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The synthesis and crystal structure of the novel ion-pair title complex, (C12H12ClN2)2[Ni(C4N2S2)2] or [ClBzMePz]2[Ni(mnt)2] [where ClBzMePz is 1-(4-chlorobenzyl)-3-methylpyrazinium and mnt is maleonitriledithiolate], is reported. The structural study shows that the asymmetric unit consists of one cation and one-half of an anion; the Ni atom lies at a centre of symmetry. The [ClBzMePz]+ ion adopts an essentially planar conformation where both the phenyl ring and the pyrazine ring are twisted with respect to the plane of the C-N-C chain which links them. It is worth noting that the anions and cations of the title complex stack in well-separated columns, and the intermolecular contacts between anions and cations observed in the crystal structure may play an important role in the crystal packing.
Supporting information
CCDC reference: 242058
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.082
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.43 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.43 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. Cl1 .. 3.39 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
0 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.
Bis[1-(4-chlorobenzyl)-3-methylpyrazinium]
bis(maleonitriledithiolato)nickelate(II)
top
Crystal data top
(C12H12ClN2)2[Ni(C4N2S2)2] | F(000) = 796 |
Mr = 778.44 | Dx = 1.499 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 918 reflections |
a = 6.940 (2) Å | θ = 2.6–25.8° |
b = 15.994 (4) Å | µ = 1.00 mm−1 |
c = 15.573 (4) Å | T = 293 K |
β = 93.93 (1)° | Block, red |
V = 1724.5 (8) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3014 independent reflections |
Radiation source: sealed tube | 2467 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→8 |
Tmin = 0.79, Tmax = 0.82 | k = −18→19 |
8430 measured reflections | l = −14→18 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.04P)2P] where P = (Fo2 + 2Fc2)/3 |
3014 reflections | (Δ/σ)max < 0.001 |
215 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. The structure was solved by direct methods (Bruker, 2000) and successive
difference Fourier syntheses. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 1.0000 | 0.0000 | 0.03940 (13) | |
S1 | 0.25878 (9) | 1.01015 (3) | 0.08538 (4) | 0.05333 (18) | |
S2 | 0.15548 (8) | 0.91051 (3) | −0.07335 (3) | 0.04978 (17) | |
N1 | 0.4522 (4) | 1.13296 (16) | 0.27379 (16) | 0.1030 (9) | |
N2 | 0.0634 (4) | 0.75601 (14) | −0.24805 (14) | 0.0905 (8) | |
C2 | 0.3380 (4) | 1.11192 (15) | 0.22219 (16) | 0.0656 (7) | |
C1 | 0.1950 (3) | 1.08616 (13) | 0.15739 (13) | 0.0491 (5) | |
C4 | 0.0284 (3) | 0.81164 (14) | −0.20647 (14) | 0.0539 (6) | |
C3 | −0.0185 (3) | 0.87897 (12) | −0.15111 (13) | 0.0458 (5) | |
C5 | 0.2633 (3) | 0.12090 (14) | 0.85730 (15) | 0.0582 (6) | |
H5 | 0.3732 | 0.1230 | 0.8949 | 0.070* | |
C6 | 0.2500 (4) | 0.06472 (15) | 0.79103 (17) | 0.0634 (6) | |
H6 | 0.3532 | 0.0287 | 0.7846 | 0.076* | |
C7 | −0.0506 (4) | 0.10927 (14) | 0.74698 (15) | 0.0562 (6) | |
C8 | −0.0418 (3) | 0.16670 (14) | 0.81376 (15) | 0.0561 (6) | |
H8 | −0.1469 | 0.2013 | 0.8213 | 0.067* | |
C9 | 0.1165 (4) | 0.23253 (15) | 0.94113 (15) | 0.0642 (7) | |
H9A | 0.0851 | 0.2019 | 0.9921 | 0.077* | |
H9B | 0.0155 | 0.2736 | 0.9291 | 0.077* | |
C10 | 0.3040 (3) | 0.27770 (13) | 0.96061 (13) | 0.0502 (5) | |
C11 | 0.3348 (3) | 0.35317 (14) | 0.92235 (14) | 0.0532 (6) | |
H11 | 0.2410 | 0.3748 | 0.8830 | 0.064* | |
C12 | 0.5023 (4) | 0.39761 (14) | 0.94121 (15) | 0.0604 (6) | |
H12 | 0.5225 | 0.4486 | 0.9145 | 0.072* | |
C13 | 0.6383 (4) | 0.36555 (16) | 0.99976 (17) | 0.0644 (7) | |
C14 | 0.6114 (4) | 0.29135 (17) | 1.03927 (16) | 0.0746 (8) | |
H14 | 0.7050 | 0.2704 | 1.0792 | 0.090* | |
C15 | 0.4434 (4) | 0.24738 (15) | 1.01941 (16) | 0.0697 (7) | |
H15 | 0.4242 | 0.1964 | 1.0462 | 0.084* | |
C16 | −0.2261 (4) | 0.10210 (17) | 0.68686 (17) | 0.0815 (8) | |
H16A | −0.1988 | 0.1238 | 0.6315 | 0.122* | |
H16B | −0.3296 | 0.1335 | 0.7091 | 0.122* | |
H16C | −0.2631 | 0.0444 | 0.6812 | 0.122* | |
Cl1 | 0.84997 (11) | 0.42090 (5) | 1.02396 (6) | 0.1034 (3) | |
N3 | 0.1155 (3) | 0.17275 (10) | 0.86706 (11) | 0.0505 (5) | |
N4 | 0.0972 (3) | 0.05911 (12) | 0.73550 (13) | 0.0624 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0462 (2) | 0.0306 (2) | 0.0410 (2) | −0.00013 (15) | −0.00067 (16) | −0.00112 (14) |
S1 | 0.0523 (4) | 0.0499 (3) | 0.0560 (4) | 0.0062 (3) | −0.0089 (3) | −0.0102 (3) |
S2 | 0.0532 (4) | 0.0420 (3) | 0.0538 (3) | 0.0045 (2) | 0.0017 (3) | −0.0070 (2) |
N1 | 0.109 (2) | 0.098 (2) | 0.0950 (19) | 0.0060 (16) | −0.0455 (16) | −0.0295 (15) |
N2 | 0.144 (2) | 0.0586 (15) | 0.0720 (15) | 0.0009 (14) | 0.0305 (15) | −0.0191 (12) |
C2 | 0.0784 (18) | 0.0531 (15) | 0.0628 (16) | 0.0042 (13) | −0.0139 (13) | −0.0080 (12) |
C1 | 0.0658 (16) | 0.0373 (12) | 0.0432 (12) | −0.0042 (11) | −0.0043 (10) | −0.0029 (9) |
C4 | 0.0691 (16) | 0.0445 (13) | 0.0489 (13) | −0.0039 (11) | 0.0112 (11) | 0.0005 (11) |
C3 | 0.0630 (15) | 0.0345 (11) | 0.0402 (12) | −0.0049 (10) | 0.0056 (10) | −0.0014 (9) |
C5 | 0.0564 (15) | 0.0484 (14) | 0.0699 (16) | −0.0048 (12) | 0.0062 (12) | 0.0051 (12) |
C6 | 0.0653 (17) | 0.0477 (14) | 0.0785 (18) | 0.0024 (12) | 0.0144 (14) | 0.0019 (12) |
C7 | 0.0683 (16) | 0.0445 (13) | 0.0559 (14) | −0.0060 (12) | 0.0053 (12) | 0.0038 (11) |
C8 | 0.0578 (15) | 0.0429 (13) | 0.0684 (16) | −0.0005 (11) | 0.0094 (12) | 0.0045 (11) |
C9 | 0.0713 (17) | 0.0599 (15) | 0.0634 (15) | −0.0171 (13) | 0.0189 (12) | −0.0116 (12) |
C10 | 0.0616 (14) | 0.0408 (12) | 0.0486 (13) | −0.0045 (11) | 0.0084 (11) | −0.0013 (10) |
C11 | 0.0598 (15) | 0.0468 (13) | 0.0517 (13) | −0.0015 (11) | −0.0050 (11) | 0.0039 (10) |
C12 | 0.0708 (17) | 0.0433 (13) | 0.0673 (16) | −0.0092 (12) | 0.0063 (13) | 0.0030 (11) |
C13 | 0.0577 (16) | 0.0530 (15) | 0.0822 (18) | −0.0005 (12) | 0.0011 (13) | −0.0166 (13) |
C14 | 0.078 (2) | 0.0545 (17) | 0.087 (2) | 0.0133 (14) | −0.0269 (15) | −0.0020 (13) |
C15 | 0.091 (2) | 0.0428 (14) | 0.0735 (17) | −0.0001 (13) | −0.0042 (15) | 0.0159 (12) |
C16 | 0.090 (2) | 0.0755 (19) | 0.0768 (19) | 0.0036 (16) | −0.0084 (15) | −0.0045 (14) |
Cl1 | 0.0587 (5) | 0.0960 (6) | 0.1540 (8) | −0.0157 (4) | −0.0026 (5) | −0.0389 (5) |
N3 | 0.0564 (12) | 0.0399 (10) | 0.0562 (11) | −0.0110 (9) | 0.0111 (9) | 0.0037 (8) |
N4 | 0.0747 (15) | 0.0496 (12) | 0.0639 (13) | −0.0005 (11) | 0.0127 (11) | −0.0005 (9) |
Geometric parameters (Å, º) top
Ni1—S2i | 2.1648 (6) | C8—N3 | 1.328 (3) |
Ni1—S2 | 2.1648 (6) | C8—H8 | 0.9300 |
Ni1—S1i | 2.1662 (7) | C9—N3 | 1.498 (3) |
Ni1—S1 | 2.1662 (7) | C9—C10 | 1.501 (3) |
S1—C1 | 1.732 (2) | C9—H9A | 0.9700 |
S2—C3 | 1.726 (2) | C9—H9B | 0.9700 |
N1—C2 | 1.140 (3) | C10—C11 | 1.369 (3) |
N2—C4 | 1.136 (3) | C10—C15 | 1.374 (3) |
C2—C1 | 1.427 (3) | C11—C12 | 1.377 (3) |
C1—C3i | 1.344 (3) | C11—H11 | 0.9300 |
C4—C3 | 1.431 (3) | C12—C13 | 1.367 (3) |
C3—C1i | 1.344 (3) | C12—H12 | 0.9300 |
C5—N3 | 1.336 (3) | C13—C14 | 1.355 (4) |
C5—C6 | 1.367 (3) | C13—Cl1 | 1.734 (3) |
C5—H5 | 0.9300 | C14—C15 | 1.378 (3) |
C6—N4 | 1.325 (3) | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C7—N4 | 1.324 (3) | C16—H16A | 0.9600 |
C7—C8 | 1.386 (3) | C16—H16B | 0.9600 |
C7—C16 | 1.489 (3) | C16—H16C | 0.9600 |
| | | |
S2i—Ni1—S2 | 180.0 | N3—C9—H9B | 108.5 |
S2i—Ni1—S1i | 87.20 (3) | C10—C9—H9B | 108.5 |
S2—Ni1—S1i | 92.80 (3) | H9A—C9—H9B | 107.5 |
S2i—Ni1—S1 | 92.80 (3) | C11—C10—C15 | 118.5 (2) |
S2—Ni1—S1 | 87.20 (3) | C11—C10—C9 | 119.7 (2) |
S1i—Ni1—S1 | 180.0 | C15—C10—C9 | 121.7 (2) |
C1—S1—Ni1 | 102.25 (8) | C10—C11—C12 | 121.1 (2) |
C3—S2—Ni1 | 102.33 (8) | C10—C11—H11 | 119.4 |
N1—C2—C1 | 179.6 (3) | C12—C11—H11 | 119.4 |
C3i—C1—C2 | 121.2 (2) | C13—C12—C11 | 118.9 (2) |
C3i—C1—S1 | 121.09 (16) | C13—C12—H12 | 120.6 |
C2—C1—S1 | 117.67 (18) | C11—C12—H12 | 120.6 |
N2—C4—C3 | 177.3 (2) | C14—C13—C12 | 121.4 (2) |
C1i—C3—C4 | 120.8 (2) | C14—C13—Cl1 | 119.3 (2) |
C1i—C3—S2 | 121.35 (16) | C12—C13—Cl1 | 119.3 (2) |
C4—C3—S2 | 117.78 (18) | C13—C14—C15 | 119.1 (2) |
N3—C5—C6 | 118.8 (2) | C13—C14—H14 | 120.5 |
N3—C5—H5 | 120.6 | C15—C14—H14 | 120.5 |
C6—C5—H5 | 120.6 | C10—C15—C14 | 121.0 (2) |
N4—C6—C5 | 123.2 (2) | C10—C15—H15 | 119.5 |
N4—C6—H6 | 118.4 | C14—C15—H15 | 119.5 |
C5—C6—H6 | 118.4 | C7—C16—H16A | 109.5 |
N4—C7—C8 | 120.5 (2) | C7—C16—H16B | 109.5 |
N4—C7—C16 | 118.4 (2) | H16A—C16—H16B | 109.5 |
C8—C7—C16 | 121.0 (2) | C7—C16—H16C | 109.5 |
N3—C8—C7 | 120.6 (2) | H16A—C16—H16C | 109.5 |
N3—C8—H8 | 119.7 | H16B—C16—H16C | 109.5 |
C7—C8—H8 | 119.7 | C8—N3—C5 | 119.2 (2) |
N3—C9—C10 | 114.92 (19) | C8—N3—C9 | 119.2 (2) |
N3—C9—H9A | 108.5 | C5—N3—C9 | 121.4 (2) |
C10—C9—H9A | 108.5 | C7—N4—C6 | 117.6 (2) |
Symmetry code: (i) −x, −y+2, −z. |
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