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The asymmetric unit of the title compound, (C
25H
22P)
2-[Ni(C
4N
2S
2)
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 mnt
2− 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.
Supporting information
CCDC reference: 647253
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (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
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)
top
Crystal data top
(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) Å3 | 0.41 × 0.34 × 0.15 mm |
Z = 2 | |
Data collection top
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 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.06P)2 + 1.2P] where P = (Fo2 + 2Fc2)/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 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Ni1—S1 | 2.1684 (8) | C12—H12 | 0.9300 |
Ni1—S1i | 2.1684 (8) | C13—C14 | 1.364 (5) |
Ni1—S2 | 2.1743 (7) | C13—H13 | 0.9300 |
Ni1—S2i | 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—C3i | 1.353 (4) | C19—H19 | 0.9300 |
C3—C2i | 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—S1i | 180.00 (4) | C14—C13—H13 | 119.6 |
S1—Ni1—S2 | 87.60 (3) | C12—C13—H13 | 119.6 |
S1i—Ni1—S2 | 92.40 (3) | C13—C14—C15 | 120.1 (3) |
S1—Ni1—S2i | 92.40 (3) | C13—C14—H14 | 119.9 |
S1i—Ni1—S2i | 87.60 (3) | C15—C14—H14 | 119.9 |
S2—Ni1—S2i | 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) |
C3i—C2—C1 | 119.9 (3) | C23—C18—H18 | 120.8 |
C3i—C2—S1 | 121.0 (2) | C19—C18—H18 | 120.8 |
C1—C2—S1 | 119.1 (2) | C20—C19—C18 | 120.9 (4) |
C2i—C3—C4 | 120.6 (3) | C20—C19—H19 | 119.5 |
C2i—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···N2ii | 0.93 | 2.57 | 3.478 (5) | 165 |
C20—H20···Cg1iii | 0.93 | 3.15 | 3.852 (5) | 133 |
C27—H27···Cg1iv | 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. |
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