Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705814X/ci2509sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705814X/ci2509Isup2.hkl |
CCDC reference: 672708
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.003 Å
- R factor = 0.025
- wR factor = 0.071
- Data-to-parameter ratio = 13.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Ni1 - S2 .. 11.08 su
Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 100 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 1000 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 6 PLAT230_ALERT_2_C Hirshfeld Test Diff for C2 - C4 .. 5.71 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - S1 .. 9.84 su PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C3 ... 1.42 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C4 ... 1.42 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 2.15
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title compound was prepared by the direct reaction of NiCl2.6H2O (0.24 g, 1 mmol), K2(imnt).H2O (0.48 g, 2 mmol) and (FBzPy)+Br- (0.54 g, 2 mmol) in H2O (50 ml). Brown crystals were obtained by slow evaporation of a CH3CN solution at room temperature over two weeks.
H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined using a riding model, with Uiso = 1.2 Ueq(parent atom).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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.
(C12H11FN)2[Ni(C4N2S2)2] | Z = 1 |
Mr = 715.51 | F(000) = 366 |
Triclinic, P1 | Dx = 1.537 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.085 (1) Å | Cell parameters from 3505 reflections |
b = 9.048 (1) Å | θ = 2.4–29.5° |
c = 13.182 (1) Å | µ = 0.94 mm−1 |
α = 71.68 (1)° | T = 291 K |
β = 74.93 (1)° | Block, brown |
γ = 82.11 (1)° | 0.30 × 0.25 × 0.20 mm |
V = 773.19 (15) Å3 |
Bruker SMART APEX CCD diffractometer | 2695 independent reflections |
Radiation source: fine-focus sealed tube | 2568 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.009 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→6 |
Tmin = 0.766, Tmax = 0.836 | k = −10→10 |
4185 measured reflections | l = −15→11 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.1686P] where P = (Fo2 + 2Fc2)/3 |
2695 reflections | (Δ/σ)max = 0.001 |
205 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
(C12H11FN)2[Ni(C4N2S2)2] | γ = 82.11 (1)° |
Mr = 715.51 | V = 773.19 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.085 (1) Å | Mo Kα radiation |
b = 9.048 (1) Å | µ = 0.94 mm−1 |
c = 13.182 (1) Å | T = 291 K |
α = 71.68 (1)° | 0.30 × 0.25 × 0.20 mm |
β = 74.93 (1)° |
Bruker SMART APEX CCD diffractometer | 2695 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2568 reflections with I > 2σ(I) |
Tmin = 0.766, Tmax = 0.836 | Rint = 0.009 |
4185 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.19 e Å−3 |
2695 reflections | Δρmin = −0.26 e Å−3 |
205 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 1.0000 | 0.0000 | 0.5000 | 0.03971 (11) | |
S1 | 0.87140 (6) | −0.02721 (5) | 0.67579 (3) | 0.04361 (12) | |
S2 | 0.86668 (7) | 0.23756 (5) | 0.49460 (3) | 0.04755 (13) | |
N1 | 0.7048 (3) | 0.1351 (2) | 0.91290 (14) | 0.0747 (5) | |
N2 | 0.6279 (3) | 0.54849 (19) | 0.63808 (14) | 0.0611 (4) | |
N3 | 0.33540 (19) | 0.96970 (15) | 0.76440 (11) | 0.0391 (3) | |
F1 | −0.34351 (17) | 0.52632 (13) | 0.90040 (10) | 0.0665 (3) | |
C1 | 0.8128 (2) | 0.17017 (19) | 0.63538 (12) | 0.0376 (3) | |
C2 | 0.7406 (2) | 0.25975 (19) | 0.70595 (13) | 0.0398 (3) | |
C3 | 0.7188 (3) | 0.1919 (2) | 0.82093 (14) | 0.0479 (4) | |
C4 | 0.6808 (2) | 0.4202 (2) | 0.66752 (13) | 0.0440 (4) | |
C5 | 0.1503 (3) | 0.64193 (18) | 0.78041 (13) | 0.0442 (4) | |
H5 | 0.2537 | 0.6311 | 0.7225 | 0.053* | |
C6 | −0.0245 (3) | 0.57681 (19) | 0.79671 (14) | 0.0472 (4) | |
H6 | −0.0406 | 0.5234 | 0.7500 | 0.057* | |
C7 | −0.1730 (3) | 0.59274 (19) | 0.88309 (14) | 0.0474 (4) | |
C8 | −0.1575 (3) | 0.6725 (2) | 0.95277 (14) | 0.0516 (4) | |
H8 | −0.2619 | 0.6824 | 1.0104 | 0.062* | |
C9 | 0.0174 (3) | 0.7379 (2) | 0.93532 (13) | 0.0486 (4) | |
H9 | 0.0310 | 0.7926 | 0.9818 | 0.058* | |
C10 | 0.1731 (2) | 0.72308 (17) | 0.84929 (12) | 0.0398 (3) | |
C11 | 0.3599 (3) | 0.8020 (2) | 0.82662 (15) | 0.0469 (4) | |
H11A | 0.3924 | 0.7936 | 0.8954 | 0.056* | |
H11B | 0.4663 | 0.7510 | 0.7843 | 0.056* | |
C12 | 0.2810 (3) | 1.0763 (2) | 0.81891 (15) | 0.0493 (4) | |
H12 | 0.2663 | 1.0465 | 0.8947 | 0.059* | |
C13 | 0.2468 (3) | 1.2291 (2) | 0.76345 (17) | 0.0586 (5) | |
H13 | 0.2076 | 1.3029 | 0.8017 | 0.070* | |
C14 | 0.2701 (3) | 1.2737 (2) | 0.65203 (17) | 0.0556 (5) | |
H14 | 0.2482 | 1.3777 | 0.6140 | 0.067* | |
C15 | 0.3260 (3) | 1.1639 (2) | 0.59723 (15) | 0.0551 (5) | |
H15 | 0.3426 | 1.1920 | 0.5214 | 0.066* | |
C16 | 0.3573 (3) | 1.0107 (2) | 0.65574 (14) | 0.0510 (4) | |
H16 | 0.3941 | 0.9349 | 0.6191 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.04242 (18) | 0.04293 (18) | 0.02804 (16) | 0.00353 (12) | −0.00639 (12) | −0.00631 (12) |
S1 | 0.0494 (2) | 0.0426 (2) | 0.0298 (2) | 0.00407 (17) | −0.00642 (16) | −0.00304 (16) |
S2 | 0.0599 (3) | 0.0461 (2) | 0.0271 (2) | 0.00719 (19) | −0.00731 (18) | −0.00378 (17) |
N1 | 0.1176 (16) | 0.0689 (11) | 0.0361 (9) | −0.0076 (11) | −0.0206 (9) | −0.0101 (8) |
N2 | 0.0720 (11) | 0.0493 (10) | 0.0542 (10) | 0.0051 (8) | −0.0146 (8) | −0.0078 (7) |
N3 | 0.0380 (7) | 0.0403 (7) | 0.0360 (7) | 0.0011 (5) | −0.0115 (5) | −0.0062 (6) |
F1 | 0.0581 (7) | 0.0592 (7) | 0.0736 (8) | −0.0097 (5) | −0.0123 (5) | −0.0073 (6) |
C1 | 0.0335 (7) | 0.0442 (8) | 0.0311 (8) | −0.0003 (6) | −0.0091 (6) | −0.0048 (6) |
C2 | 0.0410 (8) | 0.0451 (9) | 0.0301 (8) | 0.0003 (7) | −0.0100 (6) | −0.0062 (7) |
C3 | 0.0599 (10) | 0.0487 (9) | 0.0353 (9) | −0.0026 (8) | −0.0115 (8) | −0.0123 (7) |
C4 | 0.0454 (9) | 0.0506 (11) | 0.0350 (8) | −0.0019 (8) | −0.0084 (7) | −0.0120 (7) |
C5 | 0.0521 (9) | 0.0384 (8) | 0.0366 (8) | 0.0107 (7) | −0.0087 (7) | −0.0101 (7) |
C6 | 0.0591 (10) | 0.0372 (8) | 0.0454 (9) | 0.0052 (7) | −0.0166 (8) | −0.0119 (7) |
C7 | 0.0506 (9) | 0.0356 (8) | 0.0463 (10) | 0.0012 (7) | −0.0135 (8) | 0.0018 (7) |
C8 | 0.0563 (10) | 0.0501 (10) | 0.0354 (9) | 0.0035 (8) | 0.0000 (7) | −0.0058 (7) |
C9 | 0.0647 (11) | 0.0454 (9) | 0.0327 (8) | 0.0038 (8) | −0.0096 (7) | −0.0116 (7) |
C10 | 0.0494 (9) | 0.0317 (7) | 0.0328 (8) | 0.0068 (6) | −0.0136 (7) | −0.0022 (6) |
C11 | 0.0509 (10) | 0.0424 (9) | 0.0454 (9) | 0.0089 (7) | −0.0191 (8) | −0.0081 (7) |
C12 | 0.0597 (11) | 0.0470 (10) | 0.0401 (9) | −0.0018 (8) | −0.0135 (8) | −0.0103 (8) |
C13 | 0.0717 (13) | 0.0427 (10) | 0.0593 (12) | 0.0000 (9) | −0.0156 (10) | −0.0129 (9) |
C14 | 0.0527 (10) | 0.0438 (10) | 0.0616 (12) | −0.0072 (8) | −0.0185 (9) | 0.0031 (9) |
C15 | 0.0567 (11) | 0.0613 (11) | 0.0378 (9) | −0.0132 (9) | −0.0116 (8) | 0.0033 (8) |
C16 | 0.0557 (10) | 0.0561 (10) | 0.0381 (9) | −0.0030 (8) | −0.0068 (8) | −0.0128 (8) |
Ni1—S1i | 2.2058 (5) | C6—H6 | 0.93 |
Ni1—S1 | 2.2058 (4) | C7—C8 | 1.366 (3) |
Ni1—S2 | 2.2133 (5) | C8—C9 | 1.380 (3) |
Ni1—S2i | 2.2133 (5) | C8—H8 | 0.93 |
S1—C1 | 1.7201 (17) | C9—C10 | 1.387 (2) |
S2—C1 | 1.7163 (15) | C9—H9 | 0.93 |
N1—C3 | 1.142 (2) | C10—C11 | 1.507 (2) |
N2—C4 | 1.145 (2) | C11—H11A | 0.97 |
N3—C16 | 1.334 (2) | C11—H11B | 0.97 |
N3—C12 | 1.336 (2) | C12—C13 | 1.368 (3) |
N3—C11 | 1.491 (2) | C12—H12 | 0.93 |
F1—C7 | 1.357 (2) | C13—C14 | 1.366 (3) |
C1—C2 | 1.377 (2) | C13—H13 | 0.93 |
C2—C3 | 1.420 (2) | C14—C15 | 1.364 (3) |
C2—C4 | 1.423 (2) | C14—H14 | 0.93 |
C5—C6 | 1.382 (2) | C15—C16 | 1.378 (3) |
C5—C10 | 1.385 (2) | C15—H15 | 0.93 |
C5—H5 | 0.93 | C16—H16 | 0.93 |
C6—C7 | 1.365 (3) | ||
S1i—Ni1—S1 | 180 | C7—C8—H8 | 120.9 |
S1i—Ni1—S2 | 101.201 (18) | C9—C8—H8 | 120.9 |
S1—Ni1—S2 | 78.799 (19) | C8—C9—C10 | 120.87 (16) |
S1i—Ni1—S2i | 78.799 (18) | C8—C9—H9 | 119.6 |
S1—Ni1—S2i | 101.201 (18) | C10—C9—H9 | 119.6 |
S2—Ni1—S2i | 180 | C5—C10—C9 | 118.90 (16) |
C1—S1—Ni1 | 85.66 (5) | C5—C10—C11 | 120.24 (15) |
C1—S2—Ni1 | 85.51 (6) | C9—C10—C11 | 120.76 (15) |
C16—N3—C12 | 120.66 (15) | N3—C11—C10 | 109.83 (13) |
C16—N3—C11 | 119.73 (15) | N3—C11—H11A | 109.7 |
C12—N3—C11 | 119.50 (14) | C10—C11—H11A | 109.7 |
C2—C1—S2 | 125.81 (13) | N3—C11—H11B | 109.7 |
C2—C1—S1 | 124.73 (12) | C10—C11—H11B | 109.7 |
S2—C1—S1 | 109.42 (9) | H11A—C11—H11B | 108.2 |
C1—C2—C3 | 120.24 (15) | N3—C12—C13 | 120.07 (17) |
C1—C2—C4 | 121.83 (14) | N3—C12—H12 | 120.0 |
C3—C2—C4 | 117.91 (15) | C13—C12—H12 | 120.0 |
N1—C3—C2 | 178.5 (2) | C14—C13—C12 | 120.18 (19) |
N2—C4—C2 | 178.26 (19) | C14—C13—H13 | 119.9 |
C6—C5—C10 | 120.72 (16) | C12—C13—H13 | 119.9 |
C6—C5—H5 | 119.6 | C15—C14—C13 | 119.22 (17) |
C10—C5—H5 | 119.6 | C15—C14—H14 | 120.4 |
C7—C6—C5 | 118.37 (16) | C13—C14—H14 | 120.4 |
C7—C6—H6 | 120.8 | C14—C15—C16 | 119.12 (17) |
C5—C6—H6 | 120.8 | C14—C15—H15 | 120.4 |
F1—C7—C6 | 118.43 (17) | C16—C15—H15 | 120.4 |
F1—C7—C8 | 118.65 (16) | N3—C16—C15 | 120.75 (18) |
C6—C7—C8 | 122.93 (17) | N3—C16—H16 | 119.6 |
C7—C8—C9 | 118.20 (16) | C15—C16—H16 | 119.6 |
Symmetry code: (i) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N1ii | 0.93 | 2.59 | 3.471 (3) | 157 |
C15—H15···N2iii | 0.93 | 2.60 | 3.337 (3) | 136 |
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H11FN)2[Ni(C4N2S2)2] |
Mr | 715.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 7.085 (1), 9.048 (1), 13.182 (1) |
α, β, γ (°) | 71.68 (1), 74.93 (1), 82.11 (1) |
V (Å3) | 773.19 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.94 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.766, 0.836 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4185, 2695, 2568 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.071, 1.03 |
No. of reflections | 2695 |
No. of parameters | 205 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.26 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N1i | 0.93 | 2.59 | 3.471 (3) | 157 |
C15—H15···N2ii | 0.93 | 2.60 | 3.337 (3) | 136 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z+1. |
2,2-Dicyanoethene-1,1-dithiolate (imnt) or 1,2-dicyanoethene-1,2-dithiolate (mnt) transition metal complexes have attracted cosiderable interest in molecular materials research (Liu et al., 1996; Robertson & Cronin, 2002; Ni et al., 2007; Ren et al., 2002; Nishijo et al., 2003; Xie et al., 2002; Canadell, 1999). Our studies have been focused on the design, preparation, and investigation of some new salts that based on the molecular architecture of Ni(imnt)22- anions because the topology and the size of the counterions used with Ni(imnt)22- anion play an important role in tuning the stacks of anions and cations (Liu et al., 1996; Liu et al., 2006; Feng et al., 2007).
The asymmetric unit of the title compound consists of one [FBzPy]+ cation and one-half of Ni(imnt)2 anion located on an inversion center; the NiII ion lies on an inversion centre. The NiS4 core exhibits a square-planar configuration, with Ni—S distances of 2.2058 (5) and 2.2133 (5) Å. The S1—Ni1—S2 bond angle within the four-membered ring (Ni1/S1/C1/S2) is 78.80 (2)°. Atoms N1 and N2 of the –C≡N groups deviate from the Ni1/S1/C1/S2 plane by 0.607 (3) Å and 0.174 (3) Å, respectively. The [FBzPy]+ cation adopts a conformation where both the benzene and pyridinium rings are twisted with respect to the N3/C11/C10 reference plane with dihedral angles of 97.7 (2)° and 95.6 (3)°, respectively. The benzene and pyridinium rings make a dihedral angle of 77.2 (3)°. The F atom deviates from the benzene plane by 0.024 (3) Å.
In the crystal structure, C—H···N type hydrogen bonds (Table 1) and π-π interactions are observed between cations and anions. The π-π interaction is observed between ethenyl groups of the Ni(imnt)22- anion and the N3i/C12i—C16i [symmetry code: (i) x, -1 + y, z] ring of the cation, with the distance between atom C2 and the centroid of the ring being 3.492 (3) Å. The above interactions generate a three-dimensional network structure (Fig 2).