Bis[2-(4-bromo­benz­yl)isoquinolinium] bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ2S,S′)nickel(II)

Zhou, A.-Q.; Zhou, J.-R.; Ni, C.-L.

doi:10.1107/S1600536807055821

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Bis[2-(4-bromobenzyl)isoquinolinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickel(II)

A.-Q. Zhou, J.-R. Zhou and C.-L. Ni

The new title nickel(II) complex, (C₁₆H₁₃BrN)₂[Ni(C₄N₂S₂)₂], is a salt obtained by the direct reaction of NiCl₂, disodium maleonitriledithiolate (Na₂mnt) and 1-(4-bromobenzyl)isoquinolinium bromide, (BrBzIQl)⁺Br⁻, in methanol. The structure contains two (BrBzIQl)⁺ cations and an Ni(mnt)₂²⁻ anion in the asymmetric unit. In the two (BrBzIQl)⁺ cations, the dihedral angles between the benzene ring and the isoquinoline plane are 71.0 (4) and 82.1 (4)°. The [Ni(mnt)₂]²⁻ anion exhibits a slightly distorted square-planar coordination geometry. The crystal structure is stabilized by three weak C—H

N hydrogen bonds and a π–π stacking interaction involving the benzene ring and isoquinoline plane [centroid–centroid separation 3.774 (2) Å]

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055821/sj2407sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055821/sj2407Isup2.hkl Contains datablock I

CCDC reference: 672635

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.011 Å
R factor = 0.065
wR factor = 0.147
Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C15
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C19
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C25
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C28
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C4     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C8     ...       1.45 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C6     -   C7     ...       1.44 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.82

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 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
   1 ALERT type 5 Informative message, check

Comment top

1,2-Dithiolene metal complexes are important molecular materials with interesting physical properties such as electical conductivity, superconductivity, photoelectric and magnetic properties (Robertson & Cronin, 2002; Ni et al., 2004; Xie et al., 2002; Ren et al., 2002; Nishijo et al., 2003; Canadell, 1999). Recently, some substituted isoquinolinium cations have been introduced into the Ni(mnt)₂ system to obtain Ni(mnt)₂^2--based molecular solids showing unusual magnetic properties (Ni et al., 2005; Ni et al., 2006; Ni et al., 2007). To gain more insight into how the substituted groups affects the stacking mode of Ni(mnt)₂^2- anion, we herein present a new Ni(mnt)₂^2- salt containing the 1-(4-bromobenzyl)isoquinolinium cation as shown in Fig.1. The salt consists of two (BrBzIQl)⁺ cations and a Ni(mnt)₂^2- anion in the asymmetric unit. In the cations, the dihedral angles between the benzene rings and the isoquinoline groups are 71.0 (4) ° for the cation containing N5, and 82.1 (4) ° for the cation containing N6. The Ni(II) ion of the [Ni(mnt)₂]^(2-) anion and exhibits a slightly distorted square-planar coordination geometry. The four CN groups of [Ni(mnt)₂]^2- are slightly tipped out of the S1/S2/Ni1/S3/S4 plane and the deviations from the plane are -0.294 (3) Å for N1, -0.324 (3) Å for N2, -0.237 (3) Å for N3 and 0.195 (3)Å for N4, respectively.

The crystal structure is stabilized by C17—H17···N1, C31—H31A···N2 and C36—H36···N2 hydrogen bonds, Table 1, and a π···π stacking interaction between the N5/C16···C24 group and the C25ⁱ···C30ⁱ ring [Symmetry Code:(i)1 - x,1 - y,1 - z] with a distance of 3.774 (2) Å between the centroids of the two systems, Fig 2.

Related literature top

For details of other square planar 1,2-dithiolene metal complexes, see: Robertson & Cronin (2002); Ni et al. (2004) Please check – reference not in list; Xie et al. (2002); Ren et al. (2002); Nishijo et al. (2003); Canadell (1999). For the structures of related Ni(mnt)₂^- complexes with square-planar geometry and a substituted isoquinolinium counter-ion, see: Ni, Dang et al. (2005) Ni, Yang & Meng (2005), Ni et al. 2006, 2007).

Experimental top

The title compound was prepared by the direct reaction of NiCl₂.6H₂O, Na₂mnt and (BrBzIQl)⁺Br^- in in methanol. The brown block-like single crystals were obtained by slow evaporation of a mixed solution of CH₃CN and i-PrOH (1:1) at room temperature for about two weeks.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The π···π interaction in the structure of (I) [Symmetry Code:(A)1 - x,1 - y,1 - z].

Bis[2-(4-bromobenzyl)isoquinolinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickel(II) top

Crystal data top

(C₁₆H₁₃BrN)₂[Ni(C₄N₂S₂)₂]	Z = 2
M_r = 937.44	F(000) = 940
Triclinic, P1	D_x = 1.562 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.320 (4) Å	Cell parameters from 698 reflections
b = 13.354 (5) Å	θ = 2.8–20.4°
c = 14.754 (5) Å	µ = 2.74 mm⁻¹
α = 110.776 (7)°	T = 291 K
β = 101.261 (6)°	Block, brown
γ = 97.880 (7)°	0.30 × 0.30 × 0.10 mm
V = 1992.8 (12) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	6871 independent reflections
Radiation source: fine-focus sealed tube	3408 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→13
T_min = 0.461, T_max = 0.762	k = −15→9
9888 measured reflections	l = −14→17

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
6871 reflections	(Δ/σ)_max = 0.001
466 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

(C₁₆H₁₃BrN)₂[Ni(C₄N₂S₂)₂]	γ = 97.880 (7)°
M_r = 937.44	V = 1992.8 (12) Å³
Triclinic, P1	Z = 2
a = 11.320 (4) Å	Mo Kα radiation
b = 13.354 (5) Å	µ = 2.74 mm⁻¹
c = 14.754 (5) Å	T = 291 K
α = 110.776 (7)°	0.30 × 0.30 × 0.10 mm
β = 101.261 (6)°

Data collection top

Bruker SMART APEX CCD diffractometer	6871 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3408 reflections with I > 2σ(I)
T_min = 0.461, T_max = 0.762	R_int = 0.085
9888 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.04	Δρ_max = 0.96 e Å⁻³
6871 reflections	Δρ_min = −0.68 e Å⁻³
466 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.32855 (7)	0.37256 (6)	0.16612 (5)	0.0583 (2)
Br1	1.19531 (9)	0.73115 (8)	0.60159 (10)	0.1871 (6)
Br2	0.17434 (9)	0.03355 (11)	0.37778 (7)	0.1603 (5)
C1	0.4413 (5)	0.2335 (4)	0.2708 (4)	0.0585 (16)
C2	0.4826 (5)	0.2076 (4)	0.1883 (4)	0.0562 (15)
C3	0.5536 (6)	0.1275 (5)	0.1648 (4)	0.0650 (17)
C4	0.4693 (6)	0.1786 (6)	0.3371 (5)	0.0705 (18)
C5	0.1738 (5)	0.5346 (5)	0.1360 (5)	0.0657 (17)
C6	0.2167 (5)	0.5077 (4)	0.0552 (5)	0.0617 (17)
C7	0.1943 (7)	0.5541 (5)	−0.0193 (5)	0.0727 (19)
C8	0.0952 (6)	0.6130 (5)	0.1550 (5)	0.0761 (19)
C9	1.0375 (8)	0.6558 (6)	0.5121 (8)	0.107
C10	0.9467 (8)	0.6324 (6)	0.5551 (5)	0.099 (3)
H10	0.9625	0.6513	0.6241	0.119*
C11	0.8294 (7)	0.5790 (6)	0.4910 (6)	0.096 (2)
H11	0.7654	0.5617	0.5177	0.115*
C12	0.8059 (7)	0.5513 (5)	0.3897 (6)	0.0724 (19)
C13	0.9011 (8)	0.5752 (6)	0.3523 (5)	0.089 (2)
H13	0.8880	0.5555	0.2834	0.106*
C14	1.0172 (7)	0.6285 (6)	0.4156 (7)	0.102 (2)
H14	1.0818	0.6451	0.3890	0.122*
C15	0.6783 (6)	0.4941 (5)	0.3214 (5)	0.097 (2)
H15A	0.6850	0.4467	0.2563	0.117*
H15B	0.6365	0.4483	0.3493	0.117*
C16	0.5567 (9)	0.6257 (8)	0.3865 (7)	0.119 (3)
H16	0.5716	0.6073	0.4422	0.143*
C17	0.4902 (8)	0.7017 (8)	0.3868 (6)	0.124 (3)
H17	0.4604	0.7362	0.4416	0.148*
C18	0.4681 (7)	0.7266 (6)	0.3041 (7)	0.092 (2)
C19	0.3982 (8)	0.8111 (7)	0.3006 (7)	0.118 (3)
H19	0.3682	0.8494	0.3540	0.141*
C20	0.3801 (8)	0.8300 (6)	0.2136 (8)	0.107 (3)
H20	0.3358	0.8820	0.2075	0.129*
C21	0.4259 (7)	0.7737 (7)	0.1355 (6)	0.094 (2)
H21	0.4125	0.7901	0.0787	0.113*
C22	0.4893 (6)	0.6959 (6)	0.1375 (6)	0.084 (2)
H22	0.5174	0.6578	0.0828	0.101*
C23	0.5108 (6)	0.6752 (5)	0.2229 (6)	0.0746 (19)
C24	0.5810 (6)	0.5931 (5)	0.2271 (6)	0.079 (2)
H24	0.6096	0.5548	0.1727	0.095*
C25	0.1943 (7)	0.0626 (7)	0.5152 (5)	0.095
C26	0.1321 (7)	0.1321 (6)	0.5688 (6)	0.100 (2)
H26	0.0813	0.1661	0.5376	0.120*
C27	0.1436 (6)	0.1519 (5)	0.6671 (6)	0.084 (2)
H27	0.0971	0.1961	0.7019	0.100*
C28	0.2237 (5)	0.1071 (4)	0.7157 (5)	0.0587 (15)
C29	0.2878 (6)	0.0399 (5)	0.6612 (5)	0.0728 (18)
H29	0.3408	0.0077	0.6926	0.087*
C30	0.2760 (6)	0.0186 (5)	0.5605 (5)	0.087 (2)
H30	0.3227	−0.0247	0.5250	0.104*
C31	0.2412 (6)	0.1313 (5)	0.8254 (4)	0.0690 (17)
H31A	0.3078	0.1000	0.8478	0.083*
H31B	0.2649	0.2103	0.8631	0.083*
C32	0.0844 (6)	−0.0256 (5)	0.8057 (4)	0.0639 (17)
H32	0.1244	−0.0715	0.7649	0.077*
C33	−0.0166 (6)	−0.0677 (5)	0.8254 (4)	0.0648 (17)
H33	−0.0463	−0.1435	0.7965	0.078*
C34	−0.0797 (5)	−0.0037 (5)	0.8871 (4)	0.0528 (15)
C35	−0.1846 (6)	−0.0443 (5)	0.9091 (4)	0.0673 (18)
H35	−0.2181	−0.1196	0.8817	0.081*
C36	−0.2396 (6)	0.0265 (6)	0.9718 (5)	0.0749 (19)
H36	−0.3104	−0.0011	0.9862	0.090*
C37	−0.1891 (6)	0.1402 (6)	1.0139 (5)	0.0757 (19)
H37	−0.2258	0.1873	1.0570	0.091*
C38	−0.0882 (6)	0.1812 (5)	0.9925 (4)	0.0687 (17)
H38	−0.0564	0.2568	1.0201	0.082*
C39	−0.0302 (6)	0.1117 (5)	0.9290 (4)	0.0549 (15)
C40	0.0727 (6)	0.1510 (5)	0.9056 (4)	0.0563 (15)
H40	0.1046	0.2265	0.9327	0.068*
N1	0.4949 (6)	0.1342 (5)	0.3877 (4)	0.095 (2)
N2	0.6105 (6)	0.0614 (5)	0.1465 (4)	0.097 (2)
N3	0.1829 (6)	0.5868 (5)	−0.0815 (5)	0.093 (2)
N4	0.0365 (6)	0.6768 (5)	0.1724 (5)	0.098 (2)
N5	0.6030 (5)	0.5746 (5)	0.3085 (6)	0.0826 (17)
N6	0.1288 (4)	0.0869 (4)	0.8465 (3)	0.0573 (12)
S1	0.35194 (16)	0.32994 (13)	0.29755 (11)	0.0708 (5)
S2	0.44630 (15)	0.26760 (12)	0.10251 (11)	0.0654 (5)
S3	0.31046 (15)	0.41468 (12)	0.03658 (11)	0.0676 (5)
S4	0.20597 (17)	0.47605 (14)	0.22340 (13)	0.0810 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0551 (5)	0.0450 (5)	0.0682 (5)	0.0130 (3)	0.0170 (4)	0.0135 (3)
Br1	0.1028 (7)	0.0784 (7)	0.2734 (14)	0.0060 (5)	−0.0676 (8)	0.0123 (7)
Br2	0.1135 (8)	0.2950 (15)	0.0978 (7)	0.0386 (9)	0.0250 (6)	0.1107 (8)
C1	0.052 (4)	0.055 (4)	0.059 (4)	0.012 (3)	0.010 (3)	0.014 (3)
C2	0.048 (4)	0.051 (4)	0.061 (4)	0.009 (3)	0.010 (3)	0.014 (3)
C3	0.066 (4)	0.078 (5)	0.066 (4)	0.031 (4)	0.029 (3)	0.034 (3)
C4	0.067 (5)	0.078 (5)	0.064 (5)	0.022 (4)	0.014 (4)	0.025 (4)
C5	0.055 (4)	0.055 (4)	0.082 (5)	0.015 (3)	0.016 (3)	0.021 (3)
C6	0.064 (4)	0.036 (3)	0.069 (4)	0.007 (3)	0.008 (3)	0.009 (3)
C7	0.087 (5)	0.049 (4)	0.072 (5)	0.020 (4)	0.013 (4)	0.014 (4)
C8	0.079 (5)	0.064 (5)	0.097 (5)	0.028 (4)	0.035 (4)	0.035 (4)
C9	0.076	0.085	0.121	0.014	−0.011	0.015
C10	0.111 (7)	0.079 (5)	0.078 (5)	0.035 (5)	0.001 (5)	0.004 (4)
C11	0.089 (6)	0.107 (6)	0.089 (6)	0.022 (5)	0.023 (5)	0.035 (5)
C12	0.074 (5)	0.046 (4)	0.083 (5)	0.009 (3)	0.009 (4)	0.016 (3)
C13	0.087 (6)	0.092 (6)	0.085 (5)	0.026 (5)	0.022 (5)	0.031 (4)
C14	0.074 (6)	0.093 (6)	0.143 (7)	0.019 (5)	0.031 (5)	0.051 (5)
C15	0.088 (5)	0.054 (4)	0.119 (6)	0.001 (4)	−0.005 (5)	0.020 (4)
C16	0.126 (8)	0.132 (8)	0.105 (7)	0.049 (7)	0.036 (6)	0.043 (6)
C17	0.126 (8)	0.160 (9)	0.080 (6)	0.068 (7)	0.032 (6)	0.027 (6)
C18	0.083 (5)	0.087 (6)	0.080 (6)	0.017 (4)	0.013 (5)	0.009 (5)
C19	0.119 (7)	0.105 (7)	0.099 (7)	0.045 (6)	0.019 (6)	0.003 (5)
C20	0.094 (6)	0.084 (6)	0.118 (7)	0.029 (5)	0.008 (6)	0.016 (6)
C21	0.079 (5)	0.081 (6)	0.110 (6)	0.010 (5)	0.014 (5)	0.032 (5)
C22	0.065 (5)	0.084 (6)	0.093 (6)	0.008 (4)	0.020 (4)	0.026 (4)
C23	0.064 (4)	0.054 (4)	0.079 (5)	−0.003 (4)	0.009 (4)	0.007 (4)
C24	0.062 (5)	0.056 (5)	0.092 (6)	−0.003 (4)	0.006 (4)	0.011 (4)
C25	0.088	0.118	0.087	0.022	0.019	0.054
C26	0.099 (6)	0.128 (7)	0.121 (7)	0.052 (5)	0.033 (5)	0.090 (6)
C27	0.082 (5)	0.082 (5)	0.106 (6)	0.041 (4)	0.028 (5)	0.051 (4)
C28	0.053 (4)	0.050 (4)	0.076 (4)	0.012 (3)	0.016 (3)	0.028 (3)
C29	0.079 (5)	0.070 (5)	0.072 (5)	0.033 (4)	0.017 (4)	0.026 (3)
C30	0.083 (5)	0.108 (6)	0.073 (5)	0.036 (4)	0.022 (4)	0.034 (4)
C31	0.061 (4)	0.062 (4)	0.075 (5)	0.008 (3)	0.017 (3)	0.019 (3)
C32	0.066 (4)	0.048 (4)	0.072 (4)	0.015 (3)	0.013 (3)	0.018 (3)
C33	0.073 (5)	0.044 (4)	0.063 (4)	0.001 (3)	0.005 (4)	0.015 (3)
C34	0.057 (4)	0.053 (4)	0.044 (3)	0.006 (3)	−0.003 (3)	0.024 (3)
C35	0.062 (4)	0.069 (5)	0.059 (4)	−0.005 (4)	−0.002 (3)	0.027 (3)
C36	0.068 (5)	0.094 (6)	0.065 (4)	0.006 (4)	0.013 (4)	0.040 (4)
C37	0.080 (5)	0.084 (6)	0.077 (5)	0.026 (4)	0.031 (4)	0.039 (4)
C38	0.082 (5)	0.059 (4)	0.080 (5)	0.025 (4)	0.032 (4)	0.035 (3)
C39	0.063 (4)	0.049 (4)	0.059 (4)	0.016 (3)	0.015 (3)	0.029 (3)
C40	0.063 (4)	0.045 (4)	0.062 (4)	0.014 (3)	0.013 (3)	0.024 (3)
N1	0.115 (5)	0.106 (5)	0.081 (4)	0.054 (4)	0.029 (4)	0.044 (4)
N2	0.113 (5)	0.116 (5)	0.099 (4)	0.073 (4)	0.051 (4)	0.054 (4)
N3	0.124 (5)	0.072 (4)	0.083 (5)	0.035 (4)	0.015 (4)	0.030 (3)
N4	0.099 (5)	0.084 (4)	0.136 (5)	0.050 (4)	0.049 (4)	0.052 (4)
N5	0.064 (4)	0.065 (4)	0.097 (5)	0.004 (3)	0.009 (4)	0.017 (4)
N6	0.057 (3)	0.048 (3)	0.065 (3)	0.012 (3)	0.011 (3)	0.022 (3)
S1	0.0789 (12)	0.0677 (11)	0.0693 (11)	0.0304 (9)	0.0312 (9)	0.0198 (8)
S2	0.0724 (11)	0.0620 (10)	0.0691 (10)	0.0270 (9)	0.0271 (9)	0.0255 (8)
S3	0.0786 (11)	0.0489 (10)	0.0704 (10)	0.0211 (8)	0.0216 (9)	0.0143 (8)
S4	0.0877 (13)	0.0815 (13)	0.0977 (13)	0.0462 (11)	0.0460 (11)	0.0414 (10)

Geometric parameters (Å, º) top

Ni1—S3	2.1571 (19)	C19—H19	0.9300
Ni1—S2	2.1657 (17)	C20—C21	1.373 (10)
Ni1—S4	2.1691 (18)	C20—H20	0.9300
Ni1—S1	2.186 (2)	C21—C22	1.346 (9)
Br1—C9	1.895 (8)	C21—H21	0.9300
Br2—C25	1.884 (7)	C22—C23	1.367 (9)
C1—C2	1.338 (7)	C22—H22	0.9300
C1—C4	1.430 (9)	C23—C24	1.450 (9)
C1—S1	1.729 (6)	C24—N5	1.296 (8)
C2—C3	1.411 (8)	C24—H24	0.9300
C2—S2	1.737 (6)	C25—C30	1.355 (9)
C3—N2	1.149 (7)	C25—C26	1.363 (10)
C4—N1	1.127 (7)	C26—C27	1.354 (8)
C5—C6	1.325 (8)	C26—H26	0.9300
C5—C8	1.453 (9)	C27—C28	1.377 (8)
C5—S4	1.737 (7)	C27—H27	0.9300
C6—C7	1.440 (9)	C28—C29	1.368 (7)
C6—S3	1.726 (6)	C28—C31	1.500 (7)
C7—N3	1.142 (7)	C29—C30	1.385 (8)
C8—N4	1.140 (7)	C29—H29	0.9300
C9—C14	1.302 (10)	C30—H30	0.9300
C9—C10	1.366 (11)	C31—N6	1.465 (7)
C10—C11	1.393 (9)	C31—H31A	0.9700
C10—H10	0.9300	C31—H31B	0.9700
C11—C12	1.365 (9)	C32—C33	1.332 (8)
C11—H11	0.9300	C32—N6	1.380 (6)
C12—C13	1.354 (9)	C32—H32	0.9300
C12—C15	1.506 (9)	C33—C34	1.393 (8)
C13—C14	1.379 (9)	C33—H33	0.9300
C13—H13	0.9300	C34—C35	1.382 (8)
C14—H14	0.9300	C34—C39	1.422 (7)
C15—N5	1.500 (8)	C35—C36	1.380 (8)
C15—H15A	0.9700	C35—H35	0.9300
C15—H15B	0.9700	C36—C37	1.404 (8)
C16—C17	1.343 (11)	C36—H36	0.9300
C16—N5	1.357 (9)	C37—C38	1.340 (8)
C16—H16	0.9300	C37—H37	0.9300
C17—C18	1.362 (10)	C38—C39	1.401 (8)
C17—H17	0.9300	C38—H38	0.9300
C18—C23	1.369 (9)	C39—C40	1.368 (7)
C18—C19	1.474 (10)	C40—N6	1.315 (6)
C19—C20	1.377 (10)	C40—H40	0.9300

S3—Ni1—S2	86.47 (7)	C22—C23—C18	123.5 (8)
S3—Ni1—S4	91.51 (7)	C22—C23—C24	118.3 (8)
S2—Ni1—S4	177.56 (8)	C18—C23—C24	118.2 (8)
S3—Ni1—S1	178.51 (7)	N5—C24—C23	118.3 (7)
S2—Ni1—S1	92.37 (7)	N5—C24—H24	120.8
S4—Ni1—S1	89.67 (7)	C23—C24—H24	120.8
C2—C1—C4	119.3 (6)	C30—C25—C26	120.9 (7)
C2—C1—S1	121.3 (5)	C30—C25—Br2	119.1 (6)
C4—C1—S1	119.4 (5)	C26—C25—Br2	119.9 (6)
C1—C2—C3	121.7 (5)	C27—C26—C25	120.6 (7)
C1—C2—S2	121.4 (5)	C27—C26—H26	119.7
C3—C2—S2	116.9 (4)	C25—C26—H26	119.7
N2—C3—C2	178.9 (7)	C26—C27—C28	120.4 (6)
N1—C4—C1	177.4 (8)	C26—C27—H27	119.8
C6—C5—C8	121.7 (6)	C28—C27—H27	119.8
C6—C5—S4	121.8 (5)	C29—C28—C27	118.1 (6)
C8—C5—S4	116.5 (5)	C29—C28—C31	120.7 (6)
C5—C6—C7	124.4 (6)	C27—C28—C31	121.2 (6)
C5—C6—S3	119.8 (5)	C28—C29—C30	121.9 (6)
C7—C6—S3	115.7 (5)	C28—C29—H29	119.0
N3—C7—C6	174.8 (8)	C30—C29—H29	119.0
N4—C8—C5	177.9 (8)	C25—C30—C29	117.9 (6)
C14—C9—C10	122.2 (7)	C25—C30—H30	121.0
C14—C9—Br1	121.9 (8)	C29—C30—H30	121.0
C10—C9—Br1	115.9 (8)	N6—C31—C28	112.1 (5)
C9—C10—C11	116.9 (7)	N6—C31—H31A	109.2
C9—C10—H10	121.6	C28—C31—H31A	109.2
C11—C10—H10	121.6	N6—C31—H31B	109.2
C12—C11—C10	121.7 (7)	C28—C31—H31B	109.2
C12—C11—H11	119.1	H31A—C31—H31B	107.9
C10—C11—H11	119.1	C33—C32—N6	119.3 (6)
C13—C12—C11	118.0 (7)	C33—C32—H32	120.4
C13—C12—C15	120.9 (7)	N6—C32—H32	120.4
C11—C12—C15	121.1 (8)	C32—C33—C34	123.2 (6)
C12—C13—C14	120.4 (7)	C32—C33—H33	118.4
C12—C13—H13	119.8	C34—C33—H33	118.4
C14—C13—H13	119.8	C35—C34—C33	124.9 (6)
C9—C14—C13	120.7 (8)	C35—C34—C39	119.2 (6)
C9—C14—H14	119.7	C33—C34—C39	116.0 (6)
C13—C14—H14	119.7	C36—C35—C34	120.1 (6)
N5—C15—C12	111.7 (5)	C36—C35—H35	119.9
N5—C15—H15A	109.3	C34—C35—H35	119.9
C12—C15—H15A	109.3	C35—C36—C37	120.2 (6)
N5—C15—H15B	109.3	C35—C36—H36	119.9
C12—C15—H15B	109.3	C37—C36—H36	119.9
H15A—C15—H15B	107.9	C38—C37—C36	120.5 (6)
C17—C16—N5	122.9 (9)	C38—C37—H37	119.8
C17—C16—H16	118.5	C36—C37—H37	119.8
N5—C16—H16	118.5	C37—C38—C39	120.8 (6)
C16—C17—C18	117.6 (8)	C37—C38—H38	119.6
C16—C17—H17	121.2	C39—C38—H38	119.6
C18—C17—H17	121.2	C40—C39—C38	122.2 (6)
C17—C18—C23	121.3 (8)	C40—C39—C34	118.6 (5)
C17—C18—C19	120.4 (9)	C38—C39—C34	119.2 (6)
C23—C18—C19	118.3 (8)	N6—C40—C39	123.0 (6)
C20—C19—C18	116.0 (8)	N6—C40—H40	118.5
C20—C19—H19	122.0	C39—C40—H40	118.5
C18—C19—H19	122.0	C24—N5—C16	121.5 (7)
C21—C20—C19	121.5 (9)	C24—N5—C15	122.3 (7)
C21—C20—H20	119.2	C16—N5—C15	116.2 (8)
C19—C20—H20	119.2	C40—N6—C32	119.9 (5)
C22—C21—C20	123.1 (8)	C40—N6—C31	121.7 (5)
C22—C21—H21	118.5	C32—N6—C31	118.4 (5)
C20—C21—H21	118.5	C1—S1—Ni1	102.3 (2)
C21—C22—C23	117.5 (7)	C2—S2—Ni1	102.5 (2)
C21—C22—H22	121.2	C6—S3—Ni1	104.1 (2)
C23—C22—H22	121.2	C5—S4—Ni1	102.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N1ⁱ	0.93	2.40	3.226 (10)	148
C31—H31A···N2ⁱⁱ	0.97	2.48	3.359 (10)	151
C36—H36···N2ⁱⁱⁱ	0.93	2.59	3.288 (9)	132

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z+1.

Experimental details

Crystal data
Chemical formula	(C₁₆H₁₃BrN)₂[Ni(C₄N₂S₂)₂]
M_r	937.44
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	11.320 (4), 13.354 (5), 14.754 (5)
α, β, γ (°)	110.776 (7), 101.261 (6), 97.880 (7)
V (Å³)	1992.8 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.74
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.461, 0.762
No. of measured, independent and observed [I > 2σ(I)] reflections	9888, 6871, 3408
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.147, 1.04
No. of reflections	6871
No. of parameters	466
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.68

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N1ⁱ	0.930	2.400	3.226 (10)	148.0
C31—H31A···N2ⁱⁱ	0.970	2.480	3.359 (10)	151.0
C36—H36···N2ⁱⁱⁱ	0.930	2.590	3.288 (9)	132.0

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z+1.

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