Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056620/ci2505sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056620/ci2505Isup2.hkl |
CCDC reference: 672650
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.009 Å
- R factor = 0.055
- wR factor = 0.117
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.49 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.42 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (3) 2.82
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 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 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, 1.0 mmol), disodium maleonitriledithiolate (0.37 g, 2.0 mmol) and 1-(3,5-dibromobenzyl)pyridinium bromide (0.85 g, 2.1 mmol) in water (50 ml). Red block-shaped single crystals were obtained by slow evaporation of a CH3CN-i-PrOH (1:1) solution at room temperature over three weeks.
All H atoms were placed in geometrically calculated positions (C—H = 0.93–0.97 Å) and treated as riding, with Uiso = 1.2 Ueq(parent atom).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
(C12H10Br2N)2[Ni(C4N2S2)2] | Z = 1 |
Mr = 995.13 | F(000) = 486 |
Triclinic, P1 | Dx = 1.913 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.843 (3) Å | Cell parameters from 904 reflections |
b = 9.415 (3) Å | θ = 2.7–27.9° |
c = 10.861 (4) Å | µ = 5.46 mm−1 |
α = 77.701 (5)° | T = 291 K |
β = 78.427 (6)° | Block, red |
γ = 84.221 (5)° | 0.35 × 0.30 × 0.21 mm |
V = 864.0 (5) Å3 |
Bruker SMART APEX CCD diffractometer | 3309 independent reflections |
Radiation source: fine-focus sealed tube | 2482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −5→10 |
Tmin = 0.165, Tmax = 0.323 | k = −11→11 |
4584 measured reflections | l = −13→13 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.99P] where P = (Fo2 + 2Fc2)/3 |
3309 reflections | (Δ/σ)max = 0.001 |
214 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.96 e Å−3 |
(C12H10Br2N)2[Ni(C4N2S2)2] | γ = 84.221 (5)° |
Mr = 995.13 | V = 864.0 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.843 (3) Å | Mo Kα radiation |
b = 9.415 (3) Å | µ = 5.46 mm−1 |
c = 10.861 (4) Å | T = 291 K |
α = 77.701 (5)° | 0.35 × 0.30 × 0.21 mm |
β = 78.427 (6)° |
Bruker SMART APEX CCD diffractometer | 3309 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2482 reflections with I > 2σ(I) |
Tmin = 0.165, Tmax = 0.323 | Rint = 0.033 |
4584 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.59 e Å−3 |
3309 reflections | Δρmin = −0.96 e Å−3 |
214 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.36658 (7) | 0.41523 (7) | 0.40770 (6) | 0.03356 (18) | |
Br2 | 0.95637 (7) | 0.72824 (8) | 0.73580 (6) | 0.04073 (19) | |
C1 | 0.4467 (7) | 0.8563 (6) | 0.7832 (6) | 0.0340 (13) | |
C2 | 0.3762 (8) | 0.7687 (7) | 0.9091 (6) | 0.0384 (15) | |
C3 | 0.4290 (7) | 1.0569 (7) | 0.2308 (6) | 0.0323 (13) | |
C4 | 0.3562 (7) | 1.0604 (7) | 0.1245 (6) | 0.0349 (13) | |
C5 | 1.0417 (7) | 0.7617 (7) | 0.3449 (6) | 0.0317 (13) | |
C6 | 1.1611 (7) | 0.6488 (6) | 0.3263 (5) | 0.0298 (12) | |
H6 | 1.2019 | 0.6303 | 0.2450 | 0.036* | |
C7 | 1.2118 (7) | 0.5708 (7) | 0.4307 (6) | 0.0397 (15) | |
C8 | 1.1544 (7) | 0.5909 (7) | 0.5510 (5) | 0.0340 (13) | |
H8 | 1.1890 | 0.5320 | 0.6214 | 0.041* | |
C9 | 1.0407 (7) | 0.7037 (7) | 0.5658 (6) | 0.0339 (13) | |
C10 | 0.9816 (7) | 0.7898 (7) | 0.4667 (6) | 0.0358 (14) | |
H10 | 0.9052 | 0.8634 | 0.4797 | 0.043* | |
C11 | 0.9801 (7) | 0.8528 (6) | 0.2317 (5) | 0.0330 (13) | |
H11A | 1.0644 | 0.8774 | 0.1600 | 0.040* | |
H11B | 0.9290 | 0.9426 | 0.2536 | 0.040* | |
C12 | 0.9136 (8) | 0.6867 (7) | 0.1004 (6) | 0.0404 (15) | |
H12 | 1.0134 | 0.6912 | 0.0526 | 0.048* | |
C13 | 0.8089 (7) | 0.6021 (7) | 0.0802 (6) | 0.0362 (14) | |
H13 | 0.8414 | 0.5365 | 0.0258 | 0.043* | |
C14 | 0.6588 (7) | 0.6107 (6) | 0.1371 (6) | 0.0335 (13) | |
H14 | 0.5880 | 0.5571 | 0.1165 | 0.040* | |
C15 | 0.6095 (7) | 0.7000 (7) | 0.2271 (6) | 0.0361 (14) | |
H15 | 0.5077 | 0.7051 | 0.2702 | 0.043* | |
C16 | 0.7215 (7) | 0.7806 (6) | 0.2484 (6) | 0.0356 (14) | |
H16 | 0.6931 | 0.8472 | 0.3023 | 0.043* | |
N1 | 0.3176 (7) | 0.7000 (6) | 0.9957 (5) | 0.0456 (14) | |
N2 | 0.2845 (6) | 1.0553 (6) | 0.0475 (5) | 0.0373 (12) | |
N3 | 0.8642 (6) | 0.7645 (6) | 0.1946 (4) | 0.0350 (12) | |
Ni1 | 0.5000 | 1.0000 | 0.5000 | 0.0337 (3) | |
S1 | 0.34573 (18) | 0.87197 (16) | 0.65724 (15) | 0.0358 (4) | |
S2 | 0.35180 (18) | 0.96071 (17) | 0.37648 (15) | 0.0367 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0360 (3) | 0.0317 (3) | 0.0297 (3) | 0.0000 (2) | 0.0024 (2) | −0.0077 (2) |
Br2 | 0.0298 (3) | 0.0566 (4) | 0.0336 (3) | −0.0010 (3) | 0.0058 (2) | −0.0158 (3) |
C1 | 0.037 (3) | 0.023 (3) | 0.043 (3) | −0.008 (2) | −0.010 (3) | −0.004 (2) |
C2 | 0.038 (3) | 0.030 (3) | 0.040 (3) | −0.008 (3) | 0.010 (3) | −0.005 (3) |
C3 | 0.029 (3) | 0.033 (3) | 0.035 (3) | −0.013 (3) | 0.001 (2) | −0.010 (2) |
C4 | 0.031 (3) | 0.029 (3) | 0.046 (3) | −0.007 (2) | −0.003 (3) | −0.013 (3) |
C5 | 0.026 (3) | 0.037 (3) | 0.034 (3) | −0.007 (2) | 0.005 (2) | −0.019 (3) |
C6 | 0.030 (3) | 0.028 (3) | 0.027 (3) | −0.010 (2) | 0.005 (2) | −0.001 (2) |
C7 | 0.028 (3) | 0.043 (4) | 0.048 (4) | −0.011 (3) | −0.001 (3) | −0.012 (3) |
C8 | 0.035 (3) | 0.037 (3) | 0.026 (3) | −0.018 (3) | 0.005 (2) | 0.000 (2) |
C9 | 0.037 (3) | 0.035 (3) | 0.031 (3) | −0.007 (3) | −0.008 (3) | −0.006 (2) |
C10 | 0.033 (3) | 0.031 (3) | 0.040 (3) | −0.001 (3) | 0.001 (3) | −0.007 (3) |
C11 | 0.036 (3) | 0.028 (3) | 0.029 (3) | 0.002 (3) | 0.000 (2) | 0.000 (2) |
C12 | 0.049 (4) | 0.041 (3) | 0.029 (3) | 0.003 (3) | −0.018 (3) | 0.006 (3) |
C13 | 0.033 (3) | 0.044 (4) | 0.029 (3) | 0.010 (3) | −0.012 (3) | −0.002 (3) |
C14 | 0.034 (3) | 0.024 (3) | 0.047 (3) | −0.004 (2) | −0.022 (3) | −0.001 (3) |
C15 | 0.032 (3) | 0.035 (3) | 0.038 (3) | −0.005 (3) | 0.003 (3) | −0.006 (3) |
C16 | 0.035 (3) | 0.028 (3) | 0.038 (3) | 0.007 (3) | 0.000 (3) | −0.002 (3) |
N1 | 0.044 (3) | 0.045 (3) | 0.042 (3) | −0.026 (3) | −0.003 (3) | 0.010 (3) |
N2 | 0.036 (3) | 0.039 (3) | 0.031 (3) | −0.007 (2) | −0.006 (2) | 0.009 (2) |
N3 | 0.032 (3) | 0.034 (3) | 0.031 (3) | 0.023 (2) | −0.006 (2) | 0.000 (2) |
Ni1 | 0.0298 (6) | 0.0282 (5) | 0.0365 (6) | 0.0150 (4) | −0.0035 (4) | −0.0020 (4) |
S1 | 0.0322 (8) | 0.0298 (7) | 0.0382 (8) | 0.0141 (6) | −0.0039 (6) | −0.0009 (6) |
S2 | 0.0331 (8) | 0.0325 (8) | 0.0396 (8) | −0.0079 (6) | 0.0034 (6) | −0.0026 (6) |
Br1—C7 | 1.923 (7) | C10—H10 | 0.93 |
Br2—C9 | 1.901 (6) | C11—N3 | 1.543 (9) |
C1—C3i | 1.400 (8) | C11—H11A | 0.97 |
C1—C2 | 1.490 (8) | C11—H11B | 0.97 |
C1—S1 | 1.751 (7) | C12—C13 | 1.359 (10) |
C2—N1 | 1.088 (8) | C12—N3 | 1.360 (8) |
C3—C1i | 1.400 (8) | C12—H12 | 0.93 |
C3—C4 | 1.424 (9) | C13—C14 | 1.349 (9) |
C3—S2 | 1.694 (6) | C13—H13 | 0.93 |
C4—N2 | 1.158 (8) | C14—C15 | 1.400 (9) |
C5—C10 | 1.393 (8) | C14—H14 | 0.93 |
C5—C6 | 1.437 (8) | C15—C16 | 1.388 (9) |
C5—C11 | 1.507 (9) | C15—H15 | 0.93 |
C6—C7 | 1.344 (9) | C16—N3 | 1.288 (7) |
C6—H6 | 0.93 | C16—H16 | 0.93 |
C7—C8 | 1.350 (9) | Ni1—S2i | 2.1607 (18) |
C8—C9 | 1.399 (9) | Ni1—S2 | 2.1607 (18) |
C8—H8 | 0.93 | Ni1—S1i | 2.1795 (16) |
C9—C10 | 1.363 (9) | Ni1—S1 | 2.1795 (16) |
C3i—C1—C2 | 122.6 (6) | C5—C11—H11B | 110.0 |
C3i—C1—S1 | 120.0 (5) | N3—C11—H11B | 110.0 |
C2—C1—S1 | 116.4 (5) | H11A—C11—H11B | 108.4 |
N1—C2—C1 | 174.1 (8) | C13—C12—N3 | 116.2 (6) |
C1i—C3—C4 | 119.8 (5) | C13—C12—H12 | 121.9 |
C1i—C3—S2 | 120.8 (5) | N3—C12—H12 | 121.9 |
C4—C3—S2 | 119.1 (4) | C14—C13—C12 | 121.7 (6) |
N2—C4—C3 | 172.6 (6) | C14—C13—H13 | 119.2 |
C10—C5—C6 | 121.1 (6) | C12—C13—H13 | 119.2 |
C10—C5—C11 | 118.8 (5) | C13—C14—C15 | 120.1 (6) |
C6—C5—C11 | 120.1 (5) | C13—C14—H14 | 119.9 |
C7—C6—C5 | 117.6 (5) | C15—C14—H14 | 119.9 |
C7—C6—H6 | 121.2 | C16—C15—C14 | 116.2 (6) |
C5—C6—H6 | 121.2 | C16—C15—H15 | 121.9 |
C6—C7—C8 | 123.6 (6) | C14—C15—H15 | 121.9 |
C6—C7—Br1 | 118.0 (5) | N3—C16—C15 | 121.0 (6) |
C8—C7—Br1 | 118.3 (5) | N3—C16—H16 | 119.5 |
C7—C8—C9 | 117.5 (6) | C15—C16—H16 | 119.5 |
C7—C8—H8 | 121.3 | C16—N3—C12 | 123.8 (6) |
C9—C8—H8 | 121.3 | C16—N3—C11 | 116.5 (5) |
C10—C9—C8 | 123.8 (6) | C12—N3—C11 | 119.4 (5) |
C10—C9—Br2 | 118.9 (5) | S2i—Ni1—S2 | 180 |
C8—C9—Br2 | 117.3 (4) | S2i—Ni1—S1i | 86.58 (6) |
C9—C10—C5 | 116.4 (6) | S2—Ni1—S1i | 93.42 (6) |
C9—C10—H10 | 121.8 | S2i—Ni1—S1 | 93.42 (6) |
C5—C10—H10 | 121.8 | S2—Ni1—S1 | 86.58 (6) |
C5—C11—N3 | 108.5 (5) | S1i—Ni1—S1 | 180 |
C5—C11—H11A | 110.0 | C1—S1—Ni1 | 101.1 (2) |
N3—C11—H11A | 110.0 | C3—S2—Ni1 | 103.4 (2) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S1i | 0.93 | 2.75 | 3.591 (5) | 151 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H10Br2N)2[Ni(C4N2S2)2] |
Mr | 995.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 8.843 (3), 9.415 (3), 10.861 (4) |
α, β, γ (°) | 77.701 (5), 78.427 (6), 84.221 (5) |
V (Å3) | 864.0 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.46 |
Crystal size (mm) | 0.35 × 0.30 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.165, 0.323 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4584, 3309, 2482 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.117, 0.99 |
No. of reflections | 3309 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.96 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S1i | 0.930 | 2.75 | 3.591 (5) | 151 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Recently, some substituted benzylpyridinium cations have been introduced into the Ni(mnt)2 system (mnt is maleonitriledithiolate) in order to obtain some Ni(mnt)2-based molecular solids showing unusual magnetic properties (Ni et al., 2005; Xie et al., 2002; Ren et al., 2002). We report here the crystal structure of the title compound, in which 1-(3,5-dibromobenzyl)pyridinium functions as a counterion of Ni(mnt)2 anion.
As shown in Fig.1, the asymmetric unit of the title compound consists of one C12H10Br2N+ cation and one-half of a [Ni(C4N2S2)2]2- anion. The NiII ion lies on an inversion centre and exhibits a square-planar coordination geometry. The CN groups of the [Ni(mnt)2]2- unit are slightly tipped out of the C1/S1/Ni1/S2i/C3i plane, and the deviations from the plane are -0.116 (6) Å for N1 and 0.009 (6) Å for N2i [symmetry code: (i) 1 - x, 2 - y, 1 - z]. The benzene and pyridine rings of the C12H10Br2N+ unit form a dihedral angle of 74.6 (3)°. Atoms Br1 and Br2 deviate from the plane of the benzene ring by 0.038 (1) and 0.077 (1) Å, respectively.
Two C12H10Br2N+ units are linked to a [Ni(C4N2S2)2]2- unit through C16—H16···S1 hydrogen bonds (Table 1). The adjacent hydrogen-bonded units are cross-linked via weak π-π interactions between the benzene ring of the cation at (x, y, z) and (2 - x, 1 - y, 1 - z), with a centroid-centroid separation of 3.778 (3) Å. The cations and anions involved in the above interactions are arranged alternately along the [1 1 0] direction (Fig. 2).