Biphenyl-3,3′,4,4′-tetra­amine

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536810012511

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1060

https://doi.org/10.1107/S1600536810012511

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Biphenyl-3,3′,4,4′-tetraamine

Hui-Fen Qian ^a ^* and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn, whuang@nju.edu.cn

(Received 14 January 2010; accepted 3 April 2010; online 14 April 2010)

The title compound, C₁₂H₁₄N₄, has a crystallographically imposed centre of symmetry. Intermolecular N—H⋯N hydrogen bonds between amino groups link adjacent molecules into a three-dimensional network where ten-membered hydrogen-bonded rings are observed.

Related literature

For a related compound, see: Dobrzycki & Wozniak (2007 ).

Experimental

Crystal data

C₁₂H₁₄N₄
M_r = 214.27
Monoclinic, P 2₁ /c
a = 9.646 (4) Å
b = 7.476 (3) Å
c = 7.751 (3) Å
β = 95.773 (5)°
V = 556.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.14 × 0.12 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.989, T_max = 0.992
2698 measured reflections
979 independent reflections
724 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.156
S = 1.09
979 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.90	2.39	3.224 (2)	154
N2—H2A⋯N1ⁱⁱ	0.90	2.35	3.124 (2)	145
Symmetry codes: (i) -x, -y+2, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012511/bv2140sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012511/bv2140Isup2.hkl

checkCIF report

Comment top

The crystal structure of 3,3',4,4'-tetrammoniobiphenyl tetrachloride dihydrate (Dobrzycki & Wozniak, 2007) has been reported in literature. In this paper, we report the X-ray single-crystal structure of 3,3',4,4'-tetrammoniobiphenyl (I).

The molecular structure of (I) is illustrated in Fig. 1. Two amino groups in the 3-position lie in the opposite sides of the molecular plane. The dihedral angle between phenyl rings of adjacent molecules is 86.3 (2)°. Intermolecular N—H···N hydrogen bonds between amino groups link adjacent molecules into a three-dimensional network, where ten-membered hydrogen-bonded rings are observed (Fig. 2).

Related literature top

For a related compound, see: Dobrzycki & Wozniak (2007).

Experimental top

The title compound was purchased directly from TCI. Single crystals suitable for X-ray diffraction were grown from a methanol solution by slow evaporation in air at room temperature for one week.

Structure description top

For a related compound, see: Dobrzycki & Wozniak (2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Perspective view of the hydrogen bonding interactions in the crystal packing of (I), where the hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x, -y + 2, -z; (ii) -x, y - 1/2, -z + 1/2.]

Biphenyl-3,3',4,4'-tetraamine top

Crystal data top

C₁₂H₁₄N₄	F(000) = 228
M_r = 214.27	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 931 reflections
a = 9.646 (4) Å	θ = 2.5–27.0°
b = 7.476 (3) Å	µ = 0.08 mm⁻¹
c = 7.751 (3) Å	T = 291 K
β = 95.773 (5)°	Block, colourless
V = 556.1 (4) Å³	0.14 × 0.12 × 0.10 mm
Z = 2

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	979 independent reflections
Radiation source: fine-focus sealed tube	724 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→11
T_min = 0.989, T_max = 0.992	k = −6→8
2698 measured reflections	l = −8→9

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0926P)² + 0.0016P] where P = (F_o² + 2F_c²)/3
979 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₂H₁₄N₄	V = 556.1 (4) Å³
M_r = 214.27	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.646 (4) Å	µ = 0.08 mm⁻¹
b = 7.476 (3) Å	T = 291 K
c = 7.751 (3) Å	0.14 × 0.12 × 0.10 mm
β = 95.773 (5)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	979 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	724 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.992	R_int = 0.075
2698 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.09	Δρ_max = 0.18 e Å⁻³
979 reflections	Δρ_min = −0.30 e Å⁻³
73 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
C1	0.42719 (17)	0.9895 (2)	0.4590 (2)	0.0335 (5)
C2	0.37707 (18)	1.0872 (2)	0.3125 (2)	0.0356 (5)
H2	0.4378	1.1639	0.2629	0.043*
C3	0.24074 (18)	1.0749 (2)	0.2378 (2)	0.0336 (5)
C4	0.14684 (18)	0.9615 (2)	0.3120 (2)	0.0341 (5)
C5	0.1965 (2)	0.8586 (2)	0.4523 (2)	0.0391 (6)
H5	0.1367	0.7785	0.4991	0.047*
C6	0.3330 (2)	0.8714 (3)	0.5255 (2)	0.0421 (6)
H6	0.3629	0.8003	0.6205	0.051*
N1	0.18955 (16)	1.1838 (2)	0.0986 (2)	0.0442 (5)
H1A	0.1515	1.1130	0.0127	0.053*
H1B	0.2437	1.2600	0.0562	0.053*
N2	0.00747 (15)	0.9522 (2)	0.23637 (19)	0.0418 (5)
H2A	−0.0484	0.9167	0.3161	0.050*
H2B	−0.0130	1.0651	0.2025	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0327 (11)	0.0338 (10)	0.0336 (10)	0.0017 (8)	0.0013 (8)	−0.0006 (8)
C2	0.0326 (11)	0.0381 (11)	0.0362 (10)	−0.0008 (8)	0.0043 (8)	0.0023 (8)
C3	0.0355 (11)	0.0348 (10)	0.0300 (9)	0.0026 (8)	0.0004 (8)	−0.0012 (7)
C4	0.0327 (11)	0.0353 (10)	0.0337 (10)	−0.0013 (8)	0.0007 (8)	−0.0053 (8)
C5	0.0376 (12)	0.0392 (11)	0.0397 (11)	−0.0082 (8)	−0.0003 (9)	0.0049 (8)
C6	0.0422 (12)	0.0420 (11)	0.0404 (11)	−0.0036 (9)	−0.0046 (9)	0.0092 (8)
N1	0.0434 (11)	0.0480 (10)	0.0396 (10)	−0.0045 (7)	−0.0033 (8)	0.0113 (7)
N2	0.0324 (10)	0.0493 (11)	0.0424 (10)	−0.0036 (7)	−0.0026 (7)	0.0017 (7)

Geometric parameters (Å, º) top

C1—C2	1.395 (3)	C4—N2	1.413 (2)
C1—C6	1.401 (3)	C5—C6	1.384 (3)
C1—C1ⁱ	1.491 (3)	C5—H5	0.9300
C2—C3	1.386 (2)	C6—H6	0.9300
C2—H2	0.9300	N1—H1A	0.8999
C3—N1	1.401 (2)	N1—H1B	0.8600
C3—C4	1.405 (2)	N2—H2A	0.9000
C4—C5	1.379 (3)	N2—H2B	0.9000

C2—C1—C6	116.41 (17)	C4—C5—C6	121.72 (17)
C2—C1—C1ⁱ	121.8 (2)	C4—C5—H5	119.1
C6—C1—C1ⁱ	121.8 (2)	C6—C5—H5	119.1
C3—C2—C1	122.83 (17)	C5—C6—C1	121.21 (18)
C3—C2—H2	118.6	C5—C6—H6	119.4
C1—C2—H2	118.6	C1—C6—H6	119.4
C2—C3—N1	121.97 (16)	C3—N1—H1A	108.3
C2—C3—C4	119.50 (16)	C3—N1—H1B	119.9
N1—C3—C4	118.29 (16)	H1A—N1—H1B	108.9
C5—C4—C3	118.20 (17)	C4—N2—H2A	109.9
C5—C4—N2	122.70 (16)	C4—N2—H2B	104.2
C3—C4—N2	119.05 (16)	H2A—N2—H2B	110.4

C6—C1—C2—C3	2.1 (3)	N1—C3—C4—N2	4.4 (2)
C1ⁱ—C1—C2—C3	−177.55 (18)	C3—C4—C5—C6	3.2 (3)
C1—C2—C3—N1	175.14 (17)	N2—C4—C5—C6	−179.28 (17)
C1—C2—C3—C4	0.8 (3)	C4—C5—C6—C1	−0.3 (3)
C2—C3—C4—C5	−3.4 (3)	C2—C1—C6—C5	−2.3 (3)
N1—C3—C4—C5	−177.99 (15)	C1ⁱ—C1—C6—C5	177.30 (19)
C2—C3—C4—N2	178.99 (15)

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
N1—H1A···N2ⁱⁱ	0.90	2.39	3.224 (2)	154
N2—H2A···N1ⁱⁱⁱ	0.90	2.35	3.124 (2)	145

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₄
M_r	214.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	9.646 (4), 7.476 (3), 7.751 (3)
β (°)	95.773 (5)
V (Å³)	556.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.989, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	2698, 979, 724
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.156, 1.09
No. of reflections	979
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.30

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

C3—N1

1.401 (2)

C4—N2

1.413 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.90	2.39	3.224 (2)	153.9
N2—H2A···N1ⁱⁱ	0.90	2.35	3.124 (2)	144.8

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

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (grant No. 20871065) and the Jiangsu Province Department of Science and Technology (grant No. BK2009226) for financial aid.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dobrzycki, L. & Wozniak, K. (2007). CrystEngComm, 9, 1029–1040. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar