metal-organic compounds
Dibromido(N-phenylbenzamidine-κN′)tin(II)
aInstitute of Applied Chemistry, Shanxi University, Taiyuan 030006, People's Republic of China
*Correspondence e-mail: 1103148896@qq.com
The 2(C13H12N2)], contains an amidine ligand and tin(II) bromide moiety. In the amidine ligand, the phenyl rings present a head-to-tail configuration mode. The tin atom is coordinated by the terminal N atom of the amidine ligand, and the two Br atoms extend to both sides of the Sn atom in a V-shape. The phenyl rings are twisted from the mean N/C/N plane by 26.14 (18) and 79.50 (8)°. The features N—H⋯Br hydrogen bonds.
of the title compound, [SnBrKeywords: crystal structure; stannous bromide; amidinate.
CCDC reference: 1534782
Structure description
The representative amidinate ligand [RC(NR)2]− is four-electron monoanionic and has a typical conjugated N—C—N construction, through which the negative charge is able to be delocalized so as to form chelating surroundings (Bai et al., 2010). Based on this backbone, amidinates have been widely ligated to transition metals (Edelmann, 1994), particularly the group 14 metallylenes tin(II). Tin(II) amidinates belong to the family of complexes bearing so-called spectator ligands which are commonly used for fine-tuning of the electronic as well as coordination properties of the metal atom (Chlupatý et al., 2015). Interesting features in the title compound arise from the highly in the of caprolactone and aryl isocyanates to perhydro-1,3,5-triazine-2,4,6-triones (isocyanurates) in a living fashion, under mild conditions. As part of our studies in this area, the title compound (Fig. 1) was prepared in a novel manner (reaction in Schlenk bottle by PhNH2, nBuLi, SiMe2Cl2, PhCN, SnCl2 and Br2) and we have determined its The compound is closely similar to the benzamidine with an o-tolyl substituent on the N atom, namely N2-o-tolylbenzamidine (Zhang et al., 2008), which has no stannous bromine moiety attached.
The 2(C13H12N2)], contains an amidine ligand and tin(II) bromide. In the amidine ligand, the phenyl rings exhibit a head-to-tail configuration mode. The tin atom is coordinated by the terminal N atom of the amidine ligand, and the two Br atoms extend to both sides of Sn in a V-shape (Fig. 1). The outward expansion configuration of the two bromine atoms is due to the large of the nearby substituents. The C2–C7 and C8–C13 phenyl rings are twisted from the N1/C1/N2 mean plane by 26.14 (18) and 79.50 (8)°, respectively. The two N atoms connect the central C atom with bond lengths of 1.315 (5) and 1.324 (5) Å, while the Sn—N bond length is 2.176 (3) and the Sn—Br bond lengths are 2.6286 (6) and 2.6313 (6) Å.
of the title compound, [SnBrIn the crystal, the molecules are linked into chains along [100] by N—H⋯Br hydrogen bonds (Fig. 2, Table 1).
Synthesis and crystallization
The title compound was prepared by a reaction of aniline, nBuLi, SiMe2Cl2, PhCN, SnCl2 and Br2. To a solution of aniline (2.328 g, 5 mmol) in diethyl ether (30 ml) were added nBuLi (2 ml, 2.5 M, 5 mmol) at 273 K and 0.5 equiv. of dimethyl dichlorosilane (0.3 ml, 2.5 mmol) 3 h later; the solution was stirred overnight and filtered to remove the white LiCl precipitate. nBuLi (2 ml, 2.5 M, 5 mmol) was added again, then PhCN (0.5 ml, 5 mmol) was added by syringe in drops 4 h later. After stirring overnight, SnCl2 (0.474 g, 2.5 mmol) was added at 273 K and the solution was stirred for 12 h. Then the solvent was removed under vacuum followed by extraction with dichloromethane and filtration to remove the white LiCl precipitate. To the filtrate was added Br2 (0.13 ml, 2.52 mmol) and the solution was concentrated in vacuo to ca 15 ml about 24 h later. Colorless crystals (0.151 g, 76% yield) were obtained in toluene.
1H NMR (300 MHz, CDCl3): δ 6.59–7.68 (m, 11H; phenyl, C=N), 11.04 (s, 1H, C—N). 13C NMR(75 MHz, CDCl3): δ 122.03, 124.32, 124.68, 127.68, 128.21, 128.67, 130.08 (phenyls), Elemental analysis (calculated %) for C13H12Br2N2Sn: C, 30.81; H, 2.45; N, 6.09%. Found: C, 31.89; H, 2.55; N, 5.90%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1534782
https://doi.org/10.1107/S2414314617003169/zq4017sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003169/zq4017Isup2.hkl
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).[SnBr2(C13H12N2)] | Z = 2 |
Mr = 474.76 | F(000) = 448 |
Triclinic, P1 | Dx = 2.157 Mg m−3 |
a = 8.0315 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7147 (14) Å | Cell parameters from 5984 reflections |
c = 10.7577 (15) Å | θ = 2.9–28.3° |
α = 111.205 (4)° | µ = 7.20 mm−1 |
β = 90.226 (5)° | T = 200 K |
γ = 109.381 (4)° | Block, colorless |
V = 730.81 (18) Å3 | 0.06 × 0.06 × 0.05 mm |
Bruker SMART area-detector diffractometer | 2278 reflections with I > 2σ(I) |
φ and ω scan | Rint = 0.023 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25.0°, θmin = 2.9° |
Tmin = 0.672, Tmax = 0.715 | h = −9→9 |
7880 measured reflections | k = −11→10 |
2558 independent reflections | l = −12→12 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0169P)2 + 1.8927P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.055 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.64 e Å−3 |
2558 reflections | Δρmin = −0.57 e Å−3 |
164 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0035 (4) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.48568 (3) | 0.62191 (3) | 0.83884 (3) | 0.02458 (11) | |
Br1 | 0.26091 (5) | 0.38582 (5) | 0.88757 (5) | 0.03684 (14) | |
Br2 | 0.28771 (6) | 0.53282 (5) | 0.60875 (4) | 0.03595 (13) | |
N1 | 0.6254 (4) | 0.4638 (4) | 0.7385 (3) | 0.0280 (8) | |
H1 | 0.5592 | 0.3670 | 0.6847 | 0.034* | |
N2 | 0.8777 (4) | 0.3932 (4) | 0.7203 (4) | 0.0335 (8) | |
H2 | 0.9950 | 0.4287 | 0.7302 | 0.040* | |
C1 | 0.7990 (5) | 0.4990 (5) | 0.7505 (4) | 0.0272 (9) | |
C2 | 0.9223 (5) | 0.6672 (5) | 0.7996 (4) | 0.0259 (9) | |
C3 | 0.8896 (6) | 0.7654 (5) | 0.7439 (4) | 0.0314 (9) | |
H3 | 0.7885 | 0.7267 | 0.6781 | 0.038* | |
C4 | 1.0049 (6) | 0.9195 (5) | 0.7847 (4) | 0.0347 (10) | |
H4 | 0.9844 | 0.9870 | 0.7457 | 0.042* | |
C5 | 1.1505 (6) | 0.9767 (5) | 0.8821 (4) | 0.0337 (10) | |
H5 | 1.2298 | 1.0832 | 0.9096 | 0.040* | |
C6 | 1.1808 (5) | 0.8802 (5) | 0.9391 (4) | 0.0337 (10) | |
H6 | 1.2801 | 0.9206 | 1.0069 | 0.040* | |
C7 | 1.0680 (5) | 0.7248 (5) | 0.8987 (4) | 0.0294 (9) | |
H7 | 1.0893 | 0.6579 | 0.9380 | 0.035* | |
C8 | 0.7869 (5) | 0.2245 (5) | 0.6727 (4) | 0.0293 (9) | |
C9 | 0.8323 (6) | 0.1320 (5) | 0.5586 (5) | 0.0378 (11) | |
H9 | 0.9193 | 0.1796 | 0.5124 | 0.045* | |
C10 | 0.7519 (6) | −0.0305 (5) | 0.5106 (5) | 0.0396 (11) | |
H10 | 0.7858 | −0.0942 | 0.4324 | 0.048* | |
C11 | 0.6239 (6) | −0.1008 (5) | 0.5743 (5) | 0.0368 (11) | |
H11 | 0.5689 | −0.2126 | 0.5406 | 0.044* | |
C12 | 0.5753 (6) | −0.0076 (6) | 0.6882 (5) | 0.0415 (11) | |
H12 | 0.4847 | −0.0556 | 0.7318 | 0.050* | |
C13 | 0.6583 (6) | 0.1562 (5) | 0.7394 (5) | 0.0386 (11) | |
H13 | 0.6271 | 0.2202 | 0.8190 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02065 (15) | 0.02166 (15) | 0.02717 (17) | 0.00595 (11) | 0.00258 (11) | 0.00613 (12) |
Br1 | 0.0261 (2) | 0.0444 (3) | 0.0472 (3) | 0.00800 (19) | 0.00491 (19) | 0.0299 (2) |
Br2 | 0.0282 (2) | 0.0485 (3) | 0.0305 (3) | 0.0105 (2) | 0.00397 (18) | 0.0173 (2) |
N1 | 0.0163 (16) | 0.0294 (18) | 0.033 (2) | 0.0086 (14) | −0.0015 (14) | 0.0061 (15) |
N2 | 0.0177 (17) | 0.0324 (19) | 0.050 (2) | 0.0091 (15) | 0.0042 (15) | 0.0151 (17) |
C1 | 0.029 (2) | 0.030 (2) | 0.022 (2) | 0.0103 (17) | 0.0048 (17) | 0.0093 (17) |
C2 | 0.0183 (19) | 0.026 (2) | 0.025 (2) | 0.0056 (16) | 0.0083 (16) | 0.0036 (17) |
C3 | 0.028 (2) | 0.037 (2) | 0.026 (2) | 0.0080 (18) | 0.0033 (17) | 0.0114 (19) |
C4 | 0.045 (3) | 0.031 (2) | 0.030 (2) | 0.013 (2) | 0.007 (2) | 0.0142 (19) |
C5 | 0.031 (2) | 0.025 (2) | 0.035 (3) | 0.0023 (18) | 0.0034 (19) | 0.0075 (19) |
C6 | 0.023 (2) | 0.032 (2) | 0.034 (2) | 0.0039 (18) | −0.0029 (18) | 0.0048 (19) |
C7 | 0.025 (2) | 0.030 (2) | 0.038 (3) | 0.0141 (17) | 0.0087 (18) | 0.0144 (19) |
C8 | 0.028 (2) | 0.026 (2) | 0.034 (2) | 0.0109 (17) | −0.0025 (18) | 0.0104 (18) |
C9 | 0.030 (2) | 0.039 (2) | 0.046 (3) | 0.013 (2) | 0.007 (2) | 0.017 (2) |
C10 | 0.040 (3) | 0.030 (2) | 0.043 (3) | 0.017 (2) | 0.004 (2) | 0.004 (2) |
C11 | 0.035 (2) | 0.026 (2) | 0.043 (3) | 0.0060 (19) | −0.011 (2) | 0.011 (2) |
C12 | 0.037 (3) | 0.046 (3) | 0.049 (3) | 0.011 (2) | 0.004 (2) | 0.030 (2) |
C13 | 0.044 (3) | 0.039 (3) | 0.037 (3) | 0.020 (2) | 0.008 (2) | 0.015 (2) |
Sn1—N1 | 2.176 (3) | C5—H5 | 0.9500 |
Sn1—Br2 | 2.6286 (6) | C6—C7 | 1.380 (6) |
Sn1—Br1 | 2.6313 (6) | C6—H6 | 0.9500 |
N1—C1 | 1.315 (5) | C7—H7 | 0.9500 |
N1—H1 | 0.8800 | C8—C9 | 1.367 (6) |
N2—C1 | 1.324 (5) | C8—C13 | 1.385 (6) |
N2—C8 | 1.441 (5) | C9—C10 | 1.381 (6) |
N2—H2 | 0.8800 | C9—H9 | 0.9500 |
C1—C2 | 1.492 (5) | C10—C11 | 1.368 (7) |
C2—C3 | 1.384 (6) | C10—H10 | 0.9500 |
C2—C7 | 1.394 (6) | C11—C12 | 1.381 (7) |
C3—C4 | 1.376 (6) | C11—H11 | 0.9500 |
C3—H3 | 0.9500 | C12—C13 | 1.392 (6) |
C4—C5 | 1.383 (6) | C12—H12 | 0.9500 |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
C5—C6 | 1.371 (6) | ||
N1—Sn1—Br2 | 89.80 (9) | C5—C6—C7 | 120.5 (4) |
N1—Sn1—Br1 | 87.49 (9) | C5—C6—H6 | 119.8 |
Br2—Sn1—Br1 | 90.618 (18) | C7—C6—H6 | 119.8 |
C1—N1—Sn1 | 126.3 (3) | C6—C7—C2 | 119.1 (4) |
C1—N1—H1 | 116.8 | C6—C7—H7 | 120.4 |
Sn1—N1—H1 | 116.8 | C2—C7—H7 | 120.4 |
C1—N2—C8 | 125.3 (3) | C9—C8—C13 | 120.3 (4) |
C1—N2—H2 | 117.4 | C9—C8—N2 | 117.8 (4) |
C8—N2—H2 | 117.4 | C13—C8—N2 | 121.9 (4) |
N1—C1—N2 | 124.3 (4) | C8—C9—C10 | 120.0 (4) |
N1—C1—C2 | 120.4 (4) | C8—C9—H9 | 120.0 |
N2—C1—C2 | 115.2 (3) | C10—C9—H9 | 120.0 |
C3—C2—C7 | 120.4 (4) | C11—C10—C9 | 120.8 (4) |
C3—C2—C1 | 118.5 (4) | C11—C10—H10 | 119.6 |
C7—C2—C1 | 121.1 (4) | C9—C10—H10 | 119.6 |
C4—C3—C2 | 119.4 (4) | C10—C11—C12 | 119.4 (4) |
C4—C3—H3 | 120.3 | C10—C11—H11 | 120.3 |
C2—C3—H3 | 120.3 | C12—C11—H11 | 120.3 |
C3—C4—C5 | 120.4 (4) | C11—C12—C13 | 120.4 (4) |
C3—C4—H4 | 119.8 | C11—C12—H12 | 119.8 |
C5—C4—H4 | 119.8 | C13—C12—H12 | 119.8 |
C6—C5—C4 | 120.2 (4) | C8—C13—C12 | 119.1 (4) |
C6—C5—H5 | 119.9 | C8—C13—H13 | 120.4 |
C4—C5—H5 | 119.9 | C12—C13—H13 | 120.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Br1i | 0.88 | 2.95 | 3.593 (4) | 132 |
N2—H2···Br2i | 0.88 | 2.77 | 3.517 (3) | 144 |
Symmetry code: (i) x+1, y, z. |
Funding information
Funding for this research was provided by: National Natural Science Foundation of Chinahttps://doi.org/10.13039/501100001809 (award No. 20702029); Natural Science Foundation of Shanxi Provincehttps://doi.org/10.13039/501100004480 (award No. 2008011024).
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