4,4′-Bis(1,2,4-triazol-1-ylmeth­yl)biphen­yl

Xu, J.

doi:10.1107/S1600536809038604

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2589

doi:10.1107/S1600536809038604

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4,4′-Bis(1,2,4-triazol-1-ylmethyl)biphenyl

Jianjun Xu ^a ^*

^aMechanical and Electrical Engineering Institute, North University of China, Taiyuan, 030051, People's Republic of China
^*Correspondence e-mail: xujianjunzb2009@126.com

(Received 23 September 2009; accepted 24 September 2009; online 30 September 2009)

In the title compound, C₁₈H₁₆N₆, the complete molecule is generated by crystallographic inversion symmetry. The dihedral angle between the benzene and triazole rings is 84.1 (3)°. The crystal structure is stabilized by weak C—H⋯N hydrogen bonds.

Related literature

For a related structure, see: Wang et al. (2007 ). For background to the use of flexible ligands to form coordination networks, see: Martin et al. (2007 ); Yaghi et al. (1998 ); Sun et al. (2006 ).

Experimental

Crystal data

C₁₈H₁₆N₆
M_r = 316.37
Monoclinic, P 2₁ /c
a = 16.590 (3) Å
b = 5.3646 (9) Å
c = 8.8009 (14) Å
β = 92.567 (3)°
V = 782.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.21 × 0.17 × 0.11 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.982, T_max = 0.991
3679 measured reflections
1402 independent reflections
870 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.107
S = 0.83
1402 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	0.93	2.56	3.381 (2)	148
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038604/hb5117sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038604/hb5117Isup2.hkl

checkCIF report

Comment top

It is well-known that those ligands containing a flexible backbone provide a bigger number of complexes thanks to their flexibility and conformational freedom that allow for greater structural diversity (Yaghi et al., 1998; Sun et al., 2006; Martin et al., 2007).

4,4'-Bis(1,2,4-triazol-1-ylmethyl)biphenyl (bix) is a excellent building block and has been employed to construct interesting structural polymer with unique properties (Wang et al., 2007).

In an attempt to form a Zn(II) complex with bix, we adventitiously formed the title compound (I) and its crystal structure is determined herein.

The title compound cyrstallizes with one half-molecule in the asymmetric unit. As illustrated in Fig. 1, the bix adopts a anti conformation and has crystallographic 1 symmetry and the dihedral angle between the benzene and triazole rings is 84.1 (3)°.

In the crystal structure, weak intermolecular C—H···N hydrogen bond help to stabilizing the packing.

Related literature top

For a related structure, see: Wang et al. (2007). For background to the use of flexible lignads to form coordination networks, see: Martin et al. (2007); Yaghi et al. (1998); Sun et al. (2006).

Experimental top

Equimolar (28 mg, 0.1 mmol) Zn(OAC)₂.6H₂O in water (3 ml) and bix (26 mg, 0.1 mmol) in CH₃CN and CH3OH solutions (8 ml) were mixed and heated at 428 K for 72 h in a pressurized reactor. Slow evaporation of this solution resulted in the formation of some colourless blocks of (I).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of (I), showing ellipsoids drawn at the the 30% probability level. H atoms are shown as spheres of arbitrary radius. Symmetry code: (i) –x, 1–y, 1–z.

4,4'-Bis(1,2,4-triazol-1-ylmethyl)biphenyl top

Crystal data top

C₁₈H₁₆N₆	F(000) = 332
M_r = 316.37	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1402 reflections
a = 16.590 (3) Å	θ = 2.5–25.2°
b = 5.3646 (9) Å	µ = 0.09 mm⁻¹
c = 8.8009 (14) Å	T = 298 K
β = 92.567 (3)°	Block, colourless
V = 782.5 (2) Å³	0.21 × 0.17 × 0.11 mm
Z = 2

Data collection top

Bruker APEXII area-detector diffractometer	1402 independent reflections
Radiation source: fine-focus sealed tube	870 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −19→18
T_min = 0.982, T_max = 0.991	k = −6→5
3679 measured reflections	l = −10→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.05P)² + 0.3476P] where P = (F_o² + 2F_c²)/3
1402 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₈H₁₆N₆	V = 782.5 (2) Å³
M_r = 316.37	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.590 (3) Å	µ = 0.09 mm⁻¹
b = 5.3646 (9) Å	T = 298 K
c = 8.8009 (14) Å	0.21 × 0.17 × 0.11 mm
β = 92.567 (3)°

Data collection top

Bruker APEXII area-detector diffractometer	1402 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	870 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.991	R_int = 0.023
3679 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 0.83	Δρ_max = 0.12 e Å⁻³
1402 reflections	Δρ_min = −0.13 e Å⁻³
109 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N3	0.34746 (8)	0.4361 (3)	0.45637 (17)	0.0522 (4)
C7	0.04239 (10)	0.4897 (3)	0.4755 (2)	0.0465 (5)
C4	0.20243 (10)	0.4473 (4)	0.3827 (2)	0.0511 (5)
C3	0.28751 (10)	0.4191 (4)	0.3315 (2)	0.0602 (6)
H3A	0.2927	0.2590	0.2817	0.072*
H3B	0.2979	0.5479	0.2576	0.072*
N2	0.35680 (10)	0.6499 (3)	0.5390 (2)	0.0651 (5)
C2	0.41506 (12)	0.5892 (5)	0.6378 (2)	0.0656 (6)
H2	0.4352	0.7001	0.7113	0.079*
N1	0.44371 (10)	0.3558 (4)	0.6256 (2)	0.0680 (5)
C6	0.09257 (11)	0.2995 (5)	0.5269 (3)	0.0714 (7)
H6	0.0733	0.1827	0.5945	0.086*
C1	0.39952 (12)	0.2674 (4)	0.5101 (2)	0.0605 (6)
H1	0.4042	0.1071	0.4713	0.073*
C9	0.15350 (12)	0.6357 (4)	0.3306 (3)	0.0673 (6)
H9	0.1732	0.7527	0.2638	0.081*
C8	0.07478 (12)	0.6559 (4)	0.3758 (3)	0.0682 (6)
H8	0.0428	0.7858	0.3374	0.082*
C5	0.17066 (11)	0.2789 (5)	0.4804 (3)	0.0718 (7)
H5	0.2025	0.1471	0.5165	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0403 (8)	0.0588 (10)	0.0573 (9)	−0.0008 (8)	0.0015 (7)	−0.0034 (8)
C7	0.0429 (9)	0.0495 (11)	0.0467 (10)	−0.0041 (8)	−0.0038 (8)	−0.0044 (9)
C4	0.0423 (10)	0.0637 (13)	0.0470 (10)	−0.0044 (9)	−0.0030 (8)	−0.0056 (10)
C3	0.0468 (11)	0.0801 (15)	0.0535 (11)	−0.0024 (10)	0.0002 (9)	−0.0071 (11)
N2	0.0543 (10)	0.0649 (12)	0.0754 (12)	−0.0021 (9)	−0.0055 (8)	−0.0133 (10)
C2	0.0507 (11)	0.0816 (17)	0.0640 (13)	−0.0115 (12)	−0.0022 (10)	−0.0072 (12)
N1	0.0562 (10)	0.0846 (14)	0.0627 (11)	0.0017 (10)	−0.0025 (8)	0.0150 (10)
C6	0.0494 (12)	0.0846 (17)	0.0804 (15)	0.0065 (11)	0.0063 (10)	0.0323 (13)
C1	0.0572 (12)	0.0605 (13)	0.0640 (13)	0.0020 (10)	0.0057 (10)	0.0072 (11)
C9	0.0586 (12)	0.0620 (14)	0.0826 (15)	0.0013 (11)	0.0168 (11)	0.0155 (12)
C8	0.0592 (13)	0.0582 (13)	0.0880 (16)	0.0095 (11)	0.0140 (11)	0.0177 (12)
C5	0.0474 (12)	0.0834 (17)	0.0843 (16)	0.0113 (11)	0.0012 (10)	0.0264 (13)

Geometric parameters (Å, º) top

N3—C1	1.324 (2)	N2—C2	1.312 (3)
N3—N2	1.363 (2)	C2—N1	1.345 (3)
N3—C3	1.451 (2)	C2—H2	0.9300
C7—C8	1.377 (3)	N1—C1	1.315 (3)
C7—C6	1.380 (3)	C6—C5	1.380 (3)
C7—C7ⁱ	1.494 (3)	C6—H6	0.9300
C4—C9	1.363 (3)	C1—H1	0.9300
C4—C5	1.369 (3)	C9—C8	1.386 (3)
C4—C3	1.508 (3)	C9—H9	0.9300
C3—H3A	0.9700	C8—H8	0.9300
C3—H3B	0.9700	C5—H5	0.9300

C1—N3—N2	109.13 (15)	N1—C2—H2	122.3
C1—N3—C3	129.93 (18)	C1—N1—C2	102.16 (18)
N2—N3—C3	120.94 (16)	C7—C6—C5	121.5 (2)
C8—C7—C6	116.16 (17)	C7—C6—H6	119.3
C8—C7—C7ⁱ	122.4 (2)	C5—C6—H6	119.3
C6—C7—C7ⁱ	121.5 (2)	N1—C1—N3	111.2 (2)
C9—C4—C5	117.42 (18)	N1—C1—H1	124.4
C9—C4—C3	121.69 (19)	N3—C1—H1	124.4
C5—C4—C3	120.87 (19)	C4—C9—C8	121.1 (2)
N3—C3—C4	112.74 (15)	C4—C9—H9	119.5
N3—C3—H3A	109.0	C8—C9—H9	119.5
C4—C3—H3A	109.0	C7—C8—C9	122.1 (2)
N3—C3—H3B	109.0	C7—C8—H8	118.9
C4—C3—H3B	109.0	C9—C8—H8	118.9
H3A—C3—H3B	107.8	C4—C5—C6	121.7 (2)
C2—N2—N3	101.99 (17)	C4—C5—H5	119.1
N2—C2—N1	115.49 (19)	C6—C5—H5	119.1
N2—C2—H2	122.3

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱⁱ	0.93	2.56	3.381 (2)	148

Symmetry code: (ii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₆
M_r	316.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	16.590 (3), 5.3646 (9), 8.8009 (14)
β (°)	92.567 (3)
V (Å³)	782.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.17 × 0.11

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	3679, 1402, 870
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.107, 0.83
No. of reflections	1402
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.13

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.93	2.56	3.381 (2)	148

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

The author is grateful for funding from the Natural Science Foundation of Shanxi Province (2007011033), the Program of Technological Industrialization in Universities of Shanxi Province (20070308) and the Start-up Fund of the Northern University of China.

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