![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
metal-organic compounds
![Open Access](/logos/open.png)
Bromidotricarbonyl[2-phenyl-5-(pyridin-2-yl-κN)-1,3,4-oxadiazole-κN4]rhenium(I) dichloromethane monosolvate
aCollege of Sciences, Zhejiang A&F University, Lin'an, Hangzhou, Zhejiang 311300, People's Republic of China, bSchool of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130000, People's Republic of China, and cSchool of Chemical Engineering & Technology, Harbin Institute of Technology, Harbin 150001, People's Republic of China
*Correspondence e-mail: lfshi2003@163.com
In the title rhenium(I) complex, [ReBr(C13H9N3O)(CO)3]·CH2Cl2, the dichloromethane solvent molecule is disordered over two positions with an occupancy ratio of 0.81 (15):0.19 (15). The ReI atom is coordinated by two N atoms from a 2-phenyl-5-(pyridin-2-yl-κN)-1,3,4-oxadiazole (L) ligand, three C atoms from three carbonyl groups and a Br atom in a distorted octahedral geometry. The three rings in L are almost coplanar (a mean plane fitted through all non-H atoms of this ligand has an r.m.s. deviation of 0.063 Å), and the carbonyl ligands are coordinated in a fac arrangement.
Related literature
For background to organic light emitting diodes, see: Li et al. (2005); Wong et al. (2005
). For phosphorescent materials, see: Kim et al. (2006
); Lee et al. (2005
); Bernhard et al. (2002
). For the use of ReI complexes as phosphorescent materials, see: Gong et al. (1998
); Li et al. (2001
); Rajendran et al. (2000
); Zhang et al. (2009
). For the synthetic procecure, see: Demko & Sharpless (2001
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536810052360/nk2078sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052360/nk2078Isup2.hkl
The oxadiazole ligand was synthesized as follows: 5-(2-pyridyl)tetrazole (Demko et al., 2001)(1.48 g, 10 mmol), pyridine (25 ml) and benzoyl chloride (1.41 g, 10 mmol) were added to a 50 ml round bottom flask and refluxed for 72 h. The crude product was then purified by
Yield 1.61 g (59.6%). IR (KBr pellet): 3055 (w), 1616 (w), 1547 (s), 1481 (s), 1452 (vs), 1387 (s), 1146 (m), 1072 (m), 1024 (w), 793 (s), 715 (vs) cm-1. [Re(CO)3(L)Br] was synthesized according to the following procedure: L (0.05 g, 0.210 mmol) and Re(CO)5Br (0.08 g, 0.200 mmol) were refluxed in 15 ml of toluene for 6 h. After the mixture was cooled to RT, the solvent was removed in a water bath under reduced pressure. The resulting yellow solid was purified by silica gel with acetic acid ethyl ester and dichloromethane (v/v = 10:1). Yellow single crystals of complexes 2 suitable for X-ray diffraction studies were grown from slow evaporation of a CH2Cl2 solution.One molecule of solvent dichloromethane is present in the
This was refined as disordered over two positions, with occupancies of 0.81 (15):0.19 (15). H atoms were identified from a difference map and refined using Uiso(H) = 1.2Ueq(C) and constrained C-H distances.Interest in next generation displays and lighting technologies has stimulated research on organic light-emitting materials (Li et al., 2005; Wong et al., 2005), especially phosphorescent materials (Kim et al., 2006; Lee et al., 2005). As a result, transition metal phosphorescent complexes (Bernhard et al., 2002) have been studied intensively throughout the world. In order to further explore novel phosphorescent materials, several researchers paid attention to ReI complexes (Gong et al., 1998; Li et al., 2001), of which the d6
is identical to that of the corresponding Os(II) and Ir(III) systems. Therefore, it is pressing to explore new ReI complexes served as luminescent materials. In this article, we report the successful synthesis of a novel ReI complex which contains the oxadiazole ligand of 2-phenyl-5-(pyridin-2-yl)-1,3,4-oxadiazole, and characterized its structure by single-crystal X-ray Its luminescent property will be further studied in the coming research.The structure of complex [Re(CO)3(L)Br].CH2Cl2, is shown in Figure 1. One molecule of solvent dichloromethane is present in the
This was refined as disordered over two positions, with occupancies of 0.81 (15):0.19 (15).. The coordination geometry at the Re atom is a distorted octahedron with the three CO ligands arranged in a fac-fashion. The distances of C(1), C(2), and C(3) to Re(1) are 1.884 (7), 1.920 (7), and 1.893 (7)Å, respectively, and the Re—N bonds distances are 2.228 (4) and 2.173 (4)Å. The CO ligands are linearly coordinated for the bond angles of O—C—Re are 174.8 (6), 177.5 (7) and 177.4 (7)°, respectively, which are close to 180°. Furthermore, the bond angles between adjacent CO carbon atoms are 87.9 (3), 89.1 (3) and 89.8 (3)°, respectively, which are close to 90°, but the bond angle between the coordinated nitrogen atoms of ligand is 73.71 (17)°, which is much less than 90°. All other bond distances and angles are comparable to those found for the related ReI complexes (Rajendran et al., 2000).Furthermore, a kind of inter-molecular face-to-face stacking present in the molecular structure of [Re(CO)3(L)Br].CH2Cl2: the 1,3,4-oxadiazole moiety in one molecule is almost parallel to the other one from another complex , and the approximate distance between the two closest atoms (N2—N3) is only 3.376°. Thus a bonded dual-molecule structure is constructed in the complex molecule which is believed a rigid one and will prevent geometric relaxation effectively (Zhang et al., 2009). Such rigid structure is promised possessing excellent luminescent properties.
For background to organic light emitting diodes, see: Li et al. (2005); Wong et al. (2005). For phosphorescent materials, see: Kim et al. (2006); Lee et al. (2005); Bernhard et al. (2002). For the use of ReI complexes as phosphorescent materials, see: Gong et al. (1998); Li et al. (2001); Rajendran et al. (2000); Zhang et al. (2009). For the synthetic procecure, see: Demko & Sharpless (2001).
Data collection: SMART (Bruker, 2007); cell
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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[ReBr(C13H9N3O)(CO)3]·CH2Cl2 | F(000) = 2480 |
Mr = 658.30 | Dx = 2.160 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4631 reflections |
a = 12.492 (3) Å | θ = 2.3–27.5° |
b = 19.513 (4) Å | µ = 8.27 mm−1 |
c = 16.835 (3) Å | T = 293 K |
β = 99.45 (3)° | Block, yellow |
V = 4047.9 (15) Å3 | 0.20 × 0.16 × 0.11 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 4631 independent reflections |
Radiation source: fine-focus sealed tube | 3992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.104 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −16→15 |
Tmin = 0.229, Tmax = 0.409 | k = −25→25 |
19615 measured reflections | l = −21→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0507P)2 + 6.9046P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
4631 reflections | Δρmax = 2.88 e Å−3 |
276 parameters | Δρmin = −1.44 e Å−3 |
36 restraints | Extinction correction: SHELXS97(Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00089 (8) |
[ReBr(C13H9N3O)(CO)3]·CH2Cl2 | V = 4047.9 (15) Å3 |
Mr = 658.30 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.492 (3) Å | µ = 8.27 mm−1 |
b = 19.513 (4) Å | T = 293 K |
c = 16.835 (3) Å | 0.20 × 0.16 × 0.11 mm |
β = 99.45 (3)° |
Bruker SMART CCD area-detector diffractometer | 4631 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3992 reflections with I > 2σ(I) |
Tmin = 0.229, Tmax = 0.409 | Rint = 0.104 |
19615 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 36 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.88 e Å−3 |
4631 reflections | Δρmin = −1.44 e Å−3 |
276 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Re1 | 0.763878 (16) | 0.394333 (9) | 0.240070 (14) | 0.03250 (12) | |
Br1 | 0.62778 (5) | 0.40803 (3) | 0.10476 (4) | 0.04074 (16) | |
O1 | 0.9100 (4) | 0.3751 (3) | 0.4011 (3) | 0.0696 (16) | |
O2 | 0.8889 (5) | 0.2798 (3) | 0.1726 (4) | 0.0808 (18) | |
O3 | 0.6198 (4) | 0.2847 (3) | 0.2967 (4) | 0.0825 (19) | |
O4 | 0.8670 (3) | 0.59195 (17) | 0.1890 (3) | 0.0314 (8) | |
N1 | 0.6852 (3) | 0.4871 (2) | 0.2817 (3) | 0.0314 (9) | |
N2 | 0.8475 (3) | 0.4820 (2) | 0.1993 (3) | 0.0309 (9) | |
N3 | 0.9313 (3) | 0.4917 (2) | 0.1559 (3) | 0.0335 (10) | |
C1 | 0.8579 (5) | 0.3847 (3) | 0.3391 (4) | 0.0444 (15) | |
C2 | 0.8427 (5) | 0.3231 (3) | 0.1961 (5) | 0.0508 (16) | |
C3 | 0.6735 (5) | 0.3274 (4) | 0.2764 (4) | 0.0527 (16) | |
C4 | 0.6067 (4) | 0.4881 (3) | 0.3268 (4) | 0.0384 (12) | |
H4 | 0.5784 | 0.4464 | 0.3403 | 0.046* | |
C5 | 0.5655 (5) | 0.5467 (3) | 0.3545 (4) | 0.0468 (14) | |
H5 | 0.5123 | 0.5446 | 0.3871 | 0.056* | |
C6 | 0.6049 (5) | 0.6097 (3) | 0.3328 (4) | 0.0445 (15) | |
H6 | 0.5779 | 0.6504 | 0.3505 | 0.053* | |
C7 | 0.6850 (5) | 0.6109 (3) | 0.2844 (4) | 0.0396 (14) | |
H7 | 0.7113 | 0.6520 | 0.2673 | 0.047* | |
C8 | 0.7239 (4) | 0.5490 (3) | 0.2628 (3) | 0.0308 (11) | |
C9 | 0.8113 (4) | 0.5412 (2) | 0.2168 (3) | 0.0297 (10) | |
C10 | 0.9406 (4) | 0.5585 (2) | 0.1511 (3) | 0.0304 (10) | |
C11 | 1.0160 (4) | 0.5964 (2) | 0.1110 (3) | 0.0320 (11) | |
C12 | 1.0231 (5) | 0.6674 (3) | 0.1184 (4) | 0.0441 (14) | |
H12 | 0.9795 | 0.6912 | 0.1487 | 0.053* | |
C13 | 1.0960 (5) | 0.7015 (3) | 0.0798 (5) | 0.0534 (16) | |
H13 | 1.1024 | 0.7488 | 0.0849 | 0.064* | |
C14 | 1.1604 (5) | 0.6663 (4) | 0.0334 (4) | 0.0516 (16) | |
H14 | 1.2089 | 0.6901 | 0.0073 | 0.062* | |
C15 | 1.1523 (5) | 0.5966 (3) | 0.0260 (4) | 0.0442 (15) | |
H15 | 1.1948 | 0.5732 | −0.0056 | 0.053* | |
C16 | 1.0816 (4) | 0.5609 (3) | 0.0651 (3) | 0.0342 (11) | |
H16 | 1.0774 | 0.5134 | 0.0611 | 0.041* | |
Cl1 | 0.6313 (10) | 0.7067 (5) | 0.0785 (8) | 0.115 (3) | 0.810 (15) |
Cl2 | 0.6782 (3) | 0.57172 (14) | 0.0268 (2) | 0.0650 (12) | 0.810 (15) |
C17 | 0.6743 (17) | 0.6573 (6) | 0.0037 (9) | 0.102 (5) | 0.810 (15) |
H17A | 0.7460 | 0.6722 | −0.0037 | 0.123* | 0.810 (15) |
H17B | 0.6254 | 0.6644 | −0.0466 | 0.123* | 0.810 (15) |
Cl1' | 0.666 (5) | 0.7100 (17) | 0.087 (3) | 0.121 (16) | 0.190 (15) |
Cl2' | 0.715 (4) | 0.591 (3) | 0.0034 (16) | 0.201 (18) | 0.190 (15) |
C17' | 0.660 (9) | 0.681 (3) | 0.017 (5) | 0.102 (5) | 0.19 |
H17C | 0.6951 | 0.7113 | −0.0162 | 0.123* | 0.190 (15) |
H17D | 0.5835 | 0.6799 | −0.0067 | 0.123* | 0.190 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.03620 (16) | 0.02314 (14) | 0.0399 (2) | −0.00311 (6) | 0.01139 (11) | 0.00443 (7) |
Br1 | 0.0422 (3) | 0.0423 (3) | 0.0395 (4) | 0.0007 (2) | 0.0119 (2) | −0.0024 (2) |
O1 | 0.086 (3) | 0.054 (3) | 0.061 (4) | −0.020 (3) | −0.013 (3) | 0.018 (3) |
O2 | 0.089 (4) | 0.043 (3) | 0.115 (5) | 0.024 (3) | 0.032 (3) | −0.016 (3) |
O3 | 0.079 (3) | 0.072 (4) | 0.100 (5) | −0.041 (3) | 0.026 (3) | 0.025 (3) |
O4 | 0.0387 (18) | 0.0246 (15) | 0.034 (2) | −0.0016 (14) | 0.0167 (16) | 0.0007 (15) |
N1 | 0.037 (2) | 0.027 (2) | 0.031 (2) | −0.0016 (16) | 0.0096 (18) | 0.0030 (18) |
N2 | 0.0291 (19) | 0.025 (2) | 0.041 (3) | −0.0015 (16) | 0.0141 (17) | 0.0053 (18) |
N3 | 0.033 (2) | 0.026 (2) | 0.043 (3) | 0.0001 (16) | 0.0143 (18) | 0.0019 (19) |
C1 | 0.046 (3) | 0.028 (2) | 0.058 (5) | −0.009 (2) | 0.005 (3) | 0.000 (3) |
C2 | 0.055 (3) | 0.035 (3) | 0.065 (5) | −0.006 (3) | 0.016 (3) | 0.001 (3) |
C3 | 0.054 (3) | 0.055 (4) | 0.050 (4) | −0.006 (3) | 0.009 (3) | 0.004 (3) |
C4 | 0.038 (3) | 0.042 (3) | 0.037 (3) | −0.007 (2) | 0.014 (2) | 0.006 (2) |
C5 | 0.046 (3) | 0.056 (4) | 0.042 (4) | −0.003 (3) | 0.021 (3) | −0.003 (3) |
C6 | 0.045 (3) | 0.043 (3) | 0.049 (4) | 0.003 (2) | 0.019 (3) | −0.009 (3) |
C7 | 0.045 (3) | 0.029 (3) | 0.047 (4) | −0.001 (2) | 0.015 (3) | −0.004 (2) |
C8 | 0.032 (2) | 0.029 (2) | 0.033 (3) | −0.0020 (18) | 0.011 (2) | 0.0009 (19) |
C9 | 0.038 (2) | 0.022 (2) | 0.030 (3) | −0.0014 (18) | 0.009 (2) | 0.0001 (19) |
C10 | 0.033 (2) | 0.029 (2) | 0.031 (3) | −0.0012 (19) | 0.008 (2) | −0.001 (2) |
C11 | 0.039 (3) | 0.028 (2) | 0.032 (3) | −0.0015 (19) | 0.012 (2) | 0.001 (2) |
C12 | 0.055 (3) | 0.025 (2) | 0.057 (4) | −0.001 (2) | 0.023 (3) | 0.004 (2) |
C13 | 0.060 (4) | 0.031 (3) | 0.072 (5) | −0.013 (3) | 0.018 (3) | 0.004 (3) |
C14 | 0.057 (3) | 0.053 (4) | 0.049 (4) | −0.014 (3) | 0.021 (3) | 0.010 (3) |
C15 | 0.041 (3) | 0.057 (4) | 0.039 (4) | −0.005 (3) | 0.020 (3) | −0.005 (3) |
C16 | 0.043 (3) | 0.030 (2) | 0.032 (3) | −0.006 (2) | 0.012 (2) | −0.004 (2) |
Cl1 | 0.143 (5) | 0.073 (4) | 0.129 (7) | 0.003 (3) | 0.029 (5) | −0.024 (3) |
Cl2 | 0.087 (2) | 0.0521 (17) | 0.053 (2) | −0.0020 (11) | 0.0019 (14) | −0.0019 (11) |
C17 | 0.209 (15) | 0.038 (7) | 0.074 (9) | 0.007 (9) | 0.064 (9) | 0.010 (6) |
Cl1' | 0.24 (5) | 0.034 (8) | 0.084 (13) | −0.008 (15) | −0.01 (2) | −0.005 (8) |
Cl2' | 0.24 (3) | 0.32 (4) | 0.044 (12) | 0.11 (3) | 0.014 (16) | −0.036 (18) |
C17' | 0.209 (15) | 0.038 (7) | 0.074 (9) | 0.007 (9) | 0.064 (9) | 0.010 (6) |
Re1—C1 | 1.884 (7) | C7—H7 | 0.9300 |
Re1—C3 | 1.893 (7) | C8—C9 | 1.446 (7) |
Re1—C2 | 1.920 (7) | C10—C11 | 1.448 (7) |
Re1—N2 | 2.173 (4) | C11—C12 | 1.391 (7) |
Re1—N1 | 2.228 (4) | C11—C16 | 1.399 (7) |
Re1—Br1 | 2.6228 (11) | C12—C13 | 1.374 (9) |
O1—C1 | 1.152 (8) | C12—H12 | 0.9300 |
O2—C2 | 1.132 (8) | C13—C14 | 1.392 (10) |
O3—C3 | 1.157 (8) | C13—H13 | 0.9300 |
O4—C9 | 1.337 (6) | C14—C15 | 1.368 (9) |
O4—C10 | 1.369 (6) | C14—H14 | 0.9300 |
N1—C4 | 1.335 (7) | C15—C16 | 1.375 (8) |
N1—C8 | 1.357 (6) | C15—H15 | 0.9300 |
N2—C9 | 1.293 (6) | C16—H16 | 0.9300 |
N2—N3 | 1.385 (6) | Cl1—C17 | 1.739 (19) |
N3—C10 | 1.314 (6) | Cl2—C17 | 1.713 (12) |
C4—C5 | 1.367 (9) | C17—H17A | 0.9700 |
C4—H4 | 0.9300 | C17—H17B | 0.9700 |
C5—C6 | 1.395 (8) | Cl1'—C17' | 1.30 (9) |
C5—H5 | 0.9300 | Cl2'—C17' | 1.90 (6) |
C6—C7 | 1.391 (9) | C17'—H17C | 0.9700 |
C6—H6 | 0.9300 | C17'—H17D | 0.9700 |
C7—C8 | 1.373 (7) | ||
C1—Re1—C3 | 87.9 (3) | N1—C8—C9 | 111.2 (4) |
C1—Re1—C2 | 89.1 (3) | C7—C8—C9 | 124.4 (5) |
C3—Re1—C2 | 89.8 (3) | N2—C9—O4 | 111.2 (4) |
C1—Re1—N2 | 95.5 (2) | N2—C9—C8 | 122.6 (4) |
C3—Re1—N2 | 171.3 (2) | O4—C9—C8 | 126.2 (4) |
C2—Re1—N2 | 98.3 (2) | N3—C10—O4 | 111.8 (4) |
C1—Re1—N1 | 92.7 (2) | N3—C10—C11 | 127.4 (5) |
C3—Re1—N1 | 98.1 (3) | O4—C10—C11 | 120.8 (4) |
C2—Re1—N1 | 171.9 (2) | C12—C11—C16 | 120.5 (5) |
N2—Re1—N1 | 73.71 (17) | C12—C11—C10 | 120.3 (5) |
C1—Re1—Br1 | 178.2 (2) | C16—C11—C10 | 119.2 (4) |
C3—Re1—Br1 | 90.9 (2) | C13—C12—C11 | 118.6 (6) |
C2—Re1—Br1 | 92.2 (2) | C13—C12—H12 | 120.7 |
N2—Re1—Br1 | 85.55 (12) | C11—C12—H12 | 120.7 |
N1—Re1—Br1 | 86.19 (11) | C12—C13—C14 | 121.0 (6) |
C9—O4—C10 | 103.8 (4) | C12—C13—H13 | 119.5 |
C4—N1—C8 | 116.3 (5) | C14—C13—H13 | 119.5 |
C4—N1—Re1 | 126.4 (4) | C15—C14—C13 | 120.0 (6) |
C8—N1—Re1 | 117.2 (3) | C15—C14—H14 | 120.0 |
C9—N2—N3 | 108.7 (4) | C13—C14—H14 | 120.0 |
C9—N2—Re1 | 115.3 (3) | C14—C15—C16 | 120.3 (6) |
N3—N2—Re1 | 135.9 (3) | C14—C15—H15 | 119.9 |
C10—N3—N2 | 104.5 (4) | C16—C15—H15 | 119.9 |
O1—C1—Re1 | 174.8 (6) | C15—C16—C11 | 119.6 (5) |
O2—C2—Re1 | 177.5 (7) | C15—C16—H16 | 120.2 |
O3—C3—Re1 | 177.4 (7) | C11—C16—H16 | 120.2 |
N1—C4—C5 | 123.9 (5) | Cl1—C17—Cl2 | 112.2 (9) |
N1—C4—H4 | 118.0 | Cl1—C17—H17A | 109.2 |
C5—C4—H4 | 118.0 | Cl2—C17—H17A | 109.2 |
C4—C5—C6 | 118.7 (6) | Cl1—C17—H17B | 109.2 |
C4—C5—H5 | 120.6 | Cl2—C17—H17B | 109.2 |
C6—C5—H5 | 120.6 | H17A—C17—H17B | 107.9 |
C7—C6—C5 | 119.1 (5) | Cl1'—C17'—Cl2' | 123 (5) |
C7—C6—H6 | 120.5 | Cl1'—C17'—H17C | 106.7 |
C5—C6—H6 | 120.5 | Cl2'—C17'—H17C | 106.7 |
C8—C7—C6 | 117.4 (5) | Cl1'—C17'—H17D | 106.7 |
C8—C7—H7 | 121.3 | Cl2'—C17'—H17D | 106.7 |
C6—C7—H7 | 121.3 | H17C—C17'—H17D | 106.6 |
N1—C8—C7 | 124.4 (5) | ||
C1—Re1—N1—C4 | −81.4 (5) | C8—N1—C4—C5 | −0.4 (8) |
C3—Re1—N1—C4 | 6.9 (5) | Re1—N1—C4—C5 | 176.1 (4) |
C2—Re1—N1—C4 | 176.2 (15) | N1—C4—C5—C6 | 1.9 (10) |
N2—Re1—N1—C4 | −176.3 (5) | C4—C5—C6—C7 | −0.5 (10) |
Br1—Re1—N1—C4 | 97.2 (4) | C5—C6—C7—C8 | −2.2 (10) |
C1—Re1—N1—C8 | 95.2 (4) | C4—N1—C8—C7 | −2.6 (8) |
C3—Re1—N1—C8 | −176.6 (4) | Re1—N1—C8—C7 | −179.5 (4) |
C2—Re1—N1—C8 | −7.3 (18) | C4—N1—C8—C9 | 177.6 (5) |
N2—Re1—N1—C8 | 0.2 (3) | Re1—N1—C8—C9 | 0.7 (6) |
Br1—Re1—N1—C8 | −86.3 (4) | C6—C7—C8—N1 | 3.9 (9) |
C1—Re1—N2—C9 | −92.4 (4) | C6—C7—C8—C9 | −176.3 (6) |
C3—Re1—N2—C9 | 20.2 (18) | N3—N2—C9—O4 | −1.1 (6) |
C2—Re1—N2—C9 | 177.7 (4) | Re1—N2—C9—O4 | −179.6 (3) |
N1—Re1—N2—C9 | −1.2 (4) | N3—N2—C9—C8 | −179.4 (5) |
Br1—Re1—N2—C9 | 86.1 (4) | Re1—N2—C9—C8 | 2.2 (7) |
C1—Re1—N2—N3 | 89.7 (5) | C10—O4—C9—N2 | 1.0 (6) |
C3—Re1—N2—N3 | −157.6 (15) | C10—O4—C9—C8 | 179.2 (5) |
C2—Re1—N2—N3 | −0.2 (6) | N1—C8—C9—N2 | −1.9 (8) |
N1—Re1—N2—N3 | −179.1 (5) | C7—C8—C9—N2 | 178.3 (5) |
Br1—Re1—N2—N3 | −91.8 (5) | N1—C8—C9—O4 | −179.9 (4) |
C9—N2—N3—C10 | 0.8 (6) | C7—C8—C9—O4 | 0.3 (9) |
Re1—N2—N3—C10 | 178.7 (4) | N2—N3—C10—O4 | −0.1 (6) |
C3—Re1—C1—O1 | 0 (7) | N2—N3—C10—C11 | −179.4 (5) |
C2—Re1—C1—O1 | −90 (7) | C9—O4—C10—N3 | −0.5 (6) |
N2—Re1—C1—O1 | 172 (7) | C9—O4—C10—C11 | 178.8 (5) |
N1—Re1—C1—O1 | 98 (7) | N3—C10—C11—C12 | −173.4 (6) |
Br1—Re1—C1—O1 | 47 (11) | O4—C10—C11—C12 | 7.4 (8) |
C1—Re1—C2—O2 | 47 (14) | N3—C10—C11—C16 | 6.4 (8) |
C3—Re1—C2—O2 | −41 (14) | O4—C10—C11—C16 | −172.8 (5) |
N2—Re1—C2—O2 | 142 (14) | C16—C11—C12—C13 | −0.1 (9) |
N1—Re1—C2—O2 | 150 (13) | C10—C11—C12—C13 | 179.6 (6) |
Br1—Re1—C2—O2 | −132 (14) | C11—C12—C13—C14 | 0.9 (10) |
C1—Re1—C3—O3 | −103 (14) | C12—C13—C14—C15 | −0.5 (11) |
C2—Re1—C3—O3 | −13 (14) | C13—C14—C15—C16 | −0.7 (10) |
N2—Re1—C3—O3 | 144 (13) | C14—C15—C16—C11 | 1.5 (9) |
N1—Re1—C3—O3 | 165 (14) | C12—C11—C16—C15 | −1.1 (8) |
Br1—Re1—C3—O3 | 79 (14) | C10—C11—C16—C15 | 179.1 (5) |
Experimental details
Crystal data | |
Chemical formula | [ReBr(C13H9N3O)(CO)3]·CH2Cl2 |
Mr | 658.30 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.492 (3), 19.513 (4), 16.835 (3) |
β (°) | 99.45 (3) |
V (Å3) | 4047.9 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 8.27 |
Crystal size (mm) | 0.20 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.229, 0.409 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19615, 4631, 3992 |
Rint | 0.104 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.107, 1.07 |
No. of reflections | 4631 |
No. of parameters | 276 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.88, −1.44 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Re1—C1 | 1.884 (7) | Re1—N2 | 2.173 (4) |
Re1—C3 | 1.893 (7) | Re1—N1 | 2.228 (4) |
Re1—C2 | 1.920 (7) | Re1—Br1 | 2.6228 (11) |
Acknowledgements
This work was supported by the Zhejiang A & F University Science Foundation (2009FR068).
References
Bernhard, S., Gao, X., Malliaras, G. G. & Abruna, H. D. (2002). Adv. Mater. 14, 433–436. Web of Science CrossRef CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Demko, Z.-P. & Sharpless, K.-B. (2001). J. Org. Chem. 66, 7945–7950. Web of Science CrossRef PubMed CAS Google Scholar
Gong, X., Ng, P.-K. & Chan, W.-K. (1998). Adv. Mater. 10, 1337–1340. CrossRef CAS Google Scholar
Kim, T.-H., Lee, H.-K., Park, O., Chin, B.-D., Lee, S.-H. & Kim, J.-K. (2006). Adv. Funct. Mater. 16, 611–617. Web of Science CrossRef CAS Google Scholar
Lee, S. K., Hwang, D.-H., Jung, B.-J., Cho, N. S., Lee, J., Lee, J.-D. & Shim, H.-K. (2005). Adv. Funct. Mater. 15, 1647–1655. Web of Science CrossRef CAS Google Scholar
Li, Y., Liu, Y., Guo, J., Wu, F., Tian, W., Li, B. & Wang, Y. (2001). Synth. Met. 118, 175–179. Web of Science CrossRef CAS Google Scholar
Li, J., Liu, D., Li, Y., Lee, C.-S., Kwong, H.-L. & Lee, S. (2005). Chem. Mater. 17, 1208–1212. Web of Science CrossRef CAS Google Scholar
Rajendran, T., Manimaran, B., Lee, F.-Y., Lee, G.-H., Peng, S.-M., Wang, C.-C. & Lu, K.-L. (2000). Inorg. Chem. 39, 2016–2017. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wong, K.-T., Chen, Y.-M., Lin, Y.-T., Su, H.-C. & Wu, C.-C. (2005). Org. Lett. 7, 5361–5364. Web of Science CrossRef PubMed CAS Google Scholar
Zhang, L.-M., Li, B. & Su, Z.-M. (2009). Langmuir, 25, 2068–2074. Web of Science CrossRef PubMed Google Scholar
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.
![Open Access](/logos/open.png)
Interest in next generation displays and lighting technologies has stimulated research on organic light-emitting materials (Li et al., 2005; Wong et al., 2005), especially phosphorescent materials (Kim et al., 2006; Lee et al., 2005). As a result, transition metal phosphorescent complexes (Bernhard et al., 2002) have been studied intensively throughout the world. In order to further explore novel phosphorescent materials, several researchers paid attention to ReI complexes (Gong et al., 1998; Li et al., 2001), of which the d6 electronic configuration is identical to that of the corresponding Os(II) and Ir(III) systems. Therefore, it is pressing to explore new ReI complexes served as luminescent materials. In this article, we report the successful synthesis of a novel ReI complex which contains the oxadiazole ligand of 2-phenyl-5-(pyridin-2-yl)-1,3,4-oxadiazole, and characterized its structure by single-crystal X-ray diffraction analysis. Its luminescent property will be further studied in the coming research.
The structure of complex [Re(CO)3(L)Br].CH2Cl2, is shown in Figure 1. One molecule of solvent dichloromethane is present in the asymmetric unit. This was refined as disordered over two positions, with occupancies of 0.81 (15):0.19 (15).. The coordination geometry at the Re atom is a distorted octahedron with the three CO ligands arranged in a fac-fashion. The distances of C(1), C(2), and C(3) to Re(1) are 1.884 (7), 1.920 (7), and 1.893 (7)Å, respectively, and the Re—N bonds distances are 2.228 (4) and 2.173 (4)Å. The CO ligands are linearly coordinated for the bond angles of O—C—Re are 174.8 (6), 177.5 (7) and 177.4 (7)°, respectively, which are close to 180°. Furthermore, the bond angles between adjacent CO carbon atoms are 87.9 (3), 89.1 (3) and 89.8 (3)°, respectively, which are close to 90°, but the bond angle between the coordinated nitrogen atoms of ligand is 73.71 (17)°, which is much less than 90°. All other bond distances and angles are comparable to those found for the related ReI complexes (Rajendran et al., 2000).
Furthermore, a kind of inter-molecular face-to-face stacking present in the molecular structure of [Re(CO)3(L)Br].CH2Cl2: the 1,3,4-oxadiazole moiety in one molecule is almost parallel to the other one from another complex , and the approximate distance between the two closest atoms (N2—N3) is only 3.376°. Thus a bonded dual-molecule structure is constructed in the complex molecule which is believed a rigid one and will prevent geometric relaxation effectively (Zhang et al., 2009). Such rigid structure is promised possessing excellent luminescent properties.