Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029844/hb2442sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029844/hb2442Isup2.hkl |
CCDC reference: 652063
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.047
- wR factor = 0.123
- Data-to-parameter ratio = 19.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni - S2 .. 6.33 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni - P1 .. 6.36 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C43 H33 Cl2 N Ni O2 P2 S3
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni (9) 2.93
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Allen et al. (1987); Cavell et al. (1998); Foulds et al. (1994); Franca et al. (2006); Oliveira et al. (2002, 2003); Orpen et al. (1989); Bruno et al. (2002).
The potassium dithiocarbimate dihydrate was prepared according to Franca et al.,(2006). The title compound was prepared in 30:20 ml e thanol:water mixture from nickel chloride hexahydrate (1.0 mmol), triphenylphosphine (2.0 mmol) and potassium 2,5-dichlorophenylsulfonyldithiocarbimate dihydrate (1.0 mmol) analogously as described in the literature for similar compounds (Oliveira et al., 2002). Suitable crystals were obtained after slow evaporation of a solution of the compound in dichloromethane/ethanol (2:3 v/v). Elemental analysis: Found (calculated)%: C 56.77 (58.46), H 3.81 (3.76), N 1.54 (1.59) and Ni 6.79 (6.64). M.p. 175.0–176.5°C. IR (most important bands) (cm-1): 1449 ν(C?N); 1312 νass(SO2); 1153 νsym(SO2); 939 νass(CS2) and 370 ν(NiS).
All the H atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2 Ueq(C).
We became interested in the syntheses and characterization of nickel(II) complexes with dithiocarbimates and phosphines due to their similarities with the dithiocarbimate compounds, which have shown catalytic activity, especially for oligomerization of olefins (Cavell et al., 1998; Foulds et al., 1994). As only the nickel complexes with general formulae Ni(RSO2N?CS2)(PPh3)2 (R = 2-CH3C6H4, 4-CH3C6H4 and 4-BrC6H4) have had their structures determined by X-ray diffraction techniques (Oliveira et al., 2002), the title compound (I) was prepared.
As shown in Fig. 1, the structure of (I) is composed of neutral Ni(2,5-Cl2C6H3SO2NCS2)(Ph3P)2 complex molecules. The NiII atom is coordinated by two sulfur atoms from the dithiocarbimate anion and by two phosphorus atoms of the triphenylphosphine ligands into a distorted square-planar geometry. The small S—Ni—S angle is determined by the geometry of the chelate ligand, while the opposite P—Ni—P angle is rather large, probably due to the steric effect of the large triphenylphosphine ligands (Table 1). The two Ni—S bond lenghts are not significantly different, although the two Ni—P distances are. The C—S [1.732 (3) and 1.722 (3) Å] bond lengths of the NCS2 fragment are nearly equal and are much shorter than typical C—S single bonds [ca 1.81 Å]. The C1?N bond distance of 1.303 (3)Å is shorter than normal single Csp2—Nsp2 bond length [ca 1.35 Å] and similar to that of the double bond C?N [1.275–1.300 Å] (Allen et al., 1987; Orpen et al., 1989). This behavior indicates that the electron density is delocalized over the entire NCS2 moiety. Similar behavior is observed for related nickel complexes (Oliveira et al., 2002; Oliveira et al., 2003; Franca et al., 2006). The repulsive interaction cis between the SO2(2,5-Cl2C6H3) group and the S1 atom, which are in greater position in relation to the C1—N bond, is responsible for the difference between the angles S1—C1—N [132.6 (2)°] and S2—C1—N [121.8 (2)°].
The torsion angle C1—N—S3—C2 describing the conformation of the ligands along the N—S3 bond is 85.1 (3)°. The Car—Car bond lengths of the triphenylphosphine aromatic rings involved in the intermolecular interactions are shorter than typical values described in the literature[1.372–1.388 Å] (Allen et al., 1987).
In the crystal structure of (I), the molecules are linked through C—H···O and C—H···S interactions (Table 2 and Fig. 2).
For related literature, see: Allen et al. (1987); Cavell et al. (1998); Foulds et al. (1994); Franca et al. (2006); Oliveira et al. (2002, 2003); Orpen et al. (1989); Bruno et al. (2002).
Data collection: COLLECT (Enraf–Nonius, 2000); cell refinement: SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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: WinGX (Farrugia, 1999).
[Ni(C7H3Cl2NO2S3)(C18H15P)2] | F(000) = 3632 |
Mr = 883.43 | Dx = 1.445 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 41144 reflections |
a = 18.4654 (3) Å | θ = 2.9–27.5° |
b = 15.2416 (2) Å | µ = 0.88 mm−1 |
c = 28.8619 (5) Å | T = 293 K |
V = 8123.0 (2) Å3 | Prism, brown |
Z = 8 | 0.20 × 0.18 × 0.03 mm |
Nonius KappaCCD diffractometer | 5597 reflections with I > 2σ(I) |
CCD rotation images, thick slices scans | Rint = 0.063 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | θmax = 27.5°, θmin = 2.9° |
Tmin = 0.844, Tmax = 0.974 | h = −23→22 |
41274 measured reflections | k = −17→19 |
9277 independent reflections | l = −28→37 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.6249P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max = 0.031 |
S = 1.02 | Δρmax = 0.44 e Å−3 |
9277 reflections | Δρmin = −0.38 e Å−3 |
487 parameters |
[Ni(C7H3Cl2NO2S3)(C18H15P)2] | V = 8123.0 (2) Å3 |
Mr = 883.43 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 18.4654 (3) Å | µ = 0.88 mm−1 |
b = 15.2416 (2) Å | T = 293 K |
c = 28.8619 (5) Å | 0.20 × 0.18 × 0.03 mm |
Nonius KappaCCD diffractometer | 9277 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 5597 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.974 | Rint = 0.063 |
41274 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.44 e Å−3 |
9277 reflections | Δρmin = −0.38 e Å−3 |
487 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni | −0.108821 (19) | 0.29799 (2) | 0.164898 (11) | 0.03513 (11) | |
P2 | −0.17650 (4) | 0.20227 (5) | 0.12389 (2) | 0.03769 (18) | |
S1 | −0.05827 (4) | 0.38162 (5) | 0.21807 (2) | 0.04220 (19) | |
S2 | −0.16167 (5) | 0.25340 (5) | 0.22963 (2) | 0.0505 (2) | |
P1 | −0.04277 (4) | 0.36360 (5) | 0.11063 (2) | 0.03681 (18) | |
S3 | −0.07421 (5) | 0.41888 (6) | 0.33031 (3) | 0.0564 (2) | |
Cl1 | −0.23725 (6) | 0.44726 (8) | 0.37366 (4) | 0.0924 (3) | |
Cl2 | −0.09475 (9) | 0.74289 (9) | 0.25675 (7) | 0.1463 (6) | |
O2 | −0.07530 (15) | 0.39752 (17) | 0.37835 (7) | 0.0786 (8) | |
O1 | −0.00420 (13) | 0.43555 (16) | 0.31015 (8) | 0.0709 (7) | |
N | −0.12051 (14) | 0.34355 (16) | 0.30359 (8) | 0.0505 (7) | |
C26 | −0.26532 (16) | 0.24552 (17) | 0.10822 (9) | 0.0419 (7) | |
C37 | −0.26867 (18) | 0.0864 (2) | 0.17204 (10) | 0.0519 (8) | |
H37 | −0.3068 | 0.1161 | 0.158 | 0.062* | |
C14 | 0.03409 (16) | 0.29937 (19) | 0.09022 (9) | 0.0416 (7) | |
C27 | −0.29528 (18) | 0.31181 (18) | 0.13457 (11) | 0.0505 (8) | |
H27 | −0.2686 | 0.3369 | 0.1585 | 0.061* | |
C1 | −0.11252 (16) | 0.33135 (18) | 0.25921 (9) | 0.0399 (7) | |
C15 | 0.03301 (18) | 0.2090 (2) | 0.09561 (11) | 0.0534 (8) | |
H15 | −0.006 | 0.182 | 0.1102 | 0.064* | |
C8 | −0.00162 (17) | 0.46596 (18) | 0.13038 (9) | 0.0411 (7) | |
C32 | −0.19791 (17) | 0.10864 (18) | 0.16150 (9) | 0.0416 (7) | |
C39 | −0.14815 (18) | 0.1978 (2) | 0.02842 (10) | 0.0517 (8) | |
H39 | −0.1675 | 0.2542 | 0.0281 | 0.062* | |
C38 | −0.14443 (16) | 0.15119 (18) | 0.07007 (9) | 0.0411 (7) | |
C9 | 0.06137 (17) | 0.4641 (2) | 0.15675 (10) | 0.0507 (8) | |
H9 | 0.085 | 0.4111 | 0.1617 | 0.061* | |
C25 | −0.16342 (18) | 0.42726 (18) | 0.06566 (11) | 0.0519 (8) | |
H25 | −0.183 | 0.4295 | 0.0953 | 0.062* | |
C43 | −0.11539 (18) | 0.06701 (19) | 0.06948 (10) | 0.0525 (8) | |
H43 | −0.1124 | 0.0349 | 0.0968 | 0.063* | |
C41 | −0.0948 (2) | 0.0775 (2) | −0.01238 (12) | 0.0689 (11) | |
H41 | −0.0782 | 0.0529 | −0.0399 | 0.083* | |
C36 | −0.2827 (2) | 0.0201 (2) | 0.20334 (12) | 0.0667 (10) | |
H36 | −0.3303 | 0.0057 | 0.2105 | 0.08* | |
C20 | −0.09327 (16) | 0.39802 (18) | 0.05934 (9) | 0.0417 (7) | |
C35 | −0.2269 (3) | −0.0250 (2) | 0.22402 (11) | 0.0677 (11) | |
H35 | −0.2367 | −0.0699 | 0.2449 | 0.081* | |
C21 | −0.06526 (19) | 0.3956 (2) | 0.01444 (10) | 0.0583 (9) | |
H21 | −0.018 | 0.3767 | 0.0094 | 0.07* | |
C34 | −0.1570 (2) | −0.0035 (2) | 0.21386 (10) | 0.0603 (9) | |
H34 | −0.1192 | −0.0342 | 0.2276 | 0.072* | |
C33 | −0.14217 (19) | 0.06362 (19) | 0.18324 (10) | 0.0495 (8) | |
H33 | −0.0943 | 0.0788 | 0.1771 | 0.059* | |
C40 | −0.1235 (2) | 0.1611 (2) | −0.01208 (11) | 0.0641 (10) | |
H40 | −0.1261 | 0.1928 | −0.0395 | 0.077* | |
C3 | −0.1939 (2) | 0.5287 (2) | 0.34238 (12) | 0.0669 (10) | |
C29 | −0.40438 (19) | 0.3065 (2) | 0.09024 (13) | 0.0628 (9) | |
H29 | −0.4507 | 0.3275 | 0.084 | 0.075* | |
C13 | −0.03587 (19) | 0.5454 (2) | 0.12431 (12) | 0.0593 (9) | |
H13 | −0.078 | 0.5486 | 0.1068 | 0.071* | |
C12 | −0.0077 (3) | 0.6202 (2) | 0.14415 (15) | 0.0856 (13) | |
H12 | −0.0315 | 0.6734 | 0.1402 | 0.103* | |
C28 | −0.36505 (19) | 0.3412 (2) | 0.12564 (13) | 0.0606 (9) | |
H28 | −0.3851 | 0.385 | 0.144 | 0.073* | |
C31 | −0.30672 (18) | 0.2095 (2) | 0.07258 (11) | 0.0581 (9) | |
H31 | −0.2878 | 0.1643 | 0.0546 | 0.07* | |
C10 | 0.0891 (2) | 0.5400 (3) | 0.17565 (11) | 0.0621 (10) | |
H10 | 0.1318 | 0.5379 | 0.1927 | 0.075* | |
C24 | −0.2048 (2) | 0.4534 (2) | 0.02786 (15) | 0.0700 (10) | |
H24 | −0.2519 | 0.4734 | 0.0323 | 0.084* | |
C17 | 0.1492 (2) | 0.1978 (3) | 0.05903 (13) | 0.0802 (12) | |
H17 | 0.1876 | 0.1637 | 0.0484 | 0.096* | |
C19 | 0.09431 (18) | 0.3380 (2) | 0.06974 (11) | 0.0574 (9) | |
H19 | 0.0961 | 0.3986 | 0.0663 | 0.069* | |
C4 | −0.2293 (2) | 0.6077 (3) | 0.33782 (15) | 0.0851 (13) | |
H4 | −0.2738 | 0.6167 | 0.3523 | 0.102* | |
C2 | −0.12607 (18) | 0.5160 (2) | 0.32230 (11) | 0.0547 (8) | |
C42 | −0.0909 (2) | 0.0307 (2) | 0.02816 (11) | 0.0643 (10) | |
H42 | −0.0716 | −0.0257 | 0.028 | 0.077* | |
C30 | −0.37536 (19) | 0.2404 (2) | 0.06382 (12) | 0.0656 (10) | |
H30 | −0.4023 | 0.2163 | 0.0398 | 0.079* | |
C22 | −0.1073 (3) | 0.4210 (3) | −0.02223 (12) | 0.0775 (12) | |
H22 | −0.0884 | 0.4185 | −0.0521 | 0.093* | |
C18 | 0.1515 (2) | 0.2872 (3) | 0.05452 (12) | 0.0764 (11) | |
H18 | 0.1917 | 0.3138 | 0.0411 | 0.092* | |
C7 | −0.0958 (2) | 0.5822 (3) | 0.29587 (12) | 0.0699 (10) | |
H7 | −0.051 | 0.5741 | 0.2818 | 0.084* | |
C16 | 0.0905 (2) | 0.1588 (2) | 0.07918 (13) | 0.0722 (11) | |
H16 | 0.0889 | 0.0981 | 0.0819 | 0.087* | |
C5 | −0.1980 (3) | 0.6738 (3) | 0.31137 (17) | 0.0919 (14) | |
H5 | −0.2218 | 0.7272 | 0.3079 | 0.11* | |
C6 | −0.1327 (3) | 0.6609 (3) | 0.29047 (16) | 0.0864 (13) | |
C23 | −0.1763 (3) | 0.4497 (3) | −0.01572 (14) | 0.0790 (12) | |
H23 | −0.2041 | 0.4669 | −0.041 | 0.095* | |
C11 | 0.0547 (3) | 0.6171 (3) | 0.16952 (14) | 0.0816 (12) | |
H11 | 0.0734 | 0.6682 | 0.1825 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0387 (2) | 0.0379 (2) | 0.02878 (18) | −0.00171 (16) | 0.00288 (15) | −0.00028 (14) |
P2 | 0.0394 (4) | 0.0402 (4) | 0.0334 (4) | −0.0018 (3) | 0.0043 (3) | −0.0045 (3) |
S1 | 0.0436 (5) | 0.0507 (4) | 0.0323 (4) | −0.0052 (4) | 0.0008 (3) | −0.0028 (3) |
S2 | 0.0643 (6) | 0.0518 (5) | 0.0354 (4) | −0.0143 (4) | 0.0103 (4) | −0.0024 (3) |
P1 | 0.0373 (4) | 0.0401 (4) | 0.0330 (4) | −0.0005 (3) | 0.0014 (3) | 0.0018 (3) |
S3 | 0.0527 (5) | 0.0816 (6) | 0.0348 (4) | 0.0103 (4) | −0.0072 (4) | −0.0117 (4) |
Cl1 | 0.0748 (7) | 0.1148 (9) | 0.0875 (7) | 0.0109 (6) | 0.0260 (6) | −0.0013 (6) |
Cl2 | 0.1631 (15) | 0.0837 (9) | 0.1921 (15) | −0.0407 (9) | −0.0270 (12) | 0.0282 (10) |
O2 | 0.0895 (19) | 0.116 (2) | 0.0306 (11) | 0.0289 (17) | −0.0115 (12) | −0.0063 (12) |
O1 | 0.0446 (15) | 0.1049 (19) | 0.0631 (14) | 0.0028 (13) | −0.0065 (12) | −0.0231 (14) |
N | 0.0566 (17) | 0.0619 (16) | 0.0329 (13) | 0.0060 (14) | 0.0042 (12) | −0.0008 (12) |
C26 | 0.0423 (18) | 0.0439 (16) | 0.0394 (15) | −0.0005 (14) | 0.0034 (14) | −0.0007 (13) |
C37 | 0.051 (2) | 0.0528 (18) | 0.0520 (18) | −0.0115 (16) | 0.0086 (16) | −0.0057 (15) |
C14 | 0.0406 (18) | 0.0492 (17) | 0.0351 (14) | 0.0010 (14) | 0.0006 (13) | −0.0009 (13) |
C27 | 0.051 (2) | 0.0460 (17) | 0.0545 (19) | 0.0027 (16) | 0.0006 (15) | −0.0080 (15) |
C1 | 0.0403 (17) | 0.0435 (15) | 0.0357 (15) | 0.0092 (13) | 0.0023 (12) | 0.0006 (13) |
C15 | 0.053 (2) | 0.0528 (19) | 0.0541 (19) | 0.0094 (16) | −0.0067 (16) | 0.0001 (15) |
C8 | 0.0439 (18) | 0.0463 (16) | 0.0331 (14) | −0.0062 (15) | 0.0044 (13) | 0.0025 (12) |
C32 | 0.050 (2) | 0.0405 (15) | 0.0348 (15) | −0.0060 (15) | 0.0064 (13) | −0.0075 (13) |
C39 | 0.064 (2) | 0.0492 (18) | 0.0423 (17) | −0.0053 (16) | 0.0049 (16) | −0.0046 (14) |
C38 | 0.0388 (17) | 0.0446 (17) | 0.0399 (16) | −0.0074 (14) | 0.0059 (13) | −0.0060 (13) |
C9 | 0.046 (2) | 0.060 (2) | 0.0462 (18) | −0.0042 (16) | 0.0019 (15) | 0.0051 (15) |
C25 | 0.054 (2) | 0.0465 (17) | 0.0556 (19) | 0.0008 (16) | −0.0089 (16) | 0.0033 (15) |
C43 | 0.062 (2) | 0.0534 (19) | 0.0424 (17) | 0.0034 (16) | 0.0089 (15) | −0.0024 (15) |
C41 | 0.087 (3) | 0.073 (2) | 0.046 (2) | 0.005 (2) | 0.0177 (19) | −0.0136 (18) |
C36 | 0.072 (3) | 0.061 (2) | 0.067 (2) | −0.025 (2) | 0.023 (2) | −0.0069 (19) |
C20 | 0.0435 (19) | 0.0435 (16) | 0.0380 (15) | −0.0059 (14) | −0.0032 (13) | 0.0049 (13) |
C35 | 0.104 (3) | 0.0481 (19) | 0.051 (2) | −0.021 (2) | 0.022 (2) | 0.0010 (16) |
C21 | 0.058 (2) | 0.076 (2) | 0.0411 (17) | −0.0096 (19) | −0.0001 (15) | 0.0096 (16) |
C34 | 0.092 (3) | 0.0468 (18) | 0.0424 (17) | 0.0018 (19) | 0.0033 (18) | 0.0024 (15) |
C33 | 0.053 (2) | 0.0535 (18) | 0.0419 (16) | −0.0006 (16) | 0.0078 (15) | −0.0048 (15) |
C40 | 0.086 (3) | 0.064 (2) | 0.0420 (18) | 0.002 (2) | 0.0125 (17) | 0.0024 (16) |
C3 | 0.058 (2) | 0.078 (2) | 0.065 (2) | 0.004 (2) | −0.0110 (18) | −0.0194 (19) |
C29 | 0.047 (2) | 0.073 (2) | 0.069 (2) | 0.0107 (18) | 0.0001 (18) | 0.0132 (19) |
C13 | 0.058 (2) | 0.0492 (19) | 0.071 (2) | 0.0044 (17) | −0.0144 (18) | −0.0059 (17) |
C12 | 0.101 (3) | 0.046 (2) | 0.110 (3) | 0.006 (2) | −0.029 (3) | −0.016 (2) |
C28 | 0.054 (2) | 0.0497 (19) | 0.078 (2) | 0.0084 (17) | 0.0094 (19) | −0.0071 (18) |
C31 | 0.049 (2) | 0.073 (2) | 0.0522 (19) | 0.0042 (18) | −0.0030 (16) | −0.0184 (17) |
C10 | 0.058 (2) | 0.079 (3) | 0.0494 (19) | −0.024 (2) | −0.0110 (17) | 0.0016 (18) |
C24 | 0.055 (2) | 0.060 (2) | 0.095 (3) | −0.0007 (18) | −0.025 (2) | 0.013 (2) |
C17 | 0.071 (3) | 0.108 (3) | 0.061 (2) | 0.042 (3) | 0.005 (2) | −0.007 (2) |
C19 | 0.056 (2) | 0.063 (2) | 0.0533 (19) | 0.0029 (18) | 0.0134 (16) | 0.0000 (16) |
C4 | 0.064 (3) | 0.087 (3) | 0.105 (3) | 0.010 (3) | −0.025 (2) | −0.028 (3) |
C2 | 0.049 (2) | 0.066 (2) | 0.0495 (18) | −0.0003 (17) | −0.0147 (16) | −0.0180 (17) |
C42 | 0.083 (3) | 0.056 (2) | 0.053 (2) | 0.0124 (19) | 0.0149 (18) | −0.0098 (17) |
C30 | 0.047 (2) | 0.096 (3) | 0.054 (2) | 0.000 (2) | −0.0100 (16) | −0.009 (2) |
C22 | 0.095 (3) | 0.094 (3) | 0.044 (2) | −0.021 (3) | −0.013 (2) | 0.0176 (19) |
C18 | 0.057 (3) | 0.115 (3) | 0.057 (2) | 0.015 (2) | 0.0179 (18) | 0.000 (2) |
C7 | 0.066 (3) | 0.081 (3) | 0.063 (2) | −0.012 (2) | −0.0185 (19) | −0.010 (2) |
C16 | 0.081 (3) | 0.064 (2) | 0.071 (2) | 0.033 (2) | −0.011 (2) | −0.0080 (19) |
C5 | 0.084 (4) | 0.076 (3) | 0.116 (4) | 0.010 (3) | −0.047 (3) | −0.022 (3) |
C6 | 0.095 (4) | 0.064 (3) | 0.100 (3) | −0.017 (3) | −0.039 (3) | −0.004 (2) |
C23 | 0.082 (3) | 0.086 (3) | 0.069 (3) | −0.016 (2) | −0.031 (2) | 0.028 (2) |
C11 | 0.100 (3) | 0.060 (2) | 0.085 (3) | −0.025 (2) | −0.019 (2) | −0.013 (2) |
Ni—S1 | 2.2027 (8) | C36—C35 | 1.374 (5) |
Ni—S2 | 2.2147 (8) | C36—H36 | 0.93 |
Ni—P1 | 2.2227 (8) | C20—C21 | 1.396 (4) |
Ni—P2 | 2.2564 (8) | C35—C34 | 1.363 (5) |
P2—C26 | 1.824 (3) | C35—H35 | 0.93 |
P2—C38 | 1.836 (3) | C21—C22 | 1.369 (5) |
P2—C32 | 1.836 (3) | C21—H21 | 0.93 |
S1—C1 | 1.732 (3) | C34—C33 | 1.379 (4) |
S2—C1 | 1.722 (3) | C34—H34 | 0.93 |
P1—C14 | 1.822 (3) | C33—H33 | 0.93 |
P1—C8 | 1.827 (3) | C40—H40 | 0.93 |
P1—C20 | 1.827 (3) | C3—C4 | 1.376 (5) |
S3—O2 | 1.425 (2) | C3—C2 | 1.394 (5) |
S3—O1 | 1.440 (3) | C29—C28 | 1.360 (5) |
S3—N | 1.626 (3) | C29—C30 | 1.373 (5) |
S3—C2 | 1.779 (3) | C29—H29 | 0.93 |
Cl1—C3 | 1.731 (4) | C13—C12 | 1.377 (5) |
Cl2—C6 | 1.732 (5) | C13—H13 | 0.93 |
N—C1 | 1.303 (3) | C12—C11 | 1.366 (6) |
C26—C27 | 1.380 (4) | C12—H12 | 0.93 |
C26—C31 | 1.394 (4) | C28—H28 | 0.93 |
C37—C36 | 1.380 (4) | C31—C30 | 1.376 (5) |
C37—C32 | 1.384 (4) | C31—H31 | 0.93 |
C37—H37 | 0.93 | C10—C11 | 1.348 (5) |
C14—C15 | 1.386 (4) | C10—H10 | 0.93 |
C14—C19 | 1.390 (4) | C24—C23 | 1.365 (5) |
C27—C28 | 1.388 (5) | C24—H24 | 0.93 |
C27—H27 | 0.93 | C17—C16 | 1.367 (6) |
C15—C16 | 1.391 (5) | C17—C18 | 1.369 (5) |
C15—H15 | 0.93 | C17—H17 | 0.93 |
C8—C13 | 1.378 (4) | C19—C18 | 1.381 (5) |
C8—C9 | 1.390 (4) | C19—H19 | 0.93 |
C32—C33 | 1.387 (4) | C4—C5 | 1.391 (6) |
C39—C40 | 1.374 (4) | C4—H4 | 0.93 |
C39—C38 | 1.398 (4) | C2—C7 | 1.382 (5) |
C39—H39 | 0.93 | C42—H42 | 0.93 |
C38—C43 | 1.391 (4) | C30—H30 | 0.93 |
C9—C10 | 1.377 (4) | C22—C23 | 1.360 (6) |
C9—H9 | 0.93 | C22—H22 | 0.93 |
C25—C20 | 1.382 (4) | C18—H18 | 0.93 |
C25—C24 | 1.390 (4) | C7—C6 | 1.387 (5) |
C25—H25 | 0.93 | C7—H7 | 0.93 |
C43—C42 | 1.390 (4) | C16—H16 | 0.93 |
C43—H43 | 0.93 | C5—C6 | 1.363 (6) |
C41—C42 | 1.372 (5) | C5—H5 | 0.93 |
C41—C40 | 1.380 (5) | C23—H23 | 0.93 |
C41—H41 | 0.93 | C11—H11 | 0.93 |
S1—Ni—S2 | 77.09 (3) | C22—C21—C20 | 120.0 (4) |
S1—Ni—P1 | 89.89 (3) | C22—C21—H21 | 120 |
S2—Ni—P1 | 166.98 (3) | C20—C21—H21 | 120 |
S1—Ni—P2 | 167.01 (3) | C35—C34—C33 | 120.3 (4) |
S2—Ni—P2 | 90.00 (3) | C35—C34—H34 | 119.9 |
P1—Ni—P2 | 103.02 (3) | C33—C34—H34 | 119.9 |
C26—P2—C38 | 103.50 (13) | C34—C33—C32 | 120.6 (3) |
C26—P2—C32 | 103.53 (14) | C34—C33—H33 | 119.7 |
C38—P2—C32 | 103.90 (12) | C32—C33—H33 | 119.7 |
C26—P2—Ni | 113.22 (9) | C39—C40—C41 | 120.6 (3) |
C38—P2—Ni | 122.64 (10) | C39—C40—H40 | 119.7 |
C32—P2—Ni | 108.16 (9) | C41—C40—H40 | 119.7 |
C1—S1—Ni | 88.66 (10) | C4—C3—C2 | 120.6 (4) |
C1—S2—Ni | 88.53 (10) | C4—C3—Cl1 | 117.2 (3) |
C14—P1—C8 | 103.64 (14) | C2—C3—Cl1 | 122.2 (3) |
C14—P1—C20 | 106.85 (13) | C28—C29—C30 | 119.6 (3) |
C8—P1—C20 | 102.70 (13) | C28—C29—H29 | 120.2 |
C14—P1—Ni | 114.43 (9) | C30—C29—H29 | 120.2 |
C8—P1—Ni | 113.12 (9) | C12—C13—C8 | 120.1 (3) |
C20—P1—Ni | 114.85 (10) | C12—C13—H13 | 120 |
O2—S3—O1 | 116.51 (15) | C8—C13—H13 | 120 |
O2—S3—N | 107.03 (15) | C11—C12—C13 | 120.9 (4) |
O1—S3—N | 113.89 (13) | C11—C12—H12 | 119.6 |
O2—S3—C2 | 108.00 (15) | C13—C12—H12 | 119.6 |
O1—S3—C2 | 106.50 (16) | C29—C28—C27 | 120.6 (3) |
N—S3—C2 | 104.08 (14) | C29—C28—H28 | 119.7 |
C1—N—S3 | 120.5 (2) | C27—C28—H28 | 119.7 |
C27—C26—C31 | 118.4 (3) | C30—C31—C26 | 120.4 (3) |
C27—C26—P2 | 119.2 (2) | C30—C31—H31 | 119.8 |
C31—C26—P2 | 122.2 (2) | C26—C31—H31 | 119.8 |
C36—C37—C32 | 120.0 (3) | C11—C10—C9 | 120.4 (3) |
C36—C37—H37 | 120 | C11—C10—H10 | 119.8 |
C32—C37—H37 | 120 | C9—C10—H10 | 119.8 |
C15—C14—C19 | 118.7 (3) | C23—C24—C25 | 119.9 (4) |
C15—C14—P1 | 119.1 (2) | C23—C24—H24 | 120 |
C19—C14—P1 | 122.2 (2) | C25—C24—H24 | 120 |
C26—C27—C28 | 120.4 (3) | C16—C17—C18 | 119.8 (4) |
C26—C27—H27 | 119.8 | C16—C17—H17 | 120.1 |
C28—C27—H27 | 119.8 | C18—C17—H17 | 120.1 |
N—C1—S2 | 121.8 (2) | C18—C19—C14 | 120.6 (3) |
N—C1—S1 | 132.6 (2) | C18—C19—H19 | 119.7 |
S2—C1—S1 | 105.68 (15) | C14—C19—H19 | 119.7 |
C14—C15—C16 | 119.8 (3) | C3—C4—C5 | 119.3 (4) |
C14—C15—H15 | 120.1 | C3—C4—H4 | 120.4 |
C16—C15—H15 | 120.1 | C5—C4—H4 | 120.4 |
C13—C8—C9 | 118.1 (3) | C7—C2—C3 | 119.4 (3) |
C13—C8—P1 | 121.4 (2) | C7—C2—S3 | 117.5 (3) |
C9—C8—P1 | 120.1 (2) | C3—C2—S3 | 123.1 (3) |
C37—C32—C33 | 118.7 (3) | C41—C42—C43 | 120.5 (3) |
C37—C32—P2 | 121.6 (2) | C41—C42—H42 | 119.7 |
C33—C32—P2 | 119.5 (2) | C43—C42—H42 | 119.7 |
C40—C39—C38 | 120.5 (3) | C29—C30—C31 | 120.6 (3) |
C40—C39—H39 | 119.8 | C29—C30—H30 | 119.7 |
C38—C39—H39 | 119.7 | C31—C30—H30 | 119.7 |
C43—C38—C39 | 118.5 (3) | C23—C22—C21 | 121.0 (4) |
C43—C38—P2 | 121.7 (2) | C23—C22—H22 | 119.5 |
C39—C38—P2 | 119.7 (2) | C21—C22—H22 | 119.5 |
C10—C9—C8 | 120.7 (3) | C17—C18—C19 | 120.3 (4) |
C10—C9—H9 | 119.6 | C17—C18—H18 | 119.9 |
C8—C9—H9 | 119.6 | C19—C18—H18 | 119.9 |
C20—C25—C24 | 120.3 (3) | C2—C7—C6 | 119.6 (4) |
C20—C25—H25 | 119.9 | C2—C7—H7 | 120.2 |
C24—C25—H25 | 119.9 | C6—C7—H7 | 120.2 |
C42—C43—C38 | 120.2 (3) | C17—C16—C15 | 120.8 (3) |
C42—C43—H43 | 119.9 | C17—C16—H16 | 119.6 |
C38—C43—H43 | 119.9 | C15—C16—H16 | 119.6 |
C42—C41—C40 | 119.6 (3) | C6—C5—C4 | 120.4 (4) |
C42—C41—H41 | 120.2 | C6—C5—H5 | 119.8 |
C40—C41—H41 | 120.2 | C4—C5—H5 | 119.8 |
C35—C36—C37 | 120.6 (3) | C5—C6—C7 | 120.6 (4) |
C35—C36—H36 | 119.7 | C5—C6—Cl2 | 120.1 (4) |
C37—C36—H36 | 119.7 | C7—C6—Cl2 | 119.2 (4) |
C25—C20—C21 | 118.6 (3) | C22—C23—C24 | 120.1 (4) |
C25—C20—P1 | 117.7 (2) | C22—C23—H23 | 119.9 |
C21—C20—P1 | 123.7 (2) | C24—C23—H23 | 119.9 |
C34—C35—C36 | 119.8 (3) | C10—C11—C12 | 119.8 (3) |
C34—C35—H35 | 120.1 | C10—C11—H11 | 120.1 |
C36—C35—H35 | 120.1 | C12—C11—H11 | 120.1 |
S1—Ni—P2—C26 | 78.94 (17) | C26—P2—C38—C39 | 48.7 (3) |
S2—Ni—P2—C26 | 85.25 (10) | C32—P2—C38—C39 | 156.6 (2) |
P1—Ni—P2—C26 | −94.30 (10) | Ni—P2—C38—C39 | −80.7 (3) |
S1—Ni—P2—C38 | −155.86 (16) | C13—C8—C9—C10 | −0.9 (4) |
S2—Ni—P2—C38 | −149.54 (12) | P1—C8—C9—C10 | −173.6 (2) |
P1—Ni—P2—C38 | 30.90 (12) | C39—C38—C43—C42 | −0.1 (5) |
S1—Ni—P2—C32 | −35.17 (19) | P2—C38—C43—C42 | −179.3 (3) |
S2—Ni—P2—C32 | −28.86 (11) | C32—C37—C36—C35 | −0.6 (5) |
P1—Ni—P2—C32 | 151.58 (10) | C24—C25—C20—C21 | 0.1 (4) |
S2—Ni—S1—C1 | −1.55 (9) | C24—C25—C20—P1 | −179.3 (2) |
P1—Ni—S1—C1 | 178.34 (9) | C14—P1—C20—C25 | 163.2 (2) |
P2—Ni—S1—C1 | 4.93 (18) | C8—P1—C20—C25 | −88.1 (2) |
S1—Ni—S2—C1 | 1.56 (10) | Ni—P1—C20—C25 | 35.1 (3) |
P1—Ni—S2—C1 | 1.09 (19) | C14—P1—C20—C21 | −16.1 (3) |
P2—Ni—S2—C1 | −176.99 (10) | C8—P1—C20—C21 | 92.6 (3) |
S1—Ni—P1—C14 | 103.14 (10) | Ni—P1—C20—C21 | −144.2 (2) |
S2—Ni—P1—C14 | 103.59 (18) | C37—C36—C35—C34 | 0.6 (5) |
P2—Ni—P1—C14 | −78.38 (10) | C25—C20—C21—C22 | −0.6 (5) |
S1—Ni—P1—C8 | −15.26 (11) | P1—C20—C21—C22 | 178.7 (3) |
S2—Ni—P1—C8 | −14.8 (2) | C36—C35—C34—C33 | 0.5 (5) |
P2—Ni—P1—C8 | 163.23 (11) | C35—C34—C33—C32 | −1.6 (4) |
S1—Ni—P1—C20 | −132.72 (10) | C37—C32—C33—C34 | 1.6 (4) |
S2—Ni—P1—C20 | −132.27 (17) | P2—C32—C33—C34 | 176.0 (2) |
P2—Ni—P1—C20 | 45.76 (11) | C38—C39—C40—C41 | 0.2 (5) |
O2—S3—N—C1 | −160.7 (2) | C42—C41—C40—C39 | −0.1 (6) |
O1—S3—N—C1 | −30.4 (3) | C9—C8—C13—C12 | −0.1 (5) |
C2—S3—N—C1 | 85.1 (3) | P1—C8—C13—C12 | 172.5 (3) |
C38—P2—C26—C27 | −159.0 (2) | C8—C13—C12—C11 | 0.9 (6) |
C32—P2—C26—C27 | 92.9 (2) | C30—C29—C28—C27 | 1.5 (5) |
Ni—P2—C26—C27 | −24.0 (3) | C26—C27—C28—C29 | −1.4 (5) |
C38—P2—C26—C31 | 26.1 (3) | C27—C26—C31—C30 | 0.8 (5) |
C32—P2—C26—C31 | −82.1 (3) | P2—C26—C31—C30 | 175.8 (3) |
Ni—P2—C26—C31 | 161.0 (2) | C8—C9—C10—C11 | 1.2 (5) |
C8—P1—C14—C15 | 146.1 (2) | C20—C25—C24—C23 | 0.4 (5) |
C20—P1—C14—C15 | −105.8 (2) | C15—C14—C19—C18 | 0.8 (5) |
Ni—P1—C14—C15 | 22.5 (3) | P1—C14—C19—C18 | −179.8 (3) |
C8—P1—C14—C19 | −33.3 (3) | C2—C3—C4—C5 | 2.5 (6) |
C20—P1—C14—C19 | 74.8 (3) | Cl1—C3—C4—C5 | −177.4 (3) |
Ni—P1—C14—C19 | −156.9 (2) | C4—C3—C2—C7 | −2.9 (5) |
C31—C26—C27—C28 | 0.2 (4) | Cl1—C3—C2—C7 | 176.9 (2) |
P2—C26—C27—C28 | −175.0 (2) | C4—C3—C2—S3 | 175.2 (3) |
S3—N—C1—S2 | −178.96 (15) | Cl1—C3—C2—S3 | −5.0 (4) |
S3—N—C1—S1 | 0.3 (4) | O2—S3—C2—C7 | 132.2 (3) |
Ni—S2—C1—N | 177.4 (2) | O1—S3—C2—C7 | 6.4 (3) |
Ni—S2—C1—S1 | −2.01 (12) | N—S3—C2—C7 | −114.3 (2) |
Ni—S1—C1—N | −177.3 (3) | O2—S3—C2—C3 | −45.9 (3) |
Ni—S1—C1—S2 | 2.02 (12) | O1—S3—C2—C3 | −171.8 (3) |
C19—C14—C15—C16 | −2.2 (5) | N—S3—C2—C3 | 67.6 (3) |
P1—C14—C15—C16 | 178.4 (2) | C40—C41—C42—C43 | −0.1 (6) |
C14—P1—C8—C13 | 143.4 (3) | C38—C43—C42—C41 | 0.2 (5) |
C20—P1—C8—C13 | 32.3 (3) | C28—C29—C30—C31 | −0.6 (5) |
Ni—P1—C8—C13 | −92.1 (2) | C26—C31—C30—C29 | −0.6 (5) |
C14—P1—C8—C9 | −44.1 (3) | C20—C21—C22—C23 | 0.7 (6) |
C20—P1—C8—C9 | −155.2 (2) | C16—C17—C18—C19 | −0.8 (6) |
Ni—P1—C8—C9 | 80.4 (2) | C14—C19—C18—C17 | 0.6 (6) |
C36—C37—C32—C33 | −0.5 (4) | C3—C2—C7—C6 | 1.3 (5) |
C36—C37—C32—P2 | −174.8 (2) | S3—C2—C7—C6 | −176.9 (3) |
C26—P2—C32—C37 | −0.5 (3) | C18—C17—C16—C15 | −0.6 (6) |
C38—P2—C32—C37 | −108.4 (2) | C14—C15—C16—C17 | 2.1 (5) |
Ni—P2—C32—C37 | 119.9 (2) | C3—C4—C5—C6 | −0.5 (6) |
C26—P2—C32—C33 | −174.7 (2) | C4—C5—C6—C7 | −1.1 (6) |
C38—P2—C32—C33 | 77.4 (2) | C4—C5—C6—Cl2 | 178.8 (3) |
Ni—P2—C32—C33 | −54.4 (2) | C2—C7—C6—C5 | 0.7 (6) |
C40—C39—C38—C43 | −0.1 (5) | C2—C7—C6—Cl2 | −179.3 (3) |
C40—C39—C38—P2 | 179.1 (3) | C21—C22—C23—C24 | −0.2 (6) |
C26—P2—C38—C43 | −132.1 (3) | C25—C24—C23—C22 | −0.3 (6) |
C32—P2—C38—C43 | −24.2 (3) | C9—C10—C11—C12 | −0.4 (6) |
Ni—P2—C38—C43 | 98.5 (2) | C13—C12—C11—C10 | −0.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C36—H36···S1i | 0.93 | 2.8 | 3.641 (3) | 151 |
C34—H34···O1ii | 0.93 | 2.57 | 3.194 (5) | 125 |
C41—H41···O2iii | 0.93 | 2.48 | 3.197 (4) | 134 |
Symmetry codes: (i) −x−1/2, y−1/2, z; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C7H3Cl2NO2S3)(C18H15P)2] |
Mr | 883.43 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 18.4654 (3), 15.2416 (2), 28.8619 (5) |
V (Å3) | 8123.0 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.20 × 0.18 × 0.03 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.844, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41274, 9277, 5597 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.124, 1.02 |
No. of reflections | 9277 |
No. of parameters | 487 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.38 |
Computer programs: COLLECT (Enraf–Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Ni—S1 | 2.2027 (8) | Ni—P1 | 2.2227 (8) |
Ni—S2 | 2.2147 (8) | Ni—P2 | 2.2564 (8) |
S1—Ni—S2 | 77.09 (3) | S2—Ni—P2 | 90.00 (3) |
S1—Ni—P1 | 89.89 (3) | P1—Ni—P2 | 103.02 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C36—H36···S1i | 0.93 | 2.8 | 3.641 (3) | 151 |
C34—H34···O1ii | 0.93 | 2.57 | 3.194 (5) | 125 |
C41—H41···O2iii | 0.93 | 2.48 | 3.197 (4) | 134 |
Symmetry codes: (i) −x−1/2, y−1/2, z; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2. |
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We became interested in the syntheses and characterization of nickel(II) complexes with dithiocarbimates and phosphines due to their similarities with the dithiocarbimate compounds, which have shown catalytic activity, especially for oligomerization of olefins (Cavell et al., 1998; Foulds et al., 1994). As only the nickel complexes with general formulae Ni(RSO2N?CS2)(PPh3)2 (R = 2-CH3C6H4, 4-CH3C6H4 and 4-BrC6H4) have had their structures determined by X-ray diffraction techniques (Oliveira et al., 2002), the title compound (I) was prepared.
As shown in Fig. 1, the structure of (I) is composed of neutral Ni(2,5-Cl2C6H3SO2NCS2)(Ph3P)2 complex molecules. The NiII atom is coordinated by two sulfur atoms from the dithiocarbimate anion and by two phosphorus atoms of the triphenylphosphine ligands into a distorted square-planar geometry. The small S—Ni—S angle is determined by the geometry of the chelate ligand, while the opposite P—Ni—P angle is rather large, probably due to the steric effect of the large triphenylphosphine ligands (Table 1). The two Ni—S bond lenghts are not significantly different, although the two Ni—P distances are. The C—S [1.732 (3) and 1.722 (3) Å] bond lengths of the NCS2 fragment are nearly equal and are much shorter than typical C—S single bonds [ca 1.81 Å]. The C1?N bond distance of 1.303 (3)Å is shorter than normal single Csp2—Nsp2 bond length [ca 1.35 Å] and similar to that of the double bond C?N [1.275–1.300 Å] (Allen et al., 1987; Orpen et al., 1989). This behavior indicates that the electron density is delocalized over the entire NCS2 moiety. Similar behavior is observed for related nickel complexes (Oliveira et al., 2002; Oliveira et al., 2003; Franca et al., 2006). The repulsive interaction cis between the SO2(2,5-Cl2C6H3) group and the S1 atom, which are in greater position in relation to the C1—N bond, is responsible for the difference between the angles S1—C1—N [132.6 (2)°] and S2—C1—N [121.8 (2)°].
The torsion angle C1—N—S3—C2 describing the conformation of the ligands along the N—S3 bond is 85.1 (3)°. The Car—Car bond lengths of the triphenylphosphine aromatic rings involved in the intermolecular interactions are shorter than typical values described in the literature[1.372–1.388 Å] (Allen et al., 1987).
In the crystal structure of (I), the molecules are linked through C—H···O and C—H···S interactions (Table 2 and Fig. 2).