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Acta Cryst. (2013). E69, o292    [ doi:10.1107/S1600536813001992 ]

N,N,N',N',N''-Pentamethyl-N''-[3-(trimethylazaniumyl)propyl]guanidinium bis(tetraphenylborate)

I. Tiritiris

Abstract top

In the crystal structure of the title salt, C12H30N42+·2C24H20B-, the C-N bond lengths in the central CN3 unit of the guanidinium ion are 1.3388 (17), 1.3390 (16) and 1.3540 (17) Å, indicating partial double-bond character in each. The central C atom is bonded to the three N atoms in a nearly ideal trigonal-planar geometry and the positive charge is delocalized in the CN3 plane. The bonds between the N atoms and the terminal C-methyl groups of the guanidinium moiety, all have values close to a typical single bond [1.4630 (16)-1.4697 (17) Å]. C-H...[pi] interactions are present between the guanidinium H atoms and the phenyl C atoms of one tetraphenylborate ion. The phenyl rings form a kind of aromatic pocket, in which the guanidinium ion is embedded.

Comment top

Molecules in which alkylamino groups are connected with a guanidine function represent promising candidates for CO2 capture, since in such type of compounds two nitrogen centers with different basicity are present, which can react with CO2. Guanidines with additional basic nitrogen functions like tertiary amino groups are well known in the literature (Tiritiris & Kantlehner, 2012), except of their peralkylated guanidinium salts. By alkylation of the corresponding aminoguanidine with dimethyl sulfate and subsequent anion exchange, it was possible to obtain the here presented title compound. According to the structure analysis, the C1–N1 bond of the the CN3 unit is 1.3390 (16) Å, C1–N2 = 1.3388 (17) Å and C1–N3 = 1.3540 (17) Å, showing partial double-bond character. The N–C1–N angles are: 121.12 (12)° (N1–C1–N2), 120.28 (12)° (N1–C1–N3) and 118.60 (11)° (N2–C1–N3), which indicates a nearly ideal trigonal-planar surrounding of the carbon centre by the nitrogen atoms. The positive charge is completely delocalized on the CN3 plane (Fig. 1). The bonds between the N atoms and the terminal C-methyl groups of the guanidinium moiety all have values close to a typical single bond [1.4630 (16)–1.4697 (17) Å]. The C–N bond lengths in the terminal trimethylammonium group are slightly elongated [1.4983 (17)–1.5171 (16) Å]. The bond lengths and angles in the tetraphenylborate ions are in good agreement with the data from the crystal structure analysis of the alkali metal tetraphenylborates (Behrens et al., 2012). C–H···π interactions between the hydrogen atoms of –N(CH3)2, –CH2 and –N+(CH3)3 groups of the guanidinium ion and the phenyl carbon atoms of only one tetraphenylborate ion are mainly present, ranging from 2.724 (2) to 2.895 (2) Å (Fig. 2).

Related literature top

For the synthesis of N''-[3-(dimethylamino)propyl]- N,N,N',N'-tetramethylguanidine, see: Tiritiris & Kantlehner (2012). For the crystal structures of alkali metal tetraphenylborates, see: Behrens et al. (2012).

Experimental top

The title compound was obtained by reaction of N''-[3-(dimethylamino)propyl]-N,N,N',N'-tetramethylguanidine (Tiritiris & Kantlehner, 2012) with two equivalents dimethyl sulfate in acetonitrile at room temperature. After evaporation of the solvent the crude N,N,N',N',N''-pentamethyl-N''-[3-(trimethylazaniumyl)propyl]-guanidinium bis(methylsulfate) (I) was washed with diethylether and dried in vacuo. 1.0 g (2.2 mmol) of (I) was dissolved in 20 ml acetonitrile and 1.51 g (4.4 mmol) of sodium tetraphenylborate in 20 ml acetonitrile were added. After stirring for one hour at room temperature, the precipitated sodium methylsulfate was filtered off. The title compound crystallized from a saturated acetone solution after several days at 273 K, forming colorless single crystals. Yield: 1.34 g (68.2%). 1H NMR (500 MHz, CD3CN/TMS): δ = 2.10 (broad s, 1 H, –CH2), 2.35 (broad s, 1 H, –CH2), 2.95 (s, 3 H, –NCH3), 2.98 [s, 12 H, –N(CH3)2], 3.13 [s, 9 H, –N+(CH3)3], 3.20–3.40 (m, 4 H, –CH2), 6.86–6.91 (t, 8 H, –C6H5), 6.96–7.04 (t, 16 H,–C6H5), 7.25–7.30 (m, 16 H, –C6H5). 13C NMR (125 MHz, CD3CN/TMS): δ = 22.5 (–CH2), 37.9 (–NCH3), 40.5 [–N(CH3)2], 49.8 (–CH2), 53.6–53.9 [–N+(CH3)3], 64.3 (–CH2), 122.3 (–C6H5), 126.1 – 126.7 (–C6H5), 137.0 (–C6H5), 162.9 – 164.0 (–C6H5), 165.5 (N3C+).

Refinement top

The hydrogen atoms of the methyl groups were allowed to rotate with a fixed angle around the C–N bond to best fit the experimental electron density, with U(H) set to 1.5 Ueq(C) and d(C—H) = 0.98 Å. The remaining H atoms were placed in calculated positions with d(C—H) = 0.99 Å (H atoms in CH2 groups) and (C—H) = 0.95 Å (H atoms in aromatic rings). They were included in the refinement in the riding model approximation, with U(H) set to 1.2 Ueq(C).

Computing details top

Data collection: COLLECT (Hooft, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound with displacement ellipsoids at the 50% probability level. All hydrogen atoms were omitted for the sake of clarity.
[Figure 2] Fig. 2. C–H···π interactions (brown dashed lines) between the hydrogen atoms of the guanidinium ion and the phenyl carbon atoms of one tetraphenylborate ion.
N,N,N',N',N''-Pentamethyl-N''-[3-(trimethylazaniumyl)propyl]guanidinium bis(tetraphenylborate) top
Crystal data top
C12H30N4+·2C24H20B−F(000) = 1872
Mr = 868.82Dx = 1.168 Mg m−3
Monoclinic, P21/cMelting point: 502 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 17.7622 (4) ÅCell parameters from 11929 reflections
b = 16.1667 (3) Åθ = 0.4–28.3°
c = 17.3787 (4) ŵ = 0.07 mm−1
β = 98.045 (1)°T = 100 K
V = 4941.29 (18) Å3Polyhedral, colorless
Z = 40.27 × 0.25 × 0.20 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer		8821 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.038
Graphite monochromatorθmax = 28.3°, θmin = 1.2°
φ scans, and ω scansh = −23→23
22713 measured reflectionsk = −21→21
12056 independent reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: difference Fourier map
wR(F2) = 0.108H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0389P)2 + 2.0808P]
where P = (Fo2 + 2Fc2)/3
12056 reflections(Δ/σ)max < 0.001
603 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C12H30N4+·2C24H20B−V = 4941.29 (18) Å3
Mr = 868.82Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.7622 (4) ŵ = 0.07 mm−1
b = 16.1667 (3) ÅT = 100 K
c = 17.3787 (4) Å0.27 × 0.25 × 0.20 mm
β = 98.045 (1)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer		8821 reflections with I > 2σ(I)
22713 measured reflectionsRint = 0.038
12056 independent reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.31 e Å−3
S = 1.02Δρmin = −0.27 e Å−3
12056 reflectionsAbsolute structure: ?
603 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
N10.72188 (6)0.33127 (7)0.03324 (6)0.0155 (2)
N20.82034 (6)0.28130 (7)0.12425 (6)0.0163 (2)
N30.81518 (6)0.42077 (7)0.09366 (6)0.0152 (2)
N40.73663 (6)0.66166 (7)0.24912 (6)0.0134 (2)
C10.78526 (7)0.34387 (8)0.08336 (7)0.0136 (2)
C20.70205 (8)0.38292 (9)−0.03593 (8)0.0205 (3)
H2A0.65720.4163−0.03000.031*
H2B0.69090.3475−0.08190.031*
H2C0.74480.4195−0.04220.031*
C30.66849 (8)0.26374 (9)0.04174 (9)0.0216 (3)
H3A0.67740.21830.00680.032*
H3B0.61620.28390.02850.032*
H3C0.67620.24390.09560.032*
C40.82067 (8)0.19610 (9)0.09563 (9)0.0211 (3)
H4A0.78720.16200.12290.032*
H4B0.87250.17410.10510.032*
H4C0.80250.19520.03970.032*
C50.86344 (8)0.29427 (10)0.20146 (8)0.0231 (3)
H5A0.91790.28870.19860.035*
H5B0.84820.25300.23760.035*
H5C0.85310.34980.21990.035*
C60.89702 (7)0.43361 (9)0.09621 (9)0.0208 (3)
H6A0.92110.38160.08380.031*
H6B0.91880.45180.14840.031*
H6C0.90600.47590.05820.031*
C70.76724 (7)0.49447 (8)0.09672 (7)0.0156 (3)
H7A0.71330.47730.09200.019*
H7B0.77310.53090.05210.019*
C80.78810 (7)0.54320 (8)0.17278 (7)0.0153 (3)
H8A0.79890.50450.21710.018*
H8B0.83410.57710.17000.018*
C90.72114 (7)0.59887 (8)0.18394 (7)0.0146 (2)
H9A0.70500.62890.13480.017*
H9B0.67810.56350.19420.017*
C100.78839 (8)0.72864 (8)0.22812 (8)0.0183 (3)
H10A0.79860.76780.27140.027*
H10B0.76410.75780.18170.027*
H10C0.83640.70420.21750.027*
C110.66238 (7)0.70012 (9)0.26196 (8)0.0183 (3)
H11A0.67190.74430.30080.027*
H11B0.62970.65790.28060.027*
H11C0.63710.72330.21290.027*
C120.77035 (8)0.62061 (9)0.32345 (7)0.0176 (3)
H12A0.82130.60010.31830.026*
H12B0.73800.57420.33460.026*
H12C0.77380.66070.36610.026*
B10.92120 (8)0.77122 (9)0.01258 (8)0.0130 (3)
C130.84884 (7)0.70967 (8)−0.01978 (7)0.0139 (2)
C140.85773 (8)0.64051 (9)−0.06727 (8)0.0197 (3)
H14A0.90760.6256−0.07590.024*
C150.79684 (9)0.59327 (9)−0.10199 (8)0.0230 (3)
H15A0.80580.5482−0.13470.028*
C160.72308 (9)0.61134 (9)−0.08931 (8)0.0222 (3)
H16A0.68120.5800−0.11380.027*
C170.71217 (8)0.67606 (9)−0.04010 (8)0.0211 (3)
H17A0.66240.6884−0.02920.025*
C180.77377 (8)0.72337 (9)−0.00630 (8)0.0172 (3)
H18A0.76440.76710.02760.021*
C190.90010 (7)0.83216 (8)0.08230 (7)0.0131 (2)
C200.84233 (7)0.89228 (8)0.06892 (7)0.0148 (2)
H20A0.81380.89590.01860.018*
C210.82520 (7)0.94659 (8)0.12597 (8)0.0170 (3)
H21A0.78620.98670.11390.020*
C220.86491 (8)0.94244 (9)0.20072 (8)0.0180 (3)
H22A0.85290.97880.24020.022*
C230.92215 (8)0.88448 (9)0.21657 (8)0.0179 (3)
H23A0.94990.88100.26730.021*
C240.93943 (7)0.83101 (8)0.15836 (7)0.0157 (3)
H24A0.97950.79220.17070.019*
C250.99644 (7)0.71673 (8)0.04716 (7)0.0144 (2)
C260.99181 (8)0.63813 (9)0.08039 (8)0.0189 (3)
H26A0.94340.61250.07780.023*
C271.05539 (8)0.59606 (9)0.11711 (8)0.0212 (3)
H27A1.04990.54260.13830.025*
C281.12671 (8)0.63228 (9)0.12264 (8)0.0201 (3)
H28A1.17020.60420.14800.024*
C291.13376 (8)0.71018 (9)0.09060 (8)0.0186 (3)
H29A1.18230.73570.09410.022*
C301.06967 (7)0.75080 (8)0.05334 (8)0.0163 (3)
H30A1.07580.80370.03120.020*
C310.94239 (7)0.82836 (8)−0.06068 (7)0.0135 (2)
C320.95366 (7)0.79298 (8)−0.13195 (8)0.0159 (3)
H32A0.94830.7348−0.13810.019*
C330.97242 (7)0.83945 (9)−0.19412 (7)0.0170 (3)
H33A0.97940.8126−0.24130.020*
C340.98100 (7)0.92435 (9)−0.18763 (8)0.0179 (3)
H34A0.99290.9564−0.23020.022*
C350.97190 (8)0.96169 (9)−0.11763 (8)0.0189 (3)
H35A0.97861.0197−0.11170.023*
C360.95301 (7)0.91444 (8)−0.05604 (7)0.0161 (3)
H36A0.94700.9416−0.00880.019*
B20.56950 (8)0.36867 (9)0.27014 (8)0.0139 (3)
C370.49422 (7)0.35924 (8)0.31507 (8)0.0165 (3)
C380.49765 (8)0.31050 (9)0.38226 (8)0.0215 (3)
H38A0.54290.28030.39900.026*
C390.43758 (9)0.30464 (10)0.42539 (9)0.0284 (3)
H39A0.44260.27180.47110.034*
C400.37027 (9)0.34683 (10)0.40166 (10)0.0325 (4)
H40A0.32970.34490.43190.039*
C410.36309 (9)0.39164 (10)0.33346 (11)0.0300 (4)
H41A0.31650.41880.31540.036*
C420.42396 (8)0.39720 (9)0.29082 (9)0.0213 (3)
H42A0.41750.42780.24370.026*
C430.55692 (7)0.44382 (8)0.20609 (7)0.0147 (3)
C440.53044 (7)0.52126 (8)0.22770 (8)0.0168 (3)
H44A0.52210.52900.28000.020*
C450.51585 (7)0.58709 (9)0.17622 (8)0.0188 (3)
H45A0.49560.63740.19290.023*
C460.53105 (8)0.57886 (9)0.10041 (8)0.0194 (3)
H46A0.52130.62330.06460.023*
C470.56067 (7)0.50486 (9)0.07758 (8)0.0185 (3)
H47A0.57310.49930.02640.022*
C480.57231 (7)0.43850 (9)0.12931 (7)0.0159 (3)
H48A0.59130.38800.11180.019*
C490.58100 (7)0.27853 (8)0.22960 (7)0.0149 (3)
C500.52557 (8)0.25007 (9)0.16949 (8)0.0182 (3)
H50A0.48360.28490.15200.022*
C510.52972 (8)0.17294 (9)0.13454 (8)0.0216 (3)
H51A0.49110.15640.09410.026*
C520.59017 (9)0.12011 (9)0.15866 (8)0.0229 (3)
H52A0.59380.06800.13420.027*
C530.64505 (9)0.14484 (9)0.21901 (9)0.0222 (3)
H53A0.68600.10890.23710.027*
C540.64020 (8)0.22249 (9)0.25323 (8)0.0182 (3)
H54A0.67860.23810.29430.022*
C550.64417 (7)0.39616 (8)0.33197 (7)0.0149 (3)
C560.71816 (7)0.38922 (8)0.31254 (8)0.0166 (3)
H56A0.72430.36890.26250.020*
C570.78282 (8)0.41093 (8)0.36350 (8)0.0183 (3)
H57A0.83180.40350.34850.022*
C580.77572 (8)0.44333 (8)0.43604 (8)0.0193 (3)
H58A0.81960.45720.47150.023*
C590.70356 (8)0.45515 (9)0.45582 (8)0.0205 (3)
H59A0.69770.47940.50440.025*
C600.63950 (8)0.43173 (9)0.40482 (8)0.0186 (3)
H60A0.59070.44020.42000.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0156 (5)0.0144 (5)0.0166 (5)−0.0024 (4)0.0024 (4)−0.0029 (4)
N20.0192 (6)0.0131 (5)0.0168 (5)−0.0002 (4)0.0038 (4)−0.0011 (4)
N30.0128 (5)0.0127 (5)0.0204 (5)0.0001 (4)0.0036 (4)−0.0029 (4)
N40.0144 (5)0.0099 (5)0.0154 (5)0.0000 (4)0.0009 (4)−0.0007 (4)
C10.0141 (6)0.0144 (6)0.0135 (6)−0.0014 (5)0.0061 (5)−0.0028 (5)
C20.0220 (7)0.0228 (7)0.0161 (6)0.0030 (6)0.0009 (5)−0.0023 (5)
C30.0171 (7)0.0188 (7)0.0290 (7)−0.0066 (5)0.0041 (5)−0.0073 (6)
C40.0253 (7)0.0116 (6)0.0272 (7)0.0014 (5)0.0072 (6)−0.0014 (5)
C50.0255 (7)0.0260 (8)0.0170 (6)0.0066 (6)0.0004 (5)−0.0008 (6)
C60.0135 (6)0.0182 (7)0.0318 (7)−0.0025 (5)0.0064 (5)−0.0047 (6)
C70.0167 (6)0.0138 (6)0.0163 (6)0.0020 (5)0.0022 (5)−0.0027 (5)
C80.0157 (6)0.0135 (6)0.0164 (6)−0.0003 (5)0.0013 (5)−0.0022 (5)
C90.0156 (6)0.0137 (6)0.0141 (6)−0.0016 (5)0.0007 (5)−0.0031 (5)
C100.0192 (6)0.0125 (6)0.0232 (7)−0.0039 (5)0.0029 (5)0.0014 (5)
C110.0170 (6)0.0158 (7)0.0222 (6)0.0030 (5)0.0034 (5)−0.0036 (5)
C120.0219 (7)0.0166 (6)0.0137 (6)0.0016 (5)0.0001 (5)0.0013 (5)
B10.0133 (6)0.0110 (7)0.0149 (6)−0.0004 (5)0.0025 (5)0.0008 (5)
C130.0177 (6)0.0116 (6)0.0125 (5)−0.0011 (5)0.0028 (5)0.0028 (5)
C140.0229 (7)0.0159 (7)0.0219 (7)−0.0038 (5)0.0090 (5)−0.0007 (5)
C150.0356 (8)0.0172 (7)0.0172 (6)−0.0076 (6)0.0078 (6)−0.0038 (5)
C160.0268 (7)0.0189 (7)0.0188 (6)−0.0087 (6)−0.0045 (5)0.0033 (5)
C170.0156 (6)0.0201 (7)0.0266 (7)−0.0008 (5)−0.0004 (5)0.0035 (6)
C180.0191 (6)0.0141 (6)0.0183 (6)0.0003 (5)0.0023 (5)0.0005 (5)
C190.0147 (6)0.0104 (6)0.0147 (6)−0.0025 (5)0.0039 (5)0.0018 (5)
C200.0151 (6)0.0140 (6)0.0149 (6)−0.0019 (5)0.0008 (5)0.0010 (5)
C210.0160 (6)0.0144 (6)0.0215 (6)0.0000 (5)0.0055 (5)−0.0001 (5)
C220.0212 (7)0.0174 (7)0.0166 (6)−0.0047 (5)0.0074 (5)−0.0031 (5)
C230.0201 (6)0.0197 (7)0.0137 (6)−0.0053 (5)0.0023 (5)0.0018 (5)
C240.0171 (6)0.0135 (6)0.0165 (6)−0.0019 (5)0.0025 (5)0.0037 (5)
C250.0170 (6)0.0122 (6)0.0147 (6)0.0016 (5)0.0044 (5)−0.0003 (5)
C260.0182 (6)0.0153 (7)0.0242 (7)−0.0001 (5)0.0067 (5)0.0036 (5)
C270.0240 (7)0.0147 (7)0.0259 (7)0.0033 (5)0.0076 (6)0.0062 (5)
C280.0190 (7)0.0210 (7)0.0204 (6)0.0071 (5)0.0030 (5)0.0026 (5)
C290.0149 (6)0.0201 (7)0.0210 (6)0.0004 (5)0.0030 (5)−0.0014 (5)
C300.0181 (6)0.0132 (6)0.0182 (6)0.0007 (5)0.0047 (5)0.0011 (5)
C310.0105 (6)0.0146 (6)0.0150 (6)−0.0004 (5)0.0001 (4)0.0018 (5)
C320.0154 (6)0.0128 (6)0.0197 (6)0.0012 (5)0.0029 (5)0.0002 (5)
C330.0156 (6)0.0215 (7)0.0145 (6)0.0011 (5)0.0035 (5)−0.0012 (5)
C340.0170 (6)0.0210 (7)0.0158 (6)−0.0037 (5)0.0021 (5)0.0036 (5)
C350.0217 (7)0.0153 (6)0.0191 (6)−0.0062 (5)0.0012 (5)0.0004 (5)
C360.0180 (6)0.0168 (7)0.0133 (6)−0.0028 (5)0.0018 (5)−0.0019 (5)
B20.0127 (6)0.0133 (7)0.0158 (6)−0.0006 (5)0.0024 (5)−0.0026 (5)
C370.0156 (6)0.0146 (6)0.0197 (6)−0.0054 (5)0.0041 (5)−0.0061 (5)
C380.0211 (7)0.0232 (7)0.0204 (7)−0.0070 (6)0.0041 (5)−0.0033 (6)
C390.0372 (9)0.0284 (8)0.0218 (7)−0.0173 (7)0.0122 (6)−0.0069 (6)
C400.0298 (8)0.0272 (8)0.0463 (10)−0.0156 (7)0.0254 (7)−0.0185 (7)
C410.0180 (7)0.0207 (8)0.0538 (10)−0.0053 (6)0.0144 (7)−0.0102 (7)
C420.0165 (6)0.0156 (7)0.0324 (8)−0.0035 (5)0.0061 (6)−0.0049 (6)
C430.0099 (6)0.0146 (6)0.0193 (6)−0.0020 (5)0.0011 (5)−0.0014 (5)
C440.0148 (6)0.0166 (7)0.0193 (6)−0.0011 (5)0.0033 (5)−0.0036 (5)
C450.0137 (6)0.0151 (6)0.0271 (7)0.0023 (5)0.0004 (5)−0.0022 (5)
C460.0166 (6)0.0180 (7)0.0218 (6)0.0029 (5)−0.0036 (5)0.0024 (5)
C470.0157 (6)0.0225 (7)0.0164 (6)0.0011 (5)−0.0012 (5)−0.0011 (5)
C480.0125 (6)0.0164 (6)0.0183 (6)0.0002 (5)0.0000 (5)−0.0035 (5)
C490.0164 (6)0.0130 (6)0.0163 (6)−0.0028 (5)0.0053 (5)0.0002 (5)
C500.0183 (6)0.0163 (6)0.0198 (6)−0.0027 (5)0.0024 (5)−0.0004 (5)
C510.0275 (7)0.0182 (7)0.0196 (6)−0.0084 (6)0.0048 (5)−0.0030 (5)
C520.0335 (8)0.0132 (6)0.0244 (7)−0.0037 (6)0.0129 (6)−0.0027 (6)
C530.0261 (7)0.0143 (7)0.0274 (7)0.0027 (6)0.0081 (6)0.0034 (6)
C540.0201 (7)0.0157 (6)0.0193 (6)−0.0004 (5)0.0042 (5)0.0026 (5)
C550.0158 (6)0.0112 (6)0.0173 (6)−0.0007 (5)0.0014 (5)0.0006 (5)
C560.0174 (6)0.0142 (6)0.0181 (6)−0.0008 (5)0.0024 (5)−0.0003 (5)
C570.0142 (6)0.0145 (6)0.0258 (7)0.0001 (5)0.0009 (5)0.0023 (5)
C580.0212 (7)0.0130 (6)0.0210 (6)−0.0028 (5)−0.0057 (5)0.0033 (5)
C590.0267 (7)0.0171 (7)0.0171 (6)−0.0036 (6)0.0015 (5)−0.0026 (5)
C600.0187 (6)0.0168 (7)0.0205 (6)−0.0019 (5)0.0033 (5)−0.0015 (5)
Geometric parameters (Å, º) top
N1—C11.3390 (16)C25—C301.4029 (18)
N1—C21.4655 (17)C25—C261.4029 (18)
N1—C31.4671 (17)C26—C271.3942 (19)
N2—C11.3388 (17)C26—H26A0.9500
N2—C51.4638 (17)C27—C281.387 (2)
N2—C41.4648 (17)C27—H27A0.9500
N3—C11.3540 (17)C28—C291.390 (2)
N3—C61.4630 (16)C28—H28A0.9500
N3—C71.4697 (17)C29—C301.3928 (19)
N4—C101.4983 (17)C29—H29A0.9500
N4—C121.5006 (16)C30—H30A0.9500
N4—C111.5027 (16)C31—C321.4039 (18)
N4—C91.5171 (16)C31—C361.4051 (18)
C2—H2A0.9800C32—C331.3941 (19)
C2—H2B0.9800C32—H32A0.9500
C2—H2C0.9800C33—C341.384 (2)
C3—H3A0.9800C33—H33A0.9500
C3—H3B0.9800C34—C351.3875 (19)
C3—H3C0.9800C34—H34A0.9500
C4—H4A0.9800C35—C361.3937 (19)
C4—H4B0.9800C35—H35A0.9500
C4—H4C0.9800C36—H36A0.9500
C5—H5A0.9800B2—C431.642 (2)
C5—H5B0.9800B2—C491.6438 (19)
C5—H5C0.9800B2—C551.6470 (19)
C6—H6A0.9800B2—C371.6471 (19)
C6—H6B0.9800C37—C421.4015 (19)
C6—H6C0.9800C37—C381.403 (2)
C7—C81.5389 (17)C38—C391.390 (2)
C7—H7A0.9900C38—H38A0.9500
C7—H7B0.9900C39—C401.388 (3)
C8—C91.5254 (18)C39—H39A0.9500
C8—H8A0.9900C40—C411.380 (3)
C8—H8B0.9900C40—H40A0.9500
C9—H9A0.9900C41—C421.397 (2)
C9—H9B0.9900C41—H41A0.9500
C10—H10A0.9800C42—H42A0.9500
C10—H10B0.9800C43—C481.4017 (18)
C10—H10C0.9800C43—C441.4067 (18)
C11—H11A0.9800C44—C451.3911 (19)
C11—H11B0.9800C44—H44A0.9500
C11—H11C0.9800C45—C461.388 (2)
C12—H12A0.9800C45—H45A0.9500
C12—H12B0.9800C46—C471.387 (2)
C12—H12C0.9800C46—H46A0.9500
B1—C251.6427 (19)C47—C481.3963 (19)
B1—C191.6451 (19)C47—H47A0.9500
B1—C311.6584 (19)C48—H48A0.9500
B1—C131.6600 (19)C49—C541.4051 (19)
C13—C181.4034 (18)C49—C501.4088 (18)
C13—C141.4116 (19)C50—C511.393 (2)
C14—C151.391 (2)C50—H50A0.9500
C14—H14A0.9500C51—C521.390 (2)
C15—C161.390 (2)C51—H51A0.9500
C15—H15A0.9500C52—C531.387 (2)
C16—C171.382 (2)C52—H52A0.9500
C16—H16A0.9500C53—C541.397 (2)
C17—C181.3955 (19)C53—H53A0.9500
C17—H17A0.9500C54—H54A0.9500
C18—H18A0.9500C55—C601.4034 (18)
C19—C241.4060 (17)C55—C561.4063 (18)
C19—C201.4089 (18)C56—C571.3935 (18)
C20—C211.3895 (19)C56—H56A0.9500
C20—H20A0.9500C57—C581.387 (2)
C21—C221.3904 (19)C57—H57A0.9500
C21—H21A0.9500C58—C591.386 (2)
C22—C231.382 (2)C58—H58A0.9500
C22—H22A0.9500C59—C601.3933 (19)
C23—C241.3971 (19)C59—H59A0.9500
C23—H23A0.9500C60—H60A0.9500
C24—H24A0.9500
C1—N1—C2122.05 (11)C22—C23—C24120.35 (12)
C1—N1—C3122.97 (11)C22—C23—H23A119.8
C2—N1—C3114.96 (11)C24—C23—H23A119.8
C1—N2—C5121.54 (11)C23—C24—C19122.82 (12)
C1—N2—C4123.64 (11)C23—C24—H24A118.6
C5—N2—C4114.80 (11)C19—C24—H24A118.6
C1—N3—C6120.28 (11)C30—C25—C26115.54 (12)
C1—N3—C7122.04 (11)C30—C25—B1121.04 (11)
C6—N3—C7117.52 (11)C26—C25—B1123.01 (12)
C10—N4—C12110.16 (10)C27—C26—C25122.68 (13)
C10—N4—C11108.57 (10)C27—C26—H26A118.7
C12—N4—C11107.94 (10)C25—C26—H26A118.7
C10—N4—C9110.79 (10)C28—C27—C26119.96 (13)
C12—N4—C9110.83 (10)C28—C27—H27A120.0
C11—N4—C9108.45 (10)C26—C27—H27A120.0
N2—C1—N1121.12 (12)C27—C28—C29119.18 (13)
N2—C1—N3118.60 (11)C27—C28—H28A120.4
N1—C1—N3120.28 (12)C29—C28—H28A120.4
N1—C2—H2A109.5C28—C29—C30119.99 (13)
N1—C2—H2B109.5C28—C29—H29A120.0
H2A—C2—H2B109.5C30—C29—H29A120.0
N1—C2—H2C109.5C29—C30—C25122.63 (13)
H2A—C2—H2C109.5C29—C30—H30A118.7
H2B—C2—H2C109.5C25—C30—H30A118.7
N1—C3—H3A109.5C32—C31—C36114.81 (12)
N1—C3—H3B109.5C32—C31—B1121.74 (11)
H3A—C3—H3B109.5C36—C31—B1123.41 (11)
N1—C3—H3C109.5C33—C32—C31122.91 (13)
H3A—C3—H3C109.5C33—C32—H32A118.5
H3B—C3—H3C109.5C31—C32—H32A118.5
N2—C4—H4A109.5C34—C33—C32120.45 (12)
N2—C4—H4B109.5C34—C33—H33A119.8
H4A—C4—H4B109.5C32—C33—H33A119.8
N2—C4—H4C109.5C33—C34—C35118.55 (12)
H4A—C4—H4C109.5C33—C34—H34A120.7
H4B—C4—H4C109.5C35—C34—H34A120.7
N2—C5—H5A109.5C34—C35—C36120.34 (13)
N2—C5—H5B109.5C34—C35—H35A119.8
H5A—C5—H5B109.5C36—C35—H35A119.8
N2—C5—H5C109.5C35—C36—C31122.92 (12)
H5A—C5—H5C109.5C35—C36—H36A118.5
H5B—C5—H5C109.5C31—C36—H36A118.5
N3—C6—H6A109.5C43—B2—C49112.26 (10)
N3—C6—H6B109.5C43—B2—C55105.27 (10)
H6A—C6—H6B109.5C49—B2—C55112.44 (10)
N3—C6—H6C109.5C43—B2—C37110.33 (11)
H6A—C6—H6C109.5C49—B2—C37106.20 (10)
H6B—C6—H6C109.5C55—B2—C37110.42 (10)
N3—C7—C8112.02 (10)C42—C37—C38115.43 (13)
N3—C7—H7A109.2C42—C37—B2124.38 (12)
C8—C7—H7A109.2C38—C37—B2120.19 (12)
N3—C7—H7B109.2C39—C38—C37122.67 (14)
C8—C7—H7B109.2C39—C38—H38A118.7
H7A—C7—H7B107.9C37—C38—H38A118.7
C9—C8—C7108.24 (10)C40—C39—C38120.02 (15)
C9—C8—H8A110.1C40—C39—H39A120.0
C7—C8—H8A110.1C38—C39—H39A120.0
C9—C8—H8B110.1C41—C40—C39119.05 (14)
C7—C8—H8B110.1C41—C40—H40A120.5
H8A—C8—H8B108.4C39—C40—H40A120.5
N4—C9—C8115.25 (10)C40—C41—C42120.28 (15)
N4—C9—H9A108.5C40—C41—H41A119.9
C8—C9—H9A108.5C42—C41—H41A119.9
N4—C9—H9B108.5C41—C42—C37122.35 (15)
C8—C9—H9B108.5C41—C42—H42A118.8
H9A—C9—H9B107.5C37—C42—H42A118.8
N4—C10—H10A109.5C48—C43—C44115.20 (12)
N4—C10—H10B109.5C48—C43—B2125.02 (12)
H10A—C10—H10B109.5C44—C43—B2119.76 (11)
N4—C10—H10C109.5C45—C44—C43123.25 (12)
H10A—C10—H10C109.5C45—C44—H44A118.4
H10B—C10—H10C109.5C43—C44—H44A118.4
N4—C11—H11A109.5C46—C45—C44119.58 (13)
N4—C11—H11B109.5C46—C45—H45A120.2
H11A—C11—H11B109.5C44—C45—H45A120.2
N4—C11—H11C109.5C47—C46—C45119.10 (13)
H11A—C11—H11C109.5C47—C46—H46A120.5
H11B—C11—H11C109.5C45—C46—H46A120.5
N4—C12—H12A109.5C46—C47—C48120.43 (13)
N4—C12—H12B109.5C46—C47—H47A119.8
H12A—C12—H12B109.5C48—C47—H47A119.8
N4—C12—H12C109.5C47—C48—C43122.32 (13)
H12A—C12—H12C109.5C47—C48—H48A118.8
H12B—C12—H12C109.5C43—C48—H48A118.8
C25—B1—C19108.02 (10)C54—C49—C50115.02 (12)
C25—B1—C31108.60 (10)C54—C49—B2125.40 (11)
C19—B1—C31109.35 (10)C50—C49—B2119.43 (12)
C25—B1—C13110.74 (10)C51—C50—C49122.77 (13)
C19—B1—C13111.30 (10)C51—C50—H50A118.6
C31—B1—C13108.78 (10)C49—C50—H50A118.6
C18—C13—C14114.15 (12)C52—C51—C50120.28 (13)
C18—C13—B1123.89 (12)C52—C51—H51A119.9
C14—C13—B1121.89 (11)C50—C51—H51A119.9
C15—C14—C13123.02 (13)C53—C52—C51118.84 (13)
C15—C14—H14A118.5C53—C52—H52A120.6
C13—C14—H14A118.5C51—C52—H52A120.6
C16—C15—C14120.59 (13)C52—C53—C54120.16 (13)
C16—C15—H15A119.7C52—C53—H53A119.9
C14—C15—H15A119.7C54—C53—H53A119.9
C17—C16—C15118.31 (13)C53—C54—C49122.90 (13)
C17—C16—H16A120.8C53—C54—H54A118.6
C15—C16—H16A120.8C49—C54—H54A118.6
C16—C17—C18120.38 (13)C60—C55—C56115.11 (12)
C16—C17—H17A119.8C60—C55—B2123.72 (12)
C18—C17—H17A119.8C56—C55—B2121.08 (11)
C17—C18—C13123.41 (13)C57—C56—C55122.83 (13)
C17—C18—H18A118.3C57—C56—H56A118.6
C13—C18—H18A118.3C55—C56—H56A118.6
C24—C19—C20114.76 (12)C58—C57—C56120.06 (13)
C24—C19—B1123.37 (11)C58—C57—H57A120.0
C20—C19—B1121.83 (11)C56—C57—H57A120.0
C21—C20—C19123.05 (12)C59—C58—C57118.84 (12)
C21—C20—H20A118.5C59—C58—H58A120.6
C19—C20—H20A118.5C57—C58—H58A120.6
C20—C21—C22120.20 (13)C58—C59—C60120.40 (13)
C20—C21—H21A119.9C58—C59—H59A119.8
C22—C21—H21A119.9C60—C59—H59A119.8
C23—C22—C21118.81 (12)C59—C60—C55122.62 (13)
C23—C22—H22A120.6C59—C60—H60A118.7
C21—C22—H22A120.6C55—C60—H60A118.7
C5—N2—C1—N1−150.00 (13)C13—B1—C31—C36131.83 (12)
C4—N2—C1—N131.57 (19)C36—C31—C32—C33−1.25 (18)
C5—N2—C1—N329.97 (18)B1—C31—C32—C33−179.20 (12)
C4—N2—C1—N3−148.46 (12)C31—C32—C33—C340.1 (2)
C2—N1—C1—N2−150.60 (12)C32—C33—C34—C351.2 (2)
C3—N1—C1—N227.44 (19)C33—C34—C35—C36−1.3 (2)
C2—N1—C1—N329.43 (18)C34—C35—C36—C310.1 (2)
C3—N1—C1—N3−152.53 (12)C32—C31—C36—C351.12 (19)
C6—N3—C1—N244.91 (17)B1—C31—C36—C35179.04 (12)
C7—N3—C1—N2−139.78 (12)C43—B2—C37—C4212.69 (17)
C6—N3—C1—N1−135.12 (13)C49—B2—C37—C42−109.20 (14)
C7—N3—C1—N140.19 (18)C55—B2—C37—C42128.64 (13)
C1—N3—C7—C8122.96 (13)C43—B2—C37—C38−167.47 (12)
C6—N3—C7—C8−61.61 (15)C49—B2—C37—C3870.64 (15)
N3—C7—C8—C9−160.81 (11)C55—B2—C37—C38−51.52 (16)
C10—N4—C9—C871.23 (14)C42—C37—C38—C39−4.5 (2)
C12—N4—C9—C8−51.38 (14)B2—C37—C38—C39175.68 (13)
C11—N4—C9—C8−169.70 (11)C37—C38—C39—C401.2 (2)
C7—C8—C9—N4−170.40 (10)C38—C39—C40—C412.5 (2)
C25—B1—C13—C18137.19 (12)C39—C40—C41—C42−2.7 (2)
C19—B1—C13—C1817.01 (17)C40—C41—C42—C37−0.8 (2)
C31—B1—C13—C18−103.53 (14)C38—C37—C42—C414.2 (2)
C25—B1—C13—C14−46.18 (16)B2—C37—C42—C41−175.91 (13)
C19—B1—C13—C14−166.35 (11)C49—B2—C43—C48−14.96 (17)
C31—B1—C13—C1473.10 (15)C55—B2—C43—C48107.68 (13)
C18—C13—C14—C154.09 (19)C37—B2—C43—C48−133.20 (12)
B1—C13—C14—C15−172.85 (12)C49—B2—C43—C44166.63 (11)
C13—C14—C15—C16−1.8 (2)C55—B2—C43—C44−70.74 (14)
C14—C15—C16—C17−1.4 (2)C37—B2—C43—C4448.39 (15)
C15—C16—C17—C182.0 (2)C48—C43—C44—C453.72 (19)
C16—C17—C18—C130.5 (2)B2—C43—C44—C45−177.71 (12)
C14—C13—C18—C17−3.47 (19)C43—C44—C45—C46−3.1 (2)
B1—C13—C18—C17173.40 (12)C44—C45—C46—C47−0.1 (2)
C25—B1—C19—C24−3.37 (16)C45—C46—C47—C482.4 (2)
C31—B1—C19—C24−121.39 (13)C46—C47—C48—C43−1.7 (2)
C13—B1—C19—C24118.40 (13)C44—C43—C48—C47−1.27 (18)
C25—B1—C19—C20174.10 (11)B2—C43—C48—C47−179.75 (12)
C31—B1—C19—C2056.08 (15)C43—B2—C49—C54129.63 (13)
C13—B1—C19—C20−64.13 (15)C55—B2—C49—C5411.14 (18)
C24—C19—C20—C210.12 (19)C37—B2—C49—C54−109.72 (14)
B1—C19—C20—C21−177.55 (12)C43—B2—C49—C50−55.04 (15)
C19—C20—C21—C22−1.0 (2)C55—B2—C49—C50−173.52 (11)
C20—C21—C22—C231.0 (2)C37—B2—C49—C5065.62 (15)
C21—C22—C23—C24−0.2 (2)C54—C49—C50—C51−1.45 (19)
C22—C23—C24—C19−0.8 (2)B2—C49—C50—C51−177.25 (12)
C20—C19—C24—C230.77 (19)C49—C50—C51—C520.2 (2)
B1—C19—C24—C23178.40 (12)C50—C51—C52—C531.4 (2)
C19—B1—C25—C30−79.63 (14)C51—C52—C53—C54−1.6 (2)
C31—B1—C25—C3038.87 (16)C52—C53—C54—C490.3 (2)
C13—B1—C25—C30158.26 (11)C50—C49—C54—C531.20 (19)
C19—B1—C25—C2692.75 (14)B2—C49—C54—C53176.72 (13)
C31—B1—C25—C26−148.75 (12)C43—B2—C55—C60100.23 (14)
C13—B1—C25—C26−29.36 (17)C49—B2—C55—C60−137.25 (13)
C30—C25—C26—C27−0.1 (2)C37—B2—C55—C60−18.83 (17)
B1—C25—C26—C27−172.88 (13)C43—B2—C55—C56−76.22 (15)
C25—C26—C27—C280.8 (2)C49—B2—C55—C5646.29 (16)
C26—C27—C28—C29−0.6 (2)C37—B2—C55—C56164.71 (12)
C27—C28—C29—C30−0.1 (2)C60—C55—C56—C574.0 (2)
C28—C29—C30—C250.8 (2)B2—C55—C56—C57−179.26 (12)
C26—C25—C30—C29−0.66 (19)C55—C56—C57—C58−2.1 (2)
B1—C25—C30—C29172.25 (12)C56—C57—C58—C59−1.4 (2)
C25—B1—C31—C3270.22 (14)C57—C58—C59—C602.6 (2)
C19—B1—C31—C32−172.13 (11)C58—C59—C60—C55−0.4 (2)
C13—B1—C31—C32−50.39 (15)C56—C55—C60—C59−2.8 (2)
C25—B1—C31—C36−107.56 (13)B2—C55—C60—C59−179.40 (13)
C19—B1—C31—C3610.09 (16)
Hydrogen-bond geometry (Å, º) top
Cg1, Cg4, Cg5, Cg6, and Cg8 are the centroids of the C13–C18,C31–C36, C37–C42, C43–C48 and C55–C60 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C3—H3C···Cg70.982.623.3783 (16)134
C7—H7B···Cg10.992.803.7805 (14)169
C9—H9B···Cg60.992.523.4075 (14)149
C11—H11C···Cg5i0.982.623.4852 (15)147
C12—H12A···Cg40.982.593.4044 (15)141
C12—H12B···Cg8ii0.982.693.5990 (15)155
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
Cg1, Cg4, Cg5, Cg6, and Cg8 are the centroids of the C13–C18,C31–C36, C37–C42, C43–C48 and C55–C60 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C3—H3C···Cg70.982.623.3783 (16)134
C7—H7B···Cg10.992.803.7805 (14)169
C9—H9B···Cg60.992.523.4075 (14)149
C11—H11C···Cg5i0.982.623.4852 (15)147
C12—H12A···Cg40.982.593.4044 (15)141
C12—H12B···Cg8ii0.982.693.5990 (15)155
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2.
Acknowledgements top

The author thanks Dr F. Lissner (Institut für Anorganische Chemie, Universität Stuttgart) for measuring the crystal data.

references
References top

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