organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 5| May 2010| Page o1060

Bi­phenyl-3,3′,4,4′-tetra­amine

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[Dobrzycki, L. & Wozniak, K. (2007). CrystEngComm, 9, 1029-1040.]).

[Scheme 1]

Experimental

Crystal data
  • C12H14N4

  • Mr = 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.989, Tmax = 0.992

  • 2698 measured reflections

  • 979 independent reflections

  • 724 reflections with I > 2σ(I)

  • Rint = 0.075

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

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).

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
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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
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 top
Bruker SMART 1K CCD area-detector
diffractometer
979 independent reflections
Radiation source: fine-focus sealed tube724 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 911
Tmin = 0.989, Tmax = 0.992k = 68
2698 measured reflectionsl = 89
Refinement top
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 = 1.09 w = 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
Crystal data top
C12H14N4V = 556.1 (4) Å3
Mr = 214.27Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.646 (4) ŵ = 0.08 mm1
b = 7.476 (3) ÅT = 291 K
c = 7.751 (3) Å0.14 × 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)
Tmin = 0.989, Tmax = 0.992Rint = 0.075
2698 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.156H-atom parameters constrained
S = 1.09Δρmax = 0.18 e Å3
979 reflectionsΔρmin = 0.30 e Å3
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
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)
H2A0.04840.91670.31610.050*
H2B0.01301.06510.20250.050*
Atomic displacement parameters (Å2) top
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, º) top
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—C3177.55 (18)C3—C4—C5—C63.2 (3)
C1—C2—C3—N1175.14 (17)N2—C4—C5—C6179.28 (17)
C1—C2—C3—C40.8 (3)C4—C5—C6—C10.3 (3)
C2—C3—C4—C53.4 (3)C2—C1—C6—C52.3 (3)
N1—C3—C4—C5177.99 (15)C1i—C1—C6—C5177.30 (19)
C2—C3—C4—N2178.99 (15)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
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, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H14N4
Mr214.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)291
a, b, c (Å)9.646 (4), 7.476 (3), 7.751 (3)
β (°) 95.773 (5)
V3)556.1 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.14 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.989, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
2698, 979, 724
Rint0.075
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.156, 1.09
No. of reflections979
No. of parameters73
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.30

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

Selected bond lengths (Å) top
C3—N11.401 (2)C4—N21.413 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.902.393.224 (2)153.9
N2—H2A···N1ii0.902.353.124 (2)144.8
Symmetry codes: (i) x, y+2, z; (ii) x, y1/2, 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

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 5| May 2010| Page o1060
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