Bis­[1,2-bis­(di­phenyl­phosphino)­ethene]­nickel(II) diperchlorate

In the title compound, [Ni(C₂₆H₂₂P₂)₂](ClO₄)₂, the Ni atom lies on an inversion centre and is square-planar coordinated by four P atoms from two bidentate ligands. The average Ni-P bond length is 2.2374 (7) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.032
• wR factor = 0.106
• Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

S1. Comment

In recent years, much attention has been given to transition metal phosphine complexes for their antitumor activities and catalysis. We have synthesized the title compound, (I), and determined its crystal structure. The Ni atom lies on an inversion centre and is square-planar coordinated by four P atoms from two bidentate ligands. The average Ni—P bond length is 2.2374 (7) Å, with individual values of 2.2258 (7) and 2.2490 (8) Å. The connection of two phosphine groups by an ethene bridge is unusual, most diphosphines having saturated links composed of one or more methylene groups (Li et al., 2000).

In the title compound, (I) (Fig. 1), the phenyl groups lie approximately perpendicular to the metal coordination plane, with dihedral angles ranging from 76.0 (2) to 88.7 (2)°. The nickel centre is relatively exposed, and this may be the reason for the anti-tumor and catalytic activity of the complex.

The crystal packing is shown in Fig. 2.

S2. Experimental

1,2-Bis(diphenylphosphino)ethene was prepared from chlorodiphenylphosphine, by treatment with lithium, trimethylsilyl chloride and 1,2-dichloroethene in three stages. The ligand (88 mg, 0.22 mmol) was dissolved in ethanol (1 mmol) and Ni(ClO₄)·6H₂O (40 mg, 0.11 mmol) was added in acetonitrile, with stirring at room temperature. The filtered red solution was subjected to vapour diffussion by diethyl ether for several weeks, yielding orange crystals suitable for X-ray diffraction analysis.

S3. Refinement

All H atoms were placed in geometrically calculated positions and constrained with C—H = 0.96 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CAD-4-PC (Enraf-Nonius, 1989); cell refinement: CAD-4-PC; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The cation of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing, viewed down the c axis.

Bis[1,2-bis(diphenylphosphino)ethene)]nickel(II) diperchlorate

Crystal data

[Ni(C26H22P2)2](ClO4)2	F(000) = 1084
Mr = 1050.34	Dx = 1.511 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.845 (1) Å	θ = 9.2–13.9°
b = 16.198 (1) Å	µ = 0.73 mm^−1
c = 13.198 (1) Å	T = 293 K
β = 95.26 (1)°	Block, orange
V = 2308.7 (3) Å^3	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	3195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.839, Tmax = 0.864	l = 0→15
4029 measured reflections	5 standard reflections every 100 reflections
4029 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.03P)^2 + 0.65P] where P = (Fo^2 + 2Fc^2)/3
4029 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 0.7755 (0.0187) x - 15.3579 (0.0091) y + 4.1569 (0.0211) z = 1.9792 (0.0164)

* 0.0169 (0.0024) C41 * -0.0200 (0.0028) C42 * 0.0013 (0.0034) C43 * 0.0209 (0.0036) C44 * -0.0249 (0.0034) C45 * 0.0058 (0.0029) C46

Rms deviation of fitted atoms = 0.0172

8.6617 (0.0098) x + 9.6128 (0.0200) y + 0.3423 (0.0229) z = 2.0423 (0.0142)

Angle to previous plane (with approximate e.s.d.) = 53.92 (0.13)

* -0.0083 (0.0022) C31 * -0.0020 (0.0029) C32 * 0.0136 (0.0030) C33 * -0.0150 (0.0028) C34 * 0.0048 (0.0027) C35 * 0.0069 (0.0023) C36

Rms deviation of fitted atoms = 0.0096

8.2028 (0.0121) x - 2.9101 (0.0245) y + 7.3513 (0.0184) z = 3.1605 (0.0128)

Angle to previous plane (with approximate e.s.d.) = 55.94 (0.12)

* -0.0084 (0.0023) C21 * 0.0226 (0.0025) C22 * -0.0176 (0.0030) C23 * -0.0019 (0.0031) C24 * 0.0153 (0.0030) C25 * -0.0101 (0.0027) C26

Rms deviation of fitted atoms = 0.0143

7.2749 (0.0144) x + 11.7191 (0.0203) y - 2.9546 (0.0232) z = 0.6019 (0.0082)

Angle to previous plane (with approximate e.s.d.) = 74.05 (0.12)

* -0.0165 (0.0027) C11 * 0.0037 (0.0026) C12 * 0.0135 (0.0029) C13 * -0.0171 (0.0032) C14 * 0.0033 (0.0035) C15 * 0.0132 (0.0033) C16

Rms deviation of fitted atoms = 0.0126

- 8.7419 (0.0039) x - 9.3212 (0.0075) y + 2.7912 (0.0010) z = 0.2791 (0.0001)

Angle to previous plane (with approximate e.s.d.) = 11.60 (0.18)

* -0.5297 (0.0003) P1 * -0.5696 (0.0003) P2 * 1.1165 (0.0004) Ni * -0.0285 (0.0003) P1_$1 * 0.0114 (0.0002) P2_$1

Rms deviation of fitted atoms = 0.6087

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni	0.0000	0.0000	0.5000	0.02783 (15)
P1	0.03577 (7)	0.12371 (5)	0.43539 (7)	0.0517 (2)
P2	0.20327 (7)	0.00574 (5)	0.55170 (7)	0.0529 (2)
C11	−0.0311 (3)	0.1488 (2)	0.3155 (3)	0.0626 (7)
C12	−0.1252 (3)	0.2047 (2)	0.2989 (2)	0.0548 (7)
H12A	−0.1466	0.2369	0.3558	0.080*
C13	−0.1830 (4)	0.2181 (2)	0.2064 (3)	0.0700 (9)
H13A	−0.2395	0.2636	0.1961	0.080*
C14	−0.1479 (5)	0.1753 (3)	0.1330 (3)	0.0825 (11)
H14A	−0.2011	0.1735	0.0707	0.080*
C16	0.0085 (5)	0.1068 (2)	0.2365 (3)	0.0889 (13)
H16A	0.0811	0.0727	0.2429	0.080*
C21	0.0017 (3)	0.21010 (18)	0.5101 (2)	0.0516 (6)
C22	−0.0696 (3)	0.2012 (2)	0.5903 (3)	0.0648 (8)
H22A	−0.0958	0.1468	0.6076	0.080*
C23	−0.0975 (4)	0.2652 (3)	0.6413 (3)	0.0827 (10)
H23A	−0.1538	0.2581	0.6927	0.080*
C24	−0.0539 (5)	0.3428 (3)	0.6255 (3)	0.0901 (12)
H24A	−0.0758	0.3897	0.6645	0.080*
C25	0.0208 (5)	0.3528 (2)	0.5485 (3)	0.0910 (12)
H25A	0.0594	0.4051	0.5382	0.080*
C26	0.0448 (4)	0.2875 (2)	0.4924 (3)	0.0744 (10)
H26A	0.0869	0.2959	0.4324	0.080*
C31	0.3042 (2)	−0.0818 (2)	0.5411 (2)	0.0489 (6)
C32	0.3373 (4)	−0.1077 (3)	0.4522 (3)	0.0802 (11)
H32A	0.3000	−0.0800	0.3928	0.080*
C34	0.4558 (4)	−0.2185 (3)	0.5240 (3)	0.0756 (9)
H34A	0.5105	−0.2642	0.5165	0.080*
C35	0.4264 (4)	−0.1930 (2)	0.6098 (3)	0.0699 (9)
H35A	0.4534	−0.2248	0.6691	0.080*
C36	0.3524 (3)	−0.12651 (17)	0.6227 (2)	0.0481 (6)
H36A	0.3349	−0.1104	0.6899	0.080*
C41	0.2284 (3)	0.04100 (18)	0.6743 (2)	0.0536 (6)
C42	0.3471 (3)	0.0498 (2)	0.7199 (3)	0.0698 (9)
H42A	0.4165	0.0398	0.6814	0.080*
C43	0.3644 (4)	0.0742 (3)	0.8185 (4)	0.0876 (12)
H43A	0.4459	0.0781	0.8533	0.080*
C44	0.2653 (4)	0.0915 (3)	0.8686 (4)	0.0913 (13)
H44A	0.2751	0.1050	0.9397	0.080*
C45	0.1476 (4)	0.0869 (3)	0.8187 (4)	0.0835 (11)
H45A	0.0808	0.1065	0.8552	0.080*
C46	0.1280 (3)	0.0608 (2)	0.7261 (3)	0.0670 (8)
H46A	0.0462	0.0521	0.6937	0.080*
Cl	0.76535 (10)	0.08822 (7)	0.83109 (7)	0.0756 (3)
O1	0.7351 (9)	0.1666 (4)	0.8218 (5)	0.247 (4)
O2	0.6706 (7)	0.0509 (5)	0.8487 (6)	0.222 (3)
O3	0.8277 (6)	0.0642 (4)	0.7527 (4)	0.187 (2)
O4	0.8352 (8)	0.0572 (6)	0.9128 (4)	0.235 (3)
C33	0.4117 (4)	−0.1728 (4)	0.4433 (3)	0.0872 (11)
H33A	0.4339	−0.1894	0.3776	0.080*
C15	−0.0543 (6)	0.1213 (3)	0.1428 (3)	0.1006 (16)
H15A	−0.0263	0.0950	0.0839	0.080*
C1	0.2030 (3)	0.1316 (3)	0.4225 (4)	0.0854 (13)
H1A	0.2353	0.1691	0.3752	0.080*
C2	0.2741 (4)	0.0861 (3)	0.4816 (4)	0.0959 (15)
H2A	0.3624	0.0925	0.4869	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0327 (3)	0.0270 (3)	0.0234 (2)	−0.00064 (13)	0.00114 (18)	0.00066 (13)
P1	0.0394 (4)	0.0417 (4)	0.0749 (5)	0.0012 (3)	0.0095 (4)	0.0254 (4)
P2	0.0356 (4)	0.0636 (5)	0.0574 (5)	−0.0090 (3)	−0.0069 (3)	0.0296 (4)
C11	0.0597 (17)	0.0582 (19)	0.0720 (15)	0.0056 (14)	0.0172 (14)	0.0246 (14)
C12	0.0562 (17)	0.0597 (19)	0.0493 (14)	0.0057 (13)	0.0084 (13)	0.0111 (13)
C13	0.080 (2)	0.068 (2)	0.0611 (17)	0.0027 (17)	0.0045 (16)	0.0132 (16)
C14	0.117 (3)	0.074 (3)	0.0549 (17)	−0.0213 (19)	0.0006 (19)	0.0068 (16)
C16	0.122 (3)	0.066 (2)	0.0870 (19)	0.037 (2)	0.053 (2)	0.024 (2)
C21	0.0505 (16)	0.0306 (13)	0.0689 (16)	−0.0037 (10)	−0.0197 (12)	0.0199 (10)
C22	0.065 (2)	0.0527 (16)	0.075 (2)	−0.0027 (15)	−0.0084 (14)	0.0098 (14)
C23	0.091 (3)	0.080 (2)	0.075 (2)	−0.001 (2)	−0.0045 (19)	0.0022 (18)
C24	0.116 (3)	0.066 (2)	0.080 (2)	−0.009 (2)	−0.0355 (19)	−0.0189 (19)
C25	0.132 (4)	0.0461 (18)	0.087 (3)	−0.015 (2)	−0.033 (2)	0.0144 (16)
C26	0.096 (3)	0.0480 (16)	0.075 (2)	−0.0243 (18)	−0.0176 (17)	0.0184 (14)
C31	0.0280 (11)	0.0775 (17)	0.0407 (12)	−0.0078 (11)	−0.0004 (10)	0.0128 (11)
C32	0.0555 (19)	0.143 (3)	0.0412 (14)	−0.0018 (19)	−0.0010 (14)	0.0051 (18)
C34	0.055 (2)	0.085 (3)	0.088 (2)	−0.0041 (17)	0.0127 (17)	−0.0165 (19)
C35	0.073 (2)	0.069 (2)	0.0681 (18)	0.0105 (16)	0.0099 (17)	0.0032 (17)
C36	0.0566 (17)	0.0425 (14)	0.0440 (13)	−0.0058 (11)	−0.0023 (12)	0.0058 (11)
C41	0.0483 (14)	0.0400 (14)	0.0687 (12)	−0.0061 (11)	−0.0141 (11)	0.0128 (11)
C42	0.0480 (15)	0.0561 (18)	0.101 (2)	−0.0084 (15)	−0.0154 (16)	−0.0110 (18)
C43	0.065 (2)	0.076 (2)	0.115 (3)	−0.008 (2)	−0.0263 (19)	−0.036 (2)
C44	0.086 (2)	0.098 (3)	0.085 (3)	−0.012 (2)	−0.0181 (18)	−0.028 (2)
C45	0.070 (2)	0.091 (3)	0.089 (2)	−0.009 (2)	0.0048 (18)	−0.019 (2)
C46	0.0511 (16)	0.066 (2)	0.0813 (19)	−0.0173 (15)	−0.0077 (14)	0.0014 (17)
Cl	0.0793 (6)	0.0904 (7)	0.0606 (5)	0.0006 (5)	0.0257 (5)	−0.0144 (4)
O1	0.434 (11)	0.128 (3)	0.207 (6)	0.077 (4)	0.182 (7)	0.021 (4)
O2	0.181 (4)	0.216 (6)	0.284 (8)	−0.042 (5)	0.104 (4)	−0.019 (6)
O3	0.235 (6)	0.212 (5)	0.126 (3)	0.083 (4)	0.088 (4)	−0.005 (3)
O4	0.260 (6)	0.330 (9)	0.114 (3)	0.101 (7)	0.014 (4)	0.010 (5)
C33	0.063 (2)	0.139 (4)	0.0630 (19)	−0.013 (2)	0.0220 (17)	0.001 (2)
C15	0.175 (5)	0.066 (3)	0.0690 (18)	0.017 (3)	0.055 (2)	0.005 (2)
C1	0.0373 (15)	0.081 (2)	0.131 (3)	0.0041 (15)	0.0244 (17)	0.063 (2)
C2	0.0382 (16)	0.134 (3)	0.106 (3)	−0.0185 (19)	0.0065 (19)	0.069 (3)

Geometric parameters (Å, º)

Ni—P1^i	2.2258 (7)	C31—C32	1.327 (5)
Ni—P1	2.2258 (7)	C31—C36	1.361 (4)
Ni—P2	2.2490 (8)	C32—C33	1.339 (7)
Ni—P2^i	2.2490 (8)	C32—H32A	0.960
P1—C11	1.728 (4)	C34—C35	1.272 (5)
P1—C21	1.770 (4)	C34—C33	1.347 (6)
P1—C1	1.841 (4)	C34—H34A	0.960
P2—C41	1.714 (3)	C35—C36	1.364 (5)
P2—C31	1.805 (3)	C35—H35A	0.960
P2—C2	1.809 (4)	C36—H36A	0.960
C11—C16	1.348 (5)	C41—C42	1.378 (4)
C11—C12	1.367 (5)	C41—C46	1.376 (5)
C12—C13	1.338 (5)	C42—C43	1.356 (6)
C12—H12A	0.960	C42—H42A	0.960
C13—C14	1.277 (6)	C43—C44	1.343 (7)
C13—H13A	0.960	C43—H43A	0.960
C14—C15	1.337 (7)	C44—C45	1.383 (6)
C14—H14A	0.960	C44—H44A	0.960
C16—C15	1.376 (7)	C45—C46	1.292 (6)
C16—H16A	0.960	C45—H45A	0.960
C21—C26	1.365 (4)	C46—H46A	0.960
C21—C22	1.374 (5)	Cl—O2	1.232 (6)
C22—C23	1.287 (6)	Cl—O1	1.314 (6)
C22—H22A	0.960	Cl—O4	1.357 (7)
C23—C24	1.365 (6)	Cl—O3	1.344 (4)
C23—H23A	0.960	C33—H33A	0.960
C24—C25	1.366 (7)	C15—H15A	0.960
C24—H24A	0.960	C1—C2	1.279 (5)
C25—C26	1.331 (6)	C1—H1A	0.960
C25—H25A	0.960	C2—H2A	0.960
C26—H26A	0.960
P1^i—Ni—P1	180.00	C32—C31—C36	114.6 (3)
P1^i—Ni—P2	96.97 (3)	C32—C31—P2	122.2 (3)
P1—Ni—P2	83.03 (3)	C36—C31—P2	123.3 (2)
P1^i—Ni—P2^i	83.03 (3)	C31—C32—C33	122.7 (4)
P1—Ni—P2^i	96.97 (3)	C31—C32—H32A	116.6
P2—Ni—P2^i	180.0	C33—C32—H32A	120.6
C11—P1—C21	103.44 (15)	C35—C34—C33	115.2 (4)
C11—P1—C1	103.50 (18)	C35—C34—H34A	123.3
C21—P1—C1	104.74 (19)	C33—C34—H34A	121.3
C11—P1—Ni	119.31 (13)	C34—C35—C36	124.4 (4)
C21—P1—Ni	116.45 (10)	C34—C35—H35A	118.0
C1—P1—Ni	107.80 (12)	C36—C35—H35A	117.4
C41—P2—C31	106.85 (14)	C31—C36—C35	120.6 (3)
C41—P2—C2	101.8 (2)	C31—C36—H36A	119.5
C31—P2—C2	103.7 (2)	C35—C36—H36A	119.9
C41—P2—Ni	111.51 (12)	C42—C41—C46	120.5 (3)
C31—P2—Ni	121.93 (10)	C42—C41—P2	120.6 (3)
C2—P2—Ni	108.96 (13)	C46—C41—P2	118.9 (2)
C16—C11—C12	119.8 (4)	C43—C42—C41	119.5 (4)
C16—C11—P1	116.9 (3)	C43—C42—H42A	120.7
C12—C11—P1	123.2 (3)	C41—C42—H42A	119.8
C13—C12—C11	122.3 (4)	C44—C43—C42	119.1 (4)
C13—C12—H12A	120.0	C44—C43—H43A	119.6
C11—C12—H12A	117.6	C42—C43—H43A	121.3
C14—C13—C12	117.2 (4)	C43—C44—C45	120.0 (4)
C14—C13—H13A	122.7	C43—C44—H44A	120.5
C12—C13—H13A	119.5	C45—C44—H44A	119.5
C13—C14—C15	123.9 (4)	C46—C45—C44	122.2 (5)
C13—C14—H14A	117.9	C46—C45—H45A	121.1
C15—C14—H14A	117.1	C44—C45—H45A	116.7
C11—C16—C15	116.3 (4)	C45—C46—C41	118.5 (4)
C11—C16—H16A	122.7	C45—C46—H46A	122.3
C15—C16—H16A	120.7	C41—C46—H46A	119.0
C26—C21—C22	117.0 (4)	O2—Cl—O1	106.6 (5)
C26—C21—P1	122.5 (3)	O2—Cl—O4	94.7 (6)
C22—C21—P1	120.5 (2)	O1—Cl—O4	123.3 (5)
C23—C22—C21	119.6 (4)	O2—Cl—O3	119.4 (5)
C23—C22—H22A	121.7	O1—Cl—O3	110.3 (4)
C21—C22—H22A	118.6	O4—Cl—O3	102.8 (4)
C22—C23—C24	124.1 (5)	C32—C33—C34	122.4 (4)
C22—C23—H23A	117.9	C32—C33—H33A	120.2
C24—C23—H23A	118.0	C34—C33—H33A	117.4
C25—C24—C23	117.4 (4)	C14—C15—C16	120.5 (4)
C25—C24—H24A	119.8	C14—C15—H15A	120.3
C23—C24—H24A	122.8	C16—C15—H15A	119.0
C26—C25—C24	118.6 (4)	C2—C1—P1	116.6 (3)
C26—C25—H25A	120.8	C2—C1—H1A	121.7
C24—C25—H25A	120.4	P1—C1—H1A	121.7
C25—C26—C21	123.2 (4)	C1—C2—P2	117.8 (3)
C25—C26—H26A	118.6	C1—C2—H2A	121.6
C21—C26—H26A	117.9	P2—C2—H2A	120.6

Symmetry code: (i) −x, −y, −z+1.