 (1)	3.047 (2)	175 (2)
N3—H3N⋯N4ⁱⁱ	0.86 (1)	2.24 (1)	3.104 (2)	177 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku Corporation, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2007 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063878/sg2210sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063878/sg2210Isup2.hkl

checkCIF report

Related literature top

In the orthorhombic polymorph, the molecule lies on a twofold rotation axis that relates one half of the molecule to the other; adjacent molecules are hydrogen-bonded into a linear chain, see: Zhu et al. (2007).

Experimental top

The compound was synthesized as described (Zhu et al., 2007), and crystals were obtained upon recrystallization from methanol.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top

Fig. 1. Thermal ellipsoid plot of a portion of the hydrogen-bonded structure; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius.

1,3-bis(2-pyridylaminomethyl)benzene top

Crystal data top

C₁₈H₁₈N₄	F(000) = 1232
M_r = 290.36	D_x = 1.257 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7473 reflections
a = 35.647 (2) Å	θ = 3.0–27.5°
b = 5.7899 (4) Å	µ = 0.08 mm⁻¹
c = 14.9019 (9) Å	T = 295 K
β = 94.074 (2)°	Prism, colorless
V = 3067.9 (3) Å³	0.32 × 0.28 × 0.24 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID diffractometer	3512 independent reflections
Radiation source: fine-focus sealed tube	1833 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω–scans	h = −46→46
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→7
T_min = 0.589, T_max = 0.982	l = −19→19
13991 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0752P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3512 reflections	Δρ_max = 0.18 e Å⁻³
208 parameters	Δρ_min = −0.17 e Å⁻³
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (5)

Crystal data top

C₁₈H₁₈N₄	V = 3067.9 (3) Å³
M_r = 290.36	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 35.647 (2) Å	µ = 0.08 mm⁻¹
b = 5.7899 (4) Å	T = 295 K
c = 14.9019 (9) Å	0.32 × 0.28 × 0.24 mm
β = 94.074 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3512 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1833 reflections with I > 2σ(I)
T_min = 0.589, T_max = 0.982	R_int = 0.047
13991 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	2 restraints
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.18 e Å⁻³
3512 reflections	Δρ_min = −0.17 e Å⁻³
208 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.26513 (4)	0.1786 (3)	0.38622 (11)	0.0551 (4)
N2	0.28167 (4)	0.5057 (3)	0.46611 (11)	0.0571 (4)
H2N	0.2672 (5)	0.452 (3)	0.5052 (12)	0.076 (7)*
N3	0.47595 (4)	0.7010 (3)	0.58328 (13)	0.0615 (5)
H3N	0.4725 (6)	0.599 (3)	0.5412 (11)	0.080 (7)*
N4	0.53909 (4)	0.6575 (3)	0.56996 (12)	0.0632 (5)
C1	0.27020 (6)	0.0330 (4)	0.31870 (14)	0.0648 (6)
H1	0.2536	−0.0903	0.3102	0.078*
C2	0.29845 (6)	0.0538 (4)	0.26093 (14)	0.0717 (6)
H2	0.3009	−0.0517	0.2146	0.086*
C3	0.32289 (6)	0.2357 (4)	0.27402 (15)	0.0682 (6)
H3	0.3424	0.2542	0.2364	0.082*
C4	0.31870 (5)	0.3903 (4)	0.34224 (14)	0.0597 (5)
H4	0.3352	0.5141	0.3513	0.072*
C5	0.28904 (5)	0.3579 (3)	0.39817 (12)	0.0491 (4)
C6	0.30779 (5)	0.6811 (3)	0.49945 (14)	0.0566 (5)
H6A	0.2950	0.7808	0.5398	0.068*
H6B	0.3144	0.7747	0.4490	0.068*
C7	0.34377 (5)	0.5957 (3)	0.54853 (12)	0.0469 (4)
C8	0.34573 (6)	0.3867 (3)	0.59374 (13)	0.0566 (5)
H8	0.3249	0.2898	0.5912	0.068*
C9	0.37829 (6)	0.3207 (3)	0.64242 (15)	0.0630 (6)
H9	0.3792	0.1803	0.6728	0.076*
C10	0.40950 (5)	0.4621 (3)	0.64621 (13)	0.0601 (5)
H10	0.4313	0.4171	0.6796	0.072*
C11	0.40859 (5)	0.6714 (3)	0.60048 (12)	0.0496 (5)
C12	0.37567 (5)	0.7345 (3)	0.55229 (12)	0.0480 (4)
H12	0.3748	0.8741	0.5214	0.058*
C13	0.44274 (5)	0.8269 (3)	0.60434 (15)	0.0573 (5)
H13A	0.4384	0.9527	0.5619	0.069*
H13B	0.4466	0.8928	0.6641	0.069*
C14	0.51105 (5)	0.7920 (3)	0.59598 (13)	0.0525 (5)
C15	0.51840 (5)	1.0098 (3)	0.63396 (13)	0.0600 (5)
H15	0.4987	1.1056	0.6482	0.072*
C16	0.55490 (6)	1.0800 (4)	0.64988 (14)	0.0664 (6)
H16	0.5602	1.2243	0.6751	0.080*
C17	0.58374 (6)	0.9363 (4)	0.62849 (15)	0.0667 (6)
H17	0.6088	0.9778	0.6412	0.080*
C18	0.57426 (6)	0.7309 (4)	0.58794 (16)	0.0681 (6)
H18	0.5937	0.6357	0.5718	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0488 (9)	0.0608 (10)	0.0551 (10)	−0.0034 (7)	0.0003 (7)	−0.0014 (8)
N2	0.0473 (9)	0.0641 (10)	0.0604 (10)	−0.0077 (8)	0.0084 (8)	−0.0103 (9)
N3	0.0474 (9)	0.0637 (11)	0.0737 (12)	−0.0021 (8)	0.0062 (8)	−0.0216 (9)
N4	0.0485 (10)	0.0596 (10)	0.0820 (12)	−0.0003 (7)	0.0071 (9)	−0.0096 (9)
C1	0.0689 (13)	0.0630 (12)	0.0615 (12)	−0.0010 (10)	−0.0031 (11)	−0.0067 (10)
C2	0.0773 (15)	0.0803 (15)	0.0573 (13)	0.0147 (12)	0.0043 (12)	−0.0080 (11)
C3	0.0612 (13)	0.0913 (15)	0.0530 (12)	0.0132 (12)	0.0111 (10)	0.0059 (12)
C4	0.0474 (11)	0.0717 (12)	0.0603 (12)	−0.0037 (9)	0.0058 (9)	0.0065 (10)
C5	0.0391 (9)	0.0574 (10)	0.0503 (10)	0.0008 (8)	−0.0006 (8)	0.0036 (9)
C6	0.0507 (11)	0.0534 (11)	0.0649 (12)	−0.0010 (9)	−0.0013 (9)	−0.0014 (9)
C7	0.0471 (10)	0.0456 (10)	0.0484 (10)	0.0008 (8)	0.0054 (8)	−0.0038 (8)
C8	0.0578 (12)	0.0499 (11)	0.0628 (12)	−0.0049 (9)	0.0086 (10)	0.0036 (9)
C9	0.0671 (13)	0.0556 (12)	0.0666 (13)	0.0046 (10)	0.0052 (11)	0.0162 (10)
C10	0.0543 (12)	0.0654 (12)	0.0600 (12)	0.0093 (10)	−0.0009 (10)	0.0063 (10)
C11	0.0487 (11)	0.0519 (10)	0.0486 (10)	0.0042 (8)	0.0065 (9)	−0.0029 (8)
C12	0.0507 (10)	0.0437 (9)	0.0500 (10)	0.0027 (8)	0.0056 (8)	0.0009 (8)
C13	0.0468 (11)	0.0598 (11)	0.0648 (12)	0.0014 (9)	0.0011 (9)	−0.0083 (10)
C14	0.0478 (11)	0.0531 (11)	0.0563 (11)	−0.0012 (8)	0.0014 (9)	−0.0037 (9)
C15	0.0580 (12)	0.0596 (12)	0.0618 (12)	−0.0011 (9)	0.0008 (10)	−0.0120 (10)
C16	0.0708 (14)	0.0676 (13)	0.0598 (12)	−0.0146 (11)	−0.0022 (11)	−0.0083 (10)
C17	0.0519 (12)	0.0822 (14)	0.0650 (13)	−0.0120 (11)	−0.0034 (10)	0.0022 (11)
C18	0.0488 (12)	0.0708 (13)	0.0848 (16)	0.0002 (10)	0.0050 (11)	−0.0039 (12)

Geometric parameters (Å, º) top

N1—C1	1.335 (2)	C7—C8	1.384 (2)
N1—C5	1.347 (2)	C7—C12	1.390 (2)
N2—C5	1.365 (2)	C8—C9	1.378 (3)
N2—C6	1.442 (2)	C8—H8	0.9300
N2—H2N	0.86 (1)	C9—C10	1.379 (3)
N3—C14	1.358 (2)	C9—H9	0.9300
N3—C13	1.444 (2)	C10—C11	1.389 (2)
N3—H3N	0.86 (1)	C10—H10	0.9300
N4—C18	1.333 (2)	C11—C12	1.381 (3)
N4—C14	1.346 (2)	C11—C13	1.512 (2)
C1—C2	1.376 (3)	C12—H12	0.9300
C1—H1	0.9300	C13—H13A	0.9700
C2—C3	1.372 (3)	C13—H13B	0.9700
C2—H2	0.9300	C14—C15	1.399 (3)
C3—C4	1.371 (3)	C15—C16	1.368 (3)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.405 (2)	C16—C17	1.377 (3)
C4—H4	0.9300	C16—H16	0.9300
C6—C7	1.514 (3)	C17—C18	1.366 (3)
C6—H6A	0.9700	C17—H17	0.9300
C6—H6B	0.9700	C18—H18	0.9300

C1—N1—C5	117.91 (15)	C7—C8—H8	119.7
C5—N2—C6	122.91 (15)	C8—C9—C10	120.23 (18)
C5—N2—H2N	115.5 (15)	C8—C9—H9	119.9
C6—N2—H2N	115.1 (15)	C10—C9—H9	119.9
C14—N3—C13	122.39 (16)	C9—C10—C11	120.47 (19)
C14—N3—H3N	116.7 (14)	C9—C10—H10	119.8
C13—N3—H3N	115.2 (15)	C11—C10—H10	119.8
C18—N4—C14	117.70 (17)	C12—C11—C10	118.35 (17)
N1—C1—C2	124.1 (2)	C12—C11—C13	120.98 (16)
N1—C1—H1	118.0	C10—C11—C13	120.67 (17)
C2—C1—H1	118.0	C11—C12—C7	122.05 (16)
C3—C2—C1	117.6 (2)	C11—C12—H12	119.0
C3—C2—H2	121.2	C7—C12—H12	119.0
C1—C2—H2	121.2	N3—C13—C11	111.21 (15)
C4—C3—C2	120.34 (18)	N3—C13—H13A	109.4
C4—C3—H3	119.8	C11—C13—H13A	109.4
C2—C3—H3	119.8	N3—C13—H13B	109.4
C3—C4—C5	118.65 (19)	C11—C13—H13B	109.4
C3—C4—H4	120.7	H13A—C13—H13B	108.0
C5—C4—H4	120.7	N4—C14—N3	115.54 (16)
N1—C5—N2	115.33 (14)	N4—C14—C15	121.11 (17)
N1—C5—C4	121.35 (17)	N3—C14—C15	123.36 (16)
N2—C5—C4	123.30 (17)	C16—C15—C14	119.09 (18)
N2—C6—C7	116.16 (15)	C16—C15—H15	120.5
N2—C6—H6A	108.2	C14—C15—H15	120.5
C7—C6—H6A	108.2	C15—C16—C17	119.81 (19)
N2—C6—H6B	108.2	C15—C16—H16	120.1
C7—C6—H6B	108.2	C17—C16—H16	120.1
H6A—C6—H6B	107.4	C18—C17—C16	117.59 (19)
C8—C7—C12	118.21 (17)	C18—C17—H17	121.2
C8—C7—C6	122.17 (16)	C16—C17—H17	121.2
C12—C7—C6	119.55 (15)	N4—C18—C17	124.49 (18)
C9—C8—C7	120.67 (17)	N4—C18—H18	117.8
C9—C8—H8	119.7	C17—C18—H18	117.8

C5—N1—C1—C2	0.4 (3)	C9—C10—C11—C13	−179.93 (17)
N1—C1—C2—C3	0.2 (3)	C10—C11—C12—C7	0.1 (3)
C1—C2—C3—C4	−0.4 (3)	C13—C11—C12—C7	−179.27 (16)
C2—C3—C4—C5	0.1 (3)	C8—C7—C12—C11	−1.0 (3)
C1—N1—C5—N2	177.71 (17)	C6—C7—C12—C11	176.15 (16)
C1—N1—C5—C4	−0.7 (3)	C14—N3—C13—C11	−169.32 (18)
C6—N2—C5—N1	168.25 (17)	C12—C11—C13—N3	−130.03 (18)
C6—N2—C5—C4	−13.4 (3)	C10—C11—C13—N3	50.6 (2)
C3—C4—C5—N1	0.4 (3)	C18—N4—C14—N3	−174.51 (19)
C3—C4—C5—N2	−177.85 (19)	C18—N4—C14—C15	5.1 (3)
C5—N2—C6—C7	−67.6 (2)	C13—N3—C14—N4	−177.51 (17)
N2—C6—C7—C8	−27.6 (2)	C13—N3—C14—C15	2.9 (3)
N2—C6—C7—C12	155.37 (16)	N4—C14—C15—C16	−4.1 (3)
C12—C7—C8—C9	1.2 (3)	N3—C14—C15—C16	175.4 (2)
C6—C7—C8—C9	−175.93 (18)	C14—C15—C16—C17	0.0 (3)
C7—C8—C9—C10	−0.4 (3)	C15—C16—C17—C18	2.9 (3)
C8—C9—C10—C11	−0.6 (3)	C14—N4—C18—C17	−2.1 (3)
C9—C10—C11—C12	0.7 (3)	C16—C17—C18—N4	−1.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1ⁱ	0.86 (1)	2.19 (1)	3.047 (2)	175 (2)
N3—H3N···N4ⁱⁱ	0.86 (1)	2.24 (1)	3.104 (2)	177 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈N₄
M_r	290.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	35.647 (2), 5.7899 (4), 14.9019 (9)
β (°)	94.074 (2)
V (Å³)	3067.9 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.28 × 0.24

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.589, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	13991, 3512, 1833
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.150, 1.02
No. of reflections	3512
No. of parameters	208
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: RAPID-AUTO (Rigaku Corporation, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1ⁱ	0.86 (1)	2.19 (1)	3.047 (2)	175 (2)
N3—H3N···N4ⁱⁱ	0.86 (1)	2.24 (1)	3.104 (2)	177 (2)

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

Acknowledgements

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this work.

References

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