metal-organic compounds
Bis(diisobutylammonium) tetrachloridobis[3-(trifluoromethyl)phenyl]stannate
aUniversity of the District of Columbia, Chemistry, 4200 Connecticut Avenue, NW, Washington DC, 20008, USA
*Correspondence e-mail: xsong@udc.edu
The 8H20N)2[SnCl4(C7H4Cl2F3)2], features a di-isobutylammonium cation in a general position and a diorganotin tetrachloride dianion, i.e. tetrachloridobis(3-trifuoromethylphenyl)stannate(IV), located on a centre of inversion; the SnIV atom is octahedrally coordinated. In the crystal, charge-assisted N+—H⋯Cl hydrogen bonds along with C—H⋯F contacts occur within supramolecular layers that interdigitate along the a-axis direction.
in the title salt, (CKeywords: stannate; ammonium cation; crystal structure; hydrogen bonding; salt.
CCDC reference: 2301782
Structure description
The title salt, bis(di-isobutylammonium) tetrachloridobis(3-trifluoromethylphenyl)stannate, was obtained as a by-product in a reaction of tris(3-trifluoromethylphenyl)tin chloride with acetic acid in the presence of di-isobutylamine. An interesting Sn—C cleavage occurred during this reaction.
The crystal comprises di-isobutylammonium cations and tetrachloridobis-(3-trifluoromethylphenyl)stannate(IV) anions, with the SnIV atom of the latter located on a centre of inversion, Fig. 1. The coordination geometry about the SnIV atom is based on an octahedron, Table 1. This observation resembles literature precedents, e.g. Teoh et al. (1992) and Hazell et al. (1998).
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In the crystal, charge-assisted N+—H⋯Cl hydrogen bonds along with C—H⋯F contacts link molecules into a supramolecular layer parallel to (011). As noted from Table 2, the Cll atom accepts two N+—H⋯Cl hydrogen bonds, each of which is significantly shorter than the N+—H⋯Cl hydrogen bond involving the Cl2 atom. This observation accounts for the disparity in the Sn—Cl bond lengths, Table 1. The supramolecular layers interdigitate along [100], Fig. 2.
Synthesis and crystallization
The crystal was obtained as a by-product in an attempt to poduce tris(3-trifluoromethylphenyl)tin acetate in a reaction involving tris(3-trifluoromethylphenyl)tin chloride and acetic acid in the presence of di-isobutylamine. The anticipated tris(3-trifluoromethylphenyl)tin acetate was isolated as the major product along with a few smaller crystals of the title compound in the mother liquid, comprising a mixture of dichloromethane and hexane.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 3Structural data
CCDC reference: 2301782
https://doi.org/10.1107/S2414314623009136/tk4096sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623009136/tk4096Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2023); cell
CrysAlis PRO (Rigaku OD, 2023); data reduction: CrysAlis PRO (Rigaku OD, 2023); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).(C8H20N)2[SnCl4(C7H4Cl2F3)2] | F(000) = 828 |
Mr = 811.19 | Dx = 1.462 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 12.2614 (1) Å | Cell parameters from 14287 reflections |
b = 10.8318 (1) Å | θ = 3.8–77.8° |
c = 14.6297 (1) Å | µ = 8.64 mm−1 |
β = 108.523 (1)° | T = 100 K |
V = 1842.36 (3) Å3 | Block, clear brown-orange |
Z = 2 | 0.1 × 0.07 × 0.03 mm |
XtaLAB Synergy, Single source at home/near, HyPix diffractometer | 3652 reflections with I > 2σ(I) |
Detector resolution: 10.0000 pixels mm-1 | Rint = 0.057 |
ω scans | θmax = 78.0°, θmin = 3.8° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023) | h = −15→15 |
Tmin = 0.293, Tmax = 1.000 | k = −13→11 |
18706 measured reflections | l = −18→17 |
3822 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.7503P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3822 reflections | Δρmax = 0.66 e Å−3 |
200 parameters | Δρmin = −0.90 e Å−3 |
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 | ||
C1 | 0.35270 (19) | 0.5478 (2) | 0.13703 (15) | 0.0239 (4) | |
H1A | 0.358554 | 0.457309 | 0.130324 | 0.029* | |
H1B | 0.326308 | 0.583776 | 0.071441 | 0.029* | |
C2 | 0.26367 (19) | 0.5751 (2) | 0.18694 (15) | 0.0260 (5) | |
H2 | 0.295430 | 0.546221 | 0.255225 | 0.031* | |
C3 | 0.23739 (19) | 0.7127 (2) | 0.18845 (16) | 0.0275 (5) | |
H3A | 0.306651 | 0.756553 | 0.226965 | 0.041* | |
H3B | 0.175849 | 0.724982 | 0.216927 | 0.041* | |
H3C | 0.212799 | 0.744875 | 0.122425 | 0.041* | |
C4 | 0.1551 (3) | 0.5004 (2) | 0.1380 (3) | 0.0411 (8) | |
H4A | 0.121094 | 0.528525 | 0.071310 | 0.062* | |
H4B | 0.099624 | 0.511991 | 0.172948 | 0.062* | |
H4C | 0.174867 | 0.412669 | 0.138369 | 0.062* | |
C5 | 0.56054 (19) | 0.55525 (19) | 0.14964 (15) | 0.0222 (4) | |
H5A | 0.537390 | 0.577720 | 0.080518 | 0.027* | |
H5B | 0.565458 | 0.464099 | 0.154047 | 0.027* | |
C6 | 0.67905 (19) | 0.60917 (19) | 0.20024 (15) | 0.0218 (4) | |
H6 | 0.674857 | 0.700698 | 0.190829 | 0.026* | |
C7 | 0.7618 (2) | 0.5571 (2) | 0.15105 (19) | 0.0328 (5) | |
H7A | 0.765195 | 0.467094 | 0.157844 | 0.049* | |
H7B | 0.838600 | 0.591970 | 0.181228 | 0.049* | |
H7C | 0.734647 | 0.578953 | 0.082497 | 0.049* | |
C8 | 0.72259 (19) | 0.5828 (2) | 0.30827 (16) | 0.0274 (5) | |
H8A | 0.669735 | 0.619158 | 0.338881 | 0.041* | |
H8B | 0.799278 | 0.618867 | 0.336388 | 0.041* | |
H8C | 0.726737 | 0.493329 | 0.318920 | 0.041* | |
N1 | 0.46944 (15) | 0.59824 (15) | 0.19037 (12) | 0.0177 (3) | |
H1C | 0.466464 | 0.682178 | 0.188412 | 0.021* | |
H1D | 0.488962 | 0.574815 | 0.253256 | 0.021* | |
C9 | 0.68457 (19) | 0.50380 (16) | 0.54647 (16) | 0.0146 (4) | |
C10 | 0.74444 (18) | 0.6150 (2) | 0.56702 (15) | 0.0178 (4) | |
H10 | 0.702813 | 0.690201 | 0.560520 | 0.021* | |
C11 | 0.86397 (19) | 0.6180 (2) | 0.59687 (16) | 0.0220 (4) | |
H11 | 0.903295 | 0.694773 | 0.610510 | 0.026* | |
C12 | 0.9258 (2) | 0.50866 (18) | 0.60672 (18) | 0.0215 (5) | |
H12 | 1.007476 | 0.509922 | 0.627119 | 0.026* | |
C13 | 0.86647 (18) | 0.3971 (2) | 0.58629 (14) | 0.0180 (4) | |
C14 | 0.74712 (18) | 0.39424 (19) | 0.55628 (14) | 0.0157 (4) | |
H14 | 0.707913 | 0.317433 | 0.542374 | 0.019* | |
C15 | 0.93450 (17) | 0.2801 (2) | 0.59848 (15) | 0.0205 (4) | |
Cl1 | 0.50101 (4) | 0.38477 (4) | 0.34558 (3) | 0.01643 (11) | |
Cl2 | 0.49391 (4) | 0.70843 (4) | 0.41432 (3) | 0.01725 (11) | |
F1 | 0.86867 (11) | 0.17902 (12) | 0.57535 (11) | 0.0291 (3) | |
F2 | 1.00453 (12) | 0.27762 (13) | 0.54416 (10) | 0.0306 (3) | |
F3 | 1.00321 (13) | 0.26451 (14) | 0.69011 (10) | 0.0364 (3) | |
Sn1 | 0.500000 | 0.500000 | 0.500000 | 0.01258 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0260 (11) | 0.0198 (11) | 0.0220 (9) | −0.0067 (9) | 0.0021 (8) | −0.0019 (8) |
C2 | 0.0229 (10) | 0.0294 (11) | 0.0233 (10) | −0.0069 (9) | 0.0038 (8) | 0.0065 (9) |
C3 | 0.0221 (11) | 0.0338 (13) | 0.0268 (10) | 0.0007 (9) | 0.0080 (8) | 0.0042 (9) |
C4 | 0.0291 (15) | 0.0419 (19) | 0.0480 (18) | −0.0161 (10) | 0.0061 (13) | 0.0051 (10) |
C5 | 0.0301 (11) | 0.0173 (10) | 0.0218 (9) | 0.0001 (8) | 0.0118 (8) | −0.0026 (8) |
C6 | 0.0270 (10) | 0.0160 (9) | 0.0269 (10) | 0.0026 (8) | 0.0151 (8) | 0.0001 (8) |
C7 | 0.0383 (13) | 0.0285 (13) | 0.0404 (13) | 0.0049 (10) | 0.0249 (11) | −0.0024 (10) |
C8 | 0.0212 (10) | 0.0331 (12) | 0.0300 (11) | −0.0014 (9) | 0.0112 (8) | 0.0022 (10) |
N1 | 0.0220 (8) | 0.0135 (8) | 0.0181 (7) | −0.0022 (6) | 0.0071 (6) | −0.0008 (6) |
C9 | 0.0117 (10) | 0.0175 (11) | 0.0161 (10) | −0.0006 (6) | 0.0063 (8) | −0.0003 (6) |
C10 | 0.0190 (10) | 0.0152 (10) | 0.0204 (9) | 0.0002 (8) | 0.0081 (7) | −0.0026 (8) |
C11 | 0.0199 (10) | 0.0188 (11) | 0.0275 (10) | −0.0063 (8) | 0.0077 (8) | −0.0041 (8) |
C12 | 0.0155 (11) | 0.0232 (12) | 0.0254 (11) | −0.0015 (7) | 0.0057 (9) | 0.0001 (7) |
C13 | 0.0189 (9) | 0.0194 (10) | 0.0176 (9) | 0.0016 (8) | 0.0086 (7) | 0.0013 (8) |
C14 | 0.0170 (9) | 0.0158 (10) | 0.0155 (8) | 0.0007 (7) | 0.0070 (7) | 0.0017 (7) |
C15 | 0.0136 (9) | 0.0234 (10) | 0.0250 (9) | 0.0015 (8) | 0.0068 (7) | 0.0033 (8) |
Cl1 | 0.0205 (2) | 0.0118 (2) | 0.0188 (2) | −0.00014 (15) | 0.00893 (16) | −0.00113 (15) |
Cl2 | 0.0188 (2) | 0.0129 (2) | 0.0212 (2) | 0.00085 (15) | 0.00785 (16) | 0.00294 (16) |
F1 | 0.0222 (6) | 0.0172 (6) | 0.0500 (8) | 0.0021 (5) | 0.0143 (6) | 0.0042 (6) |
F2 | 0.0271 (7) | 0.0289 (7) | 0.0442 (8) | 0.0067 (5) | 0.0235 (6) | 0.0043 (6) |
F3 | 0.0351 (8) | 0.0389 (8) | 0.0284 (6) | 0.0168 (6) | 0.0005 (6) | 0.0061 (6) |
Sn1 | 0.01231 (11) | 0.01048 (12) | 0.01599 (11) | 0.00097 (5) | 0.00599 (8) | 0.00084 (5) |
C1—C2 | 1.523 (3) | C11—C12 | 1.389 (3) |
C1—N1 | 1.499 (3) | C12—C13 | 1.393 (3) |
C2—C3 | 1.527 (3) | C13—C14 | 1.388 (3) |
C2—C4 | 1.528 (3) | C13—C15 | 1.497 (3) |
C5—C6 | 1.522 (3) | C15—F1 | 1.338 (3) |
C5—N1 | 1.497 (3) | C15—F2 | 1.343 (2) |
C6—C7 | 1.526 (3) | C15—F3 | 1.348 (2) |
C6—C8 | 1.526 (3) | Sn1—Cl1 | 2.5845 (4) |
C9—C10 | 1.393 (3) | Sn1—Cl2 | 2.5719 (4) |
C9—C14 | 1.396 (3) | Sn1—C9 | 2.147 (2) |
C10—C11 | 1.390 (3) | ||
N1—C1—C2 | 113.03 (17) | F1—C15—F2 | 106.35 (17) |
C1—C2—C3 | 112.52 (18) | F1—C15—F3 | 106.55 (17) |
C1—C2—C4 | 108.9 (2) | F2—C15—C13 | 112.55 (17) |
C3—C2—C4 | 111.5 (2) | F2—C15—F3 | 105.72 (16) |
N1—C5—C6 | 113.87 (16) | F3—C15—C13 | 111.92 (17) |
C5—C6—C7 | 107.69 (18) | C9—Sn1—C9i | 180.0 |
C5—C6—C8 | 113.43 (18) | C9i—Sn1—Cl1i | 89.36 (6) |
C7—C6—C8 | 110.67 (19) | C9—Sn1—Cl1 | 89.36 (6) |
C5—N1—C1 | 112.90 (16) | C9—Sn1—Cl1i | 90.64 (6) |
C10—C9—C14 | 118.6 (2) | C9i—Sn1—Cl1 | 90.64 (6) |
C10—C9—Sn1 | 121.02 (14) | C9—Sn1—Cl2i | 89.89 (5) |
C14—C9—Sn1 | 120.40 (14) | C9i—Sn1—Cl2i | 90.11 (5) |
C11—C10—C9 | 121.3 (2) | C9i—Sn1—Cl2 | 89.89 (5) |
C12—C11—C10 | 119.9 (2) | C9—Sn1—Cl2 | 90.11 (5) |
C11—C12—C13 | 119.1 (2) | Cl1i—Sn1—Cl1 | 180.0 |
C12—C13—C15 | 118.4 (2) | Cl1—Sn1—Cl2 | 90.308 (14) |
C14—C13—C12 | 120.9 (2) | Cl2i—Sn1—Cl1i | 90.308 (14) |
C14—C13—C15 | 120.68 (19) | Cl2i—Sn1—Cl1 | 89.692 (14) |
C13—C14—C9 | 120.20 (19) | Cl2—Sn1—Cl1i | 89.693 (14) |
F1—C15—C13 | 113.22 (17) | Cl2i—Sn1—Cl2 | 180.00 (3) |
C2—C1—N1—C5 | 171.26 (17) | C12—C13—C14—C9 | −0.3 (3) |
C6—C5—N1—C1 | 177.79 (17) | C12—C13—C15—F1 | −178.98 (19) |
N1—C1—C2—C3 | 66.3 (2) | C12—C13—C15—F2 | −58.3 (3) |
N1—C1—C2—C4 | −169.55 (19) | C12—C13—C15—F3 | 60.6 (3) |
N1—C5—C6—C7 | 179.98 (17) | C14—C9—C10—C11 | −0.1 (3) |
N1—C5—C6—C8 | 57.2 (2) | C14—C13—C15—F1 | 1.7 (3) |
C9—C10—C11—C12 | −0.1 (3) | C14—C13—C15—F2 | 122.3 (2) |
C10—C9—C14—C13 | 0.2 (3) | C14—C13—C15—F3 | −118.8 (2) |
C10—C11—C12—C13 | 0.0 (4) | C15—C13—C14—C9 | 179.09 (19) |
C11—C12—C13—C14 | 0.1 (4) | Sn1—C9—C10—C11 | −179.81 (16) |
C11—C12—C13—C15 | −179.2 (2) | Sn1—C9—C14—C13 | 179.96 (15) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···Cl1ii | 0.91 | 2.31 | 3.1877 (17) | 161 |
N1—H1D···Cl1 | 0.91 | 2.44 | 3.1771 (17) | 138 |
N1—H1D···Cl2 | 0.91 | 2.75 | 3.4094 (17) | 130 |
C7—H7A···F1iii | 0.98 | 2.56 | 3.227 (3) | 125 |
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2. |
Funding information
Financial assistance from the National Science Foundation (NSF grants Nos. 2117621, 1622811 and 1833656) and the University of the District of Columbia (UDC) is gratefully acknowledged.
References
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hazell, A., Khoo, L. E., Ouyang, J., Rausch, B. J. & Tavares, Z. M. (1998). Acta Cryst. C54, 728–732. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Teoh, S. G., Teo, S. B., Yeap, G. Y. & Declercq, J. P. (1992). Polyhedron, 11, 2351–2356. CSD CrossRef CAS Web of Science Google Scholar
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