Bis(benzyl­triphenylphosphonium) bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickel(II)

The asymmetric unit of the title compound, (C₂₅H₂₂P)₂-[Ni(C₄N₂S₂)₂] or (BzTPP)₂[Ni(mnt)₂] (where BzTPP is 1-benzyl­triphenyl­phosphonium and mnt is maleonitrile­dithiol­ate), consists of one (BzTPP)⁺ cation and one-half of a centrosymmetric [Ni(mnt)₂]²⁻ anion. The Ni^II atom of the anion is coordinated by four S atoms from two mnt²⁻ ligands and exhibits the expected square-planar coordination geometry. The (BzTPP)⁺ cation adopts a conformation where the four phenyl rings are twisted with respect to the plane of the P—C—C chain that links them. Weak C—H...N and C—H...π inter­actions are present in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.038
• wR factor = 0.107
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.42 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Bis(benzyltripenylphosphinium) bis(1,2-dicyanoethene-1,2-dithiolato)nickel(II)

Crystal data

(C25H22P)2[Ni(C4N2S2)2]	F(000) = 1084
Mr = 1045.86	Dx = 1.354 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6873 reflections
a = 9.3845 (5) Å	θ = 2.3–28.5°
b = 14.6825 (9) Å	µ = 0.65 mm^−1
c = 18.8748 (11) Å	T = 291 K
β = 99.443 (1)°	Block, red
V = 2565.5 (3) Å^3	0.41 × 0.34 × 0.15 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4508 independent reflections
Radiation source: fine-focus sealed tube	3985 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.766, Tmax = 0.901	k = −17→16
13425 measured reflections	l = −18→22

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 1.2P] where P = (Fo^2 + 2Fc^2)/3
4508 reflections	(Δ/σ)max = 0.001
313 parameters	Δρmax = 0.40 e Å^−3
175 restraints	Δρmin = −0.36 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.

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
Ni1	0.0000	0.0000	0.0000	0.04382 (17)
P1	0.71262 (8)	0.85014 (5)	0.16816 (4)	0.0472 (2)
S1	0.09417 (8)	0.09747 (6)	0.08059 (4)	0.0601 (2)
S2	0.17963 (8)	−0.09001 (5)	0.03927 (4)	0.0543 (2)
N1	0.0244 (3)	0.3313 (2)	0.14578 (16)	0.0726 (7)
N2	0.3221 (3)	−0.3185 (2)	0.00175 (18)	0.0836 (9)
C1	0.0024 (3)	0.2666 (2)	0.11185 (16)	0.0567 (6)
C2	−0.0268 (3)	0.1870 (2)	0.06848 (15)	0.0507 (6)
C3	0.1457 (3)	−0.1837 (2)	−0.01717 (15)	0.0524 (6)
C4	0.2437 (3)	−0.2583 (2)	−0.00691 (17)	0.0602 (7)
C5	0.9392 (4)	0.6951 (3)	0.08592 (19)	0.0689 (7)
H5	1.0107	0.7389	0.0976	0.083*
C6	0.9776 (5)	0.6048 (3)	0.0796 (2)	0.0817 (8)
H6	1.0745	0.5883	0.0867	0.098*
C7	0.8731 (5)	0.5398 (3)	0.0630 (2)	0.0860 (8)
H7	0.8992	0.4791	0.0594	0.103*
C8	0.7315 (5)	0.5638 (3)	0.0516 (2)	0.0863 (8)
H8	0.6608	0.5194	0.0401	0.104*
C9	0.6917 (4)	0.6544 (3)	0.0572 (2)	0.0767 (8)
H9	0.5945	0.6705	0.0490	0.092*
C10	0.7960 (3)	0.7205 (2)	0.07501 (16)	0.0610 (6)
C11	0.7531 (4)	0.8188 (2)	0.08065 (16)	0.0617 (7)
H11A	0.6688	0.8308	0.0447	0.074*
H11B	0.8309	0.8571	0.0698	0.074*
C12	1.0078 (3)	0.8754 (2)	0.21253 (18)	0.0578 (6)
H12	1.0159	0.8784	0.1641	0.069*
C13	1.1286 (3)	0.8868 (2)	0.2650 (2)	0.0653 (7)
H13	1.2186	0.8956	0.2515	0.078*
C14	1.1172 (4)	0.8852 (2)	0.3361 (2)	0.0694 (7)
H14	1.1990	0.8931	0.3707	0.083*
C15	0.9853 (4)	0.8720 (2)	0.35666 (19)	0.0669 (7)
H15	0.9777	0.8725	0.4052	0.080*
C16	0.8640 (3)	0.8581 (2)	0.30593 (17)	0.0584 (6)
H16	0.7751	0.8479	0.3202	0.070*
C17	0.8745 (3)	0.8594 (2)	0.23325 (16)	0.0510 (6)
C18	0.6183 (4)	1.0140 (2)	0.1030 (2)	0.0703 (7)
H18	0.6650	0.9969	0.0653	0.084*
C19	0.5460 (4)	1.0968 (3)	0.1017 (2)	0.0792 (8)
H19	0.5458	1.1359	0.0629	0.095*
C20	0.4756 (4)	1.1214 (3)	0.1563 (2)	0.0786 (8)
H20	0.4257	1.1763	0.1539	0.094*
C21	0.4778 (4)	1.0661 (2)	0.2145 (2)	0.0744 (7)
H21	0.4305	1.0837	0.2519	0.089*
C22	0.5501 (4)	0.9838 (2)	0.2180 (2)	0.0644 (7)
H22	0.5522	0.9463	0.2578	0.077*
C23	0.6193 (3)	0.9575 (2)	0.16196 (18)	0.0572 (6)
C24	0.4480 (3)	0.7734 (2)	0.17503 (16)	0.0545 (6)
H24	0.4090	0.8246	0.1499	0.065*
C25	0.3591 (3)	0.7053 (2)	0.19190 (18)	0.0625 (7)
H25	0.2596	0.7105	0.1782	0.075*
C26	0.4156 (4)	0.6299 (2)	0.22854 (19)	0.0655 (7)
H26	0.3545	0.5844	0.2400	0.079*
C27	0.5628 (4)	0.6212 (2)	0.24860 (19)	0.0651 (7)
H27	0.6010	0.5696	0.2733	0.078*
C28	0.6530 (3)	0.6886 (2)	0.23222 (17)	0.0578 (6)
H28	0.7525	0.6826	0.2457	0.069*
C29	0.5967 (3)	0.76547 (19)	0.19574 (15)	0.0488 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0415 (3)	0.0562 (3)	0.0348 (3)	0.0038 (2)	0.00948 (19)	0.00040 (19)
P1	0.0487 (4)	0.0508 (4)	0.0436 (4)	0.0054 (3)	0.0128 (3)	0.0076 (3)
S1	0.0543 (4)	0.0701 (5)	0.0516 (4)	0.0119 (4)	−0.0042 (3)	−0.0112 (3)
S2	0.0483 (4)	0.0646 (5)	0.0478 (4)	0.0083 (3)	0.0010 (3)	−0.0056 (3)
N1	0.0767 (18)	0.0715 (18)	0.0669 (17)	0.0032 (14)	0.0042 (14)	−0.0129 (14)
N2	0.0759 (19)	0.087 (2)	0.083 (2)	0.0262 (17)	−0.0008 (15)	−0.0105 (16)
C1	0.0550 (14)	0.0654 (16)	0.0491 (14)	0.0039 (12)	0.0068 (11)	−0.0031 (12)
C2	0.0502 (13)	0.0606 (15)	0.0425 (13)	0.0035 (12)	0.0110 (11)	−0.0014 (11)
C3	0.0505 (14)	0.0629 (15)	0.0452 (13)	0.0059 (12)	0.0119 (11)	−0.0021 (12)
C4	0.0565 (14)	0.0702 (16)	0.0528 (14)	0.0092 (13)	0.0055 (12)	−0.0068 (13)
C5	0.0686 (14)	0.0747 (15)	0.0673 (14)	0.0006 (13)	0.0225 (13)	−0.0119 (13)
C6	0.0843 (17)	0.0817 (17)	0.0815 (16)	0.0076 (14)	0.0212 (14)	−0.0141 (15)
C7	0.0985 (18)	0.0780 (17)	0.0839 (17)	−0.0002 (15)	0.0224 (16)	−0.0139 (15)
C8	0.0939 (17)	0.0829 (17)	0.0844 (17)	−0.0162 (15)	0.0215 (15)	−0.0175 (15)
C9	0.0752 (16)	0.0844 (16)	0.0721 (15)	−0.0089 (14)	0.0167 (13)	−0.0162 (14)
C10	0.0648 (13)	0.0722 (14)	0.0495 (12)	−0.0015 (11)	0.0205 (11)	−0.0059 (11)
C11	0.0695 (16)	0.0730 (17)	0.0449 (14)	0.0052 (14)	0.0164 (12)	0.0040 (13)
C12	0.0521 (13)	0.0570 (13)	0.0679 (14)	0.0009 (11)	0.0204 (11)	−0.0047 (12)
C13	0.0513 (13)	0.0620 (14)	0.0840 (16)	0.0002 (12)	0.0152 (12)	−0.0093 (13)
C14	0.0584 (14)	0.0668 (15)	0.0797 (16)	0.0022 (13)	0.0017 (13)	−0.0066 (13)
C15	0.0627 (14)	0.0709 (15)	0.0649 (15)	0.0014 (13)	0.0044 (12)	0.0007 (13)
C16	0.0537 (13)	0.0654 (14)	0.0573 (13)	0.0013 (12)	0.0128 (11)	0.0038 (12)
C17	0.0467 (12)	0.0524 (13)	0.0561 (13)	0.0036 (10)	0.0151 (10)	0.0021 (11)
C18	0.0670 (15)	0.0613 (14)	0.0812 (16)	0.0025 (12)	0.0082 (13)	0.0232 (13)
C19	0.0724 (16)	0.0615 (15)	0.0989 (18)	0.0009 (13)	−0.0006 (14)	0.0258 (14)
C20	0.0642 (15)	0.0558 (14)	0.1109 (19)	0.0050 (13)	0.0002 (14)	0.0105 (14)
C21	0.0642 (15)	0.0582 (14)	0.1013 (18)	0.0064 (13)	0.0151 (14)	0.0012 (14)
C22	0.0605 (14)	0.0531 (13)	0.0822 (16)	0.0057 (12)	0.0189 (13)	0.0065 (12)
C23	0.0525 (13)	0.0493 (13)	0.0708 (15)	0.0030 (11)	0.0130 (11)	0.0138 (12)
C24	0.0517 (12)	0.0529 (13)	0.0569 (13)	0.0023 (11)	0.0026 (11)	0.0018 (11)
C25	0.0543 (13)	0.0606 (14)	0.0707 (15)	−0.0036 (12)	0.0049 (12)	−0.0019 (12)
C26	0.0637 (14)	0.0567 (14)	0.0767 (15)	−0.0065 (12)	0.0135 (13)	0.0019 (12)
C27	0.0662 (14)	0.0537 (13)	0.0757 (15)	0.0027 (12)	0.0124 (13)	0.0106 (12)
C28	0.0543 (13)	0.0534 (13)	0.0656 (14)	0.0071 (11)	0.0099 (11)	0.0097 (11)
C29	0.0486 (12)	0.0481 (12)	0.0499 (12)	0.0039 (10)	0.0090 (10)	0.0040 (10)

Geometric parameters (Å, º)

Ni1—S1	2.1684 (8)	C12—H12	0.9300
Ni1—S1^i	2.1684 (8)	C13—C14	1.364 (5)
Ni1—S2	2.1743 (7)	C13—H13	0.9300
Ni1—S2^i	2.1743 (7)	C14—C15	1.370 (5)
P1—C29	1.785 (3)	C14—H14	0.9300
P1—C17	1.795 (3)	C15—C16	1.377 (4)
P1—C23	1.798 (3)	C15—H15	0.9300
P1—C11	1.814 (3)	C16—C17	1.392 (4)
S1—C2	1.727 (3)	C16—H16	0.9300
S2—C3	1.737 (3)	C18—C23	1.386 (5)
N1—C1	1.145 (4)	C18—C19	1.391 (5)
N2—C4	1.145 (4)	C18—H18	0.9300
C1—C2	1.428 (4)	C19—C20	1.361 (6)
C2—C3^i	1.353 (4)	C19—H19	0.9300
C3—C2^i	1.353 (4)	C20—C21	1.363 (6)
C3—C4	1.423 (4)	C20—H20	0.9300
C5—C10	1.377 (5)	C21—C22	1.381 (5)
C5—C6	1.384 (5)	C21—H21	0.9300
C5—H5	0.9300	C22—C23	1.384 (5)
C6—C7	1.367 (6)	C22—H22	0.9300
C6—H6	0.9300	C24—C25	1.373 (4)
C7—C8	1.358 (6)	C24—C29	1.392 (4)
C7—H7	0.9300	C24—H24	0.9300
C8—C9	1.390 (6)	C25—C26	1.365 (5)
C8—H8	0.9300	C25—H25	0.9300
C9—C10	1.380 (5)	C26—C27	1.377 (5)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.507 (5)	C27—C28	1.370 (4)
C11—H11A	0.9700	C27—H27	0.9300
C11—H11B	0.9700	C28—C29	1.381 (4)
C12—C13	1.388 (5)	C28—H28	0.9300
C12—C17	1.391 (4)
S1—Ni1—S1^i	180.00 (4)	C14—C13—H13	119.6
S1—Ni1—S2	87.60 (3)	C12—C13—H13	119.6
S1^i—Ni1—S2	92.40 (3)	C13—C14—C15	120.1 (3)
S1—Ni1—S2^i	92.40 (3)	C13—C14—H14	119.9
S1^i—Ni1—S2^i	87.60 (3)	C15—C14—H14	119.9
S2—Ni1—S2^i	180.00 (6)	C14—C15—C16	120.4 (3)
C29—P1—C17	109.94 (13)	C14—C15—H15	119.8
C29—P1—C23	108.42 (13)	C16—C15—H15	119.8
C17—P1—C23	109.06 (15)	C15—C16—C17	120.0 (3)
C29—P1—C11	108.50 (15)	C15—C16—H16	120.0
C17—P1—C11	111.25 (14)	C17—C16—H16	120.0
C23—P1—C11	109.62 (15)	C12—C17—C16	119.5 (3)
C2—S1—Ni1	103.05 (10)	C12—C17—P1	121.3 (2)
C3—S2—Ni1	102.62 (10)	C16—C17—P1	119.0 (2)
N1—C1—C2	178.9 (4)	C23—C18—C19	118.5 (4)
C3^i—C2—C1	119.9 (3)	C23—C18—H18	120.8
C3^i—C2—S1	121.0 (2)	C19—C18—H18	120.8
C1—C2—S1	119.1 (2)	C20—C19—C18	120.9 (4)
C2^i—C3—C4	120.6 (3)	C20—C19—H19	119.5
C2^i—C3—S2	120.9 (2)	C18—C19—H19	119.5
C4—C3—S2	118.5 (2)	C19—C20—C21	120.5 (4)
N2—C4—C3	179.5 (4)	C19—C20—H20	119.8
C10—C5—C6	120.5 (4)	C21—C20—H20	119.8
C10—C5—H5	119.7	C20—C21—C22	120.1 (4)
C6—C5—H5	119.7	C20—C21—H21	120.0
C7—C6—C5	120.1 (4)	C22—C21—H21	120.0
C7—C6—H6	120.0	C21—C22—C23	119.8 (3)
C5—C6—H6	120.0	C21—C22—H22	120.1
C8—C7—C6	120.2 (4)	C23—C22—H22	120.1
C8—C7—H7	119.9	C22—C23—C18	120.3 (3)
C6—C7—H7	119.9	C22—C23—P1	118.7 (2)
C7—C8—C9	120.2 (4)	C18—C23—P1	121.0 (3)
C7—C8—H8	119.9	C25—C24—C29	119.5 (3)
C9—C8—H8	119.9	C25—C24—H24	120.2
C10—C9—C8	120.2 (4)	C29—C24—H24	120.2
C10—C9—H9	119.9	C26—C25—C24	120.5 (3)
C8—C9—H9	119.9	C26—C25—H25	119.7
C5—C10—C9	118.8 (3)	C24—C25—H25	119.7
C5—C10—C11	121.0 (3)	C25—C26—C27	120.3 (3)
C9—C10—C11	120.3 (3)	C25—C26—H26	119.9
C10—C11—P1	113.9 (2)	C27—C26—H26	119.9
C10—C11—H11A	108.8	C28—C27—C26	120.0 (3)
P1—C11—H11A	108.8	C28—C27—H27	120.0
C10—C11—H11B	108.8	C26—C27—H27	120.0
P1—C11—H11B	108.8	C27—C28—C29	120.2 (3)
H11A—C11—H11B	107.7	C27—C28—H28	119.9
C13—C12—C17	119.1 (3)	C29—C28—H28	119.9
C13—C12—H12	120.4	C28—C29—C24	119.5 (3)
C17—C12—H12	120.4	C28—C29—P1	120.9 (2)
C14—C13—C12	120.9 (3)	C24—C29—P1	119.4 (2)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N2^ii	0.93	2.57	3.478 (5)	165
C20—H20···Cg1^iii	0.93	3.15	3.852 (5)	133
C27—H27···Cg1^iv	0.93	3.17	3.727 (3)	120

Symmetry codes: (ii) x, y+1, z; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2.