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The four-coordinate CoII complex, (azido-[kappa]N)[1,1,',1''-(phenyl­boranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(II), [Co(C27H38BN6)(N3)], (1), denoted PhB(t-BuIm)3CoN3, was pre­pared by the reaction of the corresponding chloride complex with NaN3. One-electron oxidation results in the isolation of the five-coordinate CoIII complex, bis(azido-[kappa]N)[1,1,',1''-(phenyl­boranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(III), [Co(C27H38BN6)(N3)2], (2), denoted PhB(t-BuIm)3Co(N3)2. Attempts to prepare cobalt nitrides by thermolysis or photolysis of these complexes were unsuccessful.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017022/yp3036sup1.cif
Contains datablocks global, 1, 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017022/yp30361sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017022/yp30362sup3.hkl
Contains datablock 2

CCDC references: 964747; 964748

Synthesis and crystallization top

(type here to add preparation details)

Refinement top

(type here to add refinement details)

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012). Software used to prepare material for publication: WinGX (Farrugia, 20120) for (1); WinGX (Farrugia, 2012) for (2).

(1) (Azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(II) top
Crystal data top
[Co(C27H38BN6)(N3)]Z = 4
Mr = 558.40F(000) = 1180
Monoclinic, P21/nDx = 1.308 Mg m3
a = 9.8910 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 17.7415 (5) ŵ = 0.64 mm1
c = 16.1660 (5) ÅT = 223 K
β = 92.016 (2)°Plate, blue
V = 2835.07 (15) Å30.17 × 0.07 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
7050 independent reflections
Radiation source: fine-focus sealed tube4482 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
phi and ω scansθmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
h = 1312
Tmin = 0.675, Tmax = 0.746k = 2323
50578 measured reflectionsl = 2121
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0427P)2 + 0.921P]
where P = (Fo2 + 2Fc2)/3
7050 reflections(Δ/σ)max = 0.002
361 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
[Co(C27H38BN6)(N3)]V = 2835.07 (15) Å3
Mr = 558.40Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.8910 (3) ŵ = 0.64 mm1
b = 17.7415 (5) ÅT = 223 K
c = 16.1660 (5) Å0.17 × 0.07 × 0.05 mm
β = 92.016 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
7050 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
4482 reflections with I > 2σ(I)
Tmin = 0.675, Tmax = 0.746Rint = 0.086
50578 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.01Δρmax = 0.31 e Å3
7050 reflectionsΔρmin = 0.32 e Å3
361 parameters
Special details top

Experimental. The quality of the glove-box atmosphere was periodically checked with a toluene solution of 'titanocene' (Watt et al., 1966). Glassware was dried at 423 K overnight. Diethyl ether, pentane, tetrahydrofuran (THF) and toluene were purified using the Glass Contour solvent purification system. Deuterated benzene was dried first over CaH2, then over Na/benzophenone, before vacuum transfer into a storage container. Before use, aliquots of Et2O, THF and toluene were tested with a drop of Na/benzophenone in THF solution. 1H NMR data were recorded on a Varian Unity 400 spectrometer (400 MHz) at 295 K. All resonances in the 1H NMR spectra are referenced to residual C6D5H (δ 7.16 p.p.m.). IR spectra were recorded on a Thermo Scientific Nicolet iS10 SMART iTR spectrophotometer.

Watt, G. W., Baye, L. D. & Drummond, F. O. (1966). J. Am. Chem. Soc. 88, 1138–1140.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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*/UeqOcc. (<1)
Co10.53081 (3)0.281366 (17)0.923847 (18)0.02599 (10)
B10.3498 (3)0.14526 (14)0.94792 (15)0.0249 (5)
N10.6491 (3)0.36786 (13)0.91310 (14)0.0567 (7)
N20.7069 (3)0.40560 (14)0.86969 (16)0.0587 (7)
N3A0.7950 (13)0.4334 (9)0.8389 (11)0.118 (6)0.50
N3B0.7312 (14)0.4542 (7)0.8198 (8)0.097 (5)0.50
N110.44370 (18)0.15999 (10)1.02720 (10)0.0241 (4)
N120.59306 (18)0.21796 (10)1.10630 (10)0.0249 (4)
C110.5364 (2)0.21725 (12)1.02858 (13)0.0252 (5)
C120.4417 (2)0.12730 (13)1.10507 (13)0.0275 (5)
H120.38550.08751.12090.033*
C130.5342 (2)0.16252 (13)1.15372 (13)0.0297 (5)
H130.55530.15171.20960.036*
C140.6974 (2)0.27364 (13)1.13612 (14)0.0304 (5)
C150.6302 (3)0.35045 (14)1.14288 (18)0.0449 (7)
H15A0.59460.36581.08880.067*
H15B0.69630.38711.16300.067*
H15C0.55700.34741.18110.067*
C160.7536 (3)0.24987 (17)1.22019 (15)0.0462 (7)
H16A0.68130.24921.25920.069*
H16B0.82280.28531.23890.069*
H16C0.79270.19991.21640.069*
C170.8104 (3)0.27707 (15)1.07513 (16)0.0406 (6)
H17A0.77380.29271.02140.061*
H17B0.85140.22771.07050.061*
H17C0.87820.31311.09450.061*
N210.26605 (18)0.22091 (10)0.93681 (10)0.0244 (4)
N220.2248 (2)0.34016 (11)0.92153 (12)0.0325 (5)
C210.3259 (2)0.28846 (12)0.92296 (13)0.0270 (5)
C220.1289 (2)0.23182 (13)0.94674 (14)0.0325 (5)
H220.06530.19430.95850.039*
C230.1031 (3)0.30579 (14)0.93647 (15)0.0368 (6)
H230.01830.32950.93900.044*
C240.2462 (3)0.42341 (13)0.90890 (16)0.0409 (6)
C250.3329 (4)0.45248 (16)0.97996 (18)0.0759 (12)
H25A0.28490.44721.03090.114*
H25B0.35360.50520.97090.114*
H25C0.41640.42380.98400.114*
C260.1103 (4)0.46268 (19)0.9048 (3)0.0916 (14)
H26A0.05340.44010.86140.137*
H26B0.12310.51570.89300.137*
H26C0.06720.45730.95750.137*
C270.3148 (4)0.43462 (15)0.82745 (17)0.0569 (9)
H27A0.25550.41720.78240.085*
H27B0.39850.40610.82790.085*
H27C0.33440.48770.81990.085*
N310.44609 (18)0.13749 (10)0.87232 (10)0.0234 (4)
N320.59785 (18)0.16278 (11)0.78303 (11)0.0291 (4)
C310.5341 (2)0.19142 (13)0.84874 (13)0.0261 (5)
C320.4577 (2)0.07508 (13)0.82140 (14)0.0314 (5)
H320.40830.03000.82490.038*
C330.5520 (3)0.09049 (14)0.76632 (15)0.0372 (6)
H330.58130.05830.72440.045*
C340.7049 (2)0.20494 (15)0.73852 (14)0.0356 (6)
C350.8251 (3)0.21573 (17)0.79946 (16)0.0470 (7)
H35A0.79720.24570.84610.070*
H35B0.89750.24140.77200.070*
H35C0.85680.16690.81900.070*
C360.6468 (3)0.28044 (16)0.70991 (16)0.0442 (6)
H36A0.61570.30820.75730.066*
H36B0.57150.27190.67100.066*
H36C0.71630.30930.68320.066*
C370.7463 (3)0.15995 (18)0.66382 (16)0.0521 (8)
H37A0.78650.11260.68200.078*
H37B0.81170.18850.63330.078*
H37C0.66730.14990.62830.078*
C410.2559 (2)0.07130 (12)0.94747 (14)0.0271 (5)
C420.1457 (2)0.06672 (14)0.89043 (15)0.0348 (6)
H420.12370.10910.85780.042*
C430.0687 (3)0.00237 (16)0.88061 (18)0.0463 (7)
H430.00510.00180.84240.056*
C440.0993 (3)0.06083 (16)0.92643 (19)0.0514 (8)
H440.04560.10430.92080.062*
C450.2100 (3)0.05984 (15)0.98099 (18)0.0486 (7)
H450.23310.10341.01150.058*
C460.2869 (3)0.00484 (13)0.99094 (15)0.0360 (6)
H460.36230.00421.02800.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.03306 (18)0.02144 (15)0.02341 (15)0.00589 (14)0.00026 (12)0.00168 (13)
B10.0266 (14)0.0212 (12)0.0268 (13)0.0011 (11)0.0002 (10)0.0010 (10)
N10.0839 (19)0.0401 (14)0.0464 (14)0.0355 (13)0.0068 (13)0.0017 (11)
N20.0706 (19)0.0429 (15)0.0634 (17)0.0262 (14)0.0149 (14)0.0060 (13)
N3A0.101 (9)0.087 (10)0.170 (15)0.050 (7)0.072 (9)0.005 (8)
N3B0.164 (14)0.060 (6)0.070 (5)0.053 (8)0.032 (8)0.018 (4)
N110.0267 (10)0.0210 (9)0.0246 (9)0.0016 (8)0.0014 (8)0.0024 (7)
N120.0275 (10)0.0239 (9)0.0231 (9)0.0002 (8)0.0014 (7)0.0001 (8)
C110.0276 (12)0.0223 (11)0.0257 (11)0.0002 (10)0.0004 (9)0.0001 (9)
C120.0338 (13)0.0246 (11)0.0242 (11)0.0014 (10)0.0037 (10)0.0036 (9)
C130.0371 (14)0.0300 (12)0.0219 (11)0.0001 (11)0.0010 (10)0.0056 (9)
C140.0324 (13)0.0312 (13)0.0269 (11)0.0052 (11)0.0059 (10)0.0026 (10)
C150.0472 (17)0.0303 (14)0.0570 (17)0.0042 (12)0.0018 (13)0.0079 (12)
C160.0468 (17)0.0571 (17)0.0334 (14)0.0159 (14)0.0167 (12)0.0030 (13)
C170.0324 (14)0.0498 (16)0.0394 (14)0.0071 (13)0.0011 (11)0.0020 (12)
N210.0269 (10)0.0223 (9)0.0240 (9)0.0005 (8)0.0010 (7)0.0020 (8)
N220.0421 (13)0.0244 (10)0.0312 (11)0.0068 (9)0.0030 (9)0.0009 (8)
C210.0352 (13)0.0226 (11)0.0233 (10)0.0027 (10)0.0008 (9)0.0003 (9)
C220.0262 (13)0.0355 (14)0.0358 (13)0.0019 (10)0.0029 (10)0.0003 (10)
C230.0332 (14)0.0385 (14)0.0389 (14)0.0085 (12)0.0030 (11)0.0012 (11)
C240.0642 (19)0.0204 (12)0.0384 (14)0.0086 (12)0.0031 (13)0.0013 (10)
C250.155 (4)0.0267 (15)0.0447 (18)0.0160 (19)0.013 (2)0.0031 (13)
C260.095 (3)0.0387 (19)0.143 (4)0.033 (2)0.029 (3)0.022 (2)
C270.102 (3)0.0250 (14)0.0444 (16)0.0000 (15)0.0069 (17)0.0061 (12)
N310.0250 (10)0.0215 (9)0.0238 (9)0.0008 (8)0.0006 (8)0.0009 (7)
N320.0269 (11)0.0337 (11)0.0268 (10)0.0021 (9)0.0029 (8)0.0029 (8)
C310.0257 (12)0.0288 (12)0.0237 (11)0.0018 (10)0.0014 (9)0.0003 (9)
C320.0356 (14)0.0226 (12)0.0360 (13)0.0017 (10)0.0021 (11)0.0071 (10)
C330.0385 (15)0.0364 (14)0.0368 (14)0.0005 (12)0.0035 (11)0.0130 (11)
C340.0266 (13)0.0514 (17)0.0292 (12)0.0068 (12)0.0051 (10)0.0008 (11)
C350.0271 (14)0.070 (2)0.0437 (15)0.0112 (14)0.0004 (11)0.0032 (14)
C360.0394 (15)0.0539 (17)0.0395 (14)0.0085 (14)0.0066 (12)0.0119 (13)
C370.0437 (17)0.077 (2)0.0366 (15)0.0056 (16)0.0120 (13)0.0094 (14)
C410.0264 (12)0.0243 (12)0.0308 (12)0.0039 (10)0.0051 (10)0.0028 (9)
C420.0327 (14)0.0290 (13)0.0425 (14)0.0027 (11)0.0012 (11)0.0019 (11)
C430.0360 (16)0.0440 (16)0.0585 (18)0.0080 (13)0.0040 (13)0.0153 (14)
C440.0505 (18)0.0332 (15)0.071 (2)0.0189 (14)0.0131 (16)0.0130 (14)
C450.066 (2)0.0238 (13)0.0567 (18)0.0064 (13)0.0121 (16)0.0014 (12)
C460.0425 (15)0.0251 (12)0.0405 (14)0.0022 (11)0.0019 (12)0.0003 (11)
Geometric parameters (Å, º) top
Co1—N11.941 (2)C24—C271.516 (4)
Co1—C112.039 (2)C25—H25A0.9700
Co1—C212.030 (2)C25—H25B0.9700
Co1—C312.006 (2)C25—H25C0.9700
B1—N111.578 (3)C26—H26A0.9700
B1—N311.582 (3)C26—H26B0.9700
B1—N211.584 (3)C26—H26C0.9700
B1—C411.607 (3)C27—H27A0.9700
N1—N21.138 (3)C27—H27B0.9700
N2—N3A1.132 (13)C27—H27C0.9700
N2—N3B1.211 (11)N31—C311.357 (3)
N3A—N3B0.786 (19)N31—C321.387 (3)
N11—C111.368 (3)N32—C311.353 (3)
N11—C121.387 (3)N32—C331.384 (3)
N12—C111.358 (3)N32—C341.501 (3)
N12—C131.388 (3)C32—C331.340 (3)
N12—C141.496 (3)C32—H320.9400
C12—C131.340 (3)C33—H330.9400
C12—H120.9400C34—C371.516 (3)
C13—H130.9400C34—C361.523 (4)
C14—C161.510 (3)C34—C351.528 (3)
C14—C171.517 (3)C35—H35A0.9700
C14—C151.522 (3)C35—H35B0.9700
C15—H15A0.9700C35—H35C0.9700
C15—H15B0.9700C36—H36A0.9700
C15—H15C0.9700C36—H36B0.9700
C16—H16A0.9700C36—H36C0.9700
C16—H16B0.9700C37—H37A0.9700
C16—H16C0.9700C37—H37B0.9700
C17—H17A0.9700C37—H37C0.9700
C17—H17B0.9700C41—C461.401 (3)
C17—H17C0.9700C41—C421.405 (3)
N21—C211.359 (3)C42—C431.379 (3)
N21—C221.385 (3)C42—H420.9400
N22—C211.357 (3)C43—C441.372 (4)
N22—C231.379 (3)C43—H430.9400
N22—C241.507 (3)C44—C451.381 (4)
C22—C231.346 (3)C44—H440.9400
C22—H220.9400C45—C461.383 (4)
C23—H230.9400C45—H450.9400
C24—C251.501 (4)C46—H460.9400
C24—C261.513 (4)
N1—Co1—C31123.50 (10)C26—C24—C27109.0 (3)
N1—Co1—C21123.72 (11)C24—C25—H25A109.5
N1—Co1—C11121.10 (10)C24—C25—H25B109.5
C11—Co1—C2192.20 (9)H25A—C25—H25B109.5
C11—Co1—C3193.34 (9)C24—C25—H25C109.5
C21—Co1—C3194.73 (9)H25A—C25—H25C109.5
N11—B1—N31106.77 (18)H25B—C25—H25C109.5
N11—B1—N21104.02 (17)C24—C26—H26A109.5
N31—B1—N21108.24 (17)C24—C26—H26B109.5
N11—B1—C41117.54 (18)H26A—C26—H26B109.5
N31—B1—C41106.80 (17)C24—C26—H26C109.5
N21—B1—C41113.05 (19)H26A—C26—H26C109.5
N2—N1—Co1146.9 (2)H26B—C26—H26C109.5
N3A—N2—N1159.8 (8)C24—C27—H27A109.5
N1—N2—N3B161.0 (7)C24—C27—H27B109.5
N3B—N3A—N275.9 (17)H27A—C27—H27B109.5
N3A—N3B—N265.1 (15)C24—C27—H27C109.5
C11—N11—C12109.06 (18)H27A—C27—H27C109.5
C11—N11—B1120.75 (17)H27B—C27—H27C109.5
C12—N11—B1129.88 (18)C31—N31—C32109.20 (18)
C11—N12—C13109.71 (18)C31—N31—B1124.41 (18)
C11—N12—C14124.19 (18)C32—N31—B1126.37 (18)
C13—N12—C14126.01 (18)C31—N32—C33110.02 (19)
N12—C11—N11106.05 (18)C31—N32—C34123.06 (19)
N12—C11—Co1139.60 (17)C33—N32—C34126.90 (19)
N11—C11—Co1113.71 (14)N32—C31—N31106.08 (18)
C13—C12—N11107.85 (19)N32—C31—Co1142.33 (17)
C13—C12—H12126.1N31—C31—Co1111.51 (14)
N11—C12—H12126.1C33—C32—N31107.8 (2)
C12—C13—N12107.29 (19)C33—C32—H32126.1
C12—C13—H13126.4N31—C32—H32126.1
N12—C13—H13126.4C32—C33—N32106.9 (2)
N12—C14—C16109.47 (19)C32—C33—H33126.6
N12—C14—C17109.42 (18)N32—C33—H33126.6
C16—C14—C17109.9 (2)N32—C34—C37109.5 (2)
N12—C14—C15108.42 (19)N32—C34—C36108.58 (19)
C16—C14—C15109.5 (2)C37—C34—C36109.3 (2)
C17—C14—C15110.1 (2)N32—C34—C35107.40 (19)
C14—C15—H15A109.5C37—C34—C35110.7 (2)
C14—C15—H15B109.5C36—C34—C35111.2 (2)
H15A—C15—H15B109.5C34—C35—H35A109.5
C14—C15—H15C109.5C34—C35—H35B109.5
H15A—C15—H15C109.5H35A—C35—H35B109.5
H15B—C15—H15C109.5C34—C35—H35C109.5
C14—C16—H16A109.5H35A—C35—H35C109.5
C14—C16—H16B109.5H35B—C35—H35C109.5
H16A—C16—H16B109.5C34—C36—H36A109.5
C14—C16—H16C109.5C34—C36—H36B109.5
H16A—C16—H16C109.5H36A—C36—H36B109.5
H16B—C16—H16C109.5C34—C36—H36C109.5
C14—C17—H17A109.5H36A—C36—H36C109.5
C14—C17—H17B109.5H36B—C36—H36C109.5
H17A—C17—H17B109.5C34—C37—H37A109.5
C14—C17—H17C109.5C34—C37—H37B109.5
H17A—C17—H17C109.5H37A—C37—H37B109.5
H17B—C17—H17C109.5C34—C37—H37C109.5
C21—N21—C22109.27 (18)H37A—C37—H37C109.5
C21—N21—B1122.47 (18)H37B—C37—H37C109.5
C22—N21—B1127.99 (18)C46—C41—C42115.6 (2)
C21—N22—C23110.23 (19)C46—C41—B1124.7 (2)
C21—N22—C24123.9 (2)C42—C41—B1119.0 (2)
C23—N22—C24125.8 (2)C43—C42—C41122.4 (2)
N22—C21—N21105.89 (19)C43—C42—H42118.8
N22—C21—Co1141.01 (17)C41—C42—H42118.8
N21—C21—Co1112.64 (15)C44—C43—C42120.3 (3)
C23—C22—N21107.8 (2)C44—C43—H43119.9
C23—C22—H22126.1C42—C43—H43119.9
N21—C22—H22126.1C43—C44—C45119.3 (3)
C22—C23—N22106.8 (2)C43—C44—H44120.3
C22—C23—H23126.6C45—C44—H44120.3
N22—C23—H23126.6C44—C45—C46120.3 (3)
C25—C24—N22108.2 (2)C44—C45—H45119.8
C25—C24—C26111.0 (3)C46—C45—H45119.8
N22—C24—C26109.2 (2)C45—C46—C41122.0 (3)
C25—C24—C27111.0 (3)C45—C46—H46119.0
N22—C24—C27108.40 (19)C41—C46—H46119.0
(2) Bis(azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(III) top
Crystal data top
[Co(C27H38BN6)(N3)2]V = 1495.2 (4) Å3
Mr = 600.43Z = 2
Triclinic, P1F(000) = 632
a = 10.1553 (14) ÅDx = 1.334 Mg m3
b = 12.3593 (18) ÅMo Kα radiation, λ = 0.71073 Å
c = 12.8113 (17) ŵ = 0.61 mm1
α = 82.350 (9)°T = 228 K
β = 69.88 (1)°Needle, green
γ = 85.26 (1)°0.28 × 0.05 × 0.02 mm
Data collection top
Bruker APEXII CCD area detector
diffractometer
6113 independent reflections
Radiation source: fine-focus sealed tube3105 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.126
phi and ω scansθmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
h = 1212
Tmin = 0.621, Tmax = 0.745k = 1415
24620 measured reflectionsl = 1616
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)] = 0.060H-atom parameters constrained
wR(F2) = 0.143 w = 1/[σ2(Fo2) + (0.0624P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max < 0.001
6113 reflectionsΔρmax = 0.34 e Å3
380 parametersΔρmin = 0.45 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0133 (15)
Crystal data top
[Co(C27H38BN6)(N3)2]γ = 85.26 (1)°
Mr = 600.43V = 1495.2 (4) Å3
Triclinic, P1Z = 2
a = 10.1553 (14) ÅMo Kα radiation
b = 12.3593 (18) ŵ = 0.61 mm1
c = 12.8113 (17) ÅT = 228 K
α = 82.350 (9)°0.28 × 0.05 × 0.02 mm
β = 69.88 (1)°
Data collection top
Bruker APEXII CCD area detector
diffractometer
6113 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2009)
3105 reflections with I > 2σ(I)
Tmin = 0.621, Tmax = 0.745Rint = 0.126
24620 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 0.92Δρmax = 0.34 e Å3
6113 reflectionsΔρmin = 0.45 e Å3
380 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Co10.61577 (6)0.71224 (4)0.74346 (5)0.0273 (2)
B10.8509 (5)0.7760 (4)0.5191 (4)0.0270 (11)
N10.7886 (3)0.6659 (3)0.5218 (3)0.0273 (8)
N20.6777 (4)0.5199 (3)0.6140 (3)0.0303 (9)
N30.7265 (3)0.8611 (2)0.5551 (3)0.0245 (8)
N40.5485 (3)0.9484 (3)0.6666 (3)0.0265 (8)
N50.9055 (3)0.7576 (3)0.6212 (3)0.0284 (8)
N60.9031 (4)0.7128 (3)0.7920 (3)0.0321 (9)
N70.5310 (4)0.7339 (3)0.8990 (3)0.0380 (9)
N80.4082 (5)0.7190 (3)0.9532 (3)0.0392 (10)
N90.2927 (5)0.7046 (4)1.0088 (3)0.0620 (13)
N100.4292 (4)0.6898 (3)0.7359 (3)0.0323 (9)
N110.4102 (4)0.7093 (3)0.6477 (3)0.0310 (9)
N120.3842 (4)0.7269 (3)0.5657 (3)0.0463 (11)
C10.6930 (4)0.6277 (3)0.6206 (3)0.0279 (10)
C20.8345 (5)0.5819 (4)0.4542 (4)0.0367 (11)
H20.90250.58650.38230.044*
C30.7643 (5)0.4931 (4)0.5100 (4)0.0391 (12)
H30.77230.42480.48340.047*
C40.5925 (5)0.4366 (3)0.7020 (4)0.0327 (11)
C50.6754 (5)0.3275 (3)0.6926 (4)0.0473 (13)
H5A0.68400.30110.62240.071*
H5B0.62670.27490.75440.071*
H5C0.76810.33720.69490.071*
C60.4545 (5)0.4263 (4)0.6819 (4)0.0453 (13)
H6A0.40200.49570.68880.068*
H6B0.39970.37070.73670.068*
H6C0.47410.40580.60730.068*
C70.5685 (5)0.4707 (4)0.8158 (4)0.0501 (13)
H7A0.65820.48020.82400.075*
H7B0.51820.41490.87300.075*
H7C0.51370.53910.82380.075*
C80.6243 (4)0.8495 (3)0.6563 (3)0.0256 (10)
C90.7179 (4)0.9647 (3)0.5033 (3)0.0280 (10)
H90.77820.99320.43290.034*
C100.6086 (4)1.0179 (3)0.5708 (3)0.0312 (10)
H100.57781.09020.55560.037*
C110.4300 (4)0.9892 (3)0.7657 (3)0.0319 (10)
C120.3854 (5)1.1058 (3)0.7302 (4)0.0382 (11)
H12A0.35761.10610.66490.057*
H12B0.46341.15330.71230.057*
H12C0.30691.13170.79090.057*
C130.4849 (5)0.9925 (4)0.8612 (3)0.0394 (12)
H13A0.41101.01990.92400.059*
H13B0.56361.04030.83700.059*
H13C0.51550.91940.88380.059*
C140.3022 (4)0.9187 (3)0.7979 (4)0.0368 (11)
H14A0.27060.92060.73420.055*
H14B0.22730.94670.85970.055*
H14C0.32750.84390.82000.055*
C150.8173 (4)0.7294 (3)0.7275 (3)0.0271 (10)
C161.0415 (4)0.7568 (3)0.6200 (4)0.0346 (11)
H161.12120.77210.55660.042*
C171.0406 (5)0.7305 (4)0.7242 (4)0.0384 (11)
H171.11920.72480.74770.046*
C180.8651 (5)0.6843 (4)0.9164 (4)0.0338 (11)
C190.7801 (5)0.5821 (4)0.9520 (4)0.0449 (13)
H19A0.69130.59750.93930.067*
H19B0.76280.55951.03090.067*
H19C0.83180.52420.90870.067*
C200.9976 (5)0.6609 (4)0.9470 (4)0.0531 (14)
H20A1.05330.60230.90670.080*
H20B0.97210.63921.02690.080*
H20C1.05190.72610.92710.080*
C210.7854 (5)0.7804 (4)0.9749 (4)0.0474 (13)
H21A0.84540.84250.95360.071*
H21B0.75690.76111.05520.071*
H21C0.70300.79910.95340.071*
C220.9599 (4)0.8224 (3)0.4000 (3)0.0290 (10)
C230.9484 (4)0.8003 (3)0.3002 (3)0.0347 (11)
H230.88080.75150.30260.042*
C241.0327 (5)0.8475 (4)0.1970 (4)0.0441 (12)
H241.02500.82760.13110.053*
C251.1269 (5)0.9227 (4)0.1908 (4)0.0497 (14)
H251.18420.95470.12080.060*
C261.1376 (5)0.9515 (4)0.2879 (4)0.0433 (12)
H261.20021.00480.28460.052*
C271.0555 (4)0.9013 (3)0.3903 (4)0.0354 (11)
H271.06450.92110.45580.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0211 (3)0.0287 (4)0.0322 (4)0.0001 (2)0.0101 (3)0.0017 (3)
B10.021 (3)0.027 (3)0.033 (3)0.001 (2)0.009 (2)0.007 (2)
N10.0208 (19)0.026 (2)0.035 (2)0.0021 (15)0.0079 (16)0.0063 (17)
N20.029 (2)0.025 (2)0.037 (2)0.0018 (16)0.0107 (18)0.0055 (17)
N30.0235 (19)0.025 (2)0.027 (2)0.0015 (15)0.0115 (16)0.0014 (15)
N40.0203 (19)0.028 (2)0.032 (2)0.0025 (15)0.0096 (16)0.0057 (16)
N50.0192 (19)0.032 (2)0.035 (2)0.0005 (15)0.0104 (17)0.0054 (16)
N60.023 (2)0.038 (2)0.037 (2)0.0008 (16)0.0130 (18)0.0042 (17)
N70.027 (2)0.051 (2)0.037 (2)0.0024 (18)0.0114 (19)0.0081 (18)
N80.041 (3)0.045 (3)0.030 (2)0.010 (2)0.014 (2)0.0005 (19)
N90.037 (3)0.090 (4)0.047 (3)0.008 (2)0.005 (2)0.007 (2)
N100.026 (2)0.032 (2)0.039 (2)0.0003 (16)0.0134 (18)0.0008 (18)
N110.023 (2)0.024 (2)0.045 (3)0.0014 (15)0.010 (2)0.0028 (18)
N120.047 (3)0.053 (3)0.046 (3)0.002 (2)0.026 (2)0.002 (2)
C10.024 (2)0.029 (3)0.036 (3)0.0022 (19)0.019 (2)0.001 (2)
C20.037 (3)0.036 (3)0.035 (3)0.002 (2)0.007 (2)0.012 (2)
C30.044 (3)0.028 (3)0.046 (3)0.001 (2)0.013 (2)0.014 (2)
C40.032 (3)0.024 (2)0.042 (3)0.0058 (19)0.014 (2)0.001 (2)
C50.046 (3)0.029 (3)0.064 (3)0.003 (2)0.019 (3)0.001 (2)
C60.040 (3)0.036 (3)0.062 (3)0.008 (2)0.022 (3)0.002 (2)
C70.059 (4)0.044 (3)0.048 (3)0.008 (3)0.021 (3)0.004 (2)
C80.022 (2)0.029 (3)0.028 (2)0.0001 (19)0.0101 (19)0.0062 (19)
C90.028 (2)0.031 (3)0.026 (2)0.005 (2)0.010 (2)0.002 (2)
C100.032 (3)0.027 (2)0.036 (3)0.005 (2)0.014 (2)0.001 (2)
C110.026 (2)0.035 (3)0.037 (3)0.006 (2)0.012 (2)0.013 (2)
C120.036 (3)0.028 (3)0.051 (3)0.004 (2)0.016 (2)0.008 (2)
C130.035 (3)0.050 (3)0.034 (3)0.007 (2)0.012 (2)0.013 (2)
C140.023 (2)0.039 (3)0.045 (3)0.004 (2)0.007 (2)0.006 (2)
C150.025 (2)0.029 (2)0.032 (3)0.0027 (18)0.015 (2)0.0040 (19)
C160.018 (2)0.043 (3)0.045 (3)0.000 (2)0.011 (2)0.006 (2)
C170.022 (3)0.050 (3)0.046 (3)0.002 (2)0.016 (2)0.005 (2)
C180.029 (3)0.042 (3)0.035 (3)0.004 (2)0.019 (2)0.002 (2)
C190.048 (3)0.046 (3)0.044 (3)0.003 (2)0.021 (2)0.001 (2)
C200.044 (3)0.068 (4)0.056 (3)0.004 (3)0.032 (3)0.004 (3)
C210.054 (3)0.047 (3)0.048 (3)0.006 (3)0.025 (3)0.012 (3)
C220.021 (2)0.029 (2)0.035 (3)0.0010 (19)0.006 (2)0.007 (2)
C230.027 (3)0.038 (3)0.039 (3)0.003 (2)0.010 (2)0.004 (2)
C240.042 (3)0.056 (3)0.032 (3)0.002 (3)0.009 (2)0.006 (2)
C250.042 (3)0.053 (3)0.043 (3)0.011 (3)0.003 (3)0.008 (3)
C260.032 (3)0.047 (3)0.047 (3)0.012 (2)0.009 (2)0.002 (2)
C270.031 (3)0.040 (3)0.037 (3)0.003 (2)0.013 (2)0.006 (2)
Geometric parameters (Å, º) top
Co1—C81.894 (4)C7—H7C0.9700
Co1—C11.907 (4)C9—C101.335 (5)
Co1—N71.926 (4)C9—H90.9400
Co1—N101.974 (4)C10—H100.9400
Co1—C152.012 (4)C11—C131.515 (6)
B1—N11.538 (6)C11—C141.529 (6)
B1—N31.557 (6)C11—C121.532 (5)
B1—N51.571 (6)C12—H12A0.9700
B1—C221.610 (6)C12—H12B0.9700
N1—C11.356 (5)C12—H12C0.9700
N1—C21.388 (5)C13—H13A0.9700
N2—C11.371 (5)C13—H13B0.9700
N2—C31.386 (5)C13—H13C0.9700
N2—C41.499 (5)C14—H14A0.9700
N3—C81.352 (5)C14—H14B0.9700
N3—C91.372 (5)C14—H14C0.9700
N4—C101.381 (5)C16—C171.328 (6)
N4—C81.386 (5)C16—H160.9400
N4—C111.528 (5)C17—H170.9400
N5—C151.366 (5)C18—C211.512 (6)
N5—C161.376 (5)C18—C191.518 (6)
N6—C151.381 (5)C18—C201.522 (6)
N6—C171.384 (5)C19—H19A0.9700
N6—C181.503 (5)C19—H19B0.9700
N7—N81.216 (5)C19—H19C0.9700
N8—N91.157 (5)C20—H20A0.9700
N10—N111.201 (5)C20—H20B0.9700
N11—N121.158 (5)C20—H20C0.9700
C2—C31.339 (6)C21—H21A0.9700
C2—H20.9400C21—H21B0.9700
C3—H30.9400C21—H21C0.9700
C4—C71.506 (6)C22—C231.387 (5)
C4—C51.525 (6)C22—C271.397 (6)
C4—C61.528 (6)C23—C241.385 (6)
C5—H5A0.9700C23—H230.9400
C5—H5B0.9700C24—C251.364 (6)
C5—H5C0.9700C24—H240.9400
C6—H6A0.9700C25—C261.380 (6)
C6—H6B0.9700C25—H250.9400
C6—H6C0.9700C26—C271.384 (6)
C7—H7A0.9700C26—H260.9400
C7—H7B0.9700C27—H270.9400
C1—Co1—C896.26 (17)C9—C10—H10125.8
C8—Co1—N7108.63 (16)N4—C10—H10125.8
C1—Co1—N7155.02 (16)C13—C11—N4108.9 (3)
C8—Co1—N1090.76 (15)C13—C11—C14113.1 (4)
C1—Co1—N1087.37 (16)N4—C11—C14110.6 (3)
N7—Co1—N1090.09 (15)C13—C11—C12108.4 (3)
C8—Co1—C1587.23 (16)N4—C11—C12108.3 (3)
C1—Co1—C1584.57 (17)C14—C11—C12107.5 (4)
N7—Co1—C1598.45 (16)C11—C12—H12A109.5
N10—Co1—C15171.42 (16)C11—C12—H12B109.5
N1—B1—N3107.6 (3)H12A—C12—H12B109.5
N1—B1—N5103.4 (3)C11—C12—H12C109.5
N3—B1—N5103.6 (3)H12A—C12—H12C109.5
N1—B1—C22115.5 (3)H12B—C12—H12C109.5
N3—B1—C22108.6 (3)C11—C13—H13A109.5
N5—B1—C22117.1 (3)C11—C13—H13B109.5
C1—N1—C2109.3 (3)H13A—C13—H13B109.5
C1—N1—B1116.1 (3)C11—C13—H13C109.5
C2—N1—B1132.2 (3)H13A—C13—H13C109.5
C1—N2—C3108.8 (3)H13B—C13—H13C109.5
C1—N2—C4129.1 (4)C11—C14—H14A109.5
C3—N2—C4122.0 (3)C11—C14—H14B109.5
C8—N3—C9109.9 (3)H14A—C14—H14B109.5
C8—N3—B1122.4 (3)C11—C14—H14C109.5
C9—N3—B1126.5 (3)H14A—C14—H14C109.5
C10—N4—C8108.0 (3)H14B—C14—H14C109.5
C10—N4—C11120.9 (3)N5—C15—N6104.9 (3)
C8—N4—C11130.7 (3)N5—C15—Co1115.7 (3)
C15—N5—C16110.0 (3)N6—C15—Co1139.2 (3)
C15—N5—B1121.5 (3)C17—C16—N5108.1 (4)
C16—N5—B1128.3 (3)C17—C16—H16126.0
C15—N6—C17109.3 (4)N5—C16—H16126.0
C15—N6—C18129.5 (3)C16—C17—N6107.8 (4)
C17—N6—C18121.3 (4)C16—C17—H17126.1
N8—N7—Co1124.0 (3)N6—C17—H17126.1
N9—N8—N7177.1 (5)N6—C18—C21109.2 (3)
N11—N10—Co1119.2 (3)N6—C18—C19109.1 (3)
N12—N11—N10176.2 (5)C21—C18—C19112.0 (4)
N1—C1—N2106.4 (3)N6—C18—C20110.0 (3)
N1—C1—Co1123.2 (3)C21—C18—C20108.1 (4)
N2—C1—Co1130.1 (3)C19—C18—C20108.3 (4)
C3—C2—N1107.6 (4)C18—C19—H19A109.5
C3—C2—H2126.2C18—C19—H19B109.5
N1—C2—H2126.2H19A—C19—H19B109.5
C2—C3—N2107.9 (4)C18—C19—H19C109.5
C2—C3—H3126.1H19A—C19—H19C109.5
N2—C3—H3126.1H19B—C19—H19C109.5
N2—C4—C7109.3 (3)C18—C20—H20A109.5
N2—C4—C5108.5 (4)C18—C20—H20B109.5
C7—C4—C5108.5 (4)H20A—C20—H20B109.5
N2—C4—C6108.6 (3)C18—C20—H20C109.5
C7—C4—C6111.8 (4)H20A—C20—H20C109.5
C5—C4—C6110.0 (4)H20B—C20—H20C109.5
C4—C5—H5A109.5C18—C21—H21A109.5
C4—C5—H5B109.5C18—C21—H21B109.5
H5A—C5—H5B109.5H21A—C21—H21B109.5
C4—C5—H5C109.5C18—C21—H21C109.5
H5A—C5—H5C109.5H21A—C21—H21C109.5
H5B—C5—H5C109.5H21B—C21—H21C109.5
C4—C6—H6A109.5C23—C22—C27115.6 (4)
C4—C6—H6B109.5C23—C22—B1121.5 (4)
H6A—C6—H6B109.5C27—C22—B1122.1 (4)
C4—C6—H6C109.5C24—C23—C22122.4 (4)
H6A—C6—H6C109.5C24—C23—H23118.8
H6B—C6—H6C109.5C22—C23—H23118.8
C4—C7—H7A109.5C25—C24—C23120.2 (4)
C4—C7—H7B109.5C25—C24—H24119.9
H7A—C7—H7B109.5C23—C24—H24119.9
C4—C7—H7C109.5C24—C25—C26119.5 (4)
H7A—C7—H7C109.5C24—C25—H25120.2
H7B—C7—H7C109.5C26—C25—H25120.2
N3—C8—N4106.0 (3)C25—C26—C27119.6 (4)
N3—C8—Co1117.3 (3)C25—C26—H26120.2
N4—C8—Co1136.6 (3)C27—C26—H26120.2
C10—C9—N3107.8 (4)C26—C27—C22122.5 (4)
C10—C9—H9126.1C26—C27—H27118.7
N3—C9—H9126.1C22—C27—H27118.7
C9—C10—N4108.3 (4)

Experimental details

(1)(2)
Crystal data
Chemical formula[Co(C27H38BN6)(N3)][Co(C27H38BN6)(N3)2]
Mr558.40600.43
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)223228
a, b, c (Å)9.8910 (3), 17.7415 (5), 16.1660 (5)10.1553 (14), 12.3593 (18), 12.8113 (17)
α, β, γ (°)90, 92.016 (2), 9082.350 (9), 69.88 (1), 85.26 (1)
V3)2835.07 (15)1495.2 (4)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.640.61
Crystal size (mm)0.17 × 0.07 × 0.050.28 × 0.05 × 0.02
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area detector
diffractometer
Absorption correctionMulti-scan
(APEX2; Bruker, 2009)
Multi-scan
(APEX2; Bruker, 2009)
Tmin, Tmax0.675, 0.7460.621, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections
50578, 7050, 4482 24620, 6113, 3105
Rint0.0860.126
(sin θ/λ)max1)0.6680.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.107, 1.01 0.060, 0.143, 0.92
No. of reflections70506113
No. of parameters361380
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.320.34, 0.45

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), WinGX (Farrugia, 20120), WinGX (Farrugia, 2012).

Selected geometric parameters (Å, º) for (1) top
Co1—N11.941 (2)Co1—C312.006 (2)
Co1—C112.039 (2)N1—N21.138 (3)
Co1—C212.030 (2)N2—N3A1.132 (13)
C11—Co1—C2192.20 (9)N2—N1—Co1146.9 (2)
C11—Co1—C3193.34 (9)N3A—N2—N1159.8 (8)
C21—Co1—C3194.73 (9)
Selected geometric parameters (Å, º) for (2) top
Co1—C81.894 (4)N7—N81.216 (5)
Co1—C11.907 (4)N8—N91.157 (5)
Co1—N71.926 (4)N10—N111.201 (5)
Co1—N101.974 (4)N11—N121.158 (5)
Co1—C152.012 (4)
C1—Co1—C896.26 (17)N10—Co1—C15171.42 (16)
C8—Co1—N7108.63 (16)N8—N7—Co1124.0 (3)
C1—Co1—N7155.02 (16)N9—N8—N7177.1 (5)
C8—Co1—N1090.76 (15)N11—N10—Co1119.2 (3)
C8—Co1—C1587.23 (16)N12—N11—N10176.2 (5)
C1—Co1—C1584.57 (17)
 

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