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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804011705/hg6041sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804011705/hg6041Isup2.hkl
Contains datablock I

CCDC reference: 242058

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Computing details top

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 = 778.44Dx = 1.499 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 918 reflections
a = 6.940 (2) Åθ = 2.6–25.8°
b = 15.994 (4) ŵ = 1.00 mm1
c = 15.573 (4) ÅT = 293 K
β = 93.93 (1)°Block, red
V = 1724.5 (8) Å30.3 × 0.2 × 0.2 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3014 independent reflections
Radiation source: sealed tube2467 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 88
Tmin = 0.79, Tmax = 0.82k = 1819
8430 measured reflectionsl = 1418
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-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 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.21 e Å3
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
xyzUiso*/Ueq
Ni10.00001.00000.00000.03940 (13)
S10.25878 (9)1.01015 (3)0.08538 (4)0.05333 (18)
S20.15548 (8)0.91051 (3)0.07335 (3)0.04978 (17)
N10.4522 (4)1.13296 (16)0.27379 (16)0.1030 (9)
N20.0634 (4)0.75601 (14)0.24805 (14)0.0905 (8)
C20.3380 (4)1.11192 (15)0.22219 (16)0.0656 (7)
C10.1950 (3)1.08616 (13)0.15739 (13)0.0491 (5)
C40.0284 (3)0.81164 (14)0.20647 (14)0.0539 (6)
C30.0185 (3)0.87897 (12)0.15111 (13)0.0458 (5)
C50.2633 (3)0.12090 (14)0.85730 (15)0.0582 (6)
H50.37320.12300.89490.070*
C60.2500 (4)0.06472 (15)0.79103 (17)0.0634 (6)
H60.35320.02870.78460.076*
C70.0506 (4)0.10927 (14)0.74698 (15)0.0562 (6)
C80.0418 (3)0.16670 (14)0.81376 (15)0.0561 (6)
H80.14690.20130.82130.067*
C90.1165 (4)0.23253 (15)0.94113 (15)0.0642 (7)
H9A0.08510.20190.99210.077*
H9B0.01550.27360.92910.077*
C100.3040 (3)0.27770 (13)0.96061 (13)0.0502 (5)
C110.3348 (3)0.35317 (14)0.92235 (14)0.0532 (6)
H110.24100.37480.88300.064*
C120.5023 (4)0.39761 (14)0.94121 (15)0.0604 (6)
H120.52250.44860.91450.072*
C130.6383 (4)0.36555 (16)0.99976 (17)0.0644 (7)
C140.6114 (4)0.29135 (17)1.03927 (16)0.0746 (8)
H140.70500.27041.07920.090*
C150.4434 (4)0.24738 (15)1.01941 (16)0.0697 (7)
H150.42420.19641.04620.084*
C160.2261 (4)0.10210 (17)0.68686 (17)0.0815 (8)
H16A0.19880.12380.63150.122*
H16B0.32960.13350.70910.122*
H16C0.26310.04440.68120.122*
Cl10.84997 (11)0.42090 (5)1.02396 (6)0.1034 (3)
N30.1155 (3)0.17275 (10)0.86706 (11)0.0505 (5)
N40.0972 (3)0.05911 (12)0.73550 (13)0.0624 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0462 (2)0.0306 (2)0.0410 (2)0.00013 (15)0.00067 (16)0.00112 (14)
S10.0523 (4)0.0499 (3)0.0560 (4)0.0062 (3)0.0089 (3)0.0102 (3)
S20.0532 (4)0.0420 (3)0.0538 (3)0.0045 (2)0.0017 (3)0.0070 (2)
N10.109 (2)0.098 (2)0.0950 (19)0.0060 (16)0.0455 (16)0.0295 (15)
N20.144 (2)0.0586 (15)0.0720 (15)0.0009 (14)0.0305 (15)0.0191 (12)
C20.0784 (18)0.0531 (15)0.0628 (16)0.0042 (13)0.0139 (13)0.0080 (12)
C10.0658 (16)0.0373 (12)0.0432 (12)0.0042 (11)0.0043 (10)0.0029 (9)
C40.0691 (16)0.0445 (13)0.0489 (13)0.0039 (11)0.0112 (11)0.0005 (11)
C30.0630 (15)0.0345 (11)0.0402 (12)0.0049 (10)0.0056 (10)0.0014 (9)
C50.0564 (15)0.0484 (14)0.0699 (16)0.0048 (12)0.0062 (12)0.0051 (12)
C60.0653 (17)0.0477 (14)0.0785 (18)0.0024 (12)0.0144 (14)0.0019 (12)
C70.0683 (16)0.0445 (13)0.0559 (14)0.0060 (12)0.0053 (12)0.0038 (11)
C80.0578 (15)0.0429 (13)0.0684 (16)0.0005 (11)0.0094 (12)0.0045 (11)
C90.0713 (17)0.0599 (15)0.0634 (15)0.0171 (13)0.0189 (12)0.0116 (12)
C100.0616 (14)0.0408 (12)0.0486 (13)0.0045 (11)0.0084 (11)0.0013 (10)
C110.0598 (15)0.0468 (13)0.0517 (13)0.0015 (11)0.0050 (11)0.0039 (10)
C120.0708 (17)0.0433 (13)0.0673 (16)0.0092 (12)0.0063 (13)0.0030 (11)
C130.0577 (16)0.0530 (15)0.0822 (18)0.0005 (12)0.0011 (13)0.0166 (13)
C140.078 (2)0.0545 (17)0.087 (2)0.0133 (14)0.0269 (15)0.0020 (13)
C150.091 (2)0.0428 (14)0.0735 (17)0.0001 (13)0.0042 (15)0.0159 (12)
C160.090 (2)0.0755 (19)0.0768 (19)0.0036 (16)0.0084 (15)0.0045 (14)
Cl10.0587 (5)0.0960 (6)0.1540 (8)0.0157 (4)0.0026 (5)0.0389 (5)
N30.0564 (12)0.0399 (10)0.0562 (11)0.0110 (9)0.0111 (9)0.0037 (8)
N40.0747 (15)0.0496 (12)0.0639 (13)0.0005 (11)0.0127 (11)0.0005 (9)
Geometric parameters (Å, º) top
Ni1—S2i2.1648 (6)C8—N31.328 (3)
Ni1—S22.1648 (6)C8—H80.9300
Ni1—S1i2.1662 (7)C9—N31.498 (3)
Ni1—S12.1662 (7)C9—C101.501 (3)
S1—C11.732 (2)C9—H9A0.9700
S2—C31.726 (2)C9—H9B0.9700
N1—C21.140 (3)C10—C111.369 (3)
N2—C41.136 (3)C10—C151.374 (3)
C2—C11.427 (3)C11—C121.377 (3)
C1—C3i1.344 (3)C11—H110.9300
C4—C31.431 (3)C12—C131.367 (3)
C3—C1i1.344 (3)C12—H120.9300
C5—N31.336 (3)C13—C141.355 (4)
C5—C61.367 (3)C13—Cl11.734 (3)
C5—H50.9300C14—C151.378 (3)
C6—N41.325 (3)C14—H140.9300
C6—H60.9300C15—H150.9300
C7—N41.324 (3)C16—H16A0.9600
C7—C81.386 (3)C16—H16B0.9600
C7—C161.489 (3)C16—H16C0.9600
S2i—Ni1—S2180.0N3—C9—H9B108.5
S2i—Ni1—S1i87.20 (3)C10—C9—H9B108.5
S2—Ni1—S1i92.80 (3)H9A—C9—H9B107.5
S2i—Ni1—S192.80 (3)C11—C10—C15118.5 (2)
S2—Ni1—S187.20 (3)C11—C10—C9119.7 (2)
S1i—Ni1—S1180.0C15—C10—C9121.7 (2)
C1—S1—Ni1102.25 (8)C10—C11—C12121.1 (2)
C3—S2—Ni1102.33 (8)C10—C11—H11119.4
N1—C2—C1179.6 (3)C12—C11—H11119.4
C3i—C1—C2121.2 (2)C13—C12—C11118.9 (2)
C3i—C1—S1121.09 (16)C13—C12—H12120.6
C2—C1—S1117.67 (18)C11—C12—H12120.6
N2—C4—C3177.3 (2)C14—C13—C12121.4 (2)
C1i—C3—C4120.8 (2)C14—C13—Cl1119.3 (2)
C1i—C3—S2121.35 (16)C12—C13—Cl1119.3 (2)
C4—C3—S2117.78 (18)C13—C14—C15119.1 (2)
N3—C5—C6118.8 (2)C13—C14—H14120.5
N3—C5—H5120.6C15—C14—H14120.5
C6—C5—H5120.6C10—C15—C14121.0 (2)
N4—C6—C5123.2 (2)C10—C15—H15119.5
N4—C6—H6118.4C14—C15—H15119.5
C5—C6—H6118.4C7—C16—H16A109.5
N4—C7—C8120.5 (2)C7—C16—H16B109.5
N4—C7—C16118.4 (2)H16A—C16—H16B109.5
C8—C7—C16121.0 (2)C7—C16—H16C109.5
N3—C8—C7120.6 (2)H16A—C16—H16C109.5
N3—C8—H8119.7H16B—C16—H16C109.5
C7—C8—H8119.7C8—N3—C5119.2 (2)
N3—C9—C10114.92 (19)C8—N3—C9119.2 (2)
N3—C9—H9A108.5C5—N3—C9121.4 (2)
C10—C9—H9A108.5C7—N4—C6117.6 (2)
Symmetry code: (i) x, y+2, z.
 

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