Bis[(2-chloro-4-fluoro-benz-yl)triphenyl-phospho-nium] bis-(1,2,5-thia-diazole-3,4-dithiol-ato)nickelate(II).

The title ion-pair complex, (C(25)H(20)ClFP)(2)[Ni(C(2)N(2)S(3))(2)], was obtained by the direct reaction of (4-F,2-ClBzTPP)(+)·Br(-) [4-F,2-ClBzTPP(+) is (2-chloro-4-fluoro-benz-yl)triphenyl-phos-pho-nium], NiCl(2)·6H(2)O and Na(2)tdas (tdas(2-) is 1,2,5-thia-diazole-3,4-dithiol-ate) in methanol. The asymmetric unit of the title structure comprises one (4-F,2-ClBzTPP)(+) cation and half of an [Ni(tdas)(2)](2-) complex anion, with the Ni(II) ion situated on a center of symmetry, leading to a slightly distorted square-planar coordination of the latter. In the cation, the tetra-hedral angles around the P atom are nearly undistorted. In the crystal, the cations and anions are linked by C-H⋯S, C-H⋯N and C-H⋯Cl hydrogen bonds.

Related literature

For background to complexes containing the [Ni(maleo­nitrile­dithiol­ate)2]2− anion, see: Chen et al. (2010 ▶); Hou et al. (2008 ▶); Ni et al. (2005 ▶); Ren et al. (2002 ▶); Robertson & Cronin (2002 ▶); Xie et al. (2002 ▶); Zhou et al. (2011 ▶). For details of other square-planar Ni(1,2,5-thia­diazole-3,4-dithiol­ate)2 complexes, see: Awaga et al. (1994 ▶); Yamochi et al. (2001 ▶); Okuno et al. (2003 ▶); Ni et al. (2004 ▶); Zuo et al. (2009 ▶).

Experimental

Crystal data

(C25H20ClFP)2[Ni(C2N2S3)2]

M = 1166.81

Triclinic,

a = 9.4447 (11) Å

b = 12.1385 (15) Å

c = 13.1309 (16) Å

α = 71.447 (1)°

β = 83.601 (2)°

γ = 68.691 (2)°

V = 1329.6 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.81 mm−1

T = 291 K

0.19 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.861, T max = 0.916

9694 measured reflections

4652 independent reflections

3807 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.118

S = 1.00

4652 reflections

322 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.39 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003625/wm2587sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003625/wm2587Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C25H20ClFP)2[Ni(C2N2S3)2]	Z = 1
Mr = 1166.81	F(000) = 598
Triclinic, P1	Dx = 1.457 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4447 (11) Å	Cell parameters from 3884 reflections
b = 12.1385 (15) Å	θ = 2.3–26.0°
c = 13.1309 (16) Å	µ = 0.81 mm−1
α = 71.447 (1)°	T = 291 K
β = 83.601 (2)°	Block, brown
γ = 68.691 (2)°	0.19 × 0.15 × 0.11 mm
V = 1329.6 (3) Å3

Bruker SMART CCD diffractometer	4652 independent reflections
Radiation source: fine-focus sealed tube	3807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→10
Tmin = 0.861, Tmax = 0.916	k = −14→14
9694 measured reflections	l = −15→15

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0368P)2 + 1.988P] where P = (Fo2 + 2Fc2)/3
4652 reflections	(Δ/σ)max < 0.001
322 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.0000	0.03811 (17)
S1	0.58693 (12)	0.34739 (9)	−0.07028 (7)	0.0552 (3)
S2	0.42586 (13)	0.38755 (9)	0.14777 (8)	0.0618 (3)
S3	0.49400 (15)	0.04337 (10)	0.12386 (9)	0.0728 (3)
Cl1	0.70371 (13)	0.46088 (10)	0.42942 (8)	0.0685 (3)
F1	0.5385 (4)	0.1177 (3)	0.4145 (3)	0.1061 (10)
N1	0.5634 (4)	0.1203 (3)	0.0147 (3)	0.0644 (9)
N2	0.4341 (4)	0.1508 (3)	0.1854 (3)	0.0654 (9)
P1	0.95727 (10)	0.22890 (8)	0.69433 (7)	0.0408 (2)
C1	0.5392 (4)	0.2291 (3)	0.0242 (3)	0.0459 (8)
C2	0.4655 (4)	0.2480 (3)	0.1213 (3)	0.0475 (8)
C3	0.6640 (4)	0.3250 (3)	0.4940 (3)	0.0505 (8)
C4	0.6126 (5)	0.2753 (4)	0.4295 (3)	0.0632 (11)
H4	0.5992	0.3136	0.3559	0.076*
C5	0.5826 (5)	0.1690 (4)	0.4779 (4)	0.0684 (11)
C6	0.5948 (5)	0.1121 (4)	0.5864 (4)	0.0680 (11)
H6	0.5686	0.0418	0.6172	0.082*
C7	0.6469 (4)	0.1618 (4)	0.6486 (3)	0.0544 (9)
H7	0.6565	0.1236	0.7224	0.065*
C8	0.6859 (4)	0.2682 (3)	0.6042 (3)	0.0436 (8)
C9	0.7547 (4)	0.3131 (3)	0.6737 (3)	0.0456 (8)
H9A	0.7042	0.3038	0.7429	0.055*
H9B	0.7376	0.4006	0.6404	0.055*
C10	0.8961 (5)	0.0449 (4)	0.8608 (3)	0.0588 (10)
H10	0.8138	0.1087	0.8753	0.071*
C11	0.9250 (6)	−0.0750 (4)	0.9244 (3)	0.0738 (12)
H11	0.8615	−0.0925	0.9819	0.089*
C12	1.0475 (6)	−0.1698 (5)	0.9035 (4)	0.0797 (14)
H12	1.0651	−0.2511	0.9461	0.096*
C13	1.1436 (5)	−0.1448 (4)	0.8202 (4)	0.0717 (12)
H13	1.2272	−0.2089	0.8075	0.086*
C14	1.1167 (4)	−0.0246 (3)	0.7551 (3)	0.0553 (9)
H14	1.1824	−0.0076	0.6990	0.066*
C15	0.9911 (4)	0.0703 (3)	0.7741 (3)	0.0454 (8)
C16	0.9476 (5)	0.3957 (4)	0.8019 (3)	0.0583 (10)
H16	0.8426	0.4258	0.7933	0.070*
C17	1.0149 (6)	0.4456 (5)	0.8554 (4)	0.0757 (13)
H17	0.9553	0.5092	0.8832	0.091*
C18	1.1704 (6)	0.4007 (5)	0.8674 (4)	0.0777 (13)
H18	1.2152	0.4347	0.9032	0.093*
C19	1.2600 (5)	0.3067 (5)	0.8274 (4)	0.0760 (13)
H19	1.3650	0.2777	0.8352	0.091*
C20	1.1938 (5)	0.2558 (4)	0.7757 (3)	0.0673 (11)
H20	1.2540	0.1904	0.7501	0.081*
C21	1.0368 (4)	0.3015 (3)	0.7614 (3)	0.0475 (8)
C22	1.1227 (4)	0.3129 (3)	0.5183 (3)	0.0559 (9)
H22	1.1355	0.3625	0.5553	0.067*
C23	1.1813 (5)	0.3194 (4)	0.4163 (4)	0.0721 (12)
H23	1.2353	0.3724	0.3855	0.087*
C24	1.1614 (5)	0.2499 (5)	0.3607 (4)	0.0773 (14)
H24	1.2011	0.2559	0.2919	0.093*
C25	1.0820 (5)	0.1692 (4)	0.4052 (3)	0.0663 (11)
H25	1.0678	0.1221	0.3662	0.080*
C26	1.0242 (4)	0.1596 (3)	0.5083 (3)	0.0524 (9)
H26	0.9721	0.1052	0.5394	0.063*
C27	1.0450 (4)	0.2327 (3)	0.5651 (3)	0.0439 (8)

	U11	U22	U33	U12	U13	U23
Ni1	0.0364 (3)	0.0470 (4)	0.0314 (3)	−0.0127 (3)	0.0052 (2)	−0.0163 (2)
S1	0.0713 (6)	0.0579 (6)	0.0441 (5)	−0.0277 (5)	0.0236 (4)	−0.0269 (4)
S2	0.0861 (7)	0.0503 (5)	0.0480 (5)	−0.0237 (5)	0.0288 (5)	−0.0230 (4)
S3	0.0978 (9)	0.0573 (6)	0.0710 (7)	−0.0355 (6)	0.0188 (6)	−0.0257 (5)
Cl1	0.0798 (7)	0.0599 (6)	0.0587 (6)	−0.0315 (5)	−0.0064 (5)	0.0020 (5)
F1	0.123 (3)	0.127 (3)	0.108 (2)	−0.064 (2)	−0.0197 (19)	−0.056 (2)
N1	0.085 (2)	0.055 (2)	0.061 (2)	−0.0268 (18)	0.0149 (17)	−0.0296 (16)
N2	0.082 (2)	0.057 (2)	0.059 (2)	−0.0284 (18)	0.0207 (17)	−0.0200 (16)
P1	0.0422 (5)	0.0435 (5)	0.0385 (4)	−0.0172 (4)	0.0047 (4)	−0.0137 (4)
C1	0.0465 (19)	0.048 (2)	0.0452 (19)	−0.0146 (16)	0.0030 (15)	−0.0204 (16)
C2	0.0447 (19)	0.054 (2)	0.0430 (18)	−0.0168 (16)	0.0083 (15)	−0.0157 (16)
C3	0.046 (2)	0.054 (2)	0.050 (2)	−0.0155 (17)	0.0012 (16)	−0.0157 (17)
C4	0.058 (2)	0.079 (3)	0.052 (2)	−0.019 (2)	−0.0064 (18)	−0.022 (2)
C5	0.063 (3)	0.081 (3)	0.077 (3)	−0.029 (2)	−0.010 (2)	−0.036 (3)
C6	0.066 (3)	0.067 (3)	0.083 (3)	−0.037 (2)	−0.003 (2)	−0.021 (2)
C7	0.050 (2)	0.061 (2)	0.054 (2)	−0.0263 (18)	0.0026 (17)	−0.0123 (18)
C8	0.0367 (17)	0.0486 (19)	0.0444 (18)	−0.0121 (15)	0.0041 (14)	−0.0168 (15)
C9	0.0443 (19)	0.050 (2)	0.0436 (18)	−0.0154 (16)	0.0045 (15)	−0.0182 (16)
C10	0.059 (2)	0.069 (3)	0.044 (2)	−0.024 (2)	0.0023 (17)	−0.0088 (18)
C11	0.083 (3)	0.078 (3)	0.052 (2)	−0.040 (3)	−0.002 (2)	0.006 (2)
C12	0.098 (4)	0.063 (3)	0.068 (3)	−0.037 (3)	−0.025 (3)	0.011 (2)
C13	0.075 (3)	0.056 (3)	0.073 (3)	−0.013 (2)	−0.019 (2)	−0.010 (2)
C14	0.053 (2)	0.054 (2)	0.056 (2)	−0.0165 (18)	−0.0012 (17)	−0.0143 (18)
C15	0.0471 (19)	0.052 (2)	0.0387 (17)	−0.0216 (16)	−0.0003 (15)	−0.0098 (15)
C16	0.059 (2)	0.064 (2)	0.060 (2)	−0.022 (2)	0.0012 (18)	−0.029 (2)
C17	0.083 (3)	0.083 (3)	0.077 (3)	−0.032 (3)	−0.001 (2)	−0.041 (3)
C18	0.094 (4)	0.091 (3)	0.068 (3)	−0.050 (3)	−0.013 (3)	−0.025 (3)
C19	0.066 (3)	0.088 (3)	0.081 (3)	−0.029 (3)	−0.018 (2)	−0.027 (3)
C20	0.054 (2)	0.074 (3)	0.074 (3)	−0.015 (2)	−0.012 (2)	−0.027 (2)
C21	0.052 (2)	0.052 (2)	0.0408 (18)	−0.0230 (17)	−0.0022 (15)	−0.0108 (15)
C22	0.060 (2)	0.051 (2)	0.058 (2)	−0.0253 (19)	0.0099 (18)	−0.0135 (18)
C23	0.072 (3)	0.073 (3)	0.068 (3)	−0.038 (2)	0.025 (2)	−0.011 (2)
C24	0.075 (3)	0.085 (3)	0.055 (2)	−0.020 (3)	0.029 (2)	−0.016 (2)
C25	0.071 (3)	0.072 (3)	0.053 (2)	−0.016 (2)	0.013 (2)	−0.030 (2)
C26	0.054 (2)	0.057 (2)	0.048 (2)	−0.0209 (18)	0.0103 (16)	−0.0185 (17)
C27	0.0429 (18)	0.0435 (19)	0.0437 (18)	−0.0155 (15)	0.0081 (14)	−0.0132 (15)

Ni1—S1i	2.1842 (9)	C10—H10	0.9300
Ni1—S1	2.1842 (9)	C11—C12	1.379 (7)
Ni1—S2i	2.1966 (9)	C11—H11	0.9300
Ni1—S2	2.1966 (9)	C12—C13	1.371 (7)
S1—C1	1.736 (4)	C12—H12	0.9300
S2—C2	1.737 (4)	C13—C14	1.381 (6)
S3—N2	1.644 (3)	C13—H13	0.9300
S3—N1	1.655 (3)	C14—C15	1.386 (5)
Cl1—C3	1.752 (4)	C14—H14	0.9300
F1—C5	1.361 (5)	C16—C21	1.373 (5)
N1—C1	1.300 (4)	C16—C17	1.384 (5)
N2—C2	1.324 (5)	C16—H16	0.9300
P1—C27	1.798 (3)	C17—C18	1.376 (7)
P1—C21	1.799 (3)	C17—H17	0.9300
P1—C15	1.802 (4)	C18—C19	1.370 (7)
P1—C9	1.816 (3)	C18—H18	0.9300
C1—C2	1.427 (5)	C19—C20	1.368 (6)
C3—C8	1.393 (5)	C19—H19	0.9300
C3—C4	1.394 (5)	C20—C21	1.394 (5)
C4—C5	1.361 (6)	C20—H20	0.9300
C4—H4	0.9300	C22—C27	1.379 (5)
C5—C6	1.368 (6)	C22—C23	1.380 (6)
C6—C7	1.375 (5)	C22—H22	0.9300
C6—H6	0.9300	C23—C24	1.349 (6)
C7—C8	1.401 (5)	C23—H23	0.9300
C7—H7	0.9300	C24—C25	1.391 (6)
C8—C9	1.503 (5)	C24—H24	0.9300
C9—H9A	0.9700	C25—C26	1.388 (5)
C9—H9B	0.9700	C25—H25	0.9300
C10—C11	1.371 (6)	C26—C27	1.400 (5)
C10—C15	1.395 (5)	C26—H26	0.9300
S1i—Ni1—S1	180.00 (4)	C10—C11—H11	119.8
S1i—Ni1—S2i	93.18 (3)	C12—C11—H11	119.8
S1—Ni1—S2i	86.82 (3)	C13—C12—C11	120.3 (4)
S1i—Ni1—S2	86.82 (3)	C13—C12—H12	119.9
S1—Ni1—S2	93.18 (3)	C11—C12—H12	119.9
S2i—Ni1—S2	180.00 (8)	C12—C13—C14	120.3 (4)
C1—S1—Ni1	103.26 (11)	C12—C13—H13	119.8
C2—S2—Ni1	102.65 (12)	C14—C13—H13	119.8
N2—S3—N1	98.37 (16)	C13—C14—C15	119.4 (4)
C1—N1—S3	106.9 (3)	C13—C14—H14	120.3
C2—N2—S3	106.6 (3)	C15—C14—H14	120.3
C27—P1—C21	109.46 (16)	C14—C15—C10	120.0 (3)
C27—P1—C15	109.54 (16)	C14—C15—P1	120.6 (3)
C21—P1—C15	109.54 (16)	C10—C15—P1	119.2 (3)
C27—P1—C9	108.25 (16)	C21—C16—C17	119.6 (4)
C21—P1—C9	109.81 (16)	C21—C16—H16	120.2
C15—P1—C9	110.22 (16)	C17—C16—H16	120.2
N1—C1—C2	114.5 (3)	C18—C17—C16	119.8 (4)
N1—C1—S1	125.5 (3)	C18—C17—H17	120.1
C2—C1—S1	120.1 (3)	C16—C17—H17	120.1
N2—C2—C1	113.6 (3)	C19—C18—C17	120.9 (4)
N2—C2—S2	125.7 (3)	C19—C18—H18	119.6
C1—C2—S2	120.7 (3)	C17—C18—H18	119.6
C8—C3—C4	121.8 (4)	C20—C19—C18	119.5 (4)
C8—C3—Cl1	121.3 (3)	C20—C19—H19	120.2
C4—C3—Cl1	116.8 (3)	C18—C19—H19	120.2
C5—C4—C3	117.8 (4)	C19—C20—C21	120.3 (4)
C5—C4—H4	121.1	C19—C20—H20	119.8
C3—C4—H4	121.1	C21—C20—H20	119.8
F1—C5—C4	117.8 (4)	C16—C21—C20	119.8 (4)
F1—C5—C6	119.0 (4)	C16—C21—P1	122.2 (3)
C4—C5—C6	123.2 (4)	C20—C21—P1	117.9 (3)
C5—C6—C7	118.1 (4)	C27—C22—C23	119.8 (4)
C5—C6—H6	120.9	C27—C22—H22	120.1
C7—C6—H6	120.9	C23—C22—H22	120.1
C6—C7—C8	122.0 (4)	C24—C23—C22	120.9 (4)
C6—C7—H7	119.0	C24—C23—H23	119.6
C8—C7—H7	119.0	C22—C23—H23	119.6
C3—C8—C7	116.9 (3)	C23—C24—C25	120.7 (4)
C3—C8—C9	122.8 (3)	C23—C24—H24	119.7
C7—C8—C9	120.2 (3)	C25—C24—H24	119.7
C8—C9—P1	112.3 (2)	C26—C25—C24	119.4 (4)
C8—C9—H9A	109.2	C26—C25—H25	120.3
P1—C9—H9A	109.2	C24—C25—H25	120.3
C8—C9—H9B	109.2	C25—C26—C27	119.4 (4)
P1—C9—H9B	109.2	C25—C26—H26	120.3
H9A—C9—H9B	107.9	C27—C26—H26	120.3
C11—C10—C15	119.5 (4)	C22—C27—C26	119.8 (3)
C11—C10—H10	120.3	C22—C27—P1	120.8 (3)
C15—C10—H10	120.3	C26—C27—P1	119.2 (3)
C10—C11—C12	120.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S1ii	0.97	2.71	3.635 (4)	160
C9—H9B···Cl1	0.97	2.66	3.129 (4)	110
C24—H24···N2iii	0.93	2.61	3.401 (7)	143

Ni1—S1	2.1842 (9)
Ni1—S2	2.1966 (9)

S1i—Ni1—S2	86.82 (3)
S1—Ni1—S2	93.18 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯S1ii	0.97	2.71	3.635 (4)	160
C9—H9B⋯Cl1	0.97	2.66	3.129 (4)	110
C24—H24⋯N2iii	0.93	2.61	3.401 (7)	143

Symmetry codes: (ii) ; (iii) .