Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027377/bh2107sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027377/bh2107Isup2.hkl |
CCDC reference: 654779
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.036
- wR factor = 0.072
- Data-to-parameter ratio = 20.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT431_ALERT_2_B Short Inter HL..A Contact I1 .. S1 .. 3.39 Ang.
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 - C2 .. 6.20 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.44 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.44 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C12 H11 I N
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 Ni1 (3) 2.83
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 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 6 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Coomber et al. (1996); Davison & Holm (1967); Gama et al. (1992); Kawamura et al. (1997); Ren et al. (2002, 2004, 2005, 2006); Xie et al. (2002, 2003).
Disodium maleonitriledithiolate (Na2mnt) was prepared following a procedure found in the literature (Davison & Holm, 1967). 1-(4'-iodobenzyl)pyridinium bromide was prepared by reacting 4-iodobenzylchlorine with 1.5 equivalent of pyridine in refluxing acetone for 4 h. The white microcrystalline product formed was filtered, washed with acetone and diethyl ether, and dried in vacuum (yield: ca. 80%). NiCl2·6H2O, Na2mnt and 1-(4'-iodobenzyl)pyridinium bromide (molar ratio 1:2:2) were mixed in water. The red precipitated product, (I), was separated, washed with water and then dissolved in a minimum amount of MeCN. This MeCN solution of (I) was kept at 277 K for 6 days, affording single crystals of (I) suitable for structure analysis. Crystals were separated, washed with Et2O and dried in vacuum (Yield: ca. 70%).
All H atoms were placed in calculated positions and refined using a riding model, with C—H bond lengths constrained to 0.93 (aromatic CH) or 0.97 Å (methylene CH2) and Uiso(H) = 1.2Ueq(parent atom).
Some charge transfer salts with their cations and anions packed in segregated stacks exhibit unusual properties in magnetism and conductivity (Gama et al., 1992; Coomber et al., 1996; Kawamura et al., 1997; Ren et al., 2002; Xie et al., 2002, 2003). In our previous studies, benzylpyridinium derivatives were employed as the countercations of [M(mnt)2]- ions (M = Ni3+ or Pt3+; mnt2- = maleonitriledithiolate) to prepare a series of compounds with segregated stacks displaying magnetic transitions (Ren et al., 2002, 2004, 2005, 2006; Xie et al., 2002, 2003).
Although all compounds exhibit similar structural features at room temperature, with the anions stacked in columns, the hysteresis loop in the plot of magnetic susceptibility vs. temperature was only observed in a compound that possesses obvious S···I interactions between anion and cations (Ren et al., 2006). In order to gain more information about the relationship between intermolecular interactions and magnetic properties, we are designing a series of [M(mnt)2]2- and [M(mnt)2]- anions (M = Ni and Pt), and investigate their crystal structures.
In the crystal of (I), the asymmetric unit consists of one cation placed on a general position and one-half [Ni(mnt)2]2- dianion lying on an inversion center (Fig. 1). The anionic moiety possesses a square-planar geometry, and the NiII ion coincides with an inversion center. The Ni—S bond lengths are 2.1629 (8) and 2.1739 (9) Å, and the bond angle within the chelate ring is 91.85 (3)°. The cation adopts a conformation in which the benzene and pyridine rings make dihedral angles of 57.4 (3) and 59.8 (3)° with the reference plane N3/C10/C11, respectively. Benzene ring makes a dihedral angle of 84.95 (11)° with the pyridine ring.
Short contacts between S atoms of anions and I atoms of symmetry related cations are observed (Fig. 2). The S1···I1i separation of 3.3863 (9) Å [symmetry code: (i) -1/2 - x, -1/2 + y, 1/2 - z) is small compared to the sum of van der Waals radii of S (1.80 Å) and I (2.04 Å).
For related literature, see: Coomber et al. (1996); Davison & Holm (1967); Gama et al. (1992); Kawamura et al. (1997); Ren et al. (2002, 2004, 2005, 2006); Xie et al. (2002, 2003).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
(C12H11IN)2[Ni(C4N2S2)2] | Z = 2 |
Mr = 931.31 | F(000) = 908 |
Monoclinic, P21/n | Dx = 1.751 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7723 (16) Å | θ = 2.5–25.1° |
b = 10.4489 (13) Å | µ = 2.57 mm−1 |
c = 13.7585 (17) Å | T = 293 K |
β = 105.889 (2)° | Block, red |
V = 1766.0 (4) Å3 | 0.30 × 0.20 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 4243 independent reflections |
Radiation source: fine-focus sealed tube | 2438 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
φ and ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −16→11 |
Tmin = 0.459, Tmax = 0.776 | k = −13→13 |
10837 measured reflections | l = −16→18 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.82 | w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3 |
4243 reflections | (Δ/σ)max = 0.002 |
205 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
(C12H11IN)2[Ni(C4N2S2)2] | V = 1766.0 (4) Å3 |
Mr = 931.31 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7723 (16) Å | µ = 2.57 mm−1 |
b = 10.4489 (13) Å | T = 293 K |
c = 13.7585 (17) Å | 0.30 × 0.20 × 0.10 mm |
β = 105.889 (2)° |
Bruker SMART CCD area-detector diffractometer | 4243 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2438 reflections with I > 2σ(I) |
Tmin = 0.459, Tmax = 0.776 | Rint = 0.070 |
10837 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.43 e Å−3 |
4243 reflections | Δρmin = −0.69 e Å−3 |
205 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.04272 (15) | |
S1 | 0.35566 (6) | 0.39970 (8) | 0.51129 (7) | 0.0500 (2) | |
S2 | 0.39653 (7) | 0.66191 (8) | 0.43750 (7) | 0.0572 (2) | |
I1 | −0.58920 (2) | 0.84666 (3) | 0.104948 (19) | 0.07120 (12) | |
N1 | 0.2621 (2) | 0.0847 (3) | 0.5759 (2) | 0.0675 (9) | |
N2 | 0.4103 (2) | 1.0011 (3) | 0.3686 (2) | 0.0642 (8) | |
N3 | −0.0135 (2) | 0.7533 (3) | 0.2672 (2) | 0.0531 (7) | |
C1 | 0.3260 (3) | 0.1552 (3) | 0.5657 (2) | 0.0481 (8) | |
C2 | 0.4039 (2) | 0.2484 (3) | 0.5530 (2) | 0.0417 (7) | |
C3 | 0.4463 (3) | 0.9027 (3) | 0.3929 (2) | 0.0473 (8) | |
C4 | 0.4887 (2) | 0.7777 (3) | 0.4259 (2) | 0.0419 (7) | |
C5 | −0.0119 (4) | 0.8025 (4) | 0.3575 (3) | 0.0818 (12) | |
H5A | −0.0656 | 0.7792 | 0.3882 | 0.098* | |
C6 | 0.0671 (4) | 0.8860 (5) | 0.4047 (3) | 0.0906 (15) | |
H6A | 0.0679 | 0.9183 | 0.4679 | 0.109* | |
C7 | 0.1447 (3) | 0.9225 (4) | 0.3605 (3) | 0.0791 (12) | |
H7A | 0.1991 | 0.9795 | 0.3927 | 0.095* | |
C8 | 0.1415 (3) | 0.8744 (4) | 0.2686 (3) | 0.0770 (12) | |
H8A | 0.1933 | 0.8994 | 0.2363 | 0.092* | |
C9 | 0.0622 (3) | 0.7889 (4) | 0.2229 (3) | 0.0619 (10) | |
H9A | 0.0612 | 0.7554 | 0.1601 | 0.074* | |
C10 | −0.0975 (3) | 0.6579 (3) | 0.2174 (3) | 0.0736 (12) | |
H10A | −0.0902 | 0.5827 | 0.2601 | 0.088* | |
H10B | −0.0848 | 0.6318 | 0.1539 | 0.088* | |
C11 | −0.2118 (3) | 0.7089 (3) | 0.1972 (3) | 0.0529 (9) | |
C12 | −0.2872 (3) | 0.6445 (3) | 0.2336 (3) | 0.0577 (9) | |
H12A | −0.2661 | 0.5729 | 0.2743 | 0.069* | |
C13 | −0.3943 (3) | 0.6858 (3) | 0.2098 (3) | 0.0552 (9) | |
H13A | −0.4447 | 0.6429 | 0.2354 | 0.066* | |
C14 | −0.4253 (3) | 0.7893 (3) | 0.1491 (2) | 0.0505 (8) | |
C15 | −0.3494 (3) | 0.8555 (3) | 0.1138 (3) | 0.0631 (10) | |
H15A | −0.3701 | 0.9279 | 0.0738 | 0.076* | |
C16 | −0.2438 (3) | 0.8144 (3) | 0.1377 (3) | 0.0623 (10) | |
H16A | −0.1931 | 0.8586 | 0.1132 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0384 (3) | 0.0356 (3) | 0.0544 (3) | −0.0057 (3) | 0.0131 (3) | 0.0053 (3) |
S1 | 0.0388 (5) | 0.0393 (5) | 0.0727 (6) | −0.0041 (4) | 0.0165 (4) | 0.0090 (4) |
S2 | 0.0403 (5) | 0.0462 (5) | 0.0845 (6) | −0.0026 (4) | 0.0161 (5) | 0.0166 (5) |
I1 | 0.05189 (17) | 0.0832 (2) | 0.07392 (19) | 0.00774 (13) | 0.00940 (13) | −0.00856 (14) |
N1 | 0.062 (2) | 0.0524 (19) | 0.089 (2) | −0.0197 (16) | 0.0215 (17) | 0.0109 (17) |
N2 | 0.064 (2) | 0.0444 (19) | 0.084 (2) | 0.0034 (16) | 0.0200 (17) | 0.0096 (17) |
N3 | 0.0456 (17) | 0.0469 (18) | 0.0687 (19) | 0.0032 (14) | 0.0187 (15) | −0.0013 (15) |
C1 | 0.047 (2) | 0.044 (2) | 0.053 (2) | −0.0009 (16) | 0.0123 (16) | 0.0025 (16) |
C2 | 0.0430 (19) | 0.0344 (17) | 0.0502 (18) | −0.0099 (14) | 0.0171 (15) | −0.0016 (15) |
C3 | 0.043 (2) | 0.046 (2) | 0.055 (2) | −0.0091 (17) | 0.0169 (16) | −0.0003 (17) |
C4 | 0.0444 (19) | 0.0369 (18) | 0.0450 (18) | −0.0046 (15) | 0.0132 (15) | 0.0000 (14) |
C5 | 0.080 (3) | 0.103 (4) | 0.075 (3) | 0.005 (3) | 0.042 (3) | 0.007 (3) |
C6 | 0.079 (3) | 0.126 (4) | 0.066 (3) | 0.001 (3) | 0.018 (3) | −0.031 (3) |
C7 | 0.053 (3) | 0.092 (3) | 0.083 (3) | −0.001 (2) | 0.004 (2) | −0.024 (3) |
C8 | 0.060 (3) | 0.097 (3) | 0.077 (3) | −0.024 (2) | 0.023 (2) | −0.017 (2) |
C9 | 0.054 (2) | 0.071 (3) | 0.065 (2) | −0.002 (2) | 0.024 (2) | −0.012 (2) |
C10 | 0.054 (2) | 0.048 (2) | 0.124 (3) | −0.0009 (18) | 0.033 (2) | −0.013 (2) |
C11 | 0.050 (2) | 0.041 (2) | 0.071 (2) | −0.0046 (17) | 0.0237 (19) | −0.0133 (18) |
C12 | 0.059 (2) | 0.043 (2) | 0.075 (2) | −0.0022 (18) | 0.024 (2) | 0.0058 (17) |
C13 | 0.049 (2) | 0.054 (2) | 0.067 (2) | −0.0093 (18) | 0.0249 (19) | −0.0024 (19) |
C14 | 0.047 (2) | 0.050 (2) | 0.054 (2) | −0.0006 (17) | 0.0126 (17) | −0.0078 (17) |
C15 | 0.064 (3) | 0.051 (2) | 0.073 (2) | 0.002 (2) | 0.018 (2) | 0.0115 (19) |
C16 | 0.065 (3) | 0.052 (2) | 0.081 (3) | −0.0044 (19) | 0.038 (2) | 0.006 (2) |
Ni1—S1i | 2.1629 (8) | C6—H6A | 0.9300 |
Ni1—S1 | 2.1629 (8) | C7—C8 | 1.351 (5) |
Ni1—S2i | 2.1739 (9) | C7—H7A | 0.9300 |
Ni1—S2 | 2.1739 (9) | C8—C9 | 1.367 (5) |
S1—C2 | 1.737 (3) | C8—H8A | 0.9300 |
S2—C4 | 1.725 (3) | C9—H9A | 0.9300 |
I1—C14 | 2.101 (3) | C10—C11 | 1.507 (4) |
N1—C1 | 1.136 (4) | C10—H10A | 0.9700 |
N2—C3 | 1.138 (4) | C10—H10B | 0.9700 |
N3—C9 | 1.329 (4) | C11—C16 | 1.367 (5) |
N3—C5 | 1.340 (5) | C11—C12 | 1.377 (4) |
N3—C10 | 1.487 (4) | C12—C13 | 1.385 (4) |
C1—C2 | 1.436 (4) | C12—H12A | 0.9300 |
C2—C4i | 1.351 (4) | C13—C14 | 1.357 (4) |
C3—C4 | 1.439 (5) | C13—H13A | 0.9300 |
C4—C2i | 1.351 (4) | C14—C15 | 1.384 (4) |
C5—C6 | 1.358 (6) | C15—C16 | 1.367 (5) |
C5—H5A | 0.9300 | C15—H15A | 0.9300 |
C6—C7 | 1.351 (5) | C16—H16A | 0.9300 |
S1i—Ni1—S1 | 180.0 | C7—C8—H8A | 119.9 |
S1i—Ni1—S2i | 88.15 (3) | C9—C8—H8A | 119.9 |
S1—Ni1—S2i | 91.85 (3) | N3—C9—C8 | 120.9 (3) |
S1i—Ni1—S2 | 91.85 (3) | N3—C9—H9A | 119.6 |
S1—Ni1—S2 | 88.15 (3) | C8—C9—H9A | 119.6 |
S2i—Ni1—S2 | 180.0 | N3—C10—C11 | 112.8 (3) |
C2—S1—Ni1 | 103.46 (10) | N3—C10—H10A | 109.0 |
C4—S2—Ni1 | 103.07 (11) | C11—C10—H10A | 109.0 |
C9—N3—C5 | 119.3 (3) | N3—C10—H10B | 109.0 |
C9—N3—C10 | 120.0 (3) | C11—C10—H10B | 109.0 |
C5—N3—C10 | 120.7 (3) | H10A—C10—H10B | 107.8 |
N1—C1—C2 | 177.8 (4) | C16—C11—C12 | 119.2 (3) |
C4i—C2—C1 | 122.3 (3) | C16—C11—C10 | 120.8 (3) |
C4i—C2—S1 | 120.1 (2) | C12—C11—C10 | 119.9 (3) |
C1—C2—S1 | 117.5 (2) | C11—C12—C13 | 120.4 (3) |
N2—C3—C4 | 177.7 (3) | C11—C12—H12A | 119.8 |
C2i—C4—C3 | 121.5 (3) | C13—C12—H12A | 119.8 |
C2i—C4—S2 | 121.2 (2) | C14—C13—C12 | 119.8 (3) |
C3—C4—S2 | 117.3 (2) | C14—C13—H13A | 120.1 |
N3—C5—C6 | 120.7 (4) | C12—C13—H13A | 120.1 |
N3—C5—H5A | 119.6 | C13—C14—C15 | 120.0 (3) |
C6—C5—H5A | 119.6 | C13—C14—I1 | 120.4 (3) |
C7—C6—C5 | 120.4 (4) | C15—C14—I1 | 119.6 (3) |
C7—C6—H6A | 119.8 | C16—C15—C14 | 119.9 (3) |
C5—C6—H6A | 119.8 | C16—C15—H15A | 120.0 |
C8—C7—C6 | 118.6 (4) | C14—C15—H15A | 120.0 |
C8—C7—H7A | 120.7 | C11—C16—C15 | 120.7 (3) |
C6—C7—H7A | 120.7 | C11—C16—H16A | 119.6 |
C7—C8—C9 | 120.1 (4) | C15—C16—H16A | 119.6 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H11IN)2[Ni(C4N2S2)2] |
Mr | 931.31 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.7723 (16), 10.4489 (13), 13.7585 (17) |
β (°) | 105.889 (2) |
V (Å3) | 1766.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.57 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.459, 0.776 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10837, 4243, 2438 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.072, 0.82 |
No. of reflections | 4243 |
No. of parameters | 205 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.69 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
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Some charge transfer salts with their cations and anions packed in segregated stacks exhibit unusual properties in magnetism and conductivity (Gama et al., 1992; Coomber et al., 1996; Kawamura et al., 1997; Ren et al., 2002; Xie et al., 2002, 2003). In our previous studies, benzylpyridinium derivatives were employed as the countercations of [M(mnt)2]- ions (M = Ni3+ or Pt3+; mnt2- = maleonitriledithiolate) to prepare a series of compounds with segregated stacks displaying magnetic transitions (Ren et al., 2002, 2004, 2005, 2006; Xie et al., 2002, 2003).
Although all compounds exhibit similar structural features at room temperature, with the anions stacked in columns, the hysteresis loop in the plot of magnetic susceptibility vs. temperature was only observed in a compound that possesses obvious S···I interactions between anion and cations (Ren et al., 2006). In order to gain more information about the relationship between intermolecular interactions and magnetic properties, we are designing a series of [M(mnt)2]2- and [M(mnt)2]- anions (M = Ni and Pt), and investigate their crystal structures.
In the crystal of (I), the asymmetric unit consists of one cation placed on a general position and one-half [Ni(mnt)2]2- dianion lying on an inversion center (Fig. 1). The anionic moiety possesses a square-planar geometry, and the NiII ion coincides with an inversion center. The Ni—S bond lengths are 2.1629 (8) and 2.1739 (9) Å, and the bond angle within the chelate ring is 91.85 (3)°. The cation adopts a conformation in which the benzene and pyridine rings make dihedral angles of 57.4 (3) and 59.8 (3)° with the reference plane N3/C10/C11, respectively. Benzene ring makes a dihedral angle of 84.95 (11)° with the pyridine ring.
Short contacts between S atoms of anions and I atoms of symmetry related cations are observed (Fig. 2). The S1···I1i separation of 3.3863 (9) Å [symmetry code: (i) -1/2 - x, -1/2 + y, 1/2 - z) is small compared to the sum of van der Waals radii of S (1.80 Å) and I (2.04 Å).