Crystal structure of 4,4′-(ethane-1,2-di­yl)bis­(2,6-di­bromo­aniline)

Hauptvogel, I.; Seichter, W.; Weber, E.

doi:10.1107/S2056989014027182

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Volume 71| Part 1| January 2015| Pages 97-99

https://doi.org/10.1107/S2056989014027182

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Crystal structure of 4,4′-(ethane-1,2-diyl)bis(2,6-dibromoaniline)

Ines Hauptvogel,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: Edwin.Weber@chemie.tu-freiberg.de

Edited by A. J. Lough, University of Toronto, Canada (Received 25 November 2014; accepted 11 December 2014; online 1 January 2015)

In the title compound, C₁₄H₁₂Br₄N₂, the molecule lies across an inversion center and hence the benzene rings are strictly coplanar. In the crystal, molecules are linked by N—H⋯N and weak N—H⋯Br hydrogen bonds, forming a two-dimensional network parallel to (101). In addition, type II Br⋯Br interactions [3.625 (4) Å] complete a three-dimensional supramolecular network.

Keywords: crystal structure; 4,4′-(ethane-1,2-diyl)bis(2,6-dibromoaniline); framework structures.

CCDC reference: 1038844

1. Chemical context

Spacer-type compounds are vital for the generation of a variety of framework structures including metal organic (MOF) (MacGillivray, 2010 ), hydrogen-bonded (HBN) (Elemans et al., 2009 ) or covalent organic (COF) (El-Kaden et al., 2007 ) network species. The title compound is an intermediate substance of a corresponding synthesis of a corresponding spacer molecule. Moreover, tecton-like molecules having terminally attached interacting sites are interesting building blocks in the field of organic crystal engineering (Tiekink et al., 2010 ), in particular involving potentially competitive groups, in itself forming hydrogen bonds (Braga & Crepioni, 2004 ) or halogen contacts (Awwadi et al., 2006 ; Metrangolo & Resnati, 2008 ) by preference in the crystal state. Such a test case is given with the oligobromoamino-containing title compound.

2. Structural commentary

The title molecule lies across an inversion center and hence the benzene rings are strictly coplanar (Fig. 1). The conformation of the molecular backbone agrees well with those found in the structure of 1,2-biphenylethane (Harada & Ogawa, 2001 ) and a great number of its ring-substituted derivatives (Kahr et al., 1995 ; Moorthy et al., 2005 ). The Csp³—Csp³ and Csp³—Csp² bond lengths of 1.535 (6) and 1.514 (4) Å are in the normal range.

Figure 1
The molecular structure of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level. Unlabeled atoms are related by the symmetry operator (−x + 1, −y + 2, −z).

3. Supramolecular features

The amino group hydrogen atoms take part in molecular association (Table 1) by forming conventional N—H⋯N hydrogen bonds (Jeffrey, 1997 , see Table 1) and weak N—H⋯Br contacts (Desiraju & Steiner, 1999 ) resulting in the formation of a layer structure parallel to (101) (Fig. 2). Interlayer association is accomplished by type II, Br⋯Br contacts [3.625 (4) Å, θ₁ = 109.7 (2), θ₂ = 150.7 (2)°] (Awwadi et al., 2006; Metrangolo & Resnati, 2008).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N1ⁱ	0.88 (2)	2.45 (3)	3.206 (4)	145 (2)
N1—H1B⋯Br1ⁱ	0.88 (2)	3.03 (3)	3.521 (4)	117 (2)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure viewed along the b axis. N atoms are displayed as blue and Br atoms as violet circles. Hydrogen bonds and Br⋯Br contacts are shown as dashed lines.

4. Synthesis and crystallization

In an imitation of a described procedure (Berger et al., 1998 ) preparation of the title compound was achieved by a bromination reaction of a solution of 4,4′-diaminobiphenyl (10.0 g, 47.14 mmol) in glacial acetic acid (760 ml) using bromine (30.3 g, 0.19 mol, dissolved in 40 ml glacial acetic acid). After having stirred for 2 h at room temperature, water was added to the mixture. The raw product which precipitated was collected, washed with water and treated with boiling glacial acetic acid to yield 19.6 g (79%) of a greenish powder. Slow crystallization from toluene gave colourless needles of the title compound suitable for X-ray structural analysis. M.p. >593 K. IR (KBr) 3329, 3190, 3033, 2940, 2915, 2851, 1617, 1581, 1542, 1486, 1060, 892, 871. MS (EI) m/z: found – 527.5; calculated for C₁₄H₁₂N₂Br₄ – 527.87. Elemental analysis: found – C 31.53, H 2.34, N 5.59; calculated for C₁₄H₁₂N₂Br₄ – C 31.85, H 2.29, N 5.31. 4,4′-Diaminobibenzyl was purchased (Sigma–Aldrich). The melting point was measured on a hot-stage microscope (Rapido Dresden). IR and mass (EI–MS) spectra were performed using Nicolet 510 FTIR and Finnigan Mat 8200 instruments, respectively.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were positioned geometrically (C—H = 0.93 Å for aromatic and C—H 0.97 Å for methylene H) and refined using a riding model with U_iso(H) = 1.2 U_eq(C). The amino H atoms were located in a Fourier map and the N—H distances restrained to 0.89 (1) Å.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₂Br₄N₂
M_r	527.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	8.1219 (4), 4.4962 (2), 21.5327 (9)
β (°)	96.706 (3)
V (Å³)	780.95 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	10.30
Crystal size (mm)	0.30 × 0.20 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.148, 0.493
No. of measured, independent and observed [I > 2σ(I)] reflections	6211, 1356, 1213
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.057, 1.05
No. of reflections	1356
No. of parameters	99
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.29
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 1038844

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989014027182/lh5742sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014027182/lh5742Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989014027182/lh5742Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4,4'-(Ethane-1,2-diyl)bis(2,6-dibromoaniline) top

Crystal data top

C₁₄H₁₂Br₄N₂	F(000) = 500
M_r = 527.86	D_x = 2.245 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3117 reflections
a = 8.1219 (4) Å	θ = 2.6–26.4°
b = 4.4962 (2) Å	µ = 10.30 mm⁻¹
c = 21.5327 (9) Å	T = 153 K
β = 96.706 (3)°	Needle, colourless
V = 780.95 (6) Å³	0.30 × 0.20 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1356 independent reflections
Radiation source: fine-focus sealed tube	1213 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 25.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.148, T_max = 0.493	k = −5→4
6211 measured reflections	l = −25→25

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0287P)² + 0.4643P] where P = (F_o² + 2F_c²)/3
1356 reflections	(Δ/σ)_max < 0.001
99 parameters	Δρ_max = 0.52 e Å⁻³
2 restraints	Δρ_min = −0.29 e Å⁻³

Special details top

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. The distances of N—H bonds were restrained to a target value of 0.89(0.01) Å.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.57978 (4)	0.36821 (8)	0.225361 (14)	0.03020 (13)
Br2	−0.06304 (4)	0.52607 (9)	0.094219 (15)	0.03690 (14)
N1	0.2009 (3)	0.2907 (7)	0.19806 (11)	0.0243 (6)
H1A	0.260 (3)	0.140 (5)	0.2143 (13)	0.020 (9)*
H1B	0.102 (2)	0.223 (8)	0.1841 (14)	0.033 (9)*
C1	0.3975 (4)	0.8813 (7)	0.07282 (13)	0.0216 (7)
C2	0.4981 (3)	0.7477 (7)	0.12150 (13)	0.0221 (7)
H2	0.6107	0.7920	0.1274	0.026*
C3	0.4334 (3)	0.5501 (7)	0.16131 (13)	0.0203 (7)
C4	0.2654 (3)	0.4736 (7)	0.15549 (12)	0.0190 (7)
C5	0.1679 (3)	0.6141 (7)	0.10623 (13)	0.0210 (7)
C6	0.2309 (4)	0.8108 (7)	0.06593 (13)	0.0222 (7)
H6	0.1604	0.8969	0.0338	0.027*
C7	0.4705 (4)	1.0862 (8)	0.02740 (14)	0.0279 (7)
H7A	0.5633	1.1936	0.0493	0.034*
H7B	0.3875	1.2306	0.0113	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02849 (19)	0.0311 (3)	0.02914 (19)	0.00445 (14)	−0.00444 (13)	−0.00097 (14)
Br2	0.02079 (19)	0.0507 (3)	0.0385 (2)	−0.00335 (15)	0.00032 (14)	0.00005 (17)
N1	0.0284 (14)	0.0220 (17)	0.0237 (13)	−0.0027 (12)	0.0073 (11)	0.0028 (13)
C1	0.0308 (16)	0.0158 (18)	0.0196 (14)	0.0001 (13)	0.0095 (12)	−0.0052 (13)
C2	0.0205 (14)	0.0208 (18)	0.0264 (15)	−0.0016 (13)	0.0089 (12)	−0.0068 (15)
C3	0.0232 (15)	0.0212 (19)	0.0171 (13)	0.0019 (13)	0.0044 (12)	−0.0044 (13)
C4	0.0234 (15)	0.0183 (18)	0.0165 (13)	−0.0006 (13)	0.0070 (12)	−0.0056 (13)
C5	0.0198 (14)	0.0220 (19)	0.0218 (14)	0.0003 (12)	0.0051 (11)	−0.0061 (14)
C6	0.0311 (16)	0.0189 (19)	0.0172 (13)	0.0041 (13)	0.0050 (12)	−0.0015 (13)
C7	0.0422 (19)	0.0171 (19)	0.0273 (16)	−0.0008 (15)	0.0159 (14)	−0.0017 (14)

Geometric parameters (Å, º) top

Br1—C3	1.898 (3)	C2—H2	0.9300
Br2—C5	1.905 (3)	C3—C4	1.398 (4)
N1—C4	1.380 (4)	C4—C5	1.398 (4)
N1—H1A	0.877 (10)	C5—C6	1.378 (4)
N1—H1B	0.879 (10)	C6—H6	0.9300
C1—C6	1.381 (4)	C7—C7ⁱ	1.535 (6)
C1—C2	1.388 (4)	C7—H7A	0.9700
C1—C7	1.514 (4)	C7—H7B	0.9700
C2—C3	1.381 (4)

C4—N1—H1A	119.6 (19)	C3—C4—C5	114.7 (3)
C4—N1—H1B	113 (2)	C6—C5—C4	123.3 (3)
H1A—N1—H1B	108 (3)	C6—C5—Br2	118.6 (2)
C6—C1—C2	117.7 (3)	C4—C5—Br2	118.1 (2)
C6—C1—C7	121.5 (3)	C5—C6—C1	120.7 (3)
C2—C1—C7	120.7 (3)	C5—C6—H6	119.7
C3—C2—C1	120.9 (3)	C1—C6—H6	119.7
C3—C2—H2	119.5	C1—C7—C7ⁱ	111.7 (4)
C1—C2—H2	119.5	C1—C7—H7A	109.3
C2—C3—C4	122.8 (3)	C7ⁱ—C7—H7A	109.3
C2—C3—Br1	118.5 (2)	C1—C7—H7B	109.3
C4—C3—Br1	118.8 (2)	C7ⁱ—C7—H7B	109.3
N1—C4—C3	122.0 (3)	H7A—C7—H7B	107.9
N1—C4—C5	123.2 (3)

C6—C1—C2—C3	0.4 (4)	C3—C4—C5—C6	0.5 (4)
C7—C1—C2—C3	−177.0 (3)	N1—C4—C5—Br2	−4.4 (4)
C1—C2—C3—C4	−0.2 (5)	C3—C4—C5—Br2	−179.9 (2)
C1—C2—C3—Br1	178.3 (2)	C4—C5—C6—C1	−0.4 (5)
C2—C3—C4—N1	−175.7 (3)	Br2—C5—C6—C1	180.0 (2)
Br1—C3—C4—N1	5.8 (4)	C2—C1—C6—C5	−0.1 (4)
C2—C3—C4—C5	−0.2 (4)	C7—C1—C6—C5	177.3 (3)
Br1—C3—C4—C5	−178.7 (2)	C6—C1—C7—C7ⁱ	−89.9 (4)
N1—C4—C5—C6	176.0 (3)	C2—C1—C7—C7ⁱ	87.4 (4)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1ⁱⁱ	0.88 (2)	2.45 (3)	3.206 (4)	145 (2)
N1—H1B···Br1ⁱⁱ	0.88 (2)	3.03 (3)	3.521 (4)	117 (2)

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

Acknowledgements

We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft within the priority program `Porous Metal-Organic Frameworks' (DFG-Project SPP 1362).

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