The 4,4′-(ethane-1,2-diyl)bis(2,6-dibromoaniline) molecule lies across an inversion center and hence the benzene rings are strictly planar. Molecules are linked by N—H⋯N and weak N—H⋯Br hydrogen bonds, forming a two-dimensional network parallel to (101). Type II Br⋯Br interactions complete a three-dimensional supramolecular network.
Keywords: crystal structure; 4,4′-(ethane-1,2-diyl)bis(2,6-dibromoaniline); framework structures
Abstract
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.
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.
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 Csp 3—Csp 3 and Csp 3—Csp 2 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).
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 (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1H1AN1i | 0.88(2) | 2.45(3) | 3.206(4) | 145(2) |
| N1H1BBr1i | 0.88(2) | 3.03(3) | 3.521(4) | 117(2) |
Symmetry code: (i) 
.
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.
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.
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 () | 8.1219(4), 4.4962(2), 21.5327(9) |
| () | 96.706(3) |
| V (3) | 780.95(6) |
| Z | 2 |
| Radiation type | Mo K |
| (mm1) | 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 > 2(I)] reflections | 6211, 1356, 1213 |
| R int | 0.034 |
| (sin /)max (1) | 0.597 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), 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 |
| max, min (e 3) | 0.52, 0.29 |
Supplementary Material
Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989014027182/lh5742sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027182/lh5742Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989014027182/lh5742Isup3.cml
CCDC reference: 1038844
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft within the priority program ‘Porous Metal-Organic Frameworks’ (DFG-Project SPP 1362).
supplementary crystallographic information
Crystal data
| C14H12Br4N2 | F(000) = 500 |
| Mr = 527.86 | Dx = 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
| Bruker APEXII CCD area-detector diffractometer | 1356 independent reflections |
| Radiation source: fine-focus sealed tube | 1213 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.034 |
| φ and ω scans | θmax = 25.1°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −9→9 |
| Tmin = 0.148, Tmax = 0.493 | k = −5→4 |
| 6211 measured reflections | l = −25→25 |
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)] = 0.023 | 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(Fo2) + (0.0287P)2 + 0.4643P] where P = (Fo2 + 2Fc2)/3 |
| 1356 reflections | (Δ/σ)max < 0.001 |
| 99 parameters | Δρmax = 0.52 e Å−3 |
| 2 restraints | Δρmin = −0.29 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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)
| 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)
| 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.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989014027182/lh5742sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027182/lh5742Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989014027182/lh5742Isup3.cml
CCDC reference: 1038844
Additional supporting information: crystallographic information; 3D view; checkCIF report