organic compounds
Powder X-ray investigation of 4,4′-diisocyano-3,3′-dimethylbiphenyl
aDepartment of Chemistry, Atomic Energy Commission of Syria (AECS), PO Box 6091, Damascus, Syrian Arab Republic
*Correspondence e-mail: cscientific@aec.org.sy
The title compound, C16H12N2, was investigated in a powder diffraction study and its structure refined utilizing the The molecule has approximate C2 symmetry. The dihedral angle between the rings is 25.6 (7)°. The crystal packing is consolidated by weak C—H⋯C≡N hydrogen-bond-like contacts, which lead to the formation of a three-dimensional network. Further stabilization of the is achived by weak non-covalent π–π interactions between aromatic rings, with a centroid–centroid distance of 3.839 (8) Å.
Related literature
For disocyano ligands and their coordination complexes, see: Harvey (2001); Sakata et al. (2003); Espinet et al. (2000); Moigno et al. (2002). For the preparation of the bidentate ligand CNCH2C(CH3)2CH2NC and its organometallic polymeric structures, see: Al-Ktaifani et al. (2008); Rukiah & Al-Ktaifani (2008, 2009); Al-Ktaifani & Rukiah (2010). For chelate complexing, see: Chemin et al. (1996). For the structure of isocyanide, see: Lentz & Preugschat (1993). For practical applications of oganometallic complexes with diisocyanide ligands, see: Fortin et al. (2000). For standard bond-lengths, see: Allen et al. (1987). For background and details of methods applied in powder diffraction, see: Boultif & Louër (2004); Rodriguez-Carvajal (2001); Roisnel & Rodriguez-Carvajal (2001); Le Bail et al. (1988); Toby (2001); Thompson et al. (1987); Finger et al. (1994); Stephens (1999).
Experimental
Crystal data
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Data collection
Refinement
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Data collection: WinXPOW (Stoe & Cie, 1999); cell GSAS (Larson & Von Dreele, 2004); data reduction: WinXPOW; program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002); program(s) used to refine structure: GSAS; molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536813004315/lh5582sup1.cif
contains datablocks global, I. DOI:Rietveld powder data: contains datablock I. DOI: 10.1107/S1600536813004315/lh5582Isup2.rtv
Supporting information file. DOI: 10.1107/S1600536813004315/lh5582Isup3.cml
All reactions and manipulations were carried out in air with reagent grade solvent. 4,4'-diamino-3,3'-dimethylbiphenyl (o-tolidine) was a commercial sample and was used as received. IR spectra were operated on FTIR Thermo Nicolet 6700. Powder X-ray diffraction was performed by Stoe Transmission diffractometre (Stadi P). A round bottom flask was charged with o-tolidine (10 g, 47 mmol), KOH (50%, 50 ml), CH2Cl2 (75 ml) and benzyltriethylammonium chloride (5.3 mmol, 1.2 g). To the mixture was added dropwise CHCl3 (10 ml). The resultant mixture was left to reflux spontaneously and stirred over night. The solution was filtered and diluted with 200 ml of H2O and the product extracted with CH2Cl2. The organic layer was separated, washed with 100 ml of H2O. The organic layer was dried over anhydrous Na2SO4, solvent removed, washed with Et2O to give beige powder. The product was purified by re-crystallization from CH2Cl2 to give light brown powder (3 g, yield 25%, m.p. 389 K). Spectroscopic analysis: IR (KBr, ν, cm-1): 2124.4 (N≡C); 1H NMR (400 MHz, CDCl3, 298 K) δ 7.39–7.47 (m, aromatic, 6H), 2.52 (s, CH3, 6H).13C{1H} NMR (100 MHz, CDCl3, 298 K) δ 166.91 (s, N≡ C), 140.55 (s, aromatic), 135.59 (s, aromatic), 129.19 (s, aromatic), 127.05 (s, aromatic), 126.15 (s, aromatic), 125.43 (s, aromatic), 18.78 (s, CH3).
No geometric soft restraints were applied during the
The methyl and aromatic H atoms were positioned in their idealized geometries. The coordinates of these H atoms were not refined. We used constant isotropic displacement parameters (0.05 Å2) for the aromatic H atoms and (0.1 Å2) for methyl H atoms.The final cycles were performed using anisotropic atomic displacement parameters for the carbon of cyano group. The final Rietveld plot of the X-ray diffraction pattern is given in Fig. 3.Over the past decade a new rich area of organometallic chemistry has been developed in which diisocyanides have been used as potential bridging ligands in the synthesis of bi- and tri- and tetra nuclear complexes and organometallic polymers (Harvey, 2001; Sakata et al., 2003; Espinet et al., 2000; Moigno et al., 2002). These new materials have been reported to have practical potential applications in different fields, such as semi- and
and photovoltaic cells (Fortin et al., 2000). Very recently, in a series of publications we have utilized the bidentate ligand 2,2-dimethylpropane-1,3-diyl diisocyanide in the syntheses of the organometallic polymers [Ag(C7H10N2)(X)]n (X = Cl-, Br-, I- or NO3-) (Al-Ktaifani et al., 2008; Al-Ktaifani & Rukiah, 2010; Rukiah & Al-Ktaifani, 2008; Rukiah &Al-Ktaifani, 2009), which have been completely characterized by X-ray powder diffraction studies, IR spectroscopy and micro-analysis. A major point of interest in the previously reported polymers {Ag(I)[CNCH2C(CH3)2CH2NC]X}n (X = Cl-, I- , Br- or NO3-) is their similar polymeric structures regardless of the counterpart anions. Also noteworthy is the bidentate ligand exhibits a very strong tendency to form polymeric complexes rather than dimeric or trimeric complexes suggesting the 2,2-dimethylpropane-1,3-diyl diisocyanide to be a potential bidentate bridging ligand in the syntheses of organometallic polymers of different transition metals. In similar manner, the bidentate bridging ligand 4,4`-diisocyano-3,3`-dimethyl-biphenyl was prepared in order to be utilized in the synthesis of new organometallic complexes. The syntheses of new organometallic complexes of this bidentate bridging ligand and their solid state characterizations are currently under investigations.In this article, the solid state characterization of the bidentate bridging ligand 4,4`-diisocyano-3,3`-dimethyl-biphenyl (I) is presented. In contrast to the extensively structurally characterized diisocyanide complexes, reports of the molecular structures of free diisocyanides are rare. This was an incentive to described the molecular structure of the uncomplexed diisocyanide 4,4'-diisocyano-3,3'-dimethylbiphenyl, C16H12N2, by powder X-ray diffraction study.
Compound (I) has a tendency to crystalize in the form of very fine beige powder. Since no single-crystal of sufficient thickness and quality could be obtained, a π—π aromatic interactions between phenyl rings of adjacent molecule [minimum centroid—centroid distances between two adjacent (but crystallographically different) Cg1···Cg1(x, 1/2 - y, -1/2 - z) = 3.839 (8) Å and Cg1···Cg1(x, 1/2 - y, 1/2 + z) = 3.838 (8) Å, where Cg1 is the centroid of the phenyl C2—C7 ring]. It is notworthy that a contact between two adjecent methyl groups is most likely repulsive and possibly even destabilizing C16···C16(-x, -y, -z-1) = 3.68 (2)Å. All bond distances (Allen et al., 1987) and angles in compound (I) are in their normal ranges.
by powder X-ray diffraction data was attempted. A view of the molecular structure is shown in Fig. 1. Compound (I) crystallizes with one molecule in the having a approximate C2 symmetry. In the of (I), weak non classical intermolecular hydrogen-bond-like contacts C—H···C (Table 1) between the carbon centre of CH3 or aromatic ring and the carbon center of cyanide group were observed . These contacts link the molecules to form a three-dimensional network and may be effective in the stabilization of the (Fig. 2). The crystal packing of (I) is also further stabilized by noncovalent weakFor disocyano ligands and their coordination complexes, see: Harvey (2001); Sakata et al. (2003); Espinet et al. (2000); Moigno et al. (2002). For the preparation of the bidentate ligand CNCH2C(CH3)2CH2NC and its organometallic polymeric structures, see: Al-Ktaifani et al. (2008); Rukiah & Al-Ktaifani (2008, 2009); Al-Ktaifani & Rukiah (2010). For chelate complexing, see: Chemin et al. (1996). For the structure of isocyanide, see: Lentz & Preugschat (1993). For practical applications of oganometallic complexes with diisocyanide ligands, see: Fortin et al. (2000). For standard bond-lengths, see: Allen et al. (1987). For background and details of methods applied in powder diffraction, see: Boultif & Louër (2004); Rodriguez-Carvajal (2001); Roisnel & Rodriguez-Carvajal (2001); Le Bail et al. (1988); Toby (2001); Thompson et al. (1987); Finger et al. (1994); Stephens (1999).
Data collection: WinXPOW (Stoe & Cie, 1999); cell
GSAS (Larson & Von Dreele, 2004); data reduction: WinXPOW (Stoe & Cie, 1999); program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002); program(s) used to refine structure: GSAS (Larson & Von Dreele, 2004); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).C16H12N2 | F(000) = 488 |
Mr = 232.28 | Dx = 1.207 Mg m−3 |
Monoclinic, P21/c | Cu Kα1 radiation, λ = 1.5406 Å |
Hall symbol: -P 2ybc | µ = 0.56 mm−1 |
a = 11.9045 (4) Å | T = 298 K |
b = 14.6235 (4) Å | Particle morphology: Fine powder |
c = 7.61672 (15) Å | light_brown |
β = 105.483 (2)° | flat sheet, 8 × 8 mm |
V = 1277.84 (7) Å3 | Specimen preparation: Prepared at 298 K and 101.3 kPa |
Z = 4 |
STOE Transmission STADI P diffractometer | Scan method: step |
Radiation source: sealed X-ray tube | Absorption correction: for a cylinder mounted on the φ axis GSAS Absorption/surface roughness correction: function number 4 Flat plate transmission absorption correction Terms = 0.17220 0.0000 Correction is not refined. |
Curved Ge(111) monochromator | Tmin = 0.685, Tmax = 0.767 |
Specimen mounting: powder loaded between two Mylar foils | 2θmin = 4.999°, 2θmax = 89.979°, 2θstep = 0.02° |
Data collection mode: transmission |
Least-squares matrix: full | Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in (Thompson et al.,1987.Asymmetry correction of Finger et al.(Finger et al.,1994). Microstrain broadening by Stephens(Stephens, 1999). #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 10.785 #4(GP) = 0.000 #5(LX) = 2.472 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0225 #12(eta) = 0.4987 #13(S400 ) = 9.0E-02 #14(S040 ) = 1.1E-02 #15(S004 ) = 2.8E+00 #16(S220 ) = 1.9E-02 #17(S202 ) = -1.5E-02 #18(S022 ) = 3.5E-02 #19(S301 ) = -2.0E-01 #20(S103 ) = 1.1E+00 #21(S121 ) = -6.1E-02 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0 |
Rp = 0.016 | 120 parameters |
Rwp = 0.021 | 0 restraints |
Rexp = 0.016 | H-atom parameters not refined |
R(F2) = 0.02609 | (Δ/σ)max = 0.02 |
4250 data points | Background function: GSAS Background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 3509.16 2: -3547.18 3: 1729.31 4: -271.390 5: -158.493 6: 133.640 7: -41.5743 8: -87.6309 9: 73.0201 10: 78.1201 11: -126.319 12: 73.5124 13: 5.65073 14: -38.9623 15: 13.5948 16: 6.87496 17: -4.39687 18: 0.392461 19: 8.77696 20: -6.87661 |
Excluded region(s): none |
C16H12N2 | V = 1277.84 (7) Å3 |
Mr = 232.28 | Z = 4 |
Monoclinic, P21/c | Cu Kα1 radiation, λ = 1.5406 Å |
a = 11.9045 (4) Å | µ = 0.56 mm−1 |
b = 14.6235 (4) Å | T = 298 K |
c = 7.61672 (15) Å | flat sheet, 8 × 8 mm |
β = 105.483 (2)° |
STOE Transmission STADI P diffractometer | Absorption correction: for a cylinder mounted on the φ axis GSAS Absorption/surface roughness correction: function number 4 Flat plate transmission absorption correction Terms = 0.17220 0.0000 Correction is not refined. |
Specimen mounting: powder loaded between two Mylar foils | Tmin = 0.685, Tmax = 0.767 |
Data collection mode: transmission | 2θmin = 4.999°, 2θmax = 89.979°, 2θstep = 0.02° |
Scan method: step |
Rp = 0.016 | 4250 data points |
Rwp = 0.021 | 120 parameters |
Rexp = 0.016 | 0 restraints |
R(F2) = 0.02609 | H-atom parameters not refined |
Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 8.0 mm internal diameter. |
Refinement. For pattern indexing, the extraction of the peak positions was carried out with the programWinPLOTR (Roisnel & Rodriguez-Carvajal, 2001). Pattern indexing was performed with the program DicVol4.0 (Boultif & Louër, 2004). The first 20 lines of powder pattern were completely indexed on the basis of monoclinic system. The absolute error on each observed line was fixed at 0.02° (2θ). The figures of merit are sufficiently high to support the obtained indexing results [M(20) = 22.5, F(20) = 41.1(0.0087, 56)]. The whole powder diffraction pattern from 5 to 90° (2θ) was subsequently refined with cell and resolution constraints (Le Bail et al., 1988) with a space group without systematic extinctions in monoclinic system, P2/m, using the "profile matching" option of the program FullProf (Rodriguez-Carvajal, 2001). The best estimated space group in the monoclinic system was P21/c which determined with the help of the program Check Group interfaced by WinPLOTR (Roisnel & Rodriguez, 2001). The number of molecules per unit cell was estimated to be equal to Z = 4, it can be concluded that the number of molecules in the asymmetric unit is Z' = 1 for the space group P21/c. The structure was solved ab initio by direct space method (Monte Carlo simulated annealing with parallel tempering algorithm) using the program FOX (Favre-Nicolin & Černý, 2002). The model found by this program was introduced in the program GSAS (Larson & Von Dreele, 2004) implemented in EXPGUI (Toby, 2001) for Rietveld refinements. The background was refined using a shifted Chebyshev polynomial with 20 coefficients. During the Rietveld refinements, the effect of the asymmetry of peaks was corrected using a pseudo-Voigt description of the peak shape (Thompson et al., 1987) which allows for angle-dependent asymmetry with axial divergence (Finger et al., 1994). The two asymmetry parameters of this function S/L and D/L were both fixed at 0.0225 during the Rietveld refinement. Intensities were corrected from absorption effects with a µ.d value of 0.1722. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7040 (15) | 0.3220 (13) | 0.546 (3) | 0.13957 | |
C2 | 0.5080 (12) | 0.2651 (12) | 0.326 (2) | 0.049 (7)* | |
C3 | 0.4211 (14) | 0.3265 (8) | 0.237 (2) | 0.031 (5)* | |
C4 | 0.3141 (13) | 0.2954 (10) | 0.1285 (17) | 0.033 (5)* | |
C5 | 0.2881 (12) | 0.2038 (10) | 0.120 (2) | 0.027 (5)* | |
C6 | 0.3738 (13) | 0.1398 (8) | 0.209 (2) | 0.035 (6)* | |
C7 | 0.4835 (12) | 0.1710 (10) | 0.3129 (17) | 0.044 (6)* | |
C8 | 0.1712 (13) | 0.1714 (10) | 0.0015 (19) | 0.022 (5)* | |
C9 | 0.1588 (12) | 0.0804 (10) | −0.075 (2) | 0.034 (5)* | |
C10 | 0.0455 (16) | 0.0559 (9) | −0.181 (2) | 0.039 (6)* | |
C11 | −0.0471 (12) | 0.1147 (11) | −0.213 (2) | 0.049 (6)* | |
C12 | −0.0348 (12) | 0.2013 (10) | −0.1276 (19) | 0.039 (6)* | |
C13 | 0.0750 (14) | 0.2270 (7) | −0.030 (2) | 0.043 (6)* | |
C14 | −0.2511 (14) | 0.0608 (10) | −0.386 (2) | 0.11783 | |
C15 | 0.4492 (9) | 0.4276 (9) | 0.2552 (18) | 0.086 (6)* | |
C16 | 0.0322 (13) | −0.0402 (9) | −0.2630 (19) | 0.060 (5)* | |
N1 | 0.6187 (12) | 0.2921 (10) | 0.449 (2) | 0.065 (7)* | |
N2 | −0.1575 (11) | 0.0800 (9) | −0.3173 (19) | 0.046 (6)* | |
H4 | 0.25719 | 0.3431 | 0.06671 | 0.05* | |
H6 | 0.35313 | 0.07403 | 0.19577 | 0.05* | |
H7 | 0.53998 | 0.12458 | 0.37635 | 0.05* | |
H9 | 0.2264 | 0.04273 | −0.05912 | 0.05* | |
H12 | −0.10372 | 0.23895 | −0.1533 | 0.05* | |
H13 | 0.08075 | 0.29047 | 0.02542 | 0.05* | |
H15a | 0.438 | 0.45236 | 0.13397 | 0.1* | |
H15b | 0.39451 | 0.45559 | 0.3131 | 0.1* | |
H15c | 0.52758 | 0.43661 | 0.32669 | 0.1* | |
H16a | 0.04874 | −0.04178 | −0.38138 | 0.1* | |
H16b | 0.08445 | −0.08471 | −0.18326 | 0.1* | |
H16c | −0.04778 | −0.06116 | −0.2777 | 0.1* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.13 (2) | 0.21 (2) | 0.07 (2) | 0.001 (18) | 0.004 (15) | −0.048 (17) |
C14 | 0.081 (18) | 0.127 (18) | 0.11 (2) | −0.014 (14) | −0.033 (19) | 0.063 (15) |
C1—N1 | 1.171 (19) | C5—C8 | 1.518 (13) |
N1—C2 | 1.451 (17) | C8—C9 | 1.446 (14) |
C2—C3 | 1.402 (18) | C9—C10 | 1.421 (18) |
C3—C4 | 1.397 (17) | C9—H9 | 0.956 |
C3—C15 | 1.513 (14) | C10—C11 | 1.367 (16) |
C15—H15a | 0.967 | C10—C16 | 1.528 (19) |
C15—H15b | 0.969 | C16—H16a | 0.973 |
C15—H15c | 0.956 | C16—H16b | 0.989 |
C4—C5 | 1.372 (13) | C16—H16c | 0.978 |
C4—H4 | 0.998 | C11—C12 | 1.414 (14) |
C5—C6 | 1.416 (14) | C11—N2 | 1.435 (15) |
C6—C7 | 1.410 (14) | C12—C13 | 1.373 (14) |
C6—H6 | 0.992 | C12—H12 | 0.964 |
C7—C2 | 1.404 (14) | C13—H13 | 1.014 |
C7—H7 | 0.987 | C14—N2 | 1.133 (15) |
C3—C2—C7 | 118.7 (14) | C9—C10—C16 | 116.3 (18) |
C3—C2—N1 | 124.3 (17) | C11—C10—C16 | 121.0 (18) |
C7—C2—N1 | 116.7 (19) | C10—C11—C12 | 120.1 (15) |
C2—C3—C4 | 121.1 (12) | C10—C11—N2 | 116.9 (18) |
C2—C3—C15 | 117.7 (16) | C12—C11—N2 | 122.6 (18) |
C4—C3—C15 | 121.2 (16) | C11—C12—C13 | 117.5 (14) |
C3—C4—C5 | 120.3 (14) | C11—C12—H12 | 116.1 |
C3—C4—H4 | 116.6 | C13—C12—H12 | 126.1 |
C5—C4—H4 | 123.0 | C8—C13—C12 | 124.2 (15) |
C4—C5—C6 | 119.9 (15) | C8—C13—H13 | 120.6 |
C4—C5—C8 | 119.5 (16) | C12—C13—H13 | 115.1 |
C6—C5—C8 | 120.5 (13) | C3—C15—H15a | 107.9 |
C5—C6—C7 | 119.7 (14) | C3—C15—H15b | 107.2 |
C5—C6—H6 | 117.7 | C3—C15—H15c | 110.2 |
C7—C6—H6 | 122.5 | H15a—C15—H15b | 109.7 |
C2—C7—C6 | 120.1 (13) | H15a—C15—H15c | 110.9 |
C2—C7—H7 | 122.5 | H15b—C15—H15c | 110.8 |
C6—C7—H7 | 117.4 | C10—C16—H16a | 112.1 |
C5—C8—C9 | 120.4 (13) | C10—C16—H16b | 112.0 |
C5—C8—C13 | 120.6 (15) | C10—C16—H16c | 109.1 |
C9—C8—C13 | 119.0 (16) | H16a—C16—H16b | 107.6 |
C8—C9—C10 | 116.1 (14) | H16a—C16—H16c | 108.6 |
C8—C9—H9 | 119.2 | H16b—C16—H16c | 107.3 |
C10—C9—H9 | 124.6 | C1—N1—C2 | 174 (3) |
C9—C10—C11 | 122.7 (14) | C11—N2—C14 | 171 (2) |
N1—C2—C3—C4 | −176.4 (14) | C6—C5—C8—C13 | 156.0 (15) |
N1—C2—C3—C15 | 6 (2) | C5—C6—C7—C2 | −1 (2) |
C7—C2—C3—C4 | −4 (2) | C5—C8—C9—C10 | 178.8 (13) |
C7—C2—C3—C15 | 179.3 (13) | C13—C8—C9—C10 | 1 (2) |
N1—C2—C7—C6 | 174.5 (13) | C5—C8—C13—C12 | −176.6 (14) |
C3—C2—C7—C6 | 1 (2) | C9—C8—C13—C12 | 2 (2) |
C2—C3—C4—C5 | 6 (2) | C8—C9—C10—C11 | 1 (2) |
C15—C3—C4—C5 | −177.1 (13) | C8—C9—C10—C16 | 179.7 (13) |
C3—C4—C5—C6 | −5 (2) | C9—C10—C11—N2 | −178.0 (14) |
C3—C4—C5—C8 | 179.9 (13) | C9—C10—C11—C12 | −5 (2) |
C4—C5—C6—C7 | 3 (2) | C16—C10—C11—N2 | 4 (2) |
C8—C5—C6—C7 | 177.6 (13) | C16—C10—C11—C12 | 176.4 (13) |
C4—C5—C8—C9 | 152.6 (14) | N2—C11—C12—C13 | 179.5 (14) |
C4—C5—C8—C13 | −29 (2) | C10—C11—C12—C13 | 7 (2) |
C6—C5—C8—C9 | −22 (2) | C11—C12—C13—C8 | −5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···C14i | 0.991 | 2.900 | 3.69 (2) | 137.36 |
C7—H7···C14ii | 0.986 | 2.815 | 3.737 (17) | 155.86 |
C16—H16b···C1iii | 0.989 | 2.809 | 3.73 (2) | 154.52 |
C16—H16a···C16iv | 0.973 | 2.883 | 3.68 (2) | 139.57 |
Symmetry codes: (i) −x, −y, −z; (ii) x+1, y, z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, −y, −z−1. |
Experimental details
Crystal data | |
Chemical formula | C16H12N2 |
Mr | 232.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.9045 (4), 14.6235 (4), 7.61672 (15) |
β (°) | 105.483 (2) |
V (Å3) | 1277.84 (7) |
Z | 4 |
Radiation type | Cu Kα1, λ = 1.5406 Å |
µ (mm−1) | 0.56 |
Specimen shape, size (mm) | Flat sheet, 8 × 8 |
Data collection | |
Diffractometer | STOE Transmission STADI P |
Specimen mounting | Powder loaded between two Mylar foils |
Data collection mode | Transmission |
Scan method | Step |
Absorption correction | For a cylinder mounted on the φ axis GSAS Absorption/surface roughness correction: function number 4 Flat plate transmission absorption correction Terms = 0.17220 0.0000 Correction is not refined. |
Tmin, Tmax | 0.685, 0.767 |
2θ values (°) | 2θmin = 4.999 2θmax = 89.979 2θstep = 0.02 |
Refinement | |
R factors and goodness of fit | Rp = 0.016, Rwp = 0.021, Rexp = 0.016, R(F2) = 0.02609, χ2 = 1.742 |
No. of parameters | 120 |
H-atom treatment | H-atom parameters not refined |
Computer programs: WinXPOW (Stoe & Cie, 1999), GSAS (Larson & Von Dreele, 2004), FOX (Favre-Nicolin & Černý, 2002), ORTEP-3 (Farrugia, 2012), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···C14i | 0.991 | 2.900 | 3.69 (2) | 137.36 |
C7—H7···C14ii | 0.986 | 2.815 | 3.737 (17) | 155.86 |
C16—H16b···C1iii | 0.989 | 2.809 | 3.73 (2) | 154.52 |
Symmetry codes: (i) −x, −y, −z; (ii) x+1, y, z+1; (iii) −x+1, y−1/2, −z+1/2. |
Acknowledgements
The authors thank Professors I. Othman, Director General, and. T. Yassine, Head of Chemistry Department, for their support and encouragement.
References
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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.
Over the past decade a new rich area of organometallic chemistry has been developed in which diisocyanides have been used as potential bridging ligands in the synthesis of bi- and tri- and tetra nuclear complexes and organometallic polymers (Harvey, 2001; Sakata et al., 2003; Espinet et al., 2000; Moigno et al., 2002). These new materials have been reported to have practical potential applications in different fields, such as semi- and photoconductivity and photovoltaic cells (Fortin et al., 2000). Very recently, in a series of publications we have utilized the bidentate ligand 2,2-dimethylpropane-1,3-diyl diisocyanide in the syntheses of the organometallic polymers [Ag(C7H10N2)(X)]n (X = Cl-, Br-, I- or NO3-) (Al-Ktaifani et al., 2008; Al-Ktaifani & Rukiah, 2010; Rukiah & Al-Ktaifani, 2008; Rukiah &Al-Ktaifani, 2009), which have been completely characterized by X-ray powder diffraction studies, IR spectroscopy and micro-analysis. A major point of interest in the previously reported polymers {Ag(I)[CNCH2C(CH3)2CH2NC]X}n (X = Cl-, I- , Br- or NO3-) is their similar polymeric structures regardless of the counterpart anions. Also noteworthy is the bidentate ligand exhibits a very strong tendency to form polymeric complexes rather than dimeric or trimeric complexes suggesting the 2,2-dimethylpropane-1,3-diyl diisocyanide to be a potential bidentate bridging ligand in the syntheses of organometallic polymers of different transition metals. In similar manner, the bidentate bridging ligand 4,4`-diisocyano-3,3`-dimethyl-biphenyl was prepared in order to be utilized in the synthesis of new organometallic complexes. The syntheses of new organometallic complexes of this bidentate bridging ligand and their solid state characterizations are currently under investigations.
In this article, the solid state characterization of the bidentate bridging ligand 4,4`-diisocyano-3,3`-dimethyl-biphenyl (I) is presented. In contrast to the extensively structurally characterized diisocyanide complexes, reports of the molecular structures of free diisocyanides are rare. This was an incentive to described the molecular structure of the uncomplexed diisocyanide 4,4'-diisocyano-3,3'-dimethylbiphenyl, C16H12N2, by powder X-ray diffraction study.
Compound (I) has a tendency to crystalize in the form of very fine beige powder. Since no single-crystal of sufficient thickness and quality could be obtained, a structure determination by powder X-ray diffraction data was attempted. A view of the molecular structure is shown in Fig. 1. Compound (I) crystallizes with one molecule in the asymmetric unit, having a approximate C2 symmetry. In the crystal structure of (I), weak non classical intermolecular hydrogen-bond-like contacts C—H···C (Table 1) between the carbon centre of CH3 or aromatic ring and the carbon center of cyanide group were observed . These contacts link the molecules to form a three-dimensional network and may be effective in the stabilization of the crystal structure (Fig. 2). The crystal packing of (I) is also further stabilized by noncovalent weak π—π aromatic interactions between phenyl rings of adjacent molecule [minimum centroid—centroid distances between two adjacent (but crystallographically different) Cg1···Cg1(x, 1/2 - y, -1/2 - z) = 3.839 (8) Å and Cg1···Cg1(x, 1/2 - y, 1/2 + z) = 3.838 (8) Å, where Cg1 is the centroid of the phenyl C2—C7 ring]. It is notworthy that a contact between two adjecent methyl groups is most likely repulsive and possibly even destabilizing C16···C16(-x, -y, -z-1) = 3.68 (2)Å. All bond distances (Allen et al., 1987) and angles in compound (I) are in their normal ranges.