metal-organic compounds
Butyltrichlorido{2-[(diisopropylammonio)methyl]phenyl}tin(IV) dichloromethane monosolvate
aFaculty of Chemistry and Chemical Engineering, Babes-Bolyai University, 11 Arany Janos St, RO-400028, Cluj Napoca, Romania
*Correspondence e-mail: adinar@chem.ubbcluj.ro
The title compound, [Sn(C4H9)(C13H21N)Cl3]·CH2Cl2, was obtained by recrystallization of [2-(diisopropylaminomethyl)phenyl]tin(IV) butyl dichloride from a CH2Cl2/n-hexane mixture (1:4 v/v) in the presence of ambient moisture. Partial hydrolysis led to the title compound, the hydrochloric acid adduct of the dichloride, having a pentacoordinated Sn atom with a trigonal–bipyramidal C2SnCl3 core. The N atom of the 2-[(diisopropylammonio)methyl]phenyl ligand forms a strong intramolecular N—H⋯Cl hydrogen bond, resulting in a zwitterionic species, [2-(iPr2HN+CH2)C6H4]SnBuCl3−·CH2Cl2. Disorder was found in the n-butyl group, which was refined as disordered over three positions, with site occupancies of 0.22 (1), 0.51 (1) and 0.27 (2).
Related literature
For related tin(IV) compounds, see: Varga et al. (2001, 2005, 2006); Varga & Silvestru (2007); Rotar et al. (2007, 2009); Rotar, Schuermann et al. (2008); Rotar, Varga & Silvestru (2008); Švec et al. (2010).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Bruker, 2000); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536810050713/zl2332sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050713/zl2332Isup2.hkl
A solution of BuLi in hexane (10.5 ml, 1.6M, 20% excess) was added dropwise to a stirred solution of 2-(N,N-diisopropylaminomethyl)benzene bromide (3.7 g, 13.7 mmol) in 100 ml of anhydrous hexane at room temperature under argon using Schlenk techniques. The reaction mixture was refluxed under stirring for four hours and then allowed to reach room temperature. The obtained liquid product was added dropwise under stirring to a cooled (195 K, -78°C) solution of BuSnCl3 (1.8 ml, 11 mmol) in 50 ml of anhydrous hexane. After the organolithiun compound was added, the reaction mixture was stirred for 1 h at 195 K (-78°C), then overnight to reach room temperature. The solvent was removed in vacuo. The oily residue was recrystallized from CH2Cl2/n-hexane, in presence of air moisture, resulting in the isolation of [2-(iPr2HN+CH2)C6H4]SnBuCl3–. CH2Cl2 (1.67 g, 32.9%).
1H NMR (300 MHz, CDCl3, 293.5K): 0.98 t (3H, SnCH2CH2CH2CH3, 3JHH = 7.3 Hz), 1.28 d (6HA, NCH(CH3)2, 3JHH = 6.7 Hz), 1.47 d (6HB, NCH(CH3)2, 3JHH = 6.8 Hz), 1.52 s (2H, SnCH2CH2CH2CH3, 3JHH = 7.4 Hz), 2.01 quin (2H, SnCH2CH2CH2CH3, 3JHH = 8.2 Hz), 2.23 t (2H, SnCH2CH2CH2CH3, 3JHH = 8.1, 2JSnH = 81.4 Hz), 3.50 H (2H, NCH(CH3)2, 3JHH = 6.5 Hz), 3.96 d (2H, –CH2–, 3JHH = 4.3 Hz), 7.49m (2H, H4,5, C6H4), 7.65m (1H, H3, C6H4), 7.71m (1H, H6, C6H4), 9.22 s,br (1H, NH).
13C NMR (75.4 MHz, CDCl3, 293.5K): 13.68 s (SnCH2CH2CH2CH3, 4JSnC = 7.8 Hz), 18.73 s (NCH(CH3)2 [B]), 19.11 s (NCH(CH3)2 [A]), 25.95 s (SnCH2CH2CH2CH3, 3JSnC = 130.6 Hz), 27.47 s (SnCH2CH2CH2CH3, 2JSnC = 51.1 Hz), 37.40 s,br (SnCH2CH2CH2CH3), 51.07 s (-CH2–), 52.90 s (NCH(CH3)2), 129.71 s (C5, C6H4, 3JSnC 51.1 = Hz), 129.86 s (C4, C6H4, 4JSnC = 16.3 Hz), 132.15 s (C1, C6H4), 134.77 s (C3, C6H4, 3JSnC = 61.8 Hz), 136.11 s (C6, C6H4, 2JSnC = 80.1 Hz), 154.98 s (C2, C6H4).
All hydrogen atoms were placed in calculated positions using a riding model, with C—H = 0.93–0.98 Å and with Uiso= 1.2 or 1.5Ueq (C) for H. The methyl groups were allowed to rotate but not to tip. The H1 atom bonded to N1 was found in a difference map and refined with a restrained N—H distance of 0.86 (1) Å.
The n-butyl group was found to be severly disordered. Attempts to refine the chain as disordered over two moieties (with appropriate distance restraints for the C—C bonds) did not give satisfactory results with ADPs of neighboring atoms being icompatible even after application of severe restraints for the thermal ellipsoids. Disorder over three moieties allowed to avoid these problems. In the final
the butyl chain was refined as disordered over three sites with equivalent bonds from the disordered components restrained to have similar lengths length. The same Uij parameters were used for atom C14/C14B/C14C, C15/C15B/C15C, C16/C16B/C16C and C17/C17B/C17C, leading to refined site occupancies of 0.21 (1):0.51 (2):0.27 (2).During our work on hypercoordinated organotin(IV) compounds with [2-(R2NCH2)C6H4]Sn fragments (Varga et al., 2001, 2005, 2006, Rotar et al., 2007, 2008, 2009) the title compound was isolated.
In an attempt to obtain single-crystals of the dichloride [2-(iPr2NCH2)C6H4]SnBuCl2 (1), recrystallization from a CH2Cl2/n-hexane mixture (1:4) in the presence of air afforded the HCl adduct 1.HCl.CH2Cl2. The nitrogen atom of the LCN ligand [LCN = 2-(diisopropylaminomethyl)phenyl] is protonated and a new Sn—Cl bond is simultaneously formed, thus leading to the formation of a zwitterionic species, [2-(iPr2HN+CH2)C6H4]SnBuCl3–.CH2Cl2. The presence of the HCl is probably due to partial hydrolysis of the diorganotin(IV) dihalide in the presence of ambient moisture from air.
The central tin atom is pentacoordinated with a distorted trigonal bipyramidal geometry (Fig. 1). The axial positions are occupied by two chlorine atoms [Cl1—Sn1—Cl2 = 178.50 (7)°], while the two carbon atoms from the two organic groups and a chlorine atom are placed in equatorial positions. The angles in the equatorial C2SnCl system are situated in the range between 97.4 (13) and 145.8 (14) °, showing a strong deviation from the ideal value of 120°. The Cl2 atom forms a strong intramolecular hydrogen bond with H1 from the nitrogen atom [Cl2···H1 = 2.37 (7) Å].
Disorder was found in the n-butyl group. This was resolved over three positions with the components of the disorder having site a occupancy ratio of 0.21 (1):0.51 (2):0.27 (2) (see
section; Fig. 2).For related tin(IV) compounds, see: Varga et al. (2001, 2005, 2006, 2007); Rotar et al. (2007, 2009); Rotar, Schuermann et al. (2008); Rotar, Varga & Silvestru (2008); Švec et al. (2010).
Data collection: SMART (Bruker, 2000); cell
SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Sn(C4H9)(C13H21N)Cl3]·CH2Cl2 | Z = 2 |
Mr = 558.39 | F(000) = 564 |
Triclinic, P1 | Dx = 1.468 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.654 (8) Å | Cell parameters from 1665 reflections |
b = 11.093 (9) Å | θ = 2.4–20.1° |
c = 12.406 (10) Å | µ = 1.54 mm−1 |
α = 115.594 (13)° | T = 297 K |
β = 100.767 (15)° | Block, colourless |
γ = 97.176 (15)° | 0.45 × 0.20 × 0.18 mm |
V = 1263.5 (17) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 4416 independent reflections |
Radiation source: fine-focus sealed tube | 3122 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
phi and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (Bruker, 2000) | h = −12→12 |
Tmin = 0.544, Tmax = 0.769 | k = −13→13 |
9126 measured reflections | l = −14→14 |
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)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.213 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1038P)2 + 0.0754P] where P = (Fo2 + 2Fc2)/3 |
4416 reflections | (Δ/σ)max = 0.008 |
257 parameters | Δρmax = 1.43 e Å−3 |
40 restraints | Δρmin = −0.73 e Å−3 |
[Sn(C4H9)(C13H21N)Cl3]·CH2Cl2 | γ = 97.176 (15)° |
Mr = 558.39 | V = 1263.5 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.654 (8) Å | Mo Kα radiation |
b = 11.093 (9) Å | µ = 1.54 mm−1 |
c = 12.406 (10) Å | T = 297 K |
α = 115.594 (13)° | 0.45 × 0.20 × 0.18 mm |
β = 100.767 (15)° |
Bruker SMART APEX CCD area-detector diffractometer | 4416 independent reflections |
Absorption correction: multi-scan (Bruker, 2000) | 3122 reflections with I > 2σ(I) |
Tmin = 0.544, Tmax = 0.769 | Rint = 0.074 |
9126 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 40 restraints |
wR(F2) = 0.213 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 1.43 e Å−3 |
4416 reflections | Δρmin = −0.73 e Å−3 |
257 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) | |
C1 | 0.4960 (8) | 0.7632 (8) | 0.8171 (7) | 0.0490 (19) | |
C2 | 0.4078 (8) | 0.8089 (8) | 0.8876 (7) | 0.052 (2) | |
C3 | 0.4102 (10) | 0.7820 (10) | 0.9900 (7) | 0.068 (3) | |
H3 | 0.3545 | 0.8145 | 1.0401 | 0.082* | |
C4 | 0.4950 (11) | 0.7076 (11) | 1.0147 (9) | 0.079 (3) | |
H4 | 0.4942 | 0.6882 | 1.0804 | 0.095* | |
C5 | 0.5813 (11) | 0.6613 (11) | 0.9442 (10) | 0.080 (3) | |
H5 | 0.6392 | 0.6124 | 0.9626 | 0.096* | |
C6 | 0.5798 (10) | 0.6891 (10) | 0.8458 (9) | 0.070 (3) | |
H6 | 0.6369 | 0.6570 | 0.7973 | 0.084* | |
C7 | 0.3141 (8) | 0.8942 (8) | 0.8704 (7) | 0.054 (2) | |
H7A | 0.3545 | 0.9547 | 0.8424 | 0.065* | |
H7B | 0.2999 | 0.9514 | 0.9501 | 0.065* | |
C8 | 0.1153 (9) | 0.6964 (9) | 0.7985 (8) | 0.061 (2) | |
H8 | 0.1822 | 0.6500 | 0.8175 | 0.073* | |
C9 | 0.0569 (11) | 0.7551 (12) | 0.9098 (10) | 0.093 (3) | |
H9A | 0.1267 | 0.8024 | 0.9852 | 0.139* | |
H9B | 0.0012 | 0.6814 | 0.9118 | 0.139* | |
H9C | 0.0064 | 0.8181 | 0.9019 | 0.139* | |
C10 | 0.0112 (9) | 0.5909 (11) | 0.6802 (9) | 0.084 (3) | |
H10A | −0.0587 | 0.6325 | 0.6632 | 0.126* | |
H10B | −0.0232 | 0.5140 | 0.6910 | 0.126* | |
H10C | 0.0501 | 0.5602 | 0.6119 | 0.126* | |
C11 | 0.0904 (9) | 0.8991 (10) | 0.7562 (8) | 0.067 (2) | |
H11 | 0.0007 | 0.8537 | 0.7457 | 0.080* | |
C12 | 0.1211 (12) | 1.0427 (11) | 0.8664 (10) | 0.098 (4) | |
H12A | 0.1148 | 1.0351 | 0.9395 | 0.147* | |
H12B | 0.0593 | 1.0926 | 0.8498 | 0.147* | |
H12C | 0.2084 | 1.0905 | 0.8791 | 0.147* | |
C13 | 0.0929 (13) | 0.9059 (15) | 0.6384 (10) | 0.109 (4) | |
H13A | 0.0260 | 0.9499 | 0.6199 | 0.163* | |
H13B | 0.0769 | 0.8145 | 0.5716 | 0.163* | |
H13C | 0.1773 | 0.9575 | 0.6483 | 0.163* | |
C14 | 0.571 (6) | 0.712 (5) | 0.490 (3) | 0.065 (6) | 0.22 |
H14A | 0.5530 | 0.6136 | 0.4589 | 0.078* | 0.22 |
H14B | 0.5079 | 0.7296 | 0.4342 | 0.078* | 0.22 |
C15 | 0.702 (6) | 0.754 (8) | 0.477 (7) | 0.089 (8) | 0.22 |
H15A | 0.7620 | 0.7795 | 0.5565 | 0.107* | 0.22 |
H15B | 0.7010 | 0.8400 | 0.4735 | 0.107* | 0.22 |
C16 | 0.772 (6) | 0.681 (6) | 0.384 (5) | 0.124 (10) | 0.22 |
H16A | 0.8528 | 0.7432 | 0.3967 | 0.148* | 0.22 |
H16B | 0.7955 | 0.6044 | 0.3948 | 0.148* | 0.22 |
C17 | 0.686 (9) | 0.632 (10) | 0.258 (7) | 0.127 (10) | 0.22 |
H17A | 0.6103 | 0.6701 | 0.2635 | 0.191* | 0.22 |
H17B | 0.6587 | 0.5331 | 0.2181 | 0.191* | 0.22 |
H17C | 0.7333 | 0.6591 | 0.2105 | 0.191* | 0.22 |
C14B | 0.587 (10) | 0.664 (4) | 0.511 (7) | 0.065 (6) | 0.51 |
H14C | 0.6522 | 0.6240 | 0.5402 | 0.078* | 0.51 |
H14D | 0.5129 | 0.5900 | 0.4515 | 0.078* | 0.51 |
C15B | 0.644 (4) | 0.733 (3) | 0.446 (3) | 0.089 (8) | 0.51 |
H15C | 0.7198 | 0.8063 | 0.5038 | 0.107* | 0.51 |
H15D | 0.5797 | 0.7743 | 0.4161 | 0.107* | 0.51 |
C16B | 0.684 (4) | 0.634 (3) | 0.340 (4) | 0.124 (10) | 0.51 |
H16C | 0.7401 | 0.5852 | 0.3687 | 0.148* | 0.51 |
H16D | 0.6065 | 0.5662 | 0.2783 | 0.148* | 0.51 |
C17B | 0.755 (3) | 0.699 (4) | 0.280 (3) | 0.127 (10) | 0.51 |
H17D | 0.6927 | 0.7125 | 0.2216 | 0.191* | 0.51 |
H17E | 0.8077 | 0.6408 | 0.2368 | 0.191* | 0.51 |
H17F | 0.8104 | 0.7862 | 0.3418 | 0.191* | 0.51 |
C14C | 0.600 (19) | 0.687 (6) | 0.512 (13) | 0.065 (6) | 0.27 |
H14E | 0.6634 | 0.6401 | 0.5342 | 0.078* | 0.27 |
H14F | 0.5301 | 0.6190 | 0.4404 | 0.078* | 0.27 |
C15C | 0.663 (7) | 0.794 (6) | 0.486 (5) | 0.089 (8) | 0.27 |
H15E | 0.7464 | 0.8457 | 0.5474 | 0.107* | 0.27 |
H15F | 0.6072 | 0.8569 | 0.4877 | 0.107* | 0.27 |
C16C | 0.685 (6) | 0.724 (4) | 0.360 (5) | 0.124 (10) | 0.27 |
H16E | 0.6005 | 0.6957 | 0.3002 | 0.148* | 0.27 |
H16F | 0.7398 | 0.7924 | 0.3497 | 0.148* | 0.27 |
C17C | 0.744 (8) | 0.603 (6) | 0.324 (7) | 0.127 (10) | 0.27 |
H17G | 0.6755 | 0.5202 | 0.2812 | 0.191* | 0.27 |
H17H | 0.7975 | 0.6054 | 0.3965 | 0.191* | 0.27 |
H17I | 0.7974 | 0.6042 | 0.2696 | 0.191* | 0.27 |
C18 | 0.7688 (13) | 0.2311 (16) | 0.7029 (15) | 0.131 (6) | |
H18A | 0.7283 | 0.1506 | 0.7073 | 0.157* | |
H18B | 0.7266 | 0.2221 | 0.6226 | 0.157* | |
Cl1 | 0.75445 (19) | 0.9363 (2) | 0.79244 (19) | 0.0594 (6) | |
Cl2 | 0.2839 (2) | 0.6520 (2) | 0.5385 (2) | 0.0644 (6) | |
Cl3 | 0.4604 (2) | 0.9945 (2) | 0.65829 (19) | 0.0549 (5) | |
Cl4 | 0.7400 (7) | 0.3745 (6) | 0.8168 (7) | 0.234 (4) | |
Cl5 | 0.9241 (6) | 0.2338 (7) | 0.7127 (7) | 0.214 (3) | |
N1 | 0.1814 (7) | 0.8103 (7) | 0.7781 (6) | 0.0557 (18) | |
H1 | 0.197 (8) | 0.773 (8) | 0.707 (4) | 0.067* | |
Sn1 | 0.52253 (6) | 0.79582 (6) | 0.66440 (5) | 0.0525 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.039 (5) | 0.055 (5) | 0.045 (4) | 0.004 (4) | 0.005 (4) | 0.020 (4) |
C2 | 0.043 (5) | 0.055 (5) | 0.047 (4) | 0.010 (4) | 0.004 (4) | 0.017 (4) |
C3 | 0.069 (6) | 0.091 (7) | 0.047 (5) | 0.012 (5) | 0.016 (4) | 0.035 (5) |
C4 | 0.096 (8) | 0.100 (8) | 0.074 (6) | 0.043 (7) | 0.026 (6) | 0.064 (6) |
C5 | 0.081 (8) | 0.090 (7) | 0.090 (7) | 0.035 (6) | 0.004 (6) | 0.063 (6) |
C6 | 0.072 (7) | 0.070 (6) | 0.076 (6) | 0.035 (5) | 0.025 (5) | 0.034 (5) |
C7 | 0.044 (5) | 0.058 (5) | 0.043 (4) | 0.011 (4) | 0.010 (4) | 0.009 (4) |
C8 | 0.047 (5) | 0.066 (5) | 0.067 (5) | 0.005 (4) | 0.019 (4) | 0.029 (5) |
C9 | 0.075 (8) | 0.103 (8) | 0.086 (7) | −0.008 (6) | 0.015 (6) | 0.042 (7) |
C10 | 0.052 (6) | 0.086 (7) | 0.078 (7) | −0.007 (5) | 0.005 (5) | 0.017 (6) |
C11 | 0.045 (5) | 0.077 (6) | 0.080 (6) | 0.020 (5) | 0.017 (5) | 0.037 (5) |
C12 | 0.094 (9) | 0.075 (7) | 0.100 (8) | 0.049 (6) | 0.010 (7) | 0.017 (6) |
C13 | 0.110 (10) | 0.158 (12) | 0.091 (8) | 0.076 (9) | 0.029 (7) | 0.075 (9) |
C14 | 0.087 (17) | 0.046 (13) | 0.066 (7) | 0.035 (16) | 0.034 (9) | 0.019 (12) |
C15 | 0.09 (2) | 0.09 (2) | 0.062 (19) | 0.00 (2) | 0.042 (19) | 0.004 (15) |
C16 | 0.15 (3) | 0.081 (18) | 0.16 (2) | 0.004 (19) | 0.10 (2) | 0.06 (2) |
C17 | 0.16 (3) | 0.14 (3) | 0.095 (16) | 0.04 (2) | 0.038 (18) | 0.060 (18) |
C14B | 0.087 (17) | 0.046 (13) | 0.066 (7) | 0.035 (16) | 0.034 (9) | 0.019 (12) |
C15B | 0.09 (2) | 0.09 (2) | 0.062 (19) | 0.00 (2) | 0.042 (19) | 0.004 (15) |
C16B | 0.15 (3) | 0.081 (18) | 0.16 (2) | 0.004 (19) | 0.10 (2) | 0.06 (2) |
C17B | 0.16 (3) | 0.14 (3) | 0.095 (16) | 0.04 (2) | 0.038 (18) | 0.060 (18) |
C14C | 0.087 (17) | 0.046 (13) | 0.066 (7) | 0.035 (16) | 0.034 (9) | 0.019 (12) |
C15C | 0.09 (2) | 0.09 (2) | 0.062 (19) | 0.00 (2) | 0.042 (19) | 0.004 (15) |
C16C | 0.15 (3) | 0.081 (18) | 0.16 (2) | 0.004 (19) | 0.10 (2) | 0.06 (2) |
C17C | 0.16 (3) | 0.14 (3) | 0.095 (16) | 0.04 (2) | 0.038 (18) | 0.060 (18) |
C18 | 0.094 (10) | 0.156 (13) | 0.208 (16) | 0.038 (9) | 0.044 (10) | 0.139 (13) |
Cl1 | 0.0326 (11) | 0.0740 (13) | 0.0603 (12) | 0.0032 (10) | 0.0069 (9) | 0.0261 (11) |
Cl2 | 0.0525 (14) | 0.0652 (13) | 0.0581 (12) | 0.0074 (11) | 0.0045 (10) | 0.0194 (11) |
Cl3 | 0.0529 (13) | 0.0512 (11) | 0.0716 (13) | 0.0172 (10) | 0.0157 (10) | 0.0374 (10) |
Cl4 | 0.316 (10) | 0.177 (5) | 0.300 (8) | 0.125 (6) | 0.220 (8) | 0.120 (5) |
Cl5 | 0.163 (5) | 0.303 (7) | 0.364 (8) | 0.147 (5) | 0.150 (5) | 0.264 (7) |
N1 | 0.045 (4) | 0.066 (4) | 0.052 (4) | 0.016 (4) | 0.016 (3) | 0.022 (4) |
Sn1 | 0.0492 (4) | 0.0576 (4) | 0.0541 (4) | 0.0190 (3) | 0.0164 (3) | 0.0262 (3) |
C1—C6 | 1.385 (12) | C15—H15B | 0.9700 |
C1—C2 | 1.396 (11) | C16—C17 | 1.48 (2) |
C1—Sn1 | 2.137 (8) | C16—H16A | 0.9700 |
C2—C3 | 1.421 (11) | C16—H16B | 0.9700 |
C2—C7 | 1.506 (12) | C17—H17A | 0.9600 |
C3—C4 | 1.376 (13) | C17—H17B | 0.9600 |
C3—H3 | 0.9300 | C17—H17C | 0.9600 |
C4—C5 | 1.380 (14) | C14B—C15B | 1.483 (18) |
C4—H4 | 0.9300 | C14B—Sn1 | 2.137 (12) |
C5—C6 | 1.380 (13) | C14B—H14C | 0.9700 |
C5—H5 | 0.9300 | C14B—H14D | 0.9700 |
C6—H6 | 0.9300 | C15B—C16B | 1.490 (18) |
C7—N1 | 1.524 (11) | C15B—H15C | 0.9700 |
C7—H7A | 0.9700 | C15B—H15D | 0.9700 |
C7—H7B | 0.9700 | C16B—C17B | 1.479 (18) |
C8—N1 | 1.509 (11) | C16B—H16C | 0.9700 |
C8—C10 | 1.529 (12) | C16B—H16D | 0.9700 |
C8—C9 | 1.537 (14) | C17B—H17D | 0.9600 |
C8—H8 | 0.9800 | C17B—H17E | 0.9600 |
C9—H9A | 0.9600 | C17B—H17F | 0.9600 |
C9—H9B | 0.9600 | C14C—C15C | 1.48 (2) |
C9—H9C | 0.9600 | C14C—Sn1 | 2.139 (16) |
C10—H10A | 0.9600 | C14C—H14E | 0.9700 |
C10—H10B | 0.9600 | C14C—H14F | 0.9700 |
C10—H10C | 0.9600 | C15C—C16C | 1.49 (2) |
C11—C13 | 1.500 (13) | C15C—H15E | 0.9700 |
C11—C12 | 1.527 (13) | C15C—H15F | 0.9700 |
C11—N1 | 1.535 (11) | C16C—C17C | 1.48 (2) |
C11—H11 | 0.9800 | C16C—H16E | 0.9700 |
C12—H12A | 0.9600 | C16C—H16F | 0.9700 |
C12—H12B | 0.9600 | C17C—H17G | 0.9600 |
C12—H12C | 0.9600 | C17C—H17H | 0.9600 |
C13—H13A | 0.9600 | C17C—H17I | 0.9600 |
C13—H13B | 0.9600 | C18—Cl5 | 1.632 (14) |
C13—H13C | 0.9600 | C18—Cl4 | 1.721 (16) |
C14—C15 | 1.481 (19) | C18—H18A | 0.9700 |
C14—Sn1 | 2.141 (18) | C18—H18B | 0.9700 |
C14—H14A | 0.9700 | Cl1—Sn1 | 2.547 (3) |
C14—H14B | 0.9700 | Cl2—Sn1 | 2.608 (3) |
C15—C16 | 1.485 (19) | Cl3—Sn1 | 2.406 (3) |
C15—H15A | 0.9700 | N1—H1 | 0.857 (10) |
C6—C1—C2 | 119.4 (8) | H17B—C17—H17C | 109.5 |
C6—C1—Sn1 | 113.1 (6) | C15B—C14B—Sn1 | 114.6 (19) |
C2—C1—Sn1 | 127.5 (6) | C15B—C14B—H14C | 108.6 |
C1—C2—C3 | 118.7 (8) | Sn1—C14B—H14C | 108.6 |
C1—C2—C7 | 125.5 (8) | C15B—C14B—H14D | 108.6 |
C3—C2—C7 | 115.7 (8) | Sn1—C14B—H14D | 108.6 |
C4—C3—C2 | 119.8 (9) | H14C—C14B—H14D | 107.6 |
C4—C3—H3 | 120.1 | C14B—C15B—C16B | 111 (2) |
C2—C3—H3 | 120.1 | C14B—C15B—H15C | 109.5 |
C3—C4—C5 | 121.5 (9) | C16B—C15B—H15C | 109.5 |
C3—C4—H4 | 119.3 | C14B—C15B—H15D | 109.5 |
C5—C4—H4 | 119.3 | C16B—C15B—H15D | 109.5 |
C6—C5—C4 | 118.5 (9) | H15C—C15B—H15D | 108.1 |
C6—C5—H5 | 120.7 | C17B—C16B—C15B | 113 (3) |
C4—C5—H5 | 120.7 | C17B—C16B—H16C | 108.9 |
C5—C6—C1 | 122.1 (9) | C15B—C16B—H16C | 108.9 |
C5—C6—H6 | 119.0 | C17B—C16B—H16D | 108.9 |
C1—C6—H6 | 119.0 | C15B—C16B—H16D | 108.9 |
C2—C7—N1 | 114.1 (7) | H16C—C16B—H16D | 107.7 |
C2—C7—H7A | 108.7 | C16B—C17B—H17D | 109.5 |
N1—C7—H7A | 108.7 | C16B—C17B—H17E | 109.5 |
C2—C7—H7B | 108.7 | H17D—C17B—H17E | 109.5 |
N1—C7—H7B | 108.7 | C16B—C17B—H17F | 109.5 |
H7A—C7—H7B | 107.6 | H17D—C17B—H17F | 109.5 |
N1—C8—C10 | 110.1 (7) | H17E—C17B—H17F | 109.5 |
N1—C8—C9 | 110.6 (8) | C15C—C14C—Sn1 | 105 (3) |
C10—C8—C9 | 111.8 (8) | C15C—C14C—H14E | 110.8 |
N1—C8—H8 | 108.1 | Sn1—C14C—H14E | 110.8 |
C10—C8—H8 | 108.1 | C15C—C14C—H14F | 110.9 |
C9—C8—H8 | 108.1 | Sn1—C14C—H14F | 110.9 |
C8—C9—H9A | 109.5 | H14E—C14C—H14F | 108.9 |
C8—C9—H9B | 109.5 | C14C—C15C—C16C | 108 (4) |
H9A—C9—H9B | 109.5 | C14C—C15C—H15E | 110.2 |
C8—C9—H9C | 109.5 | C16C—C15C—H15E | 110.2 |
H9A—C9—H9C | 109.5 | C14C—C15C—H15F | 110.1 |
H9B—C9—H9C | 109.5 | C16C—C15C—H15F | 110.1 |
C8—C10—H10A | 109.5 | H15E—C15C—H15F | 108.5 |
C8—C10—H10B | 109.5 | C17C—C16C—C15C | 121 (5) |
H10A—C10—H10B | 109.5 | C17C—C16C—H16E | 107.0 |
C8—C10—H10C | 109.5 | C15C—C16C—H16E | 107.0 |
H10A—C10—H10C | 109.5 | C17C—C16C—H16F | 107.0 |
H10B—C10—H10C | 109.5 | C15C—C16C—H16F | 107.0 |
C13—C11—C12 | 111.4 (10) | H16E—C16C—H16F | 106.8 |
C13—C11—N1 | 110.8 (8) | C16C—C17C—H17G | 109.5 |
C12—C11—N1 | 112.6 (7) | C16C—C17C—H17H | 109.5 |
C13—C11—H11 | 107.2 | H17G—C17C—H17H | 109.5 |
C12—C11—H11 | 107.2 | C16C—C17C—H17I | 109.5 |
N1—C11—H11 | 107.2 | H17G—C17C—H17I | 109.5 |
C11—C12—H12A | 109.5 | H17H—C17C—H17I | 109.5 |
C11—C12—H12B | 109.5 | Cl5—C18—Cl4 | 114.1 (10) |
H12A—C12—H12B | 109.5 | Cl5—C18—H18A | 108.7 |
C11—C12—H12C | 109.5 | Cl4—C18—H18A | 108.7 |
H12A—C12—H12C | 109.5 | Cl5—C18—H18B | 108.7 |
H12B—C12—H12C | 109.5 | Cl4—C18—H18B | 108.7 |
C11—C13—H13A | 109.5 | H18A—C18—H18B | 107.6 |
C11—C13—H13B | 109.5 | C8—N1—C7 | 114.9 (7) |
H13A—C13—H13B | 109.5 | C8—N1—C11 | 114.1 (7) |
C11—C13—H13C | 109.5 | C7—N1—C11 | 113.3 (7) |
H13A—C13—H13C | 109.5 | C8—N1—H1 | 108 (6) |
H13B—C13—H13C | 109.5 | C7—N1—H1 | 105 (6) |
C15—C14—Sn1 | 123 (4) | C11—N1—H1 | 100 (6) |
C15—C14—H14A | 106.6 | C14B—Sn1—C1 | 126.9 (17) |
Sn1—C14—H14A | 106.6 | C14B—Sn1—C14C | 7 (3) |
C15—C14—H14B | 106.6 | C1—Sn1—C14C | 132 (3) |
Sn1—C14—H14B | 106.6 | C14B—Sn1—C14 | 19 (2) |
H14A—C14—H14B | 106.5 | C1—Sn1—C14 | 145.8 (14) |
C14—C15—C16 | 132 (5) | C14C—Sn1—C14 | 15 (5) |
C14—C15—H15A | 104.4 | C14B—Sn1—Cl3 | 116.5 (18) |
C16—C15—H15A | 104.4 | C1—Sn1—Cl3 | 116.5 (2) |
C14—C15—H15B | 104.4 | C14C—Sn1—Cl3 | 111 (3) |
C16—C15—H15B | 104.4 | C14—Sn1—Cl3 | 97.4 (13) |
H15A—C15—H15B | 105.6 | C14B—Sn1—Cl1 | 93 (3) |
C17—C16—C15 | 109 (7) | C1—Sn1—Cl1 | 89.0 (2) |
C17—C16—H16A | 109.9 | C14C—Sn1—Cl1 | 89 (5) |
C15—C16—H16A | 109.9 | C14—Sn1—Cl1 | 95.1 (16) |
C15—C16—H16B | 109.9 | Cl3—Sn1—Cl1 | 90.96 (9) |
H16A—C16—H16B | 108.3 | C14B—Sn1—Cl2 | 88 (3) |
C16—C17—H17A | 109.5 | C1—Sn1—Cl2 | 89.5 (2) |
C16—C17—H17B | 109.5 | C14C—Sn1—Cl2 | 92 (5) |
H17A—C17—H17B | 109.5 | C14—Sn1—Cl2 | 86.3 (16) |
C16—C17—H17C | 109.5 | Cl3—Sn1—Cl2 | 89.46 (9) |
H17A—C17—H17C | 109.5 | Cl1—Sn1—Cl2 | 178.50 (7) |
C6—C1—C2—C3 | 2.3 (12) | C15B—C14B—Sn1—C1 | −158 (5) |
Sn1—C1—C2—C3 | −176.8 (6) | C15B—C14B—Sn1—C14 | 29 (6) |
C6—C1—C2—C7 | 177.9 (8) | C15B—C14B—Sn1—Cl3 | 26 (8) |
Sn1—C1—C2—C7 | −1.2 (12) | C15B—C14B—Sn1—Cl1 | −67 (7) |
C1—C2—C3—C4 | −2.4 (13) | C15B—C14B—Sn1—Cl2 | 114 (7) |
C7—C2—C3—C4 | −178.4 (9) | C6—C1—Sn1—C14B | 30 (4) |
C2—C3—C4—C5 | 1.8 (16) | C2—C1—Sn1—C14B | −151 (4) |
C3—C4—C5—C6 | −1.0 (17) | C6—C1—Sn1—C14C | 24 (7) |
C4—C5—C6—C1 | 0.9 (16) | C2—C1—Sn1—C14C | −157 (7) |
C2—C1—C6—C5 | −1.5 (14) | C6—C1—Sn1—C14 | 34 (3) |
Sn1—C1—C6—C5 | 177.7 (8) | C2—C1—Sn1—C14 | −147 (3) |
C1—C2—C7—N1 | 88.7 (10) | C6—C1—Sn1—Cl3 | −154.2 (6) |
C3—C2—C7—N1 | −95.6 (8) | C2—C1—Sn1—Cl3 | 25.0 (8) |
Sn1—C14—C15—C16 | 154 (8) | C6—C1—Sn1—Cl1 | −63.6 (6) |
C14—C15—C16—C17 | 52 (13) | C2—C1—Sn1—Cl1 | 115.5 (7) |
Sn1—C14B—C15B—C16B | −179 (5) | C6—C1—Sn1—Cl2 | 116.6 (6) |
C14B—C15B—C16B—C17B | −174 (6) | C2—C1—Sn1—Cl2 | −64.2 (7) |
Sn1—C14C—C15C—C16C | −164 (7) | C15C—C14C—Sn1—C1 | −147 (7) |
C14C—C15C—C16C—C17C | −47 (12) | C15C—C14C—Sn1—C14 | 54 (9) |
C10—C8—N1—C7 | −160.6 (7) | C15C—C14C—Sn1—Cl3 | 31 (13) |
C9—C8—N1—C7 | 75.3 (9) | C15C—C14C—Sn1—Cl1 | −60 (11) |
C10—C8—N1—C11 | 66.2 (9) | C15C—C14C—Sn1—Cl2 | 121 (11) |
C9—C8—N1—C11 | −57.9 (10) | C15—C14—Sn1—C14B | −91 (12) |
C2—C7—N1—C8 | 49.8 (9) | C15—C14—Sn1—C1 | −101 (6) |
C2—C7—N1—C11 | −176.6 (7) | C15—C14—Sn1—C14C | −72 (18) |
C13—C11—N1—C8 | −126.3 (9) | C15—C14—Sn1—Cl3 | 86 (6) |
C12—C11—N1—C8 | 108.2 (9) | C15—C14—Sn1—Cl1 | −5 (6) |
C13—C11—N1—C7 | 99.7 (9) | C15—C14—Sn1—Cl2 | 175 (6) |
C12—C11—N1—C7 | −25.8 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2 | 0.86 (1) | 2.37 (7) | 3.208 (8) | 165 (8) |
Experimental details
Crystal data | |
Chemical formula | [Sn(C4H9)(C13H21N)Cl3]·CH2Cl2 |
Mr | 558.39 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 297 |
a, b, c (Å) | 10.654 (8), 11.093 (9), 12.406 (10) |
α, β, γ (°) | 115.594 (13), 100.767 (15), 97.176 (15) |
V (Å3) | 1263.5 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.45 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (Bruker, 2000) |
Tmin, Tmax | 0.544, 0.769 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9126, 4416, 3122 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.213, 1.02 |
No. of reflections | 4416 |
No. of parameters | 257 |
No. of restraints | 40 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.43, −0.73 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2 | 0.86 (1) | 2.37 (7) | 3.208 (8) | 165 (8) |
Acknowledgements
This work was supported by the Romanian Ministry of Education and Research (PD 443/2010/AR). AR gratefully acknowledges the assistance of PhD student Ioana Barbul and Dr Ciprian Raţ in the two-dimensional NMR experiments. We thank the National Center for X-ray Diffraction (Babes-Bolyai University, Cluj-Napoca) collecting the diffraction data.
References
Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2000). SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rotar, A., Schuermann, M., Varga, R. A., Silvestru, C. & Jurkschat, K. (2008). Z. Anorg. Allg. Chem. 634, 1533–1536. Web of Science CSD CrossRef CAS Google Scholar
Rotar, A., Varga, R. A., Jurkschat, K. & Silvestru, C. (2009). J. Organomet. Chem. 694, 1385–1392. Web of Science CSD CrossRef CAS Google Scholar
Rotar, A., Varga, R. A. & Silvestru, C. (2007). Acta Cryst. C63, m355–m356. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rotar, A., Varga, R. A. & Silvestru, C. (2008). Acta Cryst. E64, m45. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Švec, P., Černošková, E., Padělková, Z., Růžička, A. & Holeček, J. (2010). J. Organomet. Chem. 695, 2475–2485. Google Scholar
Varga, R. A., Rotar, A., Schuermann, M., Jurkschat, K. & Silvestru, C. (2006). Eur. J. Inorg. Chem. 7, 1475–1486. Web of Science CSD CrossRef Google Scholar
Varga, R. A., Schuermann, M. & Silvestru, C. (2001). J. Organomet. Chem. 623, 161–167. Web of Science CSD CrossRef CAS Google Scholar
Varga, R. A. & Silvestru, C. (2007). Acta Cryst. C63, m48–m50. Web of Science CSD CrossRef IUCr Journals Google Scholar
Varga, R. A., Silvestru, C. & Deleanu, C. (2005). Appl. Organomet. Chem. 19, 153–160. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals 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.
During our work on hypercoordinated organotin(IV) compounds with [2-(R2NCH2)C6H4]Sn fragments (Varga et al., 2001, 2005, 2006, Rotar et al., 2007, 2008, 2009) the title compound was isolated.
In an attempt to obtain single-crystals of the dichloride [2-(iPr2NCH2)C6H4]SnBuCl2 (1), recrystallization from a CH2Cl2/n-hexane mixture (1:4) in the presence of air afforded the HCl adduct 1.HCl.CH2Cl2. The nitrogen atom of the LCN ligand [LCN = 2-(diisopropylaminomethyl)phenyl] is protonated and a new Sn—Cl bond is simultaneously formed, thus leading to the formation of a zwitterionic species, [2-(iPr2HN+CH2)C6H4]SnBuCl3–.CH2Cl2. The presence of the HCl is probably due to partial hydrolysis of the diorganotin(IV) dihalide in the presence of ambient moisture from air.
The central tin atom is pentacoordinated with a distorted trigonal bipyramidal geometry (Fig. 1). The axial positions are occupied by two chlorine atoms [Cl1—Sn1—Cl2 = 178.50 (7)°], while the two carbon atoms from the two organic groups and a chlorine atom are placed in equatorial positions. The angles in the equatorial C2SnCl system are situated in the range between 97.4 (13) and 145.8 (14) °, showing a strong deviation from the ideal value of 120°. The Cl2 atom forms a strong intramolecular hydrogen bond with H1 from the nitrogen atom [Cl2···H1 = 2.37 (7) Å].
Disorder was found in the n-butyl group. This was resolved over three positions with the components of the disorder having site a occupancy ratio of 0.21 (1):0.51 (2):0.27 (2) (see Refinement section; Fig. 2).