[N,N-Bis(diphenyl­phosphino)isopropyl­amine]dibromidonickel(II)

Hapke, M.; Wöhl, A.; Peitz, S.; Müller, B.H.; Spannenberg, A.; Rosenthal, U.

doi:10.1107/S1600536809003936

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m252

doi:10.1107/S1600536809003936

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[N,N-Bis(diphenylphosphino)isopropylamine]dibromidonickel(II)

Marko Hapke,^a ^* Anina Wöhl,^b Stephan Peitz,^a Bernd H. Müller,^a Anke Spannenberg ^a and Uwe Rosenthal ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, and ^bLinde AG, Linde Engineering Division, Dr.-Carl-von-Linde-Strasse 6-14, 82049 Pullach, Germany
^*Correspondence e-mail: marko.hapke@catalysis.de

(Received 26 January 2009; accepted 2 February 2009; online 6 February 2009)

The title compound, [NiBr₂(C₂₇H₂₇NP₂)], was synthesized by the reaction of NiBr₂(dme) (dme is 1,2-dimethoxyethane) with N,N-bis(diphenylphosphino)isopropylamine in methanol/tetrahydrofuran. The nickel(II) center is coordinated by two P atoms of the chelating PNP ligand, Ph₂PN(iPr)PPh₂, and two bromide ions in a distorted square-planar geometry.

Related literature

For derivatives of the title compound and their structural details, see: Cooley et al. (2001 ); Sushev et al. (2005 ); Sun et al. (2006 ). For structural features of a nickel complex with an arene-briged bis-PNP ligand, see: Majoumo-Mbe et al. (2005 ). For catalytic features of the PNP ligand, see: Wöhl et al. (2009 ).

Experimental

Crystal data

[NiBr₂(C₂₇H₂₇NP₂)]
M_r = 645.97
Orthorhombic, P b c a
a = 16.6720 (3) Å
b = 15.1689 (4) Å
c = 20.3777 (4) Å
V = 5153.44 (19) Å³
Z = 8
Mo Kα radiation
μ = 4.00 mm⁻¹
T = 200 (2) K
0.17 × 0.14 × 0.04 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005 ) T_min = 0.484, T_max = 0.884
73587 measured reflections
6956 independent reflections
4725 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.064
S = 0.89
6956 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003936/ci2764sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003936/ci2764Isup2.hkl

checkCIF report

Comment top

Ligands containing the "PNP" moiety as the structural motif of the coordination unit have been used for different purposes in coordination chemistry. During the recent period, they were used with different metals including nickel for investigations into oligomerizations, polymerizations (Cooley et al., 2001) or copolymerizations (Majoumo-Mbe et al., 2005) with ethene or other alkenes (Sun et al., 2006). The Ni(PNP) core was also used for investigations into the reactivity behaviour of the nickel-coordinated HN(PPH₂)₂ ligand (Sushev et al., 2005). During these studies allylation of the N—H yielded a comparable nickel complex to the one that is described here. Dinuclear Ni(PNP)-complexes with arene-bridged PNP units have been prepared that have two independent and structurally identical Ni(PNP) moities (Majoumo-Mbe et al., 2005).

We became interested in nickel complexes during our studies on the selective oligomerization of ethene via transition metal-catalyzed tri- or tetramerization, yielding 1-hexene or 1-octene (Wöhl et al., 2009). Our initial experimental work was focusing on a chromium-based catalyst system (CrCl₃(THF)₃/Ph₂PN(iPr)PPh₂/MAO) and we recently became interested in the kinetic behaviour of this catalyst system, to gain a better understanding of the underlying catalytic mechanism in dependence from different metal/ligand ratios. However, for reasons of comparison we wanted to examine the corresponding nickel complex containing the same simple isopropyl-substituted PNP ligand. We deployed a simple preparation procedure, that is described here, to obtain the complex in high yields for our screening experiments.

The molecular structure of the title compound shows that the Ni^II center is coordinated by two P atoms of the chelating Ph₂PN(iPr)PPh₂ ligand and two bromide ions (Fig. 1). Its coordination geometry can be best described as distorted square-planar (P2—Ni1—P1 73.22 (3)°, P1—Ni1—Br1 94.39 (2)°, P2—Ni1—Br2 94.74 (2)°, Br1—Ni1—Br2 98.213 (16)°). Furthermore, the chelating ligand and the metal form a four-membered Ni(PNP) ring which is nearly planar (mean deviation from the best plane defined by Ni1, P1, N1 and P2 atoms is 0.0481 Å).

Related literature top

For derivatives of the title compound and their structural details, see: Cooley et al. (2001); Sushev et al. (2005); Sun et al. (2006). For structural features of a nickel complex with an arene-briged bis-PNP ligand, see: Majoumo-Mbe et al. (2005). For catalytic features of the PNP ligand, see: Wöhl et al. (2009).

Experimental top

NiBr₂(1,2-dimethoxyethane) (334 mg, 1.08 mmol) was dissolved in dry methanol and heated to 333 K. N,N-bis(diphenylphosphino)isopropylamine (462 mg, 1.08 mmol) was dissolved in dry THF and the solution was cannulated into the nickel complex solution under argon. The red solution obtained was stirred for an hour at 333 K and after cooling, the red solid obtained was collected on a glas frit and washed twice with methanol and three times with water and finally with ether. The red solid was dried in high vacuo to yield 645 mg of pure red complex. The identity of the product was proven by ¹H, ¹³C and ³¹P NMR (solvent: CD₂Cl₂). Single crystals suitable for X-ray analysis were grown from a chloroform-diethyl ether solution (2:1).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

[N,N-Bis(diphenylphosphino)isopropylamine]dibromidonickel(II) top

Crystal data top

[NiBr₂(C₂₇H₂₇NP₂)]	F(000) = 2592
M_r = 645.97	D_x = 1.665 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 33195 reflections
a = 16.6720 (3) Å	θ = 2.1–29.5°
b = 15.1689 (4) Å	µ = 4.00 mm⁻¹
c = 20.3777 (4) Å	T = 200 K
V = 5153.44 (19) Å³	Prism, red–brown
Z = 8	0.17 × 0.14 × 0.04 mm

Data collection top

Stoe IPDS-II diffractometer	6956 independent reflections
Radiation source: fine-focus sealed tube	4725 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
rotation method scans	θ_max = 29.3°, θ_min = 2.0°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005)	h = −22→22
T_min = 0.484, T_max = 0.884	k = −20→20
73587 measured reflections	l = −27→27

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 0.89	w = 1/[σ²(F_o²) + (0.0281P)²] where P = (F_o² + 2F_c²)/3
6956 reflections	(Δ/σ)_max = 0.001
300 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[NiBr₂(C₂₇H₂₇NP₂)]	V = 5153.44 (19) Å³
M_r = 645.97	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 16.6720 (3) Å	µ = 4.00 mm⁻¹
b = 15.1689 (4) Å	T = 200 K
c = 20.3777 (4) Å	0.17 × 0.14 × 0.04 mm

Data collection top

Stoe IPDS-II diffractometer	6956 independent reflections
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005)	4725 reflections with I > 2σ(I)
T_min = 0.484, T_max = 0.884	R_int = 0.080
73587 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 0.89	Δρ_max = 0.57 e Å⁻³
6956 reflections	Δρ_min = −0.43 e Å⁻³
300 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.90625 (17)	0.87979 (17)	0.23217 (13)	0.0230 (5)
C2	0.88616 (18)	0.96307 (18)	0.20951 (14)	0.0274 (6)
H2	0.8694	0.9707	0.1653	0.033*
C3	0.89045 (19)	1.03524 (19)	0.25112 (16)	0.0337 (7)
H3	0.8760	1.0921	0.2357	0.040*
C4	0.91578 (19)	1.0242 (2)	0.31503 (15)	0.0354 (7)
H4	0.9175	1.0733	0.3439	0.043*
C5	0.9386 (2)	0.9421 (2)	0.33713 (15)	0.0334 (7)
H5	0.9575	0.9353	0.3808	0.040*
C6	0.93436 (18)	0.86966 (19)	0.29619 (14)	0.0292 (6)
H6	0.9505	0.8133	0.3116	0.035*
C7	0.87114 (17)	0.69391 (17)	0.22892 (13)	0.0227 (5)
C8	0.81317 (17)	0.70629 (18)	0.27757 (13)	0.0266 (6)
H8	0.7957	0.7640	0.2886	0.032*
C9	0.78135 (19)	0.6339 (2)	0.30950 (14)	0.0322 (7)
H9	0.7416	0.6418	0.3424	0.039*
C10	0.8074 (2)	0.5497 (2)	0.29349 (15)	0.0366 (7)
H10	0.7850	0.5001	0.3153	0.044*
C11	0.8656 (2)	0.53756 (19)	0.24623 (16)	0.0342 (7)
H11	0.8838	0.4798	0.2359	0.041*
C12	0.89720 (18)	0.60961 (17)	0.21390 (14)	0.0264 (6)
H12	0.9371	0.6013	0.1812	0.032*
C13	0.92171 (17)	0.85623 (17)	−0.00596 (13)	0.0231 (5)
C14	0.96284 (19)	0.8386 (2)	−0.06458 (13)	0.0301 (6)
H14	0.9826	0.7811	−0.0734	0.036*
C15	0.9743 (2)	0.9060 (2)	−0.10958 (14)	0.0377 (7)
H15	1.0014	0.8945	−0.1497	0.045*
C16	0.9466 (2)	0.9895 (2)	−0.09623 (15)	0.0383 (8)
H16	0.9554	1.0354	−0.1272	0.046*
C17	0.90638 (19)	1.00777 (19)	−0.03885 (15)	0.0347 (7)
H17	0.8876	1.0657	−0.0302	0.042*
C18	0.89349 (18)	0.94077 (18)	0.00636 (15)	0.0274 (6)
H18	0.8653	0.9528	0.0459	0.033*
C19	0.88235 (17)	0.67305 (17)	0.01232 (13)	0.0239 (6)
C20	0.82043 (18)	0.67961 (19)	−0.03337 (14)	0.0297 (6)
H20	0.8025	0.7359	−0.0477	0.036*
C21	0.7852 (2)	0.6040 (2)	−0.05781 (16)	0.0362 (7)
H21	0.7427	0.6081	−0.0887	0.043*
C22	0.8119 (2)	0.5222 (2)	−0.03737 (16)	0.0409 (8)
H22	0.7867	0.4705	−0.0535	0.049*
C23	0.8747 (2)	0.51497 (19)	0.00613 (15)	0.0368 (8)
H23	0.8935	0.4584	0.0189	0.044*
C24	0.9107 (2)	0.59054 (17)	0.03148 (14)	0.0295 (6)
H24	0.9542	0.5859	0.0615	0.035*
C25	0.75815 (16)	0.79720 (19)	0.10263 (13)	0.0269 (6)
H25	0.7481	0.8093	0.0551	0.032*
C26	0.71793 (19)	0.8703 (2)	0.14099 (16)	0.0382 (7)
H26A	0.7308	0.8640	0.1877	0.057*
H26B	0.6597	0.8668	0.1349	0.057*
H26C	0.7373	0.9275	0.1252	0.057*
C27	0.72121 (18)	0.7077 (2)	0.11777 (15)	0.0355 (7)
H27A	0.7526	0.6613	0.0963	0.053*
H27B	0.6659	0.7061	0.1015	0.053*
H27C	0.7213	0.6980	0.1653	0.053*
N1	0.84753 (13)	0.79808 (13)	0.11239 (10)	0.0206 (4)
P1	0.90770 (4)	0.78459 (4)	0.17912 (3)	0.01915 (13)
P2	0.91702 (4)	0.77028 (5)	0.05515 (3)	0.01925 (12)
Ni1	1.013681 (19)	0.761785 (18)	0.122690 (17)	0.01868 (7)
Br1	1.100033 (18)	0.77856 (2)	0.211279 (14)	0.03435 (8)
Br2	1.108991 (17)	0.72404 (2)	0.043377 (14)	0.03133 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0219 (14)	0.0241 (12)	0.0231 (12)	−0.0011 (11)	0.0044 (11)	−0.0029 (10)
C2	0.0303 (16)	0.0250 (13)	0.0270 (14)	−0.0001 (11)	0.0045 (12)	−0.0021 (11)
C3	0.0303 (16)	0.0259 (13)	0.0449 (17)	−0.0008 (12)	0.0109 (14)	−0.0037 (12)
C4	0.0292 (17)	0.0357 (16)	0.0414 (17)	−0.0099 (13)	0.0115 (14)	−0.0182 (13)
C5	0.0347 (18)	0.0394 (17)	0.0262 (14)	−0.0058 (13)	0.0022 (12)	−0.0094 (12)
C6	0.0306 (16)	0.0311 (15)	0.0258 (14)	−0.0013 (12)	0.0012 (12)	−0.0011 (11)
C7	0.0241 (14)	0.0227 (12)	0.0213 (12)	−0.0011 (10)	−0.0034 (10)	0.0042 (10)
C8	0.0259 (14)	0.0289 (14)	0.0250 (13)	0.0011 (11)	0.0007 (11)	0.0023 (10)
C9	0.0250 (16)	0.0439 (17)	0.0277 (15)	−0.0039 (13)	0.0029 (12)	0.0095 (12)
C10	0.0344 (18)	0.0400 (17)	0.0354 (16)	−0.0123 (14)	−0.0077 (14)	0.0151 (13)
C11	0.0381 (18)	0.0251 (13)	0.0394 (17)	−0.0028 (13)	−0.0101 (15)	0.0030 (13)
C12	0.0302 (16)	0.0229 (12)	0.0262 (13)	−0.0005 (11)	−0.0015 (13)	0.0016 (10)
C13	0.0204 (14)	0.0257 (13)	0.0231 (12)	−0.0043 (10)	−0.0036 (11)	0.0051 (10)
C14	0.0333 (17)	0.0350 (15)	0.0219 (13)	−0.0046 (12)	0.0019 (12)	0.0024 (11)
C15	0.0383 (19)	0.0511 (18)	0.0238 (15)	−0.0095 (14)	−0.0015 (13)	0.0090 (12)
C16	0.0344 (18)	0.0447 (18)	0.0357 (16)	−0.0137 (14)	−0.0132 (14)	0.0201 (14)
C17	0.0291 (16)	0.0302 (14)	0.0450 (18)	−0.0040 (12)	−0.0141 (15)	0.0112 (13)
C18	0.0218 (15)	0.0293 (14)	0.0313 (15)	0.0000 (11)	−0.0055 (12)	0.0017 (11)
C19	0.0256 (15)	0.0248 (13)	0.0214 (12)	−0.0031 (10)	0.0052 (11)	−0.0032 (10)
C20	0.0270 (15)	0.0336 (14)	0.0285 (14)	−0.0015 (12)	0.0010 (12)	−0.0080 (11)
C21	0.0280 (17)	0.0457 (18)	0.0349 (16)	−0.0097 (13)	0.0010 (13)	−0.0152 (14)
C22	0.042 (2)	0.0386 (17)	0.0425 (18)	−0.0196 (15)	0.0107 (16)	−0.0170 (14)
C23	0.051 (2)	0.0252 (15)	0.0342 (16)	−0.0063 (13)	0.0137 (15)	−0.0042 (12)
C24	0.0395 (18)	0.0235 (13)	0.0256 (13)	0.0011 (12)	0.0028 (13)	−0.0013 (11)
C25	0.0169 (13)	0.0370 (15)	0.0269 (13)	0.0022 (11)	−0.0018 (10)	0.0029 (11)
C26	0.0249 (16)	0.0482 (18)	0.0414 (18)	0.0097 (13)	0.0035 (13)	−0.0029 (14)
C27	0.0255 (15)	0.0466 (17)	0.0345 (15)	−0.0115 (12)	−0.0005 (13)	0.0015 (14)
N1	0.0174 (11)	0.0243 (10)	0.0200 (11)	0.0023 (8)	−0.0007 (8)	0.0002 (8)
P1	0.0200 (3)	0.0191 (3)	0.0183 (3)	0.0005 (3)	0.0009 (2)	−0.0003 (2)
P2	0.0198 (3)	0.0197 (3)	0.0183 (3)	−0.0001 (3)	−0.0003 (2)	−0.0003 (2)
Ni1	0.01720 (14)	0.01814 (14)	0.02069 (13)	0.00026 (11)	0.00008 (15)	0.00020 (13)
Br1	0.03006 (16)	0.03626 (16)	0.03674 (15)	0.00651 (14)	−0.01348 (13)	−0.00788 (13)
Br2	0.02687 (15)	0.03284 (14)	0.03429 (14)	0.00272 (13)	0.00987 (12)	−0.00076 (12)

Geometric parameters (Å, º) top

C1—C2	1.386 (4)	C17—C18	1.389 (4)
C1—C6	1.395 (4)	C17—H17	0.95
C1—P1	1.804 (3)	C18—H18	0.95
C2—C3	1.387 (4)	C19—C20	1.394 (4)
C2—H2	0.95	C19—C24	1.394 (4)
C3—C4	1.379 (5)	C19—P2	1.809 (3)
C3—H3	0.95	C20—C21	1.382 (4)
C4—C5	1.378 (5)	C20—H20	0.95
C4—H4	0.95	C21—C22	1.381 (5)
C5—C6	1.381 (4)	C21—H21	0.95
C5—H5	0.95	C22—C23	1.376 (5)
C6—H6	0.95	C22—H22	0.95
C7—C12	1.385 (4)	C23—C24	1.393 (4)
C7—C8	1.397 (4)	C23—H23	0.95
C7—P1	1.815 (3)	C24—H24	0.95
C8—C9	1.382 (4)	C25—N1	1.504 (3)
C8—H8	0.95	C25—C26	1.514 (4)
C9—C10	1.388 (5)	C25—C27	1.522 (4)
C9—H9	0.95	C25—H25	1.00
C10—C11	1.379 (5)	C26—H26A	0.98
C10—H10	0.95	C26—H26B	0.98
C11—C12	1.381 (4)	C26—H26C	0.98
C11—H11	0.95	C27—H27A	0.98
C12—H12	0.95	C27—H27B	0.98
C13—C18	1.389 (4)	C27—H27C	0.98
C13—C14	1.403 (4)	N1—P2	1.697 (2)
C13—P2	1.805 (3)	N1—P1	1.702 (2)
C14—C15	1.387 (4)	P1—Ni1	2.1364 (7)
C14—H14	0.95	P1—P2	2.5402 (9)
C15—C16	1.376 (5)	P2—Ni1	2.1231 (7)
C15—H15	0.95	Ni1—Br1	2.3230 (4)
C16—C17	1.376 (5)	Ni1—Br2	2.3377 (4)
C16—H16	0.95

C2—C1—C6	119.6 (3)	C19—C20—H20	120.1
C2—C1—P1	122.2 (2)	C22—C21—C20	120.0 (3)
C6—C1—P1	117.9 (2)	C22—C21—H21	120.0
C1—C2—C3	120.2 (3)	C20—C21—H21	120.0
C1—C2—H2	119.9	C23—C22—C21	120.7 (3)
C3—C2—H2	119.9	C23—C22—H22	119.6
C4—C3—C2	119.8 (3)	C21—C22—H22	119.6
C4—C3—H3	120.1	C22—C23—C24	120.1 (3)
C2—C3—H3	120.1	C22—C23—H23	120.0
C5—C4—C3	120.2 (3)	C24—C23—H23	120.0
C5—C4—H4	119.9	C23—C24—C19	119.2 (3)
C3—C4—H4	119.9	C23—C24—H24	120.4
C4—C5—C6	120.5 (3)	C19—C24—H24	120.4
C4—C5—H5	119.8	N1—C25—C26	111.4 (2)
C6—C5—H5	119.8	N1—C25—C27	112.5 (2)
C5—C6—C1	119.6 (3)	C26—C25—C27	111.7 (3)
C5—C6—H6	120.2	N1—C25—H25	107.0
C1—C6—H6	120.2	C26—C25—H25	107.0
C12—C7—C8	119.9 (2)	C27—C25—H25	107.0
C12—C7—P1	118.1 (2)	C25—C26—H26A	109.5
C8—C7—P1	121.8 (2)	C25—C26—H26B	109.5
C9—C8—C7	119.5 (3)	H26A—C26—H26B	109.5
C9—C8—H8	120.2	C25—C26—H26C	109.5
C7—C8—H8	120.2	H26A—C26—H26C	109.5
C8—C9—C10	120.0 (3)	H26B—C26—H26C	109.5
C8—C9—H9	120.0	C25—C27—H27A	109.5
C10—C9—H9	120.0	C25—C27—H27B	109.5
C11—C10—C9	120.5 (3)	H27A—C27—H27B	109.5
C11—C10—H10	119.7	C25—C27—H27C	109.5
C9—C10—H10	119.7	H27A—C27—H27C	109.5
C10—C11—C12	119.7 (3)	H27B—C27—H27C	109.5
C10—C11—H11	120.1	C25—N1—P2	125.69 (17)
C12—C11—H11	120.1	C25—N1—P1	133.53 (17)
C11—C12—C7	120.4 (3)	P2—N1—P1	96.71 (11)
C11—C12—H12	119.8	N1—P1—C1	112.00 (12)
C7—C12—H12	119.8	N1—P1—C7	109.87 (12)
C18—C13—C14	119.7 (3)	C1—P1—C7	105.49 (12)
C18—C13—P2	121.8 (2)	N1—P1—Ni1	94.41 (8)
C14—C13—P2	118.1 (2)	C1—P1—Ni1	117.60 (9)
C15—C14—C13	119.3 (3)	C7—P1—Ni1	117.13 (9)
C15—C14—H14	120.3	C1—P1—P2	131.69 (9)
C13—C14—H14	120.3	C7—P1—P2	120.79 (9)
C16—C15—C14	120.1 (3)	Ni1—P1—P2	53.15 (2)
C16—C15—H15	119.9	N1—P2—C13	108.92 (12)
C14—C15—H15	119.9	N1—P2—C19	108.43 (12)
C15—C16—C17	121.1 (3)	C13—P2—C19	105.66 (13)
C15—C16—H16	119.4	N1—P2—Ni1	95.03 (8)
C17—C16—H16	119.4	C13—P2—Ni1	117.27 (9)
C16—C17—C18	119.5 (3)	C19—P2—Ni1	120.40 (10)
C16—C17—H17	120.3	C13—P2—P1	128.84 (9)
C18—C17—H17	120.3	C19—P2—P1	122.01 (9)
C17—C18—C13	120.2 (3)	Ni1—P2—P1	53.63 (2)
C17—C18—H18	119.9	P2—Ni1—P1	73.22 (3)
C13—C18—H18	119.9	P2—Ni1—Br1	165.35 (2)
C20—C19—C24	120.2 (3)	P1—Ni1—Br1	94.39 (2)
C20—C19—P2	120.1 (2)	P2—Ni1—Br2	94.74 (2)
C24—C19—P2	119.2 (2)	P1—Ni1—Br2	166.90 (3)
C21—C20—C19	119.7 (3)	Br1—Ni1—Br2	98.213 (16)
C21—C20—H20	120.1

C6—C1—C2—C3	−3.0 (4)	C25—N1—P2—C13	72.5 (2)
P1—C1—C2—C3	−176.2 (2)	P1—N1—P2—C13	−127.71 (12)
C1—C2—C3—C4	0.8 (4)	C25—N1—P2—C19	−42.0 (2)
C2—C3—C4—C5	1.6 (5)	P1—N1—P2—C19	117.77 (12)
C3—C4—C5—C6	−1.8 (5)	C25—N1—P2—Ni1	−166.4 (2)
C4—C5—C6—C1	−0.4 (5)	P1—N1—P2—Ni1	−6.62 (9)
C2—C1—C6—C5	2.7 (4)	C25—N1—P2—P1	−159.8 (3)
P1—C1—C6—C5	176.2 (2)	C18—C13—P2—N1	19.8 (3)
C12—C7—C8—C9	−1.1 (4)	C14—C13—P2—N1	−167.1 (2)
P1—C7—C8—C9	173.4 (2)	C18—C13—P2—C19	136.1 (2)
C7—C8—C9—C10	0.4 (4)	C14—C13—P2—C19	−50.8 (3)
C8—C9—C10—C11	0.6 (5)	C18—C13—P2—Ni1	−86.5 (2)
C9—C10—C11—C12	−1.0 (5)	C14—C13—P2—Ni1	86.6 (2)
C10—C11—C12—C7	0.3 (5)	C18—C13—P2—P1	−22.7 (3)
C8—C7—C12—C11	0.7 (4)	C14—C13—P2—P1	150.41 (18)
P1—C7—C12—C11	−174.0 (2)	C20—C19—P2—N1	74.3 (2)
C18—C13—C14—C15	−0.3 (4)	C24—C19—P2—N1	−97.5 (2)
P2—C13—C14—C15	−173.6 (2)	C20—C19—P2—C13	−42.4 (3)
C13—C14—C15—C16	0.9 (5)	C24—C19—P2—C13	145.9 (2)
C14—C15—C16—C17	−0.8 (5)	C20—C19—P2—Ni1	−178.12 (19)
C15—C16—C17—C18	0.0 (5)	C24—C19—P2—Ni1	10.1 (3)
C16—C17—C18—C13	0.7 (4)	C20—C19—P2—P1	118.2 (2)
C14—C13—C18—C17	−0.5 (4)	C24—C19—P2—P1	−53.5 (3)
P2—C13—C18—C17	172.5 (2)	C1—P1—P2—N1	−75.63 (17)
C24—C19—C20—C21	2.4 (4)	C7—P1—P2—N1	85.67 (15)
P2—C19—C20—C21	−169.3 (2)	Ni1—P1—P2—N1	−171.81 (11)
C19—C20—C21—C22	−0.6 (5)	N1—P1—P2—C13	73.89 (16)
C20—C21—C22—C23	−1.5 (5)	C1—P1—P2—C13	−1.73 (18)
C21—C22—C23—C24	1.8 (5)	C7—P1—P2—C13	159.56 (16)
C22—C23—C24—C19	0.1 (5)	Ni1—P1—P2—C13	−97.92 (12)
C20—C19—C24—C23	−2.2 (4)	N1—P1—P2—C19	−81.89 (16)
P2—C19—C24—C23	169.6 (2)	C1—P1—P2—C19	−157.52 (17)
C26—C25—N1—P2	−146.0 (2)	C7—P1—P2—C19	3.78 (16)
C27—C25—N1—P2	87.8 (3)	Ni1—P1—P2—C19	106.30 (12)
C26—C25—N1—P1	62.3 (3)	N1—P1—P2—Ni1	171.81 (11)
C27—C25—N1—P1	−64.0 (3)	C1—P1—P2—Ni1	96.18 (13)
C25—N1—P1—C1	−74.0 (3)	C7—P1—P2—Ni1	−102.52 (11)
P2—N1—P1—C1	128.73 (12)	N1—P2—Ni1—P1	5.46 (7)
C25—N1—P1—C7	42.9 (3)	C13—P2—Ni1—P1	119.77 (11)
P2—N1—P1—C7	−114.38 (12)	C19—P2—Ni1—P1	−109.35 (10)
C25—N1—P1—Ni1	163.8 (2)	N1—P2—Ni1—Br1	−27.65 (13)
P2—N1—P1—Ni1	6.57 (9)	C13—P2—Ni1—Br1	86.66 (14)
C25—N1—P1—P2	157.2 (3)	C19—P2—Ni1—Br1	−142.46 (12)
C2—C1—P1—N1	−23.8 (3)	P1—P2—Ni1—Br1	−33.12 (10)
C6—C1—P1—N1	162.9 (2)	N1—P2—Ni1—Br2	−179.80 (7)
C2—C1—P1—C7	−143.3 (2)	C13—P2—Ni1—Br2	−65.49 (11)
C6—C1—P1—C7	43.4 (3)	C19—P2—Ni1—Br2	65.39 (10)
C2—C1—P1—Ni1	84.0 (3)	P1—P2—Ni1—Br2	174.74 (2)
C6—C1—P1—Ni1	−89.3 (2)	N1—P1—Ni1—P2	−5.44 (7)
C2—C1—P1—P2	20.1 (3)	C1—P1—Ni1—P2	−123.10 (10)
C6—C1—P1—P2	−153.19 (18)	C7—P1—Ni1—P2	109.55 (10)
C12—C7—P1—N1	87.2 (2)	N1—P1—Ni1—Br1	166.59 (7)
C8—C7—P1—N1	−87.4 (2)	C1—P1—Ni1—Br1	48.93 (10)
C12—C7—P1—C1	−151.9 (2)	C7—P1—Ni1—Br1	−78.41 (10)
C8—C7—P1—C1	33.5 (3)	P2—P1—Ni1—Br1	172.04 (2)
C12—C7—P1—Ni1	−18.9 (3)	N1—P1—Ni1—Br2	−29.24 (14)
C8—C7—P1—Ni1	166.51 (19)	C1—P1—Ni1—Br2	−146.90 (13)
C12—C7—P1—P2	42.5 (3)	C7—P1—Ni1—Br2	85.76 (14)
C8—C7—P1—P2	−132.1 (2)	P2—P1—Ni1—Br2	−23.79 (11)

Experimental details

Crystal data
Chemical formula	[NiBr₂(C₂₇H₂₇NP₂)]
M_r	645.97
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	16.6720 (3), 15.1689 (4), 20.3777 (4)
V (Å³)	5153.44 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.00
Crystal size (mm)	0.17 × 0.14 × 0.04

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	Numerical (X-SHAPE; Stoe & Cie, 2005)
T_min, T_max	0.484, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	73587, 6956, 4725
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.064, 0.89
No. of reflections	6956
No. of parameters	300
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.43

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Leibniz-Institut für Katalyse e. V. an der Universität Rostock.

References

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