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Acta Cryst. (2007). E63, m2545    [ doi:10.1107/S160053680704439X ]

(p-Methylbenzenethiolato)[tris(3-phenyl-5-methylpyrazolyl)borato]zinc(II)

H. Görls, W. Günther, J. Notni and E. Anders

Abstract top

The crystal structure of the title compound, [Zn(C30H28BN6)(C7H7S)], is closely related to a series of other tripod zinc thiolates. The Zn atom adopts a very distorted tetrahedral coordination geometry. In addition to the crystallographic data, 11B NMR as well as 11B-decoupled 1H NMR data are provided. A proton shift for the boron-bound hydride (5.15 p.p.m.) of a pyrazolylborato ligand is reported for the first time.

Comment top

The title compound is closely related to a class of complexes synthesized by Tekeste and Vahrenkamp (2006), which are useful model compounds for thiolate alkylating enzymes. Thus, their structural chemistry and reactivity has been extensively studied by these authors. However, to the best of our knowledge, no comment on the chemical shift of the single hydride ion at the boron atom can be found in the literature. In routine 1H spectra, this signal is usually not detected due to 11B-1H coupling: Natural boron isotopes are 10B (19.9%, spin 3/2) and 11B (80.1%, spin 3), both of them possessing large quadrupol moments. This causes the signal of the hydride to exhibit a large multiplicity and increased band width. As a result, the detected signal appears in the spectra as a slight elevation of the baseline, which normally is not considered a real peak by most processing software. Nonetheless, in a 11B decoupled 1H NMR, a slightly broadened singlet at 5.15 p.p.m. with a relative intensity of 0.8 protons is found which corresponds to the hydride. The unusual intensity is a result of the natural abundance of the 11B nucleus of ~80%, since only this portion of the signal experiences line width reduction by decoupling. The moleculare structure of (1) is shown in Fig. 1. The Zn atom is coordinated by three N atoms and one sulfur atom in a distorted tetrahedral arrangement. The Zn–S bond length is 2.2289 (6) Å and the Zn—N bond lengths are 2.038 (2), 2.058 (2) and 2.088 (2) Å, respectively. The bond angles around Zn range from 120.98 (5) to 127.46 (5)° for S–Zn–N angles and from 91.59 (7) to 94.66 (7)° for N–Zn–N angles. The Zn–N and Zn–S distances are in agreement with the corresponding distances in the other Zn complexes reported in the literature (Rombach et al., 2002; Börzel et al., 2003; Brand et al., 2001). There are no unexpected geometrical features associated with the coordination structure of zinc.

Related literature top

Tris(pyrazolyl)borato zinc thiolates and their reactions have been studied by Brand et al. (2001). A comparative kinetic study on thiolate alkylation in tripodal zinc complexes with N3S, N2S2, NS3 and S4 donor sets has been published by Tekeste & Vahrenkamp (2006).

For related literature, see: Börzel et al. (2003); Rombach et al. (2002).

Experimental top

To a solution of Tp(Ph,Me)ZnOH (1 mmol, 561 mg) in methylene chloride (20 ml) 4-methylthiophenol (1 mmol, 124 mg) were added. The mixture was stirred for 1 h, and methanol (10 ml) was added. The methylene chloride was evaporated, and the complex was allowed to precipitate at −20 °C. Obtained were colourless prisms, m. p. 230 °C, yield 640 mg (95%). Anal. calcd. for C37H35BN6SZn: C, 66.14, H, 5.25, N, 12.50, S, 4.77. Found C, 66.74, H, 5.02, N, 12.69, S, 4.89. NMR (1H, 400 MHz, CDCl3,11B-decoupled): 1.95 (s, 3H), 2.55 (s, 9H), 5.15 (s, 0.8H) 6.12 (d, 2H), 6.26 (d, 2H), 7.11 (m, 9H), 7.59 (m, 6H) p.p.m.. NMR (11B, 128.4 MHz, CDCl3): −6.3 p.p.m.. NMR (13C, 100 MHz, CDCl3): 12.9, 20.5, 105.5, 127.5, 127.8, 128.1, 128.5, 129.7, 131.0, 131.2, 136.9, 145.7, 154.5 p.p.m..

Refinement top

The hydrogen atom bonded to B was located by difference Fourier synthesis and freely refined. All other hydrogen atoms were set to idealized positions and were refined with 1.2 times (1.5 for methyl groups) the isotropic displacement parameter of the corresponding carbon atom. The methyl groups were allowed to rotate but not to tip.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level.
(p-Methylbenzenethiolato)[tris(3-phenyl-5-methylpyrazolyl)borato]zinc(II) top
Crystal data top
[Zn(C30H28BN6)(C7H7S)]Z = 4
Mr = 671.95F000 = 1400
Monoclinic, P21/nDx = 1.306 Mg m−3
Hall symbol: -P2ynMo Kα radiation
λ = 0.71073 Å
a = 16.2448 (7) ŵ = 0.82 mm−1
b = 12.3442 (3) ÅT = 183 (2) K
c = 17.3988 (7) ÅPrism, colourless
β = 101.675 (1)º0.18 × 0.12 × 0.10 mm
V = 3416.8 (2) Å3
Data collection top
Nonius KappaCCD
diffractometer		4579 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Monochromator: graphiteθmax = 27.5º
T = 183(2) Kθmin = 2.5º
phi– + ω–scanh = −21→21
Absorption correction: nonek = −14→13
13913 measured reflectionsl = −22→22
7635 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.087  w = 1/[σ2(Fo2) + (0.0428P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.87(Δ/σ)max = 0.001
7635 reflectionsΔρmax = 0.43 e Å−3
422 parametersΔρmin = −0.41 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C30H28BN6)(C7H7S)]V = 3416.8 (2) Å3
Mr = 671.95Z = 4
Monoclinic, P21/nMo Kα
a = 16.2448 (7) ŵ = 0.82 mm−1
b = 12.3442 (3) ÅT = 183 (2) K
c = 17.3988 (7) Å0.18 × 0.12 × 0.10 mm
β = 101.675 (1)º
Data collection top
Nonius KappaCCD
diffractometer		7635 independent reflections
Absorption correction: none4579 reflections with I > 2σ(I)
13913 measured reflectionsRint = 0.040
Refinement top
R[F2 > 2σ(F2)] = 0.039422 parameters
wR(F2) = 0.087H atoms treated by a mixture of
independent and constrained refinement
S = 0.87Δρmax = 0.43 e Å−3
7635 reflectionsΔρmin = −0.41 e Å−3
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn0.829763 (16)0.72798 (2)0.034357 (14)0.03008 (9)
S0.70537 (4)0.66651 (5)−0.02881 (3)0.03546 (15)
N10.93538 (11)0.70497 (13)−0.00994 (11)0.0314 (4)
N21.00753 (11)0.72512 (14)0.04482 (10)0.0325 (4)
N30.88773 (11)0.66740 (14)0.14189 (10)0.0306 (4)
N40.95800 (11)0.72717 (13)0.17318 (10)0.0297 (4)
N50.86364 (11)0.88850 (13)0.06250 (10)0.0315 (4)
N60.94927 (11)0.89614 (13)0.09183 (10)0.0312 (4)
C10.64030 (15)0.68671 (18)0.04035 (14)0.0368 (6)
C20.66207 (16)0.75162 (19)0.10691 (14)0.0440 (6)
H2A0.71390.78980.11600.053*
C30.60969 (19)0.7614 (2)0.15993 (16)0.0540 (7)
H3A0.62660.80560.20510.065*
C40.53267 (19)0.7081 (2)0.14872 (18)0.0581 (8)
C50.51059 (17)0.6458 (2)0.0817 (2)0.0581 (8)
H5A0.45800.60950.07200.070*
C60.56291 (15)0.63468 (19)0.02811 (16)0.0467 (7)
H6A0.54560.5911−0.01730.056*
C70.4756 (2)0.7200 (3)0.2067 (2)0.0938 (12)
H7A0.50880.71450.26020.141*
H7B0.43310.66250.19790.141*
H7C0.44770.79070.19960.141*
C80.95876 (15)0.64799 (17)−0.06788 (13)0.0343 (5)
C91.04514 (15)0.63145 (18)−0.05002 (14)0.0402 (6)
H9A1.07770.5938−0.08110.048*
C101.07439 (15)0.68013 (18)0.02127 (14)0.0364 (6)
C111.16243 (15)0.6886 (2)0.06763 (15)0.0476 (7)
H11A1.16510.65860.12020.071*
H11B1.17950.76480.07190.071*
H11C1.20030.64780.04110.071*
C120.89822 (15)0.61680 (17)−0.13931 (13)0.0348 (6)
C130.82745 (15)0.6780 (2)−0.16843 (14)0.0416 (6)
H13A0.81550.7398−0.14010.050*
C140.77392 (17)0.6506 (2)−0.23795 (15)0.0544 (7)
H14A0.72540.6932−0.25710.065*
C150.79142 (18)0.5604 (3)−0.27977 (16)0.0640 (8)
H15A0.75480.5411−0.32760.077*
C160.8614 (2)0.4994 (2)−0.25188 (16)0.0611 (8)
H16A0.87360.4382−0.28080.073*
C170.91456 (17)0.52619 (19)−0.18201 (15)0.0480 (7)
H17A0.96260.4827−0.16280.058*
C180.86601 (14)0.61354 (16)0.20231 (13)0.0300 (5)
C190.92140 (14)0.64100 (18)0.27169 (13)0.0346 (5)
H19A0.92020.61480.32280.042*
C200.97809 (14)0.71310 (16)0.25209 (13)0.0323 (5)
C211.04815 (15)0.77291 (19)0.30342 (14)0.0431 (6)
H21A1.03850.85100.29690.065*
H21B1.10150.75390.28880.065*
H21C1.05040.75300.35830.065*
C220.79528 (14)0.53684 (16)0.18952 (13)0.0318 (5)
C230.75279 (17)0.5145 (2)0.24959 (16)0.0481 (6)
H23A0.76960.54860.29920.058*
C240.68578 (18)0.4423 (2)0.23680 (17)0.0600 (8)
H24A0.65700.42700.27800.072*
C250.66086 (18)0.3931 (2)0.16536 (17)0.0547 (7)
H25A0.61440.34470.15680.066*
C260.70296 (16)0.41381 (18)0.10604 (16)0.0442 (6)
H26A0.68580.37920.05660.053*
C270.77029 (14)0.48485 (17)0.11794 (14)0.0351 (6)
H27A0.79960.49810.07680.042*
C280.83466 (15)0.99171 (17)0.05226 (12)0.0330 (5)
C290.90126 (15)1.06349 (18)0.07509 (13)0.0379 (6)
H29A0.89811.14030.07440.046*
C300.97251 (15)1.00187 (17)0.09878 (13)0.0348 (6)
C311.06169 (15)1.03660 (19)0.12619 (15)0.0446 (6)
H31A1.09750.97250.13860.067*
H31B1.06621.08170.17320.067*
H31C1.07991.07840.08470.067*
C320.74580 (14)1.02015 (17)0.02264 (13)0.0335 (5)
C330.71553 (16)1.11925 (18)0.04451 (14)0.0410 (6)
H33A0.75231.16670.07820.049*
C340.63253 (16)1.14877 (19)0.01753 (15)0.0465 (7)
H34A0.61311.21680.03220.056*
C350.57777 (16)1.08049 (18)−0.03043 (15)0.0451 (7)
H35A0.52061.1004−0.04840.054*
C360.60729 (16)0.98283 (19)−0.05190 (15)0.0476 (7)
H36A0.57010.9351−0.08500.057*
C370.69034 (15)0.95342 (19)−0.02595 (14)0.0422 (6)
H37A0.70950.8860−0.04190.051*
B1.00221 (17)0.79415 (19)0.11767 (16)0.0327 (6)
H1BO1.0673 (11)0.8177 (13)0.1481 (10)0.044 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.02610 (15)0.03474 (14)0.02890 (15)−0.00106 (11)0.00439 (11)0.00005 (11)
S0.0285 (3)0.0434 (3)0.0332 (3)−0.0023 (3)0.0032 (3)−0.0030 (3)
N10.0259 (11)0.0359 (10)0.0330 (11)−0.0001 (8)0.0072 (9)−0.0008 (8)
N20.0249 (11)0.0376 (10)0.0343 (11)−0.0019 (9)0.0043 (9)0.0007 (9)
N30.0252 (11)0.0363 (10)0.0297 (11)−0.0036 (8)0.0038 (9)−0.0004 (8)
N40.0238 (10)0.0344 (9)0.0295 (10)−0.0002 (8)0.0020 (8)−0.0010 (8)
N50.0276 (11)0.0346 (10)0.0320 (11)0.0010 (8)0.0052 (9)0.0027 (8)
N60.0263 (11)0.0344 (10)0.0323 (11)−0.0034 (8)0.0048 (9)−0.0003 (8)
C10.0306 (14)0.0379 (12)0.0428 (15)0.0074 (11)0.0096 (11)0.0087 (11)
C20.0381 (16)0.0530 (15)0.0410 (15)0.0025 (12)0.0084 (12)0.0014 (12)
C30.060 (2)0.0594 (16)0.0454 (16)0.0136 (15)0.0175 (15)0.0050 (13)
C40.061 (2)0.0556 (18)0.066 (2)0.0213 (15)0.0344 (17)0.0220 (15)
C50.0377 (17)0.0513 (16)0.091 (2)0.0055 (13)0.0265 (17)0.0224 (16)
C60.0357 (16)0.0387 (13)0.0659 (19)−0.0008 (12)0.0107 (14)0.0036 (12)
C70.092 (3)0.109 (3)0.102 (3)0.025 (2)0.070 (2)0.030 (2)
C80.0358 (15)0.0338 (12)0.0345 (14)0.0019 (10)0.0103 (11)0.0050 (10)
C90.0363 (15)0.0444 (14)0.0417 (15)0.0078 (11)0.0124 (12)−0.0018 (11)
C100.0304 (14)0.0390 (12)0.0409 (15)0.0030 (11)0.0097 (12)0.0060 (11)
C110.0315 (15)0.0624 (16)0.0493 (17)0.0065 (12)0.0094 (13)−0.0028 (13)
C120.0364 (15)0.0364 (12)0.0338 (14)−0.0027 (10)0.0124 (11)−0.0007 (10)
C130.0375 (16)0.0542 (14)0.0350 (14)0.0051 (12)0.0118 (12)−0.0039 (11)
C140.0362 (17)0.091 (2)0.0363 (16)0.0083 (14)0.0070 (13)−0.0078 (14)
C150.050 (2)0.096 (2)0.0432 (17)−0.0062 (17)0.0027 (15)−0.0202 (16)
C160.072 (2)0.0587 (17)0.0509 (19)0.0013 (15)0.0087 (16)−0.0222 (14)
C170.0527 (18)0.0462 (15)0.0446 (16)0.0072 (13)0.0086 (14)−0.0065 (12)
C180.0293 (13)0.0301 (11)0.0311 (13)0.0045 (9)0.0069 (11)0.0014 (9)
C190.0322 (14)0.0423 (13)0.0293 (13)0.0028 (10)0.0061 (11)0.0029 (10)
C200.0293 (13)0.0358 (13)0.0306 (13)0.0046 (10)0.0029 (10)−0.0015 (10)
C210.0378 (15)0.0543 (14)0.0349 (13)−0.0027 (12)0.0016 (11)−0.0046 (12)
C220.0300 (14)0.0297 (11)0.0361 (14)0.0050 (9)0.0072 (11)0.0059 (10)
C230.0513 (17)0.0565 (15)0.0390 (15)−0.0075 (13)0.0148 (13)0.0028 (12)
C240.056 (2)0.0752 (19)0.0548 (19)−0.0224 (16)0.0263 (16)0.0071 (16)
C250.0493 (18)0.0542 (16)0.063 (2)−0.0186 (13)0.0170 (16)0.0051 (14)
C260.0434 (16)0.0395 (13)0.0492 (16)−0.0076 (11)0.0086 (13)−0.0031 (12)
C270.0337 (14)0.0338 (12)0.0392 (14)0.0007 (10)0.0108 (11)0.0024 (10)
C280.0391 (15)0.0337 (12)0.0277 (13)0.0012 (11)0.0105 (11)0.0026 (9)
C290.0434 (16)0.0303 (12)0.0403 (14)−0.0030 (11)0.0090 (12)0.0022 (10)
C300.0392 (15)0.0363 (13)0.0299 (13)−0.0080 (11)0.0094 (11)0.0014 (10)
C310.0413 (16)0.0392 (13)0.0525 (17)−0.0104 (11)0.0078 (13)−0.0012 (12)
C320.0368 (15)0.0354 (12)0.0289 (13)−0.0001 (10)0.0080 (11)0.0075 (10)
C330.0419 (16)0.0341 (13)0.0462 (16)0.0004 (11)0.0069 (13)−0.0016 (11)
C340.0484 (18)0.0363 (13)0.0550 (17)0.0051 (12)0.0110 (14)−0.0009 (12)
C350.0389 (16)0.0427 (14)0.0521 (17)0.0064 (12)0.0055 (13)0.0129 (12)
C360.0420 (17)0.0438 (14)0.0514 (17)0.0013 (12)−0.0036 (13)−0.0043 (12)
C370.0417 (17)0.0380 (14)0.0435 (15)0.0060 (11)0.0006 (13)−0.0036 (11)
B0.0286 (16)0.0336 (15)0.0353 (16)−0.0014 (11)0.0049 (12)0.0018 (11)
Geometric parameters (Å, °) top
Zn—N12.0380 (19)C15—C161.368 (4)
Zn—N32.0575 (17)C15—H15A0.9500
Zn—N52.0880 (17)C16—C171.381 (3)
Zn—S2.2289 (6)C16—H16A0.9500
S—C11.773 (2)C17—H17A0.9500
N1—C81.345 (3)C18—C191.394 (3)
N1—N21.375 (2)C18—C221.471 (3)
N2—C101.355 (3)C19—C201.372 (3)
N2—B1.544 (3)C19—H19A0.9500
N3—C181.350 (3)C20—C211.492 (3)
N3—N41.376 (2)C21—H21A0.9800
N4—C201.357 (3)C21—H21B0.9800
N4—B1.553 (3)C21—H21C0.9800
N5—C281.357 (3)C22—C271.387 (3)
N5—N61.385 (2)C22—C231.392 (3)
N6—C301.357 (3)C23—C241.389 (3)
N6—B1.540 (3)C23—H23A0.9500
C1—C61.389 (3)C24—C251.369 (4)
C1—C21.394 (3)C24—H24A0.9500
C2—C31.381 (3)C25—C261.372 (3)
C2—H2A0.9500C25—H25A0.9500
C3—C41.392 (4)C26—C271.384 (3)
C3—H3A0.9500C26—H26A0.9500
C4—C51.381 (4)C27—H27A0.9500
C4—C71.509 (4)C28—C291.393 (3)
C5—C61.390 (4)C28—C321.474 (3)
C5—H5A0.9500C29—C301.377 (3)
C6—H6A0.9500C29—H29A0.9500
C7—H7A0.9800C30—C311.493 (3)
C7—H7B0.9800C31—H31A0.9800
C7—H7C0.9800C31—H31B0.9800
C8—C91.390 (3)C31—H31C0.9800
C8—C121.472 (3)C32—C371.377 (3)
C9—C101.374 (3)C32—C331.400 (3)
C9—H9A0.9500C33—C341.384 (3)
C10—C111.497 (3)C33—H33A0.9500
C11—H11A0.9800C34—C351.377 (3)
C11—H11B0.9800C34—H34A0.9500
C11—H11C0.9800C35—C361.377 (3)
C12—C131.383 (3)C35—H35A0.9500
C12—C171.398 (3)C36—C371.382 (3)
C13—C141.381 (3)C36—H36A0.9500
C13—H13A0.9500C37—H37A0.9500
C14—C151.391 (4)B—H1BO1.120 (17)
C14—H14A0.9500
N1—Zn—N391.59 (7)C15—C16—H16A119.8
N1—Zn—N591.08 (7)C17—C16—H16A119.8
N3—Zn—N594.66 (7)C16—C17—C12120.5 (2)
N1—Zn—S120.98 (5)C16—C17—H17A119.8
N3—Zn—S121.81 (5)C12—C17—H17A119.8
N5—Zn—S127.46 (5)N3—C18—C19109.28 (19)
C1—S—Zn102.89 (8)N3—C18—C22121.24 (19)
C8—N1—N2106.47 (18)C19—C18—C22129.5 (2)
C8—N1—Zn137.99 (16)C20—C19—C18106.9 (2)
N2—N1—Zn112.18 (13)C20—C19—H19A126.6
C10—N2—N1109.83 (18)C18—C19—H19A126.6
C10—N2—B130.98 (19)N4—C20—C19107.37 (19)
N1—N2—B119.15 (18)N4—C20—C21122.7 (2)
C18—N3—N4106.42 (16)C19—C20—C21129.9 (2)
C18—N3—Zn138.04 (15)C20—C21—H21A109.5
N4—N3—Zn110.82 (12)C20—C21—H21B109.5
C20—N4—N3110.01 (17)H21A—C21—H21B109.5
C20—N4—B130.59 (18)C20—C21—H21C109.5
N3—N4—B119.37 (17)H21A—C21—H21C109.5
C28—N5—N6106.28 (17)H21B—C21—H21C109.5
C28—N5—Zn142.37 (15)C27—C22—C23118.9 (2)
N6—N5—Zn110.39 (12)C27—C22—C18120.8 (2)
C30—N6—N5109.81 (17)C23—C22—C18120.3 (2)
C30—N6—B129.15 (19)C24—C23—C22119.9 (3)
N5—N6—B120.81 (17)C24—C23—H23A120.1
C6—C1—C2117.6 (2)C22—C23—H23A120.1
C6—C1—S118.4 (2)C25—C24—C23120.5 (3)
C2—C1—S123.99 (19)C25—C24—H24A119.7
C3—C2—C1121.2 (3)C23—C24—H24A119.7
C3—C2—H2A119.4C24—C25—C26120.0 (2)
C1—C2—H2A119.4C24—C25—H25A120.0
C2—C3—C4121.5 (3)C26—C25—H25A120.0
C2—C3—H3A119.3C25—C26—C27120.3 (2)
C4—C3—H3A119.3C25—C26—H26A119.9
C5—C4—C3117.0 (3)C27—C26—H26A119.9
C5—C4—C7121.9 (3)C26—C27—C22120.4 (2)
C3—C4—C7121.1 (3)C26—C27—H27A119.8
C4—C5—C6122.1 (3)C22—C27—H27A119.8
C4—C5—H5A118.9N5—C28—C29109.3 (2)
C6—C5—H5A118.9N5—C28—C32123.96 (19)
C5—C6—C1120.6 (3)C29—C28—C32126.7 (2)
C5—C6—H6A119.7C30—C29—C28106.94 (19)
C1—C6—H6A119.7C30—C29—H29A126.5
C4—C7—H7A109.5C28—C29—H29A126.5
C4—C7—H7B109.5N6—C30—C29107.6 (2)
H7A—C7—H7B109.5N6—C30—C31122.6 (2)
C4—C7—H7C109.5C29—C30—C31129.8 (2)
H7A—C7—H7C109.5C30—C31—H31A109.5
H7B—C7—H7C109.5C30—C31—H31B109.5
N1—C8—C9109.5 (2)H31A—C31—H31B109.5
N1—C8—C12121.9 (2)C30—C31—H31C109.5
C9—C8—C12128.5 (2)H31A—C31—H31C109.5
C10—C9—C8106.7 (2)H31B—C31—H31C109.5
C10—C9—H9A126.7C37—C32—C33117.9 (2)
C8—C9—H9A126.7C37—C32—C28123.0 (2)
N2—C10—C9107.5 (2)C33—C32—C28119.1 (2)
N2—C10—C11123.1 (2)C34—C33—C32120.6 (2)
C9—C10—C11129.4 (2)C34—C33—H33A119.7
C10—C11—H11A109.5C32—C33—H33A119.7
C10—C11—H11B109.5C35—C34—C33120.7 (2)
H11A—C11—H11B109.5C35—C34—H34A119.7
C10—C11—H11C109.5C33—C34—H34A119.7
H11A—C11—H11C109.5C36—C35—C34118.8 (2)
H11B—C11—H11C109.5C36—C35—H35A120.6
C13—C12—C17118.4 (2)C34—C35—H35A120.6
C13—C12—C8122.0 (2)C35—C36—C37120.8 (2)
C17—C12—C8119.5 (2)C35—C36—H36A119.6
C14—C13—C12121.1 (2)C37—C36—H36A119.6
C14—C13—H13A119.4C32—C37—C36121.2 (2)
C12—C13—H13A119.4C32—C37—H37A119.4
C13—C14—C15119.6 (3)C36—C37—H37A119.4
C13—C14—H14A120.2N6—B—N2109.41 (18)
C15—C14—H14A120.2N6—B—N4108.39 (19)
C16—C15—C14119.9 (3)N2—B—N4109.04 (17)
C16—C15—H15A120.1N6—B—H1BO110.1 (9)
C14—C15—H15A120.1N2—B—H1BO109.1 (9)
C15—C16—C17120.5 (3)N4—B—H1BO110.8 (9)
Acknowledgements top

The authors gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft, SFB 436 `Metal Mediated Reactions Modeled after Nature'.

references
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