The crystal structure of the title salt, [Li(CH3CN)4][B(NCS)4], is composed of discrete cations and anions. Both the Li and B atoms show a tetra­hedral coordination by four equal ligands. The aceto­nitrile and iso­thio­cyanate ligands are linear. The bond angles at the B atom are close to the ideal tetra­hedral value [108.92 (18)–109.94 (16)°], but the bond angles at the Li atom show larger deviations [106.15 (17)–113.70 (17)°]

Bolte, Michael

Breunig, Jens Michael

Lerner, Hans-Wolfram

Wietelmann, Ulrich

Acta Crystallographica Section E

English

PubMed

Hochschulschriftenserver - Universität Frankfurt am Main

Tetraacetonitrilelithium tetraisothio-cyanatoborateJens Michael Breunig,a Ulrich Wietelmann,bHans-Wolfram Lernera and Michael Boltea*aInstitut fu ¨r Anorganische und Analytische Chemie, Goethe-Universita ¨t Frankfurt,Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany, andbResearch &Development, Rockwood Lithium GmbH, Trakehner Str. 3, 60487 Frankfurt amMain, GermanyCorrespondence e-mail: bolte@chemie.uni-frankfurt.deReceived 26 March 2013; accepted 3 April 2013Key indicators: single-crystal X-ray study; T = 173 K; mean  (C–C) = 0.003 A ˚;R factor = 0.038; wR factor = 0.092; data-to-parameter ratio = 16.0.The crystal structure of the title salt, [Li(CH3CN)4][B(NCS)4],is composed of discrete cations and anions. Both the Li and Batoms show a tetrahedral coordination by four equal ligands.The acetonitrile and isothiocyanate ligands are linear. Thebond angles at the B atom are close to the ideal tetrahedralvalue [108.92 (18)–109.94 (16)], but the bond angles at the Liatom show larger deviations [106.15 (17)–113.70 (17)].Related literatureOur group is interested in the synthesis of novel and improvedelectrolytes, namely borates with alkinyl or catecholateligands, see: Lerner et al. (2007, 2012); Ro ¨der et al. (2008). Forthe preparation, see: Kleemann & Newman (1981).ExperimentalCrystal data[Li(C2H3N)4](C4BN4S4)Mr = 414.29Monoclinic, C2=ca = 21.219 (3) A ˚b = 9.4756 (14) A ˚c = 21.596 (4) A ˚  = 92.845 (10)V = 4336.8 (12) A ˚ 3Z =8Mo K  radiation  = 0.45 mm1T = 173 K0.35  0.29  0.15 mmData collectionStoe IPDS II two-circlediffractometerAbsorption correction: multi-scan(X-AREA; Stoe & Cie, 2001)Tmin = 0.858, Tmax = 0.93624466 measured reﬂections3816 independent reﬂections2681 reﬂections with I >2  (I)Rint = 0.074ReﬁnementR[F2 >2  (F2)] = 0.038wR(F2) = 0.092S = 0.973816 reﬂections239 parametersH-atom parameters constrained max = 0.18 e A ˚ 3 min = 0.25 e A ˚ 3Data collection: X-AREA (Stoe & Cie, 2001); cell reﬁnement: X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97 (Sheldrick, 2008); program(s) used to reﬁne structure:SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL(Sheldrick, 2008); software used to prepare material for publication:SHELXL97 and publCIF (Westrip, 2010).Supplementary data and ﬁgures for this paper are available from theIUCr electronic archives (Reference: NG5320).ReferencesKleemann, L. P. & Newman, G. H. (1981). US Patent No. 4 279 976.Lerner, H.-W., Ro ¨der, J., Vitze, H., Bolte, M., Wagner, M. & Wietelmann, U.(2007). Ger. Patent No. 10 2007 047 812 A1.Lerner, H.-W., Ro ¨der, J., Vitze, H., Bolte, M., Wagner, M. & Wietelmann, U.(2012). US Patent No. 8 222 457.Ro ¨der, J., Wietelmann, U., Vitze, H., Bolte, M., Lerner, H.-W. & Wagner, M.(2008). Ger. Patent No. 10 2008 041 812 A1.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.metal-organic compoundsActa Cryst. (2013). E69, m253 doi:10.1107/S1600536813009082 Breunig et al. m253Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssup-1 Acta Cryst. (2013). E69, m253    supplementary materialsActa Cryst. (2013). E69, m253    [doi:10.1107/S1600536813009082]Tetraacetonitrilelithium tetraisothiocyanatoborateJens Michael Breunig, Ulrich Wietelmann, Hans-Wolfram Lerner and Michael BolteComment Our group is interested in the synthesis of novel and improved electrolytes, namely, borates with alkinyl or catecholate ligands (Lerner et al., 2007, 2012; Röder et al., 2008). In the course of our investigations we synthesized the literature-reported borate Li[B(NCS)4] (Kleemann & Newman 1981) to compare its electrochemical properties with those of the borates which we have prepared. We were able to get crystals of this so far structurally uncharacterized borate Li(CH3CN)4[B(NCS)4]. The borate Li(CH3CN)4[B(NCS)4] was synthesized from BF3(OEt2) and Li[NCS], as shown in Figure 1.The crystal structure of [Li(CH3CN)4]+[B(NCS)4]- is composed of discrete cations and anions (Fig. 2). Both the Li and B centre, show a tetrahedral coordination by four equal ligands. The acetonitrile and the isothiocyanate ligands are linear. Whereas the bond angles at the boron centre [108.92 (18)° - 109.94 (16)°] are very close to the ideal tetrahedral value, the bond angles around the Li centre [106.15 (17)° - 113.70 (17)°] show larger deviations from the ideal value.Experimental Li(CH3CN)4[B(NCS)4]: The borate Li(CH3CN)4[B(NCS)4] was prepared according to a literature procedure (Kleemann & Newman 1981). X-ray quality crystals of Li(CH3CN)4[B(NCS)4] were grown from an acetonitrile solution at room temperature.Refinement All H atoms were located in difference Fourier maps. Nevertheless, they were geometrically positioned and refined using a riding model with C—H = 0.98 Å and with Uiso(H) = 1.5Ueq(C). The methyl groups were allowed to rotate but not to tip.Computing details Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).supplementary materialssup-2 Acta Cryst. (2013). E69, m253    Figure 1Synthesis of Li(CH3CN)4[B(NCS)4]. (i) -3LiF; in CH3CN. Figure 2A perspective view of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. supplementary materialssup-3 Acta Cryst. (2013). E69, m253    Tetraacetonitrilelithium tetraisothiocyanatoborate Crystal data [Li(C2H3N)4](C4BN4S4)Mr = 414.29Monoclinic, C2/cHall symbol: -C 2yca = 21.219 (3) Åb = 9.4756 (14) Åc = 21.596 (4) Åβ = 92.845 (10)°V = 4336.8 (12) Å3Z = 8F(000) = 1696Dx = 1.269 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 13942 reflectionsθ = 3.6–26.8°µ = 0.45 mm−1T = 173 KBlock, colourless0.35 × 0.29 × 0.15 mmData collection Stoe IPDS II two-circle diffractometerRadiation source: Genix 3D IµS microfocus X-ray sourceGenix 3D multilayer optics monochromatorω scansAbsorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)Tmin = 0.858, Tmax = 0.93624466 measured reflections3816 independent reflections2681 reflections with I > 2σ(I)Rint = 0.074θmax = 25.0°, θmin = 3.6°h = −25→25k = −11→11l = −25→25Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.038wR(F2) = 0.092S = 0.973816 reflections239 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3(Δ/σ)max = 0.032Δρmax = 0.18 e Å−3Δρmin = −0.25 e Å−3Special details 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.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) xyzU iso*/UeqB1 0.60133 (11) 0.2457 (2) 0.70356 (11) 0.0313 (4)N1 0.61748 (7) 0.15384 (18) 0.65017 (8) 0.0385 (4)C1 0.62999 (8) 0.0914 (2) 0.60595 (10) 0.0353 (4)S1 0.64743 (3) 0.00457 (7) 0.54619 (3) 0.06209 (19)supplementary materialssup-4 Acta Cryst. (2013). E69, m253    N2 0.65695 (7) 0.33656 (17) 0.72237 (8) 0.0378 (4)C2 0.69788 (9) 0.4127 (2) 0.73635 (9) 0.0384 (5)S2 0.75423 (3) 0.51599 (7) 0.75594 (3) 0.0673 (2)N3 0.54597 (7) 0.33778 (16) 0.68497 (7) 0.0355 (4)C3 0.50357 (8) 0.4078 (2) 0.66964 (8) 0.0346 (4)S3 0.44491 (3) 0.50352 (7) 0.64826 (3) 0.06058 (19)N4 0.58433 (7) 0.15490 (16) 0.75811 (8) 0.0355 (4)C4 0.57138 (8) 0.0892 (2) 0.80105 (9) 0.0349 (4)S4 0.55383 (3) −0.00256 (7) 0.85961 (3) 0.06261 (19)Li1 0.34824 (15) 0.4840 (3) 0.44482 (16) 0.0416 (8)N5 0.42234 (8) 0.6002 (2) 0.47394 (8) 0.0461 (4)C51 0.46315 (9) 0.6718 (2) 0.48727 (9) 0.0389 (5)C52 0.51502 (11) 0.7646 (3) 0.50381 (13) 0.0613 (7)H52A 0.5480 0.7536 0.4740 0.092*H52B 0.5323 0.7409 0.5455 0.092*H52C 0.5001 0.8625 0.5033 0.092*N6 0.27497 (8) 0.61203 (19) 0.42481 (8) 0.0464 (4)C61 0.23575 (9) 0.6908 (2) 0.41537 (9) 0.0386 (5)C62 0.18563 (11) 0.7913 (3) 0.40324 (13) 0.0620 (7)H62A 0.1819 0.8524 0.4395 0.093*H62B 0.1458 0.7410 0.3948 0.093*H62C 0.1952 0.8490 0.3672 0.093*N7 0.32273 (8) 0.36138 (19) 0.51545 (9) 0.0461 (4)C71 0.30814 (8) 0.3053 (2) 0.55915 (10) 0.0364 (4)C72 0.28959 (12) 0.2348 (3) 0.61477 (11) 0.0542 (6)H72A 0.3192 0.2594 0.6494 0.081*H72B 0.2901 0.1324 0.6083 0.081*H72C 0.2469 0.2647 0.6243 0.081*N8 0.37312 (8) 0.36597 (19) 0.37288 (9) 0.0444 (4)C81 0.38851 (9) 0.3023 (2) 0.33200 (11) 0.0398 (5)C82 0.40806 (13) 0.2207 (3) 0.27914 (13) 0.0646 (7)H82A 0.3716 0.1704 0.2603 0.097*H82B 0.4405 0.1525 0.2930 0.097*H82C 0.4253 0.2844 0.2485 0.097*Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23B1 0.0281 (9) 0.0337 (10) 0.0321 (11) 0.0005 (8) 0.0013 (8) 0.0031 (9)N1 0.0373 (8) 0.0408 (9) 0.0376 (10) 0.0027 (7) 0.0043 (7) −0.0003 (8)C1 0.0313 (9) 0.0317 (10) 0.0429 (12) −0.0012 (7) 0.0029 (8) 0.0024 (9)S1 0.0764 (4) 0.0521 (4) 0.0592 (4) −0.0026 (3) 0.0184 (3) −0.0211 (3)N2 0.0326 (8) 0.0397 (9) 0.0408 (10) −0.0015 (7) 0.0002 (7) 0.0026 (7)C2 0.0355 (10) 0.0433 (11) 0.0362 (11) 0.0007 (9) −0.0006 (8) 0.0079 (9)S2 0.0574 (4) 0.0733 (4) 0.0692 (4) −0.0323 (3) −0.0161 (3) 0.0098 (3)N3 0.0304 (8) 0.0381 (9) 0.0379 (9) 0.0059 (7) 0.0014 (7) 0.0063 (7)C3 0.0363 (10) 0.0379 (10) 0.0299 (10) −0.0035 (8) 0.0042 (8) 0.0033 (8)S3 0.0462 (3) 0.0712 (4) 0.0640 (4) 0.0258 (3) −0.0017 (3) 0.0165 (3)N4 0.0356 (8) 0.0364 (8) 0.0345 (9) 0.0019 (7) 0.0018 (7) 0.0053 (8)C4 0.0346 (9) 0.0342 (10) 0.0358 (11) 0.0057 (8) 0.0012 (8) −0.0002 (9)supplementary materialssup-5 Acta Cryst. (2013). E69, m253    S4 0.0843 (4) 0.0581 (4) 0.0470 (4) 0.0039 (3) 0.0194 (3) 0.0217 (3)Li1 0.0411 (16) 0.0402 (18) 0.0440 (19) 0.0036 (15) 0.0058 (14) −0.0016 (16)N5 0.0415 (9) 0.0511 (11) 0.0457 (11) −0.0003 (8) 0.0024 (8) 0.0040 (8)C51 0.0370 (10) 0.0427 (11) 0.0369 (11) 0.0075 (9) 0.0026 (8) 0.0065 (9)C52 0.0456 (14) 0.0583 (15) 0.0791 (19) −0.0065 (10) −0.0060 (13) −0.0049 (13)N6 0.0430 (9) 0.0462 (10) 0.0503 (11) 0.0022 (8) 0.0063 (8) 0.0010 (8)C61 0.0400 (10) 0.0378 (11) 0.0382 (11) −0.0022 (9) 0.0047 (8) −0.0038 (9)C62 0.0579 (14) 0.0531 (14) 0.0741 (18) 0.0181 (11) −0.0067 (13) −0.0046 (13)N7 0.0463 (9) 0.0457 (10) 0.0464 (11) −0.0019 (8) 0.0051 (8) 0.0002 (9)C71 0.0320 (9) 0.0353 (10) 0.0415 (12) −0.0019 (8) −0.0015 (8) −0.0067 (9)C72 0.0594 (14) 0.0597 (15) 0.0436 (13) −0.0108 (11) 0.0026 (11) 0.0079 (11)N8 0.0460 (9) 0.0428 (10) 0.0445 (11) 0.0013 (8) 0.0043 (8) 0.0028 (9)C81 0.0384 (10) 0.0357 (11) 0.0454 (13) −0.0015 (8) 0.0028 (9) 0.0067 (10)C82 0.0736 (17) 0.0627 (16) 0.0587 (16) 0.0072 (13) 0.0154 (13) −0.0113 (13)Geometric parameters (Å, º) B1—N1 1.498 (3) C52—H52A 0.9800B1—N2 1.501 (3) C52—H52B 0.9800B1—N3 1.502 (2) C52—H52C 0.9800B1—N4 1.516 (3) N6—C61 1.129 (2)N1—C1 1.165 (3) C61—C62 1.442 (3)C1—S1 1.589 (2) C62—H62A 0.9800N2—C2 1.158 (2) C62—H62B 0.9800C2—S2 1.586 (2) C62—H62C 0.9800N3—C3 1.153 (2) N7—C71 1.139 (3)C3—S3 1.5900 (19) C71—C72 1.446 (3)N4—C4 1.161 (2) C72—H72A 0.9800C4—S4 1.594 (2) C72—H72B 0.9800Li1—N5 1.995 (4) C72—H72C 0.9800Li1—N6 2.002 (4) N8—C81 1.131 (3)Li1—N8 2.006 (4) C81—C82 1.456 (4)Li1—N7 2.013 (4) C82—H82A 0.9800N5—C51 1.126 (2) C82—H82B 0.9800C51—C52 1.440 (3) C82—H82C 0.9800N1—B1—N2 109.56 (18) H52A—C52—H52C 109.5N1—B1—N3 109.73 (15) H52B—C52—H52C 109.5N2—B1—N3 109.44 (15) C61—N6—Li1 175.7 (2)N1—B1—N4 109.94 (16) N6—C61—C62 179.9 (3)N2—B1—N4 109.24 (16) C61—C62—H62A 109.5N3—B1—N4 108.92 (18) C61—C62—H62B 109.5C1—N1—B1 174.95 (19) H62A—C62—H62B 109.5N1—C1—S1 179.26 (19) C61—C62—H62C 109.5C2—N2—B1 176.46 (18) H62A—C62—H62C 109.5N2—C2—S2 179.5 (2) H62B—C62—H62C 109.5C3—N3—B1 178.8 (2) C71—N7—Li1 172.5 (2)N3—C3—S3 179.6 (2) N7—C71—C72 179.7 (3)C4—N4—B1 177.82 (19) C71—C72—H72A 109.5N4—C4—S4 179.3 (2) C71—C72—H72B 109.5supplementary materialssup-6 Acta Cryst. (2013). E69, m253    N5—Li1—N6 108.97 (17) H72A—C72—H72B 109.5N5—Li1—N8 108.54 (17) C71—C72—H72C 109.5N6—Li1—N8 113.70 (17) H72A—C72—H72C 109.5N5—Li1—N7 108.48 (17) H72B—C72—H72C 109.5N6—Li1—N7 106.15 (17) C81—N8—Li1 178.0 (2)N8—Li1—N7 110.86 (17) N8—C81—C82 179.7 (3)C51—N5—Li1 175.4 (2) C81—C82—H82A 109.5N5—C51—C52 179.3 (2) C81—C82—H82B 109.5C51—C52—H52A 109.5 H82A—C82—H82B 109.5C51—C52—H52B 109.5 C81—C82—H82C 109.5H52A—C52—H52B 109.5 H82A—C82—H82C 109.5C51—C52—H52C 109.5 H82B—C82—H82C 109.5

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) xyzU iso*/Ueq

metal-organic compounds Acta Cryst.

The crystal structure of [Li(CH3CN)4]+[B(NCS)4]- is composed of discrete cations

Tetra­aceto­nitrile­lithium tetra­iso­thio­cyanato­borate

Jens Michael Breunig

Ulrich Wietelmann

Hans-Wolfram Lerner

Michael Bolte

Crossref

Acta Crystallographica Section E Structure Reports Online

Tetraacetonitrilelithium tetraisothiocyanatoborate

http://dx.doi.org/10.1107/S1600536813009082

Tetraacetonitrilelithium tetraisothiocyanatoborate

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Hochschulschriftenserver - Universität Frankfurt am Main

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Tetra­aceto­nitrile­lithium tetra­iso­thio­cyanato­borate

Abstract

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Hochschulschriftenserver - Universität Frankfurt am Main

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Tetraacetonitrilelithium tetraisothiocyanatoborate