Biphenyl-3,3′,4,4′-tetra­amine

Abstract

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,

• a = 9.646 (4) Å

• b = 7.476 (3) Å

• c = 7.751 (3) Å

• β = 95.773 (5)°

• V = 556.1 (4) ų

• 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[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were placed in geometrically idealized positions and refined as riding, with C—H = 0.93 Å and N—H = 0.86–0.90 Å, and with U_iso(H) = 1.2U_eq(C,N).

Figures

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.]

Crystal data

C12H14N4	F(000) = 228
Mr = 214.27	Dx = 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

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

Refinement

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(Fo2) + (0.0926P)2 + 0.0016P] where P = (Fo2 + 2Fc2)/3
979 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

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.