1-(2-Chloro­benz­yl)-2-methyl­pyridinium bis­(maleonitrile­dithiol­ato)nickelate(III)

The title compound is a new ionic complex, (C₁₃H₁₃ClN)[Ni(C₄N₂S₂)₂] or [ClBzPyMe][Ni(mnt)₂] [where ClBzPyMe is 1-(2-chloro­benz­yl)-2-methyl­pyridinium and mnt is maleo­nitrile­­dithiol­ate]. In the anion the Ni^III atom is coordinated by the four S atoms of two mnt²⁻ ligands and exhibits the expected square-planar coordination geometry. In the [ClBzPyMe]⁺ cation the benzene and pyridine rings are twisted with respect to the C/C/N plane incorporating the methyl­ene C atom that links them. The [Ni(mnt)₂]⁻ anions and [ClBzPyMe]⁺ cations stack into well segregated columns along the a axis, and the Ni^III ions form a one-dimensional zigzag chain through weak Ni...S, S...S, and π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.059
• wR factor = 0.157
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
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.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C6     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C7     -   C8     ...       1.43 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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.

1-(2-Chlorobenzyl)-2-methylpyridinium) bis(maleonitriledithiolate) nickel(III)

Crystal data

(C13H13ClN)][Ni(C4N2S2)2]	F(000) = 1132
Mr = 557.76	Dx = 1.571 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 977 reflections
a = 6.9950 (1) Å	θ = 2.8–24.4°
b = 26.658 (5) Å	µ = 1.31 mm^−1
c = 13.013 (3) Å	T = 293 K
β = 103.700 (1)°	Block, black
V = 2357.5 (8) Å^3	0.4 × 0.25 × 0.2 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4141 independent reflections
Radiation source: sealed tube	3364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.682, Tmax = 0.770	k = −28→31
11580 measured reflections	l = −14→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.080P)^2 + 1.2P] where P = (Fo^2 + 2Fc^2)/3
4141 reflections	(Δ/σ)max < 0.001
290 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. IR (cm^-1): 3082 (w), 3060 (w), 3013 (w), 2208 (s), 1628 (s), 1591 (m), 1450 (m), 1472 (s), 1445 (s), 1384 (m), 1364 (s), 1322 (s), 1289 (s), 1194 (s), 1160 (m), 1145 (m),1056 (m), 1043 (m), 908 (m), 860 (m), 808 (m), 795 (m), 776 (m), 750 (m), 718 (m), 670 (m), 620 (m), 571 (m), 525 (s), 502 (s), 443 (m), 419 (m).

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.20130 (9)	0.02370 (2)	0.43111 (4)	0.0423 (2)
Cl1	0.9482 (2)	0.09158 (7)	0.96539 (17)	0.0928 (6)
S1	0.22787 (19)	0.09234 (4)	0.51987 (10)	0.0484 (3)
S2	0.0970 (2)	0.06190 (5)	0.28295 (10)	0.0524 (3)
S3	0.1927 (2)	−0.04437 (5)	0.34274 (10)	0.0551 (4)
S4	0.29778 (19)	−0.01483 (5)	0.57829 (9)	0.0497 (3)
N1	0.1630 (9)	0.22900 (19)	0.4812 (4)	0.0834 (16)
N2	−0.0250 (10)	0.1887 (2)	0.1728 (5)	0.0919 (18)
N3	0.2877 (9)	−0.1796 (2)	0.3737 (5)	0.0926 (18)
N4	0.4247 (8)	−0.14105 (19)	0.6896 (4)	0.0789 (15)
N5	0.4045 (7)	0.18378 (15)	0.8720 (4)	0.0572 (11)
C1	0.1552 (8)	0.1887 (2)	0.4560 (4)	0.0560 (13)
C2	0.1496 (7)	0.13708 (17)	0.4233 (4)	0.0456 (11)
C3	0.0919 (7)	0.12355 (17)	0.3205 (4)	0.0454 (11)
C4	0.0269 (9)	0.1604 (2)	0.2386 (5)	0.0615 (14)
C5	0.2754 (9)	−0.1398 (2)	0.4032 (5)	0.0631 (14)
C6	0.2638 (7)	−0.08920 (17)	0.4381 (4)	0.0480 (12)
C7	0.3114 (7)	−0.07622 (17)	0.5423 (4)	0.0445 (11)
C8	0.3749 (8)	−0.11265 (19)	0.6244 (4)	0.0533 (12)
C9	0.3743 (8)	0.07761 (19)	0.8421 (5)	0.0641 (15)
H9	0.2657	0.0984	0.8193	0.077*
C10	0.3505 (10)	0.0264 (2)	0.8351 (5)	0.0683 (16)
H10	0.2265	0.0125	0.8089	0.082*
C11	0.5123 (11)	−0.0038 (2)	0.8672 (4)	0.0687 (17)
H11	0.4974	−0.0385	0.8620	0.082*
C12	0.6932 (10)	0.0159 (2)	0.9064 (4)	0.0640 (15)
H12	0.8019	−0.0051	0.9268	0.077*
C13	0.7152 (8)	0.0667 (2)	0.9157 (4)	0.0580 (13)
C14	0.5577 (8)	0.09867 (19)	0.8825 (4)	0.0556 (13)
C15	0.5910 (8)	0.1552 (2)	0.8865 (5)	0.0684 (16)
H15A	0.6770	0.1640	0.9541	0.082*
H15B	0.6565	0.1646	0.8315	0.082*
C16	0.3278 (10)	0.2031 (2)	0.7753 (5)	0.0743 (17)
H16	0.3917	0.1985	0.7209	0.089*
C17	0.1596 (11)	0.2289 (2)	0.7579 (6)	0.086 (2)
H17	0.1058	0.2421	0.6913	0.103*
C18	0.0658 (10)	0.2358 (2)	0.8385 (6)	0.0775 (18)
H18	−0.0521	0.2535	0.8258	0.093*
C19	0.1436 (9)	0.2172 (2)	0.9357 (6)	0.0702 (16)
H19	0.0814	0.2225	0.9906	0.084*
C20	0.3197 (9)	0.18967 (18)	0.9533 (4)	0.0608 (14)
C21	0.4088 (11)	0.1680 (3)	1.0561 (5)	0.087 (2)
H21A	0.4083	0.1321	1.0506	0.130*
H21B	0.3350	0.1780	1.1062	0.130*
H21C	0.5418	0.1797	1.0793	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0448 (4)	0.0417 (4)	0.0407 (4)	−0.0001 (3)	0.0104 (3)	0.0008 (2)
Cl1	0.0586 (10)	0.0884 (12)	0.1225 (16)	0.0103 (8)	0.0037 (10)	−0.0010 (10)
S1	0.0510 (8)	0.0474 (7)	0.0449 (7)	0.0025 (6)	0.0074 (6)	−0.0033 (5)
S2	0.0682 (9)	0.0458 (7)	0.0414 (7)	0.0000 (6)	0.0095 (6)	0.0011 (5)
S3	0.0728 (9)	0.0491 (7)	0.0425 (7)	0.0051 (6)	0.0118 (6)	−0.0022 (5)
S4	0.0574 (8)	0.0509 (7)	0.0415 (7)	0.0028 (6)	0.0131 (6)	0.0018 (5)
N1	0.111 (5)	0.049 (3)	0.081 (4)	0.010 (3)	0.005 (3)	−0.010 (3)
N2	0.134 (5)	0.075 (4)	0.071 (4)	0.032 (3)	0.033 (4)	0.027 (3)
N3	0.115 (5)	0.056 (3)	0.100 (4)	0.004 (3)	0.013 (4)	−0.013 (3)
N4	0.082 (4)	0.074 (3)	0.078 (4)	0.005 (3)	0.012 (3)	0.031 (3)
N5	0.058 (3)	0.044 (2)	0.073 (3)	−0.008 (2)	0.022 (2)	−0.013 (2)
C1	0.056 (3)	0.052 (3)	0.057 (3)	0.005 (2)	0.007 (3)	0.002 (2)
C2	0.041 (3)	0.042 (3)	0.056 (3)	−0.001 (2)	0.014 (2)	−0.004 (2)
C3	0.044 (3)	0.044 (3)	0.050 (3)	−0.001 (2)	0.014 (2)	0.005 (2)
C4	0.073 (4)	0.059 (3)	0.057 (3)	0.008 (3)	0.024 (3)	0.002 (3)
C5	0.065 (4)	0.053 (3)	0.069 (4)	0.004 (3)	0.011 (3)	0.003 (3)
C6	0.045 (3)	0.043 (3)	0.056 (3)	0.005 (2)	0.013 (2)	−0.001 (2)
C7	0.035 (3)	0.051 (3)	0.049 (3)	0.001 (2)	0.013 (2)	0.007 (2)
C8	0.052 (3)	0.052 (3)	0.057 (3)	−0.005 (2)	0.015 (3)	0.004 (3)
C9	0.058 (4)	0.051 (3)	0.078 (4)	0.002 (3)	0.005 (3)	−0.007 (3)
C10	0.084 (4)	0.060 (3)	0.061 (4)	−0.013 (3)	0.017 (3)	−0.009 (3)
C11	0.113 (6)	0.045 (3)	0.047 (3)	−0.003 (3)	0.018 (3)	−0.006 (2)
C12	0.082 (4)	0.061 (4)	0.050 (3)	0.019 (3)	0.016 (3)	0.004 (3)
C13	0.071 (4)	0.056 (3)	0.048 (3)	0.008 (3)	0.016 (3)	0.002 (2)
C14	0.056 (3)	0.055 (3)	0.057 (3)	0.002 (3)	0.015 (3)	−0.005 (2)
C15	0.055 (4)	0.057 (3)	0.096 (5)	0.004 (3)	0.023 (3)	−0.006 (3)
C16	0.101 (5)	0.055 (3)	0.067 (4)	0.008 (3)	0.019 (4)	0.012 (3)
C17	0.101 (5)	0.063 (4)	0.094 (5)	0.015 (4)	0.022 (4)	0.018 (3)
C18	0.075 (4)	0.049 (3)	0.109 (6)	0.011 (3)	0.023 (4)	0.008 (3)
C19	0.071 (4)	0.048 (3)	0.095 (5)	0.002 (3)	0.027 (4)	−0.002 (3)
C20	0.078 (4)	0.040 (3)	0.059 (3)	−0.019 (3)	0.005 (3)	0.001 (2)
C21	0.108 (5)	0.087 (5)	0.060 (4)	−0.017 (4)	0.011 (4)	−0.003 (3)

Geometric parameters (Å, º)

Ni1—S1	2.1484 (13)	C9—C14	1.385 (8)
Ni1—S2	2.1496 (14)	C9—H9	0.9300
Ni1—S3	2.1416 (14)	C10—C11	1.372 (8)
Ni1—S4	2.1369 (14)	C10—H10	0.9300
S1—C2	1.725 (5)	C11—C12	1.353 (8)
S2—C3	1.717 (5)	C11—H11	0.9300
S3—C6	1.710 (5)	C12—C13	1.365 (7)
S4—C7	1.711 (5)	C12—H12	0.9300
N1—C1	1.122 (7)	C13—C14	1.379 (7)
N2—C4	1.135 (7)	C15—H15A	0.9700
N3—C5	1.140 (7)	C15—H15B	0.9700
N4—C8	1.129 (7)	C16—C17	1.334 (9)
N5—C20	1.338 (7)	C16—H16	0.9300
N5—C16	1.348 (8)	C17—C18	1.374 (9)
N5—C15	1.485 (7)	C17—H17	0.9300
C14—C15	1.523 (7)	C18—C19	1.349 (9)
C1—C2	1.438 (7)	C18—H18	0.9300
C2—C3	1.352 (7)	C19—C20	1.405 (8)
C3—C4	1.441 (7)	C19—H19	0.9300
C5—C6	1.431 (7)	C20—C21	1.455 (8)
C6—C7	1.363 (7)	C21—H21A	0.9600
C7—C8	1.434 (7)	C21—H21B	0.9600
Cl1—C13	1.737 (6)	C21—H21C	0.9600
C9—C10	1.376 (7)
S1—Ni1—S2	92.66 (5)	C10—C11—H11	119.4
S3—Ni1—S2	87.68 (5)	C11—C12—C13	119.6 (6)
S4—Ni1—S3	92.10 (5)	C11—C12—H12	120.2
S4—Ni1—S1	87.64 (5)	C13—C12—H12	120.2
S3—Ni1—S1	176.66 (6)	C12—C13—C14	121.4 (6)
S4—Ni1—S2	178.59 (6)	C12—C13—Cl1	119.3 (5)
C2—S1—Ni1	103.01 (17)	C14—C13—Cl1	119.3 (4)
C3—S2—Ni1	102.94 (17)	C13—C14—C9	117.9 (5)
C6—S3—Ni1	103.66 (17)	C13—C14—C15	119.8 (5)
C7—S4—Ni1	103.94 (17)	C9—C14—C15	122.3 (5)
C20—N5—C16	122.7 (5)	N5—C15—C14	112.4 (4)
C20—N5—C15	120.1 (5)	N5—C15—H15A	109.1
C16—N5—C15	117.2 (5)	C14—C15—H15A	109.1
N1—C1—C2	178.7 (6)	N5—C15—H15B	109.1
C3—C2—C1	122.0 (4)	C14—C15—H15B	109.1
C3—C2—S1	120.4 (4)	H15A—C15—H15B	107.9
C1—C2—S1	117.6 (4)	C17—C16—N5	119.6 (6)
C2—C3—C4	121.2 (5)	C17—C16—H16	120.2
C2—C3—S2	121.0 (4)	N5—C16—H16	120.2
C4—C3—S2	117.8 (4)	C16—C17—C18	120.1 (7)
N2—C4—C3	178.8 (7)	C16—C17—H17	120.0
N3—C5—C6	178.2 (7)	C18—C17—H17	120.0
C7—C6—C5	122.4 (5)	C19—C18—C17	120.4 (6)
C7—C6—S3	120.4 (4)	C19—C18—H18	119.8
C5—C6—S3	117.2 (4)	C17—C18—H18	119.8
C6—C7—C8	121.9 (5)	C18—C19—C20	119.2 (6)
C6—C7—S4	119.9 (4)	C18—C19—H19	120.4
C8—C7—S4	118.1 (4)	C20—C19—H19	120.4
N4—C8—C7	179.4 (6)	N5—C20—C19	117.9 (5)
C10—C9—C14	120.9 (6)	N5—C20—C21	120.4 (6)
C10—C9—H9	119.5	C19—C20—C21	121.6 (6)
C14—C9—H9	119.5	C20—C21—H21A	109.5
C11—C10—C9	119.0 (6)	C20—C21—H21B	109.5
C11—C10—H10	120.5	H21A—C21—H21B	109.5
C9—C10—H10	120.5	C20—C21—H21C	109.5
C12—C11—C10	121.1 (5)	H21A—C21—H21C	109.5
C12—C11—H11	119.4	H21B—C21—H21C	109.5