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The nickel(0) complex [Ni(dppb)2]·2.5C6H6 [dppb = Ph2P(CH2)4PPh2 or C28H28P2] was obtained from reaction of the boronic ester nickel(II) complex [NiBr{C6H4B(O2C2Me4)}(dppb)] with KOtBu. The nickel metal centre is in a tetrahedral environment characteristic of NiP4 species. Each asymmetric unit contains 2.5 disordered mol­ecules of benzene and satisfactory refinement was achieved after removal of the solvent void contribution from the data. A mixed anisotropic/isotropic model was used for the non-H-atom sites.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802011121/ob6135sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802011121/ob6135IIsup2.hkl
Contains datablock II

CCDC reference: 189879

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](C-C) = 0.017 Å
  • Some non-H atoms missing
  • R factor = 0.059
  • wR factor = 0.065
  • Data-to-parameter ratio = 9.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.6035 Proportion of unique data used 0.2583 Ratio reflections to parameters 8.9839 PLAT_602 Alert C VERY LARGE Solvent Accessible VOID(S) in Structure ! General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C71 H71 Ni1 P4 Atom count from the _atom_site data: C56 H56 Ni1 P4 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C71 H71 Ni P4 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 284.00 224.00 60.00 H 284.00 224.00 60.00 Ni 4.00 4.00 0.00 P 16.00 16.00 0.00 Difference between formula and atom_site contents detected. ALERT: Large difference may be due to a symmetry error - see SYMMG tests CHEMW_03 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 1106.95 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 56.00 672.62 H 1.01 56.00 56.45 Ni 58.69 1.00 58.69 P 30.97 4.00 123.90 Calculated formula weight 911.65 ALERT: The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.90 <> 1.10
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS and maXus (Mackay et al., 1999).

(II) top
Crystal data top
[Ni(C28H28P2)2]·2.5C6H6F(000) = 2339
Mr = 1106.96Dx = 1.242 Mg m3
Monoclinic, P21/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yabCell parameters from 37457 reflections
a = 19.9938 (5) Åθ = 2.9–25.4°
b = 11.7063 (4) ŵ = 0.48 mm1
c = 27.1914 (9) ÅT = 200 K
β = 111.5142 (13)°Plate, yellow
V = 5920.8 (3) Å30.29 × 0.28 × 0.02 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
2785 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.087
φ and ω scansθmax = 25.4°, θmin = 3.0°
Absorption correction: integration
(Coppens, 1970)
h = 2324
Tmin = 0.880, Tmax = 0.991k = 1314
65297 measured reflectionsl = 3232
10780 independent reflections
Refinement top
Refinement on FSecondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.065 Weighting scheme: Chebychev polynomial with three parameters (Carruthers & Watkin, 1979); 11.3, -0.949 and 5.26
S = 1.03(Δ/σ)max = 0.001
2785 reflectionsΔρmax = 0.44 e Å3
310 parametersΔρmin = 0.32 e Å3
Primary atom site location: structure-invariant direct methods
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.24159 (8)0.2071 (1)0.30250 (7)0.0392
P10.26602 (14)0.3041 (3)0.24149 (11)0.0416
P20.33412 (14)0.0916 (2)0.33813 (12)0.0410
P30.15175 (14)0.0873 (2)0.26600 (11)0.0437
P40.21486 (14)0.2950 (3)0.36448 (12)0.0425
C10.1970 (6)0.3496 (9)0.1767 (4)0.049 (3)*
C20.1588 (6)0.451 (1)0.1727 (5)0.057 (3)*
C30.1046 (7)0.4824 (12)0.1280 (5)0.074 (4)*
C40.0870 (7)0.4138 (11)0.0841 (5)0.073 (4)*
C50.1247 (6)0.3151 (11)0.0850 (5)0.072 (4)*
C60.1803 (6)0.285 (1)0.1315 (4)0.056 (3)*
C70.3160 (5)0.4419 (9)0.2581 (4)0.047 (3)*
C80.3394 (6)0.482 (1)0.3080 (5)0.054 (3)*
C90.3812 (7)0.5821 (11)0.3226 (5)0.071 (4)*
C100.3972 (7)0.6372 (12)0.2846 (6)0.080 (4)*
C110.3745 (7)0.6027 (11)0.2346 (5)0.075 (4)*
C120.3335 (6)0.502 (1)0.2195 (5)0.061 (3)*
C130.3310 (5)0.2266 (9)0.2187 (4)0.0445
C140.4052 (5)0.2166 (9)0.2629 (4)0.0452
C150.4279 (6)0.0936 (9)0.2796 (5)0.0522
C160.3752 (5)0.0209 (9)0.2949 (4)0.0469
C170.3130 (5)0.0360 (9)0.3711 (4)0.041 (3)*
C180.3005 (5)0.016 (1)0.4173 (4)0.051 (3)*
C190.2783 (5)0.1006 (9)0.4424 (4)0.049 (3)*
C200.2689 (6)0.2122 (11)0.4211 (4)0.060 (3)*
C210.2823 (6)0.233 (1)0.3759 (4)0.059 (3)*
C220.3056 (6)0.1450 (9)0.3520 (4)0.052 (3)*
C230.4170 (5)0.1363 (8)0.3928 (4)0.036 (2)*
C240.4665 (6)0.057 (1)0.4218 (4)0.055 (3)*
C250.5299 (7)0.0923 (11)0.4636 (5)0.072 (4)*
C260.5413 (6)0.2061 (11)0.4758 (5)0.063 (3)*
C270.4904 (6)0.2855 (11)0.4469 (4)0.061 (3)*
C280.4284 (6)0.2500 (9)0.4048 (4)0.049 (3)*
C290.0655 (6)0.1355 (9)0.2145 (4)0.048 (3)*
C300.0534 (6)0.247 (1)0.2021 (5)0.054 (3)*
C310.0113 (6)0.2848 (12)0.1635 (5)0.070 (3)*
C320.0620 (6)0.2046 (11)0.1368 (5)0.067 (3)*
C330.0505 (7)0.0933 (11)0.1487 (5)0.068 (3)*
C340.0135 (6)0.0537 (11)0.1874 (4)0.060 (3)*
C350.1723 (6)0.029 (1)0.2281 (4)0.051 (3)*
C360.1861 (6)0.002 (1)0.1832 (4)0.056 (3)*
C370.2100 (6)0.0838 (11)0.1556 (5)0.070 (4)*
C380.2166 (7)0.1931 (12)0.1713 (5)0.077 (4)*
C390.2031 (7)0.2261 (12)0.2147 (5)0.078 (4)*
C400.1795 (6)0.144 (1)0.2431 (5)0.063 (3)*
C410.1161 (5)0.0035 (9)0.3100 (4)0.0445
C420.0627 (5)0.0684 (9)0.3290 (5)0.0556
C430.0814 (5)0.1904 (9)0.3461 (4)0.0476
C440.1576 (5)0.208 (1)0.3898 (4)0.0523
C450.1612 (6)0.4271 (9)0.3480 (4)0.048 (3)*
C460.1496 (6)0.481 (1)0.3015 (5)0.057 (3)*
C470.1106 (6)0.5809 (11)0.2886 (5)0.071 (4)*
C480.0817 (7)0.6314 (12)0.3224 (5)0.073 (4)*
C490.0919 (6)0.578 (1)0.3675 (5)0.067 (3)*
C500.1301 (6)0.476 (1)0.3814 (5)0.063 (3)*
C510.2832 (6)0.3450 (9)0.4282 (4)0.048 (3)*
C520.3109 (6)0.454 (1)0.4306 (5)0.058 (3)*
C530.3661 (7)0.4903 (12)0.4778 (5)0.071 (4)*
C540.3920 (7)0.4196 (11)0.5208 (5)0.070 (4)*
C550.3641 (6)0.3162 (11)0.5185 (5)0.068 (3)*
C560.3098 (6)0.277 (1)0.4718 (4)0.053 (3)*
H210.1718 (6)0.502 (1)0.2044 (5)0.0679*
H310.0779 (7)0.5553 (12)0.1268 (5)0.0891*
H410.0461 (7)0.4355 (11)0.0511 (5)0.0876*
H510.1126 (6)0.2662 (11)0.0528 (5)0.0861*
H610.2086 (6)0.214 (1)0.1322 (4)0.0663*
H810.3271 (6)0.440 (1)0.3354 (5)0.0640*
H910.3986 (7)0.6112 (11)0.3597 (5)0.0836*
H1010.4274 (7)0.7078 (12)0.2947 (6)0.0952*
H1110.3867 (7)0.6478 (11)0.2077 (5)0.0889*
H1210.3169 (6)0.473 (1)0.1822 (5)0.0726*
H1310.3360 (5)0.2691 (9)0.1883 (4)0.0561*
H1320.3120 (5)0.1482 (9)0.2069 (4)0.0561*
H1410.4041 (5)0.2593 (9)0.2944 (4)0.0559*
H1420.4416 (5)0.2518 (9)0.2504 (4)0.0559*
H1510.4744 (6)0.0961 (9)0.3106 (5)0.0657*
H1520.4356 (6)0.0548 (9)0.2493 (5)0.0657*
H1610.4017 (5)0.0482 (9)0.3139 (4)0.0548*
H1620.3355 (5)0.0032 (9)0.2617 (4)0.0548*
H1810.3081 (5)0.063 (1)0.4327 (4)0.0614*
H1910.2687 (5)0.0839 (9)0.4753 (4)0.0591*
H2010.2525 (6)0.2753 (11)0.4388 (4)0.0721*
H2110.2754 (6)0.312 (1)0.3604 (4)0.0699*
H2210.3172 (6)0.1617 (9)0.3199 (4)0.0618*
H2410.4578 (6)0.026 (1)0.4133 (4)0.0646*
H2510.5662 (7)0.0343 (11)0.4840 (5)0.0870*
H2610.5858 (6)0.2315 (11)0.5053 (5)0.0761*
H2710.4980 (6)0.3685 (11)0.4560 (4)0.0726*
H2810.3926 (6)0.3079 (9)0.3837 (4)0.0593*
H3010.0913 (6)0.304 (1)0.2208 (5)0.0636*
H3110.0205 (6)0.3680 (12)0.1556 (5)0.0845*
H3210.1075 (6)0.2295 (11)0.1082 (5)0.0801*
H3310.0887 (7)0.0369 (11)0.1296 (5)0.0811*
H3410.0218 (6)0.0297 (11)0.1954 (4)0.0733*
H3610.1787 (6)0.078 (1)0.1700 (4)0.0684*
H3710.2218 (6)0.0605 (11)0.1243 (5)0.0838*
H3810.2321 (7)0.2514 (12)0.1508 (5)0.0923*
H3910.2098 (7)0.3077 (12)0.2265 (5)0.0940*
H4010.1677 (6)0.168 (1)0.2742 (5)0.0767*
H4110.1578 (5)0.0209 (9)0.3419 (4)0.0541*
H4120.0910 (5)0.0656 (9)0.2900 (4)0.0541*
H4210.0587 (5)0.0254 (9)0.3595 (5)0.0649*
H4220.0150 (5)0.0689 (9)0.2992 (5)0.0649*
H4310.0449 (5)0.2196 (9)0.3602 (4)0.0578*
H4320.0790 (5)0.2361 (9)0.3145 (4)0.0578*
H4410.1523 (5)0.248 (1)0.4207 (4)0.0623*
H4420.1807 (5)0.132 (1)0.4013 (4)0.0623*
H4610.1698 (6)0.447 (1)0.2761 (5)0.0680*
H4710.1030 (6)0.6178 (11)0.2538 (5)0.0870*
H4810.0543 (7)0.7048 (12)0.3132 (5)0.0879*
H4910.0715 (6)0.613 (1)0.3926 (5)0.0800*
H5010.1353 (6)0.437 (1)0.4154 (5)0.0755*
H5210.2922 (6)0.506 (1)0.3994 (5)0.0706*
H5310.3864 (7)0.5690 (12)0.4798 (5)0.0851*
H5410.4317 (7)0.4458 (11)0.5536 (5)0.0825*
H5510.3817 (6)0.2656 (11)0.5503 (5)0.0817*
H5610.2903 (6)0.198 (1)0.4707 (4)0.0631*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0313 (6)0.0361 (6)0.0521 (8)0.0007 (8)0.0173 (6)0.001 (1)
P10.0355 (15)0.0432 (16)0.0472 (17)0.0010 (15)0.0165 (14)0.0030 (16)
P20.0314 (16)0.0373 (16)0.054 (2)0.0008 (13)0.0159 (14)0.0011 (15)
P30.0348 (17)0.0440 (17)0.0493 (19)0.0025 (14)0.0119 (15)0.0010 (15)
P40.0375 (16)0.0406 (16)0.0502 (18)0.0005 (15)0.0172 (14)0.0021 (17)
C130.038 (6)0.040 (7)0.062 (7)0.006 (5)0.027 (5)0.008 (5)
C140.031 (6)0.057 (7)0.051 (7)0.001 (5)0.020 (5)0.005 (6)
C150.050 (7)0.051 (7)0.064 (8)0.006 (6)0.030 (6)0.003 (6)
C160.042 (6)0.042 (6)0.056 (7)0.012 (5)0.016 (6)0.001 (5)
C410.031 (6)0.049 (7)0.054 (7)0.002 (5)0.015 (5)0.001 (6)
C420.036 (6)0.063 (8)0.064 (8)0.010 (5)0.014 (6)0.001 (6)
C430.032 (6)0.055 (7)0.056 (7)0.003 (5)0.016 (5)0.005 (6)
C440.041 (6)0.058 (7)0.060 (7)0.010 (6)0.021 (6)0.000 (7)
Geometric parameters (Å, º) top
Ni1—P12.208 (3)C17—C221.365 (13)
Ni1—P22.208 (3)C18—C191.367 (14)
Ni1—P32.207 (3)C19—C201.413 (15)
Ni1—P42.201 (4)C20—C211.374 (15)
P1—C131.868 (9)C21—C221.390 (14)
P1—C11.873 (11)C23—C241.376 (13)
P1—C71.864 (11)C23—C281.370 (13)
P2—C161.86 (1)C24—C251.419 (15)
P2—C171.87 (1)C25—C261.372 (16)
P2—C231.85 (1)C26—C271.389 (15)
P3—C411.88 (1)C27—C281.407 (15)
P3—C291.865 (11)C29—C301.349 (14)
P3—C351.845 (11)C29—C341.407 (14)
P4—C441.845 (11)C30—C311.406 (15)
P4—C451.841 (11)C31—C321.377 (16)
P4—C511.865 (11)C32—C331.342 (16)
C13—C141.533 (13)C33—C341.405 (15)
C14—C151.528 (14)C35—C361.385 (14)
C15—C161.526 (13)C35—C401.389 (15)
C41—C421.545 (14)C36—C371.403 (15)
C42—C431.506 (14)C37—C381.340 (17)
C43—C441.563 (13)C38—C391.360 (16)
C1—C21.390 (14)C39—C401.421 (16)
C1—C61.377 (14)C45—C461.354 (14)
C2—C31.352 (15)C45—C501.396 (14)
C3—C41.373 (16)C46—C471.382 (15)
C4—C51.375 (16)C47—C481.387 (15)
C5—C61.388 (15)C48—C491.321 (15)
C7—C81.347 (14)C49—C501.396 (16)
C7—C121.408 (14)C51—C521.382 (15)
C8—C91.409 (15)C51—C561.365 (14)
C9—C101.352 (16)C52—C531.418 (15)
C10—C111.330 (16)C53—C541.369 (16)
C11—C121.412 (16)C54—C551.324 (16)
C17—C181.387 (14)C55—C561.411 (15)
P1—Ni1—P2105.31 (13)C9—C10—C11123.3 (14)
P1—Ni1—P3110.90 (14)C10—C11—C12119.7 (13)
P2—Ni1—P3102.76 (9)C7—C12—C11118.5 (11)
P1—Ni1—P4121.2 (1)P2—C17—C18116.6 (8)
P2—Ni1—P4110.48 (14)P2—C17—C22125.3 (8)
P3—Ni1—P4104.79 (13)C18—C17—C22118.0 (10)
Ni1—P1—C13111.9 (3)C17—C18—C19122.1 (11)
Ni1—P1—C1124.3 (3)C18—C19—C20118.9 (10)
C13—P1—C1100.8 (5)C19—C20—C21119.5 (11)
Ni1—P1—C7120.7 (4)C20—C21—C22119.6 (11)
C13—P1—C797.1 (5)C17—C22—C21121.7 (10)
C1—P1—C797.2 (5)P2—C23—C24120.9 (8)
Ni1—P2—C16119.3 (4)P2—C23—C28119.2 (8)
Ni1—P2—C17113.6 (3)C24—C23—C28119.8 (10)
C16—P2—C17100.2 (5)C23—C24—C25120.4 (11)
Ni1—P2—C23122.6 (3)C24—C25—C26119.8 (12)
C16—P2—C2399.3 (4)C25—C26—C27119.4 (12)
C17—P2—C2397.7 (4)C26—C27—C28120.4 (11)
Ni1—P3—C41118.8 (4)C23—C28—C27120.1 (11)
Ni1—P3—C29121.4 (4)P3—C29—C30120.8 (9)
C41—P3—C29100.0 (5)P3—C29—C34119.3 (8)
Ni1—P3—C35114.3 (4)C30—C29—C34119.9 (11)
C41—P3—C35100.5 (5)C29—C30—C31121.5 (12)
C29—P3—C3598.0 (5)C30—C31—C32118.6 (12)
Ni1—P4—C44112.7 (4)C31—C32—C33120.4 (13)
Ni1—P4—C45119.3 (4)C32—C33—C34122.0 (13)
C44—P4—C4599.7 (5)C29—C34—C33117.6 (11)
Ni1—P4—C51123.8 (4)P3—C35—C36118.5 (9)
C44—P4—C5199.8 (5)P3—C35—C40124.7 (9)
C45—P4—C5197.2 (5)C36—C35—C40116.6 (11)
P1—C13—C14111.6 (7)C35—C36—C37122.1 (12)
C13—C14—C15113.7 (9)C36—C37—C38119.5 (13)
C14—C15—C16116.5 (8)C37—C38—C39121.4 (14)
P2—C16—C15115.7 (7)C38—C39—C40119.3 (13)
P3—C41—C42115.2 (7)C35—C40—C39121.0 (12)
C41—C42—C43116.5 (9)P4—C45—C46119.9 (9)
C42—C43—C44115.0 (9)P4—C45—C50123.0 (9)
P4—C44—C43110.7 (7)C46—C45—C50117.1 (11)
P1—C1—C2120.6 (9)C45—C46—C47121.1 (12)
P1—C1—C6122.5 (9)C46—C47—C48121.9 (13)
C2—C1—C6116.9 (11)C47—C48—C49117.0 (13)
C1—C2—C3122.7 (12)C48—C49—C50122.7 (13)
C2—C3—C4119.1 (13)C45—C50—C49120.2 (12)
C3—C4—C5120.8 (13)P4—C51—C52118.5 (9)
C4—C5—C6118.8 (13)P4—C51—C56122.9 (9)
C1—C6—C5121.5 (12)C52—C51—C56118.5 (11)
P1—C7—C8120.2 (8)C51—C52—C53119.0 (12)
P1—C7—C12120.5 (8)C52—C53—C54121.1 (12)
C8—C7—C12119.2 (10)C53—C54—C55119.4 (13)
C7—C8—C9121.6 (11)C54—C55—C56120.9 (13)
C8—C9—C10117.7 (13)C51—C56—C55121.0 (11)
P—Ni—P(chelate) and Ni—P—C(metallacycle) angles (°) for selected NiP4 complexes with corresponding 31P NMR chemical shifts top
ComplexP—Ni—P(chelate)Ni—P—C(met)δ(31P)
[Ni(dppm)2]5.6
[Ni(dcpm)2]77.5 (2)93.3 (2)
[Ni(dppe)2]90.8 (1)105.6 (3)44.7
[Ni(dppb)2]105.0 (2)115.7 (4)17.7
 

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