PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1060.
Published online 2010 April 14. doi:  10.1107/S1600536810012511
PMCID: PMC2979072

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1060-scheme1.jpg

Experimental

Crystal data

  • C12H14N4
  • M r = 214.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1060-efi3.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SMART; data reduction: SAINT (Bruker, 2000 [triangle]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012511/bv2140Isup2.hkl

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

Acknowledgments

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.

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 Uiso(H) = 1.2Ueq(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

C12H14N4F(000) = 228
Mr = 214.27Dx = 1.280 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 931 reflections
a = 9.646 (4) Åθ = 2.5–27.0°
b = 7.476 (3) ŵ = 0.08 mm1
c = 7.751 (3) ÅT = 291 K
β = 95.773 (5)°Block, colourless
V = 556.1 (4) Å30.14 × 0.12 × 0.10 mm
Z = 2

Data collection

Bruker SMART 1K CCD area-detector diffractometer979 independent reflections
Radiation source: fine-focus sealed tube724 reflections with I > 2σ(I)
graphiteRint = 0.075
ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −9→11
Tmin = 0.989, Tmax = 0.992k = −6→8
2698 measured reflectionsl = −8→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0926P)2 + 0.0016P] where P = (Fo2 + 2Fc2)/3
979 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.30 e Å3

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 (Å2)

xyzUiso*/Ueq
C10.42719 (17)0.9895 (2)0.4590 (2)0.0335 (5)
C20.37707 (18)1.0872 (2)0.3125 (2)0.0356 (5)
H20.43781.16390.26290.043*
C30.24074 (18)1.0749 (2)0.2378 (2)0.0336 (5)
C40.14684 (18)0.9615 (2)0.3120 (2)0.0341 (5)
C50.1965 (2)0.8586 (2)0.4523 (2)0.0391 (6)
H50.13670.77850.49910.047*
C60.3330 (2)0.8714 (3)0.5255 (2)0.0421 (6)
H60.36290.80030.62050.051*
N10.18955 (16)1.1838 (2)0.0986 (2)0.0442 (5)
H1A0.15151.11300.01270.053*
H1B0.24371.26000.05620.053*
N20.00747 (15)0.9522 (2)0.23637 (19)0.0418 (5)
H2A−0.04840.91670.31610.050*
H2B−0.01301.06510.20250.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0327 (11)0.0338 (10)0.0336 (10)0.0017 (8)0.0013 (8)−0.0006 (8)
C20.0326 (11)0.0381 (11)0.0362 (10)−0.0008 (8)0.0043 (8)0.0023 (8)
C30.0355 (11)0.0348 (10)0.0300 (9)0.0026 (8)0.0004 (8)−0.0012 (7)
C40.0327 (11)0.0353 (10)0.0337 (10)−0.0013 (8)0.0007 (8)−0.0053 (8)
C50.0376 (12)0.0392 (11)0.0397 (11)−0.0082 (8)−0.0003 (9)0.0049 (8)
C60.0422 (12)0.0420 (11)0.0404 (11)−0.0036 (9)−0.0046 (9)0.0092 (8)
N10.0434 (11)0.0480 (10)0.0396 (10)−0.0045 (7)−0.0033 (8)0.0113 (7)
N20.0324 (10)0.0493 (11)0.0424 (10)−0.0036 (7)−0.0026 (7)0.0017 (7)

Geometric parameters (Å, °)

C1—C21.395 (3)C4—N21.413 (2)
C1—C61.401 (3)C5—C61.384 (3)
C1—C1i1.491 (3)C5—H50.9300
C2—C31.386 (2)C6—H60.9300
C2—H20.9300N1—H1A0.8999
C3—N11.401 (2)N1—H1B0.8600
C3—C41.405 (2)N2—H2A0.9000
C4—C51.379 (3)N2—H2B0.9000
C2—C1—C6116.41 (17)C4—C5—C6121.72 (17)
C2—C1—C1i121.8 (2)C4—C5—H5119.1
C6—C1—C1i121.8 (2)C6—C5—H5119.1
C3—C2—C1122.83 (17)C5—C6—C1121.21 (18)
C3—C2—H2118.6C5—C6—H6119.4
C1—C2—H2118.6C1—C6—H6119.4
C2—C3—N1121.97 (16)C3—N1—H1A108.3
C2—C3—C4119.50 (16)C3—N1—H1B119.9
N1—C3—C4118.29 (16)H1A—N1—H1B108.9
C5—C4—C3118.20 (17)C4—N2—H2A109.9
C5—C4—N2122.70 (16)C4—N2—H2B104.2
C3—C4—N2119.05 (16)H2A—N2—H2B110.4
C6—C1—C2—C32.1 (3)N1—C3—C4—N24.4 (2)
C1i—C1—C2—C3−177.55 (18)C3—C4—C5—C63.2 (3)
C1—C2—C3—N1175.14 (17)N2—C4—C5—C6−179.28 (17)
C1—C2—C3—C40.8 (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—C5177.30 (19)
C2—C3—C4—N2178.99 (15)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N2ii0.902.393.224 (2)154
N2—H2A···N1iii0.902.353.124 (2)145

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2140).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dobrzycki, L. & Wozniak, K. (2007). CrystEngComm, 9, 1029–1040.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography