In the title compound, (C
16H
13N
2O
2)[Ni(C
3S
5)
2], the Ni
III ion exhibits a square-planar coordination geometry with four S atoms of the two 2-thioxo-1,3-dithiole-4,5-dithiolate (dmit) ligands. Intermolecular S
S and C—H
O interactions are observed.
Supporting information
CCDC reference: 618123
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.035
- wR factor = 0.075
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14 .. O2 .. 2.67 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 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
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.
Crystal data top
C16H13N2O2·C6NiS10 | F(000) = 1452 |
Mr = 716.65 | Dx = 1.776 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 836 reflections |
a = 14.746 (3) Å | θ = 2.6–25.8° |
b = 9.365 (2) Å | µ = 1.53 mm−1 |
c = 19.898 (4) Å | T = 293 K |
β = 102.692 (4)° | Block, black |
V = 2680.6 (10) Å3 | 0.3 × 0.2 × 0.1 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 4702 independent reflections |
Radiation source: fine-focus sealed tube | 3776 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
φ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan SADABS (Bruker, 2000) | h = −13→17 |
Tmin = 0.70, Tmax = 0.85 | k = −11→10 |
12871 measured reflections | l = −23→23 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0331P)2] where P = (Fo2 + 2Fc2)/3 |
4702 reflections | (Δ/σ)max = 0.009 |
334 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.21 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 | 0.89224 (2) | 0.86912 (4) | 0.016059 (16) | 0.03719 (11) | |
C1 | 1.02216 (19) | 0.7508 (3) | −0.21410 (13) | 0.0439 (7) | |
C2 | 0.98426 (18) | 0.7477 (3) | −0.09256 (13) | 0.0396 (7) | |
C3 | 0.93788 (19) | 0.8618 (3) | −0.12399 (13) | 0.0390 (7) | |
C4 | 0.85388 (18) | 0.8765 (3) | 0.15854 (13) | 0.0382 (7) | |
C5 | 0.80575 (18) | 0.9894 (3) | 0.12799 (13) | 0.0377 (7) | |
C6 | 0.78159 (19) | 0.9895 (3) | 0.25383 (13) | 0.0438 (7) | |
C7 | 0.1557 (2) | 0.5199 (3) | 0.26195 (15) | 0.0484 (8) | |
C8 | 0.2021 (2) | 0.4118 (3) | 0.23786 (16) | 0.0549 (8) | |
H8 | 0.2193 | 0.3300 | 0.2641 | 0.066* | |
C9 | 0.2230 (2) | 0.4263 (3) | 0.17417 (16) | 0.0538 (8) | |
H9 | 0.2543 | 0.3531 | 0.1571 | 0.065* | |
C10 | 0.19828 (19) | 0.5477 (3) | 0.13514 (14) | 0.0451 (7) | |
C11 | 0.1500 (2) | 0.6530 (3) | 0.16037 (16) | 0.0528 (8) | |
H11 | 0.1319 | 0.7345 | 0.1341 | 0.063* | |
C12 | 0.1279 (2) | 0.6400 (3) | 0.22410 (16) | 0.0539 (8) | |
H12 | 0.0949 | 0.7114 | 0.2408 | 0.065* | |
C13 | 0.2198 (2) | 0.5675 (4) | 0.06501 (15) | 0.0588 (9) | |
H13A | 0.1692 | 0.5284 | 0.0303 | 0.071* | |
H13B | 0.2239 | 0.6688 | 0.0559 | 0.071* | |
C14 | 0.3875 (2) | 0.5420 (3) | 0.10218 (14) | 0.0475 (8) | |
H14 | 0.3855 | 0.6165 | 0.1327 | 0.057* | |
C15 | 0.4698 (2) | 0.4803 (3) | 0.10118 (13) | 0.0478 (8) | |
H15 | 0.5236 | 0.5112 | 0.1313 | 0.057* | |
C16 | 0.4741 (2) | 0.3690 (3) | 0.05444 (13) | 0.0421 (7) | |
C17 | 0.5577 (2) | 0.2994 (3) | 0.05059 (15) | 0.0530 (8) | |
H17 | 0.6132 | 0.3239 | 0.0806 | 0.064* | |
C18 | 0.5559 (2) | 0.1961 (4) | 0.00241 (16) | 0.0577 (9) | |
H18 | 0.6110 | 0.1505 | −0.0002 | 0.069* | |
C19 | 0.4739 (3) | 0.1564 (3) | −0.04312 (16) | 0.0589 (9) | |
H19 | 0.4752 | 0.0849 | −0.0754 | 0.071* | |
C20 | 0.3927 (2) | 0.2205 (3) | −0.04092 (15) | 0.0565 (9) | |
H20 | 0.3383 | 0.1946 | −0.0718 | 0.068* | |
C21 | 0.3915 (2) | 0.3275 (3) | 0.00885 (13) | 0.0423 (7) | |
C22 | 0.3089 (2) | 0.3953 (3) | 0.01378 (14) | 0.0502 (8) | |
H22 | 0.2536 | 0.3679 | −0.0157 | 0.060* | |
N1 | 0.1356 (2) | 0.5065 (4) | 0.33093 (15) | 0.0650 (8) | |
N2 | 0.30738 (16) | 0.4977 (3) | 0.05940 (11) | 0.0453 (6) | |
O1 | 0.1020 (2) | 0.6075 (3) | 0.35390 (14) | 0.1062 (10) | |
O2 | 0.15538 (17) | 0.3932 (3) | 0.36147 (12) | 0.0778 (8) | |
S1 | 1.05997 (6) | 0.71800 (11) | −0.28352 (4) | 0.0615 (3) | |
S2 | 1.04863 (6) | 0.64941 (9) | −0.13973 (4) | 0.0513 (2) | |
S3 | 0.95028 (6) | 0.89433 (9) | −0.20749 (4) | 0.0497 (2) | |
S4 | 0.97974 (5) | 0.70327 (8) | −0.00984 (3) | 0.0468 (2) | |
S5 | 0.87028 (6) | 0.96589 (8) | −0.08426 (4) | 0.0490 (2) | |
S6 | 0.91507 (5) | 0.76800 (8) | 0.11517 (4) | 0.0485 (2) | |
S7 | 0.80574 (5) | 1.03432 (8) | 0.04431 (4) | 0.0472 (2) | |
S8 | 0.85283 (6) | 0.84904 (9) | 0.24436 (4) | 0.0491 (2) | |
S9 | 0.74494 (6) | 1.08580 (9) | 0.17848 (4) | 0.0533 (2) | |
S10 | 0.75134 (6) | 1.02382 (10) | 0.32650 (4) | 0.0607 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0409 (2) | 0.0376 (2) | 0.0351 (2) | 0.00272 (16) | 0.01260 (16) | 0.00257 (16) |
C1 | 0.0411 (17) | 0.0536 (19) | 0.0375 (16) | −0.0038 (14) | 0.0094 (13) | −0.0040 (14) |
C2 | 0.0385 (16) | 0.0446 (18) | 0.0379 (15) | 0.0008 (14) | 0.0133 (13) | −0.0045 (13) |
C3 | 0.0412 (17) | 0.0424 (18) | 0.0349 (15) | −0.0035 (13) | 0.0117 (13) | −0.0001 (13) |
C4 | 0.0431 (17) | 0.0422 (18) | 0.0310 (14) | −0.0006 (14) | 0.0118 (13) | −0.0004 (13) |
C5 | 0.0359 (16) | 0.0446 (18) | 0.0346 (15) | 0.0015 (13) | 0.0123 (13) | −0.0023 (13) |
C6 | 0.0427 (17) | 0.0507 (19) | 0.0392 (16) | −0.0060 (14) | 0.0112 (13) | −0.0022 (14) |
C7 | 0.0403 (18) | 0.054 (2) | 0.0503 (18) | −0.0071 (15) | 0.0094 (15) | 0.0016 (16) |
C8 | 0.054 (2) | 0.049 (2) | 0.063 (2) | 0.0035 (16) | 0.0165 (17) | 0.0162 (16) |
C9 | 0.054 (2) | 0.046 (2) | 0.066 (2) | 0.0077 (15) | 0.0221 (17) | 0.0046 (16) |
C10 | 0.0360 (17) | 0.0478 (19) | 0.0501 (18) | −0.0017 (14) | 0.0068 (14) | 0.0073 (15) |
C11 | 0.0500 (19) | 0.0426 (19) | 0.063 (2) | 0.0055 (15) | 0.0063 (16) | 0.0099 (16) |
C12 | 0.050 (2) | 0.050 (2) | 0.063 (2) | 0.0020 (15) | 0.0132 (16) | −0.0088 (17) |
C13 | 0.050 (2) | 0.069 (2) | 0.057 (2) | 0.0093 (17) | 0.0109 (16) | 0.0138 (17) |
C14 | 0.053 (2) | 0.049 (2) | 0.0391 (17) | −0.0037 (16) | 0.0076 (15) | 0.0005 (14) |
C15 | 0.0484 (19) | 0.056 (2) | 0.0351 (16) | −0.0087 (16) | 0.0010 (14) | 0.0061 (15) |
C16 | 0.0485 (18) | 0.0440 (18) | 0.0334 (15) | −0.0045 (15) | 0.0081 (14) | 0.0111 (13) |
C17 | 0.054 (2) | 0.056 (2) | 0.0474 (19) | 0.0007 (17) | 0.0088 (16) | 0.0136 (16) |
C18 | 0.067 (2) | 0.057 (2) | 0.053 (2) | 0.0134 (18) | 0.0201 (18) | 0.0150 (17) |
C19 | 0.086 (3) | 0.048 (2) | 0.0466 (19) | 0.0003 (19) | 0.0222 (19) | 0.0058 (15) |
C20 | 0.070 (2) | 0.055 (2) | 0.0438 (18) | −0.0141 (18) | 0.0101 (17) | 0.0022 (16) |
C21 | 0.0495 (19) | 0.0418 (18) | 0.0353 (16) | −0.0073 (14) | 0.0088 (14) | 0.0064 (13) |
C22 | 0.050 (2) | 0.059 (2) | 0.0391 (17) | −0.0130 (16) | 0.0040 (14) | 0.0046 (15) |
N1 | 0.0557 (19) | 0.082 (3) | 0.0582 (19) | −0.0141 (17) | 0.0150 (15) | 0.0003 (18) |
N2 | 0.0410 (15) | 0.0543 (17) | 0.0389 (14) | −0.0020 (12) | 0.0053 (12) | 0.0048 (12) |
O1 | 0.136 (3) | 0.117 (3) | 0.0791 (19) | 0.019 (2) | 0.0519 (19) | −0.0123 (18) |
O2 | 0.0753 (18) | 0.096 (2) | 0.0636 (16) | −0.0217 (15) | 0.0188 (13) | 0.0156 (15) |
S1 | 0.0637 (6) | 0.0855 (7) | 0.0388 (4) | 0.0061 (5) | 0.0189 (4) | −0.0048 (4) |
S2 | 0.0582 (5) | 0.0574 (5) | 0.0409 (4) | 0.0149 (4) | 0.0164 (4) | 0.0001 (4) |
S3 | 0.0621 (5) | 0.0520 (5) | 0.0376 (4) | 0.0038 (4) | 0.0168 (4) | 0.0063 (3) |
S4 | 0.0579 (5) | 0.0470 (5) | 0.0379 (4) | 0.0148 (4) | 0.0160 (4) | 0.0062 (3) |
S5 | 0.0613 (5) | 0.0469 (5) | 0.0426 (4) | 0.0160 (4) | 0.0193 (4) | 0.0098 (4) |
S6 | 0.0590 (5) | 0.0488 (5) | 0.0416 (4) | 0.0159 (4) | 0.0194 (4) | 0.0102 (4) |
S7 | 0.0566 (5) | 0.0496 (5) | 0.0383 (4) | 0.0151 (4) | 0.0170 (4) | 0.0072 (3) |
S8 | 0.0644 (5) | 0.0498 (5) | 0.0359 (4) | 0.0058 (4) | 0.0169 (4) | 0.0056 (3) |
S9 | 0.0618 (5) | 0.0617 (6) | 0.0392 (4) | 0.0195 (4) | 0.0172 (4) | 0.0009 (4) |
S10 | 0.0756 (6) | 0.0718 (6) | 0.0405 (4) | 0.0082 (5) | 0.0253 (4) | −0.0018 (4) |
Geometric parameters (Å, º) top
Ni1—S4 | 2.1529 (9) | C10—C13 | 1.509 (4) |
Ni1—S5 | 2.1509 (9) | C11—C12 | 1.383 (4) |
Ni1—S6 | 2.1466 (8) | C11—H11 | 0.930 |
Ni1—S7 | 2.1567 (9) | C12—H12 | 0.930 |
C1—S1 | 1.628 (3) | C13—N2 | 1.474 (4) |
C1—S2 | 1.729 (3) | C13—H13A | 0.970 |
C1—S3 | 1.735 (3) | C13—H13B | 0.970 |
C2—C3 | 1.347 (4) | C14—C15 | 1.347 (4) |
C2—S4 | 1.713 (3) | C14—N2 | 1.361 (3) |
C2—S2 | 1.738 (3) | C14—H14 | 0.930 |
C3—S5 | 1.707 (3) | C15—C16 | 1.408 (4) |
C3—S3 | 1.738 (3) | C15—H15 | 0.930 |
C4—C5 | 1.342 (4) | C16—C21 | 1.404 (4) |
C4—S6 | 1.713 (3) | C16—C17 | 1.411 (4) |
C4—S8 | 1.730 (3) | C17—C18 | 1.358 (4) |
C5—S7 | 1.717 (3) | C17—H17 | 0.930 |
C5—S9 | 1.739 (3) | C18—C19 | 1.392 (4) |
C6—S10 | 1.636 (3) | C18—H18 | 0.930 |
C6—S8 | 1.719 (3) | C19—C20 | 1.349 (4) |
C6—S9 | 1.731 (3) | C19—H19 | 0.930 |
C7—C12 | 1.366 (4) | C20—C21 | 1.412 (4) |
C7—C8 | 1.367 (4) | C20—H20 | 0.930 |
C7—N1 | 1.472 (4) | C21—C22 | 1.395 (4) |
C8—C9 | 1.375 (4) | C22—N2 | 1.324 (4) |
C8—H8 | 0.930 | C22—H22 | 0.930 |
C9—C10 | 1.380 (4) | N1—O1 | 1.203 (4) |
C9—H9 | 0.930 | N1—O2 | 1.225 (4) |
C10—C11 | 1.374 (4) | | |
| | | |
S4—Ni1—S5 | 93.31 (3) | N2—C13—H13B | 109.1 |
S4—Ni1—S6 | 85.44 (3) | C10—C13—H13B | 109.1 |
S4—Ni1—S7 | 178.78 (3) | H13A—C13—H13B | 107.9 |
S5—Ni1—S6 | 178.66 (3) | C15—C14—N2 | 121.4 (3) |
S5—Ni1—S7 | 87.86 (3) | C15—C14—H14 | 119.3 |
S6—Ni1—S7 | 93.40 (3) | N2—C14—H14 | 119.3 |
S1—C1—S2 | 124.58 (18) | C14—C15—C16 | 120.0 (3) |
S1—C1—S3 | 122.63 (17) | C14—C15—H15 | 120.0 |
S2—C1—S3 | 112.79 (14) | C16—C15—H15 | 120.0 |
C3—C2—S4 | 121.1 (2) | C21—C16—C15 | 118.2 (3) |
C3—C2—S2 | 116.8 (2) | C21—C16—C17 | 118.8 (3) |
S4—C2—S2 | 122.11 (17) | C15—C16—C17 | 123.0 (3) |
C2—C3—S5 | 121.8 (2) | C18—C17—C16 | 119.0 (3) |
C2—C3—S3 | 115.7 (2) | C18—C17—H17 | 120.5 |
S5—C3—S3 | 122.52 (17) | C16—C17—H17 | 120.5 |
C5—C4—S6 | 121.6 (2) | C17—C18—C19 | 122.0 (3) |
C5—C4—S8 | 116.5 (2) | C17—C18—H18 | 119.0 |
S6—C4—S8 | 121.93 (16) | C19—C18—H18 | 119.0 |
C4—C5—S7 | 121.3 (2) | C20—C19—C18 | 120.6 (3) |
C4—C5—S9 | 115.8 (2) | C20—C19—H19 | 119.7 |
S7—C5—S9 | 122.88 (16) | C18—C19—H19 | 119.7 |
S10—C6—S8 | 122.61 (17) | C19—C20—C21 | 119.2 (3) |
S10—C6—S9 | 124.70 (18) | C19—C20—H20 | 120.4 |
S8—C6—S9 | 112.68 (15) | C21—C20—H20 | 120.4 |
C12—C7—C8 | 122.0 (3) | C22—C21—C16 | 118.4 (3) |
C12—C7—N1 | 119.2 (3) | C22—C21—C20 | 121.2 (3) |
C8—C7—N1 | 118.9 (3) | C16—C21—C20 | 120.4 (3) |
C7—C8—C9 | 118.8 (3) | N2—C22—C21 | 121.6 (3) |
C7—C8—H8 | 120.6 | N2—C22—H22 | 119.2 |
C9—C8—H8 | 120.6 | C21—C22—H22 | 119.2 |
C8—C9—C10 | 121.0 (3) | O1—N1—O2 | 124.4 (3) |
C8—C9—H9 | 119.5 | O1—N1—C7 | 118.1 (3) |
C10—C9—H9 | 119.5 | O2—N1—C7 | 117.5 (3) |
C11—C10—C9 | 118.7 (3) | C22—N2—C14 | 120.4 (3) |
C11—C10—C13 | 118.7 (3) | C22—N2—C13 | 121.4 (3) |
C9—C10—C13 | 122.6 (3) | C14—N2—C13 | 118.2 (3) |
C10—C11—C12 | 121.2 (3) | C1—S2—C2 | 97.13 (14) |
C10—C11—H11 | 119.4 | C1—S3—C3 | 97.54 (13) |
C12—C11—H11 | 119.4 | C2—S4—Ni1 | 101.93 (10) |
C7—C12—C11 | 118.4 (3) | C3—S5—Ni1 | 101.84 (10) |
C7—C12—H12 | 120.8 | C4—S6—Ni1 | 101.97 (9) |
C11—C12—H12 | 120.8 | C5—S7—Ni1 | 101.71 (10) |
N2—C13—C10 | 112.4 (2) | C6—S8—C4 | 97.62 (13) |
N2—C13—H13A | 109.1 | C6—S9—C5 | 97.33 (13) |
C10—C13—H13A | 109.1 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O2i | 0.93 | 2.67 | 3.456 (4) | 143 |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |