N,N,N′,N′,N′′,N′′,N′′′,N′′′-Octa­meth­yl(but-2-yne)bis­amidinium bis­(tetra­phenyl­borate)

Tiritiris, I.; Kress, R.; Kantlehner, W.

doi:10.1107/S2414314616001668

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160166

https://doi.org/10.1107/S2414314616001668

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N,N,N′,N′,N′′,N′′,N′′′,N′′′-Octamethyl(but-2-yne)bisamidinium bis(tetraphenylborate)

Ioannis Tiritiris,^a Ralf Kress ^a and Willi Kantlehner ^a ^*

^aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
^*Correspondence e-mail: willi.kantlehner@hs-aalen.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 22 December 2015; accepted 27 January 2016; online 3 February 2016)

The asymmetric unit of the title salt, C₁₂H₂₄N₄²⁺.2C₂₄H₂₀B⁻, comprises half a cation and one tetraphenylborate ion. An inversion centre is situated at the mid-point of the triple C≡C bond in the cation. The bisamidinium C—N bonds [1.3249 (11) and 1.3267 (11) Å] have double-bond character and both positive charges are delocalized between the dimethylamino groups. The bonds between the N atoms and the terminal C-methyl groups all have values characteristic for a typical single bond [1.4656 (12)–1.4687 (12) Å]. The acetylenic bond length [1.1889 (18) Å] is consistent with a triple C≡C bond and the butyne carbon chain is almost linear. C—H⋯π interactions between the bisamidinium methyl H atoms and the phenyl C atoms of the tetraphenylborate ions are present. The phenyl rings form aromatic pockets, in which the cations are embedded. This leads to the formation of a two-dimensional supramolecular pattern in the ab plane.

Keywords: crystal structure; bisamidinium salt; tetraphenylborate; C—H⋯π interactions.

CCDC reference: 1450255

Structure description

Recently, we have described the preparation of N,N,N′,N′,N′′,N′′,N′′′,N′′′-octamethyl(but-2-yne)bisamidinium bis(tetrafluoroborate) by the cleavage of 1,1,1,4,4,4-hexakis(dimethylamino)-2-butyne with trifluoroacetic anhydride (Drandarov et al., 2012 ). The salt reacts with nucleophilic reagents, yielding various amidinium and bis(amidinium) salts and ketene aminals (Drandarov et al., 2015 ). A number of heterocyclic bis(amidinium) salts could also be prepared by cycloaddition reactions (Drandarov & Kantlehner, 2012 ). The title salt is the second one in our series, which has been structurally characterized after anion exchange with sodium tetraphenylborate.

The asymmetric unit contains one half of the cation and one tetraphenylborate ion. An inversion centre is situated at the mid-point of the triple C≡C bond in the cation. Prominent bond parameters in the bisamidinium ion are: N1—C1 = 1.3249 (11) Å and N2—C1 = 1.3267 (11) Å, indicating N—C double-bond character. Both positive charges are distributed between the dimethylamino groups. The bonds between the N atoms and the terminal C-methyl groups, all have values characteristic for a typical single bond [1.4656 (12)–1.4687 (12) Å]. The butyne carbon chain is almost linear, the C1—C2—C2ⁱ angle being 179.0 (1)°. The C2≡C2ⁱ triple bond is 1.1889 (18) Å while the C1—C2 bond length is 1.4377 (12) Å (Fig. 1).

Figure 1
The structure of the title compound with displacement ellipsoids at the 50% probability level. All carbon-bonded H atoms have been omitted for clarity.

The bond lengths of the dication agree very well with the data from the crystal structure analysis of N,N,N′,N′,N′′,N′′,N′′′,N′′′-octamethyl(but-2-yne)bisamidinium bis(tetrafluoroborate) (Drandarov et al., 2012). In the tetraphenylborate salt, the angle between the N1–C1–N2 and N1ⁱ–C1ⁱ–N2ⁱ planes is 0° and the C1—C2—C2ⁱ—C1ⁱ torsion angle is 180.0 (1)°. This is completely different from the tetrafluoroborate salt (Drandarov et al., 2012), where the N–C–N planes between the two amidinium units are nearly perpendicular to each other [85.1 (2)°] and C1—C2—C2ⁱ—C1ⁱ = 101.3 (1)°. The bond lengths and angles in the tetraphenylborate ion are in good agreement with the data for alkali metal tetraphenylborates (Behrens et al., 2012 ).

C—H⋯π interactions between the hydrogen atoms of –N(CH₃)₂ groups of the cation and the phenyl carbon atoms (centroids: Cg1 = C13–C18, Cg2 = C19–C24 and Cg3 = C25–C30) of the tetraphenylborate ion are present (Fig. 2), ranging from 2.54 to 2.85 Å (Table 1). The phenyl rings form aromatic pockets in which the cations are embedded. This leads to the formation of a two-dimensional supramolecular pattern along the ab plane.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the C13–C18, C19–C24 and C25–C30 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯Cg1ⁱ	0.98	2.85	3.401 (1)	116
C5—H5B⋯Cg3ⁱⁱ	0.98	2.59	3.489 (1)	153
C6—H6B⋯Cg2ⁱⁱ	0.98	2.54	3.487 (1)	162
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
C—H⋯π interactions (brown dashed lines) between the H atoms of the bisamidinium ion and the phenyl C atoms (centroids) of the tetraphenylborate ion (ab view). H atoms not involved in hydrogen bonding have been omitted.

Synthesis and crystallization

The title compound was obtained by reacting an acetonitrile solution of N,N,N′,N′,N′′,N′′,N′′′,N′′′-octamethyl(but-2-yne)bisamidinium bis(tetrafluoroborate) (Drandarov et al., 2012b) with two equivalents of sodium tetraphenylborate. After stirring for one hour at room temperature, the precipitated sodium tetrafluoroborate was filtered off. The title compound crystallized from a saturated acetonitrile solution after several days at 273 K, forming yellow single crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	2(C₂₄H₂₀B)·C₁₂H₂₄N₄
M_r	862.77
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	13.8527 (5), 10.4892 (4), 16.7462 (6)
β (°)	103.034 (2)
V (Å³)	2370.60 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.35 × 0.23 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII Duo
No. of measured, independent and observed [I > 2σ(I)] reflections	50722, 7271, 6046
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.113, 1.02
No. of reflections	7271
No. of parameters	302
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.22
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Putz, 2005 ).

Structural data

CCDC reference: 1450255

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616001668/hb4007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001668/hb4007Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616001668/hb4007Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

N,N,N',N',N'',N'',N''',N'''-Octamethylbut-2-yne)bisamidinium bis(tetraphenylborate) top

Crystal data top

2(C₂₄H₂₀B)·C₁₂H₂₄N₄	F(000) = 924
M_r = 862.77	D_x = 1.209 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8527 (5) Å	Cell parameters from 50722 reflections
b = 10.4892 (4) Å	θ = 1.7–30.6°
c = 16.7462 (6) Å	µ = 0.07 mm⁻¹
β = 103.034 (2)°	T = 100 K
V = 2370.60 (15) Å³	Block, yellow
Z = 2	0.35 × 0.23 × 0.10 mm

Data collection top

Bruker Kappa APEXII Duo diffractometer	6046 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Triumph monochromator	θ_max = 30.6°, θ_min = 1.7°
φ scans, and ω scans	h = −19→19
50722 measured reflections	k = −14→14
7271 independent reflections	l = −23→23

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0612P)² + 0.7005P] where P = (F_o² + 2F_c²)/3
7271 reflections	(Δ/σ)_max < 0.001
302 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

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.

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 > 2sigma(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. The crystal was refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.35927 (6)	0.47150 (8)	0.10360 (5)	0.01587 (15)
C1	0.36503 (6)	0.50484 (8)	0.02850 (5)	0.01380 (16)
N2	0.28770 (5)	0.54206 (8)	−0.02893 (5)	0.01533 (15)
C2	0.46046 (7)	0.50074 (9)	0.00825 (5)	0.01554 (17)
C3	0.44900 (7)	0.46323 (11)	0.16970 (6)	0.02152 (19)
H3A	0.4792	0.3789	0.1688	0.032*
H3B	0.4315	0.4763	0.2226	0.032*
H3C	0.4962	0.5290	0.1618	0.032*
C4	0.26820 (7)	0.41956 (11)	0.12146 (6)	0.0228 (2)
H4A	0.2361	0.4851	0.1482	0.034*
H4B	0.2844	0.3458	0.1579	0.034*
H4C	0.2232	0.3931	0.0702	0.034*
C5	0.29145 (7)	0.53857 (11)	−0.11567 (6)	0.02100 (19)
H5A	0.3159	0.6204	−0.1312	0.032*
H5B	0.2249	0.5228	−0.1492	0.032*
H5C	0.3361	0.4702	−0.1246	0.032*
C6	0.20340 (7)	0.60966 (10)	−0.00906 (6)	0.02072 (19)
H6A	0.1480	0.5503	−0.0124	0.031*
H6B	0.1831	0.6795	−0.0481	0.031*
H6C	0.2228	0.6444	0.0466	0.031*
B1	0.48759 (7)	0.85310 (10)	0.22798 (6)	0.01361 (17)
C7	0.51523 (7)	0.83135 (9)	0.13802 (5)	0.01530 (17)
C8	0.44148 (7)	0.82171 (9)	0.06504 (6)	0.01623 (17)
H8	0.3741	0.8182	0.0688	0.019*
C9	0.46258 (7)	0.81705 (9)	−0.01235 (6)	0.01939 (18)
H9	0.4099	0.8123	−0.0597	0.023*
C10	0.55982 (8)	0.81925 (10)	−0.02087 (6)	0.02158 (19)
H10	0.5745	0.8168	−0.0736	0.026*
C11	0.63533 (7)	0.82504 (10)	0.04943 (6)	0.0224 (2)
H11	0.7025	0.8245	0.0450	0.027*
C12	0.61303 (7)	0.83171 (10)	0.12652 (6)	0.01945 (18)
H12	0.6662	0.8367	0.1735	0.023*
C13	0.36643 (6)	0.86150 (9)	0.21106 (5)	0.01375 (16)
C14	0.31746 (7)	0.97595 (9)	0.18302 (6)	0.01610 (17)
H14	0.3559	1.0508	0.1825	0.019*
C15	0.21492 (7)	0.98402 (9)	0.15596 (6)	0.01789 (18)
H15	0.1850	1.0629	0.1363	0.021*
C16	0.15618 (7)	0.87675 (10)	0.15760 (6)	0.01854 (18)
H16	0.0862	0.8815	0.1390	0.022*
C17	0.20162 (7)	0.76264 (10)	0.18688 (6)	0.01761 (18)
H17	0.1625	0.6890	0.1895	0.021*
C18	0.30466 (6)	0.75586 (9)	0.21241 (5)	0.01508 (17)
H18	0.3341	0.6765	0.2315	0.018*
C19	0.53348 (6)	0.74262 (8)	0.29627 (5)	0.01362 (16)
C20	0.62028 (7)	0.67306 (9)	0.29618 (6)	0.01631 (17)
H20	0.6510	0.6835	0.2513	0.020*
C21	0.66342 (7)	0.58937 (9)	0.35897 (6)	0.01956 (18)
H21	0.7224	0.5451	0.3562	0.023*
C22	0.62051 (7)	0.57050 (9)	0.42547 (6)	0.02021 (19)
H22	0.6501	0.5147	0.4688	0.024*
C23	0.53331 (7)	0.63495 (9)	0.42726 (6)	0.01810 (18)
H23	0.5021	0.6221	0.4716	0.022*
C24	0.49160 (6)	0.71839 (9)	0.36407 (5)	0.01535 (17)
H24	0.4320	0.7611	0.3669	0.018*
C25	0.53179 (6)	0.99115 (9)	0.26813 (6)	0.01544 (17)
C26	0.51539 (7)	1.02990 (9)	0.34439 (6)	0.01835 (18)
H26	0.4804	0.9740	0.3725	0.022*
C27	0.54799 (8)	1.14631 (10)	0.38057 (7)	0.0242 (2)
H27	0.5351	1.1683	0.4322	0.029*
C28	0.59942 (8)	1.23028 (10)	0.34106 (8)	0.0279 (2)
H28	0.6223	1.3097	0.3654	0.034*
C29	0.61661 (8)	1.19598 (10)	0.26577 (7)	0.0267 (2)
H29	0.6518	1.2524	0.2382	0.032*
C30	0.58281 (7)	1.07926 (10)	0.22980 (6)	0.02066 (19)
H30	0.5948	1.0588	0.1776	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0133 (3)	0.0207 (4)	0.0138 (3)	0.0001 (3)	0.0034 (3)	0.0011 (3)
C1	0.0132 (4)	0.0139 (4)	0.0144 (4)	−0.0003 (3)	0.0033 (3)	−0.0013 (3)
N2	0.0130 (3)	0.0190 (4)	0.0135 (3)	0.0013 (3)	0.0022 (3)	0.0003 (3)
C2	0.0159 (4)	0.0171 (4)	0.0132 (4)	0.0009 (3)	0.0023 (3)	0.0009 (3)
C3	0.0173 (4)	0.0317 (5)	0.0141 (4)	0.0030 (4)	0.0005 (3)	0.0005 (4)
C4	0.0190 (4)	0.0307 (5)	0.0200 (4)	−0.0057 (4)	0.0073 (3)	0.0030 (4)
C5	0.0201 (4)	0.0298 (5)	0.0124 (4)	0.0000 (4)	0.0023 (3)	0.0001 (3)
C6	0.0150 (4)	0.0251 (5)	0.0212 (4)	0.0057 (3)	0.0023 (3)	−0.0021 (4)
B1	0.0117 (4)	0.0148 (4)	0.0139 (4)	−0.0003 (3)	0.0019 (3)	0.0011 (3)
C7	0.0154 (4)	0.0152 (4)	0.0154 (4)	0.0001 (3)	0.0036 (3)	0.0021 (3)
C8	0.0173 (4)	0.0158 (4)	0.0156 (4)	−0.0005 (3)	0.0036 (3)	0.0001 (3)
C9	0.0251 (5)	0.0179 (4)	0.0148 (4)	−0.0018 (3)	0.0038 (3)	−0.0002 (3)
C10	0.0297 (5)	0.0195 (4)	0.0183 (4)	−0.0013 (4)	0.0112 (4)	0.0007 (3)
C11	0.0211 (4)	0.0248 (5)	0.0241 (5)	0.0005 (4)	0.0109 (4)	0.0029 (4)
C12	0.0157 (4)	0.0240 (5)	0.0190 (4)	0.0007 (3)	0.0046 (3)	0.0033 (4)
C13	0.0132 (4)	0.0165 (4)	0.0114 (4)	0.0000 (3)	0.0024 (3)	−0.0010 (3)
C14	0.0149 (4)	0.0175 (4)	0.0155 (4)	0.0006 (3)	0.0027 (3)	−0.0001 (3)
C15	0.0164 (4)	0.0211 (4)	0.0154 (4)	0.0049 (3)	0.0017 (3)	−0.0006 (3)
C16	0.0122 (4)	0.0280 (5)	0.0148 (4)	0.0010 (3)	0.0015 (3)	−0.0038 (3)
C17	0.0137 (4)	0.0231 (5)	0.0159 (4)	−0.0035 (3)	0.0032 (3)	−0.0040 (3)
C18	0.0139 (4)	0.0170 (4)	0.0140 (4)	−0.0007 (3)	0.0022 (3)	−0.0016 (3)
C19	0.0129 (3)	0.0131 (4)	0.0138 (4)	−0.0020 (3)	0.0010 (3)	−0.0010 (3)
C20	0.0162 (4)	0.0162 (4)	0.0162 (4)	0.0002 (3)	0.0029 (3)	−0.0008 (3)
C21	0.0187 (4)	0.0165 (4)	0.0220 (4)	0.0035 (3)	0.0015 (3)	0.0006 (3)
C22	0.0236 (4)	0.0155 (4)	0.0189 (4)	0.0005 (3)	−0.0008 (3)	0.0031 (3)
C23	0.0210 (4)	0.0170 (4)	0.0157 (4)	−0.0037 (3)	0.0028 (3)	0.0015 (3)
C24	0.0145 (4)	0.0153 (4)	0.0158 (4)	−0.0018 (3)	0.0027 (3)	−0.0003 (3)
C25	0.0113 (3)	0.0154 (4)	0.0175 (4)	0.0009 (3)	−0.0011 (3)	0.0024 (3)
C26	0.0153 (4)	0.0173 (4)	0.0210 (4)	0.0007 (3)	0.0009 (3)	−0.0009 (3)
C27	0.0208 (4)	0.0198 (5)	0.0281 (5)	0.0037 (4)	−0.0027 (4)	−0.0061 (4)
C28	0.0218 (5)	0.0147 (4)	0.0408 (6)	−0.0005 (4)	−0.0066 (4)	−0.0027 (4)
C29	0.0206 (4)	0.0177 (5)	0.0377 (6)	−0.0043 (4)	−0.0018 (4)	0.0083 (4)
C30	0.0174 (4)	0.0189 (4)	0.0237 (5)	−0.0015 (3)	0.0003 (3)	0.0063 (4)

Geometric parameters (Å, º) top

N1—C1	1.3249 (11)	C12—H12	0.9500
N1—C4	1.4656 (12)	C13—C18	1.4034 (12)
N1—C3	1.4687 (12)	C13—C14	1.4064 (13)
C1—N2	1.3267 (11)	C14—C15	1.3928 (12)
C1—C2	1.4377 (12)	C14—H14	0.9500
N2—C5	1.4656 (12)	C15—C16	1.3925 (14)
N2—C6	1.4672 (12)	C15—H15	0.9500
C2—C2ⁱ	1.1889 (18)	C16—C17	1.3892 (14)
C3—H3A	0.9800	C16—H16	0.9500
C3—H3B	0.9800	C17—C18	1.3963 (12)
C3—H3C	0.9800	C17—H17	0.9500
C4—H4A	0.9800	C18—H18	0.9500
C4—H4B	0.9800	C19—C20	1.4068 (12)
C4—H4C	0.9800	C19—C24	1.4097 (12)
C5—H5A	0.9800	C20—C21	1.3964 (13)
C5—H5B	0.9800	C20—H20	0.9500
C5—H5C	0.9800	C21—C22	1.3897 (14)
C6—H6A	0.9800	C21—H21	0.9500
C6—H6B	0.9800	C22—C23	1.3904 (14)
C6—H6C	0.9800	C22—H22	0.9500
B1—C13	1.6404 (13)	C23—C24	1.3942 (13)
B1—C19	1.6514 (13)	C23—H23	0.9500
B1—C7	1.6517 (13)	C24—H24	0.9500
B1—C25	1.6547 (14)	C25—C30	1.4037 (13)
C7—C8	1.4086 (12)	C25—C26	1.4065 (13)
C7—C12	1.4107 (12)	C26—C27	1.3923 (14)
C8—C9	1.3923 (13)	C26—H26	0.9500
C8—H8	0.9500	C27—C28	1.3905 (17)
C9—C10	1.3863 (14)	C27—H27	0.9500
C9—H9	0.9500	C28—C29	1.3826 (18)
C10—C11	1.3886 (15)	C28—H28	0.9500
C10—H10	0.9500	C29—C30	1.3978 (15)
C11—C12	1.3953 (14)	C29—H29	0.9500
C11—H11	0.9500	C30—H30	0.9500

C1—N1—C4	122.05 (8)	C11—C12—H12	118.5
C1—N1—C3	120.61 (8)	C7—C12—H12	118.5
C4—N1—C3	116.44 (8)	C18—C13—C14	115.43 (8)
N1—C1—N2	123.66 (8)	C18—C13—B1	123.96 (8)
N1—C1—C2	118.12 (8)	C14—C13—B1	120.08 (8)
N2—C1—C2	118.22 (8)	C15—C14—C13	122.70 (9)
C1—N2—C5	120.52 (8)	C15—C14—H14	118.7
C1—N2—C6	122.11 (8)	C13—C14—H14	118.7
C5—N2—C6	116.41 (8)	C16—C15—C14	120.14 (9)
C2ⁱ—C2—C1	179.01 (14)	C16—C15—H15	119.9
N1—C3—H3A	109.5	C14—C15—H15	119.9
N1—C3—H3B	109.5	C17—C16—C15	118.87 (8)
H3A—C3—H3B	109.5	C17—C16—H16	120.6
N1—C3—H3C	109.5	C15—C16—H16	120.6
H3A—C3—H3C	109.5	C16—C17—C18	120.17 (9)
H3B—C3—H3C	109.5	C16—C17—H17	119.9
N1—C4—H4A	109.5	C18—C17—H17	119.9
N1—C4—H4B	109.5	C17—C18—C13	122.66 (9)
H4A—C4—H4B	109.5	C17—C18—H18	118.7
N1—C4—H4C	109.5	C13—C18—H18	118.7
H4A—C4—H4C	109.5	C20—C19—C24	114.49 (8)
H4B—C4—H4C	109.5	C20—C19—B1	123.97 (8)
N2—C5—H5A	109.5	C24—C19—B1	121.35 (8)
N2—C5—H5B	109.5	C21—C20—C19	123.09 (9)
H5A—C5—H5B	109.5	C21—C20—H20	118.5
N2—C5—H5C	109.5	C19—C20—H20	118.5
H5A—C5—H5C	109.5	C22—C21—C20	120.35 (9)
H5B—C5—H5C	109.5	C22—C21—H21	119.8
N2—C6—H6A	109.5	C20—C21—H21	119.8
N2—C6—H6B	109.5	C21—C22—C23	118.60 (9)
H6A—C6—H6B	109.5	C21—C22—H22	120.7
N2—C6—H6C	109.5	C23—C22—H22	120.7
H6A—C6—H6C	109.5	C22—C23—C24	120.15 (9)
H6B—C6—H6C	109.5	C22—C23—H23	119.9
C13—B1—C19	112.11 (7)	C24—C23—H23	119.9
C13—B1—C7	106.77 (7)	C23—C24—C19	123.30 (8)
C19—B1—C7	113.74 (7)	C23—C24—H24	118.3
C13—B1—C25	107.07 (7)	C19—C24—H24	118.3
C19—B1—C25	106.46 (7)	C30—C25—C26	115.21 (9)
C7—B1—C25	110.54 (7)	C30—C25—B1	124.66 (8)
C8—C7—C12	114.38 (8)	C26—C25—B1	120.07 (8)
C8—C7—B1	121.95 (8)	C27—C26—C25	123.06 (10)
C12—C7—B1	123.46 (8)	C27—C26—H26	118.5
C9—C8—C7	123.14 (9)	C25—C26—H26	118.5
C9—C8—H8	118.4	C28—C27—C26	119.95 (10)
C7—C8—H8	118.4	C28—C27—H27	120.0
C10—C9—C8	120.53 (9)	C26—C27—H27	120.0
C10—C9—H9	119.7	C29—C28—C27	118.76 (10)
C8—C9—H9	119.7	C29—C28—H28	120.6
C9—C10—C11	118.50 (9)	C27—C28—H28	120.6
C9—C10—H10	120.7	C28—C29—C30	120.73 (10)
C11—C10—H10	120.7	C28—C29—H29	119.6
C10—C11—C12	120.32 (9)	C30—C29—H29	119.6
C10—C11—H11	119.8	C29—C30—C25	122.28 (10)
C12—C11—H11	119.8	C29—C30—H30	118.9
C11—C12—C7	123.09 (9)	C25—C30—H30	118.9

C4—N1—C1—N2	27.07 (14)	C15—C16—C17—C18	−1.38 (14)
C3—N1—C1—N2	−164.18 (9)	C16—C17—C18—C13	0.89 (14)
C4—N1—C1—C2	−153.09 (9)	C14—C13—C18—C17	0.72 (13)
C3—N1—C1—C2	15.67 (13)	B1—C13—C18—C17	−170.95 (8)
N1—C1—N2—C5	−160.48 (9)	C13—B1—C19—C20	149.05 (8)
C2—C1—N2—C5	19.68 (13)	C7—B1—C19—C20	27.79 (12)
N1—C1—N2—C6	31.11 (14)	C25—B1—C19—C20	−94.19 (10)
C2—C1—N2—C6	−148.73 (9)	C13—B1—C19—C24	−36.27 (11)
C13—B1—C7—C8	−0.75 (12)	C7—B1—C19—C24	−157.52 (8)
C19—B1—C7—C8	123.44 (9)	C25—B1—C19—C24	80.50 (9)
C25—B1—C7—C8	−116.87 (9)	C24—C19—C20—C21	−1.70 (13)
C13—B1—C7—C12	173.68 (8)	B1—C19—C20—C21	173.32 (9)
C19—B1—C7—C12	−62.12 (11)	C19—C20—C21—C22	0.50 (15)
C25—B1—C7—C12	57.56 (11)	C20—C21—C22—C23	1.03 (14)
C12—C7—C8—C9	−1.99 (14)	C21—C22—C23—C24	−1.24 (14)
B1—C7—C8—C9	172.92 (9)	C22—C23—C24—C19	−0.06 (14)
C7—C8—C9—C10	1.31 (15)	C20—C19—C24—C23	1.48 (13)
C8—C9—C10—C11	0.56 (15)	B1—C19—C24—C23	−173.68 (8)
C9—C10—C11—C12	−1.58 (15)	C13—B1—C25—C30	−114.00 (9)
C10—C11—C12—C7	0.83 (16)	C19—B1—C25—C30	125.92 (9)
C8—C7—C12—C11	0.92 (14)	C7—B1—C25—C30	1.93 (12)
B1—C7—C12—C11	−173.89 (9)	C13—B1—C25—C26	63.10 (10)
C19—B1—C13—C18	−34.32 (12)	C19—B1—C25—C26	−56.98 (10)
C7—B1—C13—C18	90.87 (10)	C7—B1—C25—C26	179.03 (8)
C25—B1—C13—C18	−150.71 (8)	C30—C25—C26—C27	−0.75 (13)
C19—B1—C13—C14	154.37 (8)	B1—C25—C26—C27	−178.12 (8)
C7—B1—C13—C14	−80.44 (10)	C25—C26—C27—C28	−0.03 (15)
C25—B1—C13—C14	37.98 (11)	C26—C27—C28—C29	0.36 (15)
C18—C13—C14—C15	−1.88 (13)	C27—C28—C29—C30	0.14 (15)
B1—C13—C14—C15	170.14 (8)	C28—C29—C30—C25	−1.01 (15)
C13—C14—C15—C16	1.44 (14)	C26—C25—C30—C29	1.26 (13)
C14—C15—C16—C17	0.26 (14)	B1—C25—C30—C29	178.49 (9)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C13–C18, C19–C24 and C25–C30 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cg1ⁱⁱ	0.98	2.85	3.401 (1)	116
C5—H5B···Cg3ⁱⁱⁱ	0.98	2.59	3.489 (1)	153
C6—H6B···Cg2ⁱⁱⁱ	0.98	2.54	3.487 (1)	162

Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, −y+3/2, z−1/2.

Acknowledgements

The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the diffraction data and Dr K. Drandarov (Institut für Organische Chemie, Universität Stuttgart) for the sample of N,N,N′,N′,N′′,N′′,N′′′,N′′′-octamethyl(but-2-yne)bisamidinium bis(tetrafluoroborate).

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