Charge density studies of 3d metal (Ni/Cu) complexes with a non-innocent ligand

High-resolution X-ray diffraction experiments and atom-specific X-ray absorption experiments are applied to investigate a series of square planar complexes with the non-innocent ligand of maleo­nitrile­dithiol­ate (mnt), [S₂C₂(CN)₂]^z−, containing M—S bonds. Four complexes of (PyH)_z[M(mnt)₂]^z−, where M = Ni or Cu, z = 2 or 1 and PyH⁺ = C₅NH₆⁺, were studied in order to clarify whether such one-electron oxidation–reduction, [M(mnt)₂]²⁻/[M(mnt)₂]¹⁻, is taking place at the metal or the ligand site. Combining the techniques of metal K-, L-edge and S K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density studies, it is unambiguously demonstrated that the electron redox reaction is ligand based and metal based for Ni and Cu pairs, respectively. The bonding characters in terms of topological properties associated with the bond critical points are compared between the oxidized form [ML]⁻ and the reduced form [ML]²⁻. In the case of Ni complexes, the formal oxidation state of Ni remains as Ni²⁺ and each mnt ligand carries a 2− charge in [Ni(mnt)₂]²⁻, but only one of the ligands is formally oxidized in [Ni(mnt)₂]¹⁻. In contrast, in the case of Cu complexes, the mnt remains as 2− in both complexes, but the formal oxidation states of the metal are Cu²⁺ and Cu³⁺. Bond characterizations and d-orbital populations will be presented. The complementary results of XAS, XRD and DFT calculations will be discussed. The conclusion on the redox reactions in these complexes can be firmly established.

Computing details

Data collection: NONIUS COLLECT for CCDC_1525429, CCDC_1525430, CCDC_1525431, CCDC_1525432; ? for CCDC_1544718. Cell refinement: DENZO-SMN for CCDC_1525429, CCDC_1525430, CCDC_1525431, CCDC_1525432; ? for CCDC_1544718. Data reduction: DENZO-SMN for CCDC_1525429, CCDC_1525430, CCDC_1525431, CCDC_1525432; ? for CCDC_1544718. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for CCDC_1525429, CCDC_1525430, CCDC_1525431, CCDC_1525432; SHELXS97 (Sheldrick, 2008) for CCDC_1544718, CCDC_1544719. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for CCDC_1525429, CCDC_1525430, CCDC_1525431, CCDC_1525432; SHELXL97 (Sheldrick, 2008) for CCDC_1544718, CCDC_1544719. For all structures, molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(CCDC_1525429)

Crystal data

C18H12N6NiS4	Z = 1
Mr = 499.29	F(000) = 254
Triclinic, P1	Dx = 1.626 Mg m^−3
a = 7.4460 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8942 (4) Å	Cell parameters from 10618 reflections
c = 9.2799 (6) Å	θ = 2.5–50.0°
α = 114.992 (3)°	µ = 1.38 mm^−1
β = 94.904 (4)°	T = 100 K
γ = 108.680 (3)°	Block, red
V = 509.94 (5) Å^3	0.30 × 0.20 × 0.20 mm

Data collection

CCD area detector diffractometer	9918 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 50.0°, θmin = 2.5°
Absorption correction: multi-scan sadabs	h = −16→15
Tmin = 0.683, Tmax = 0.770	k = −19→17
10618 measured reflections	l = 0→19
10618 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0295P)^2 + 0.0587P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.003
10618 reflections	Δρmax = 0.76 e Å^−3
158 parameters	Δρmin = −0.78 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (15)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ni	0.0000	0.5000	0.5000	0.008910 (10)
S1	0.317374 (14)	0.603532 (14)	0.579192 (12)	0.01237 (2)
S2	0.011539 (14)	0.580577 (14)	0.309528 (13)	0.01265 (2)
N3	0.87139 (6)	0.86157 (5)	0.19770 (5)	0.01601 (5)
N1	0.76338 (5)	0.88534 (6)	0.51254 (5)	0.01721 (5)
N2	0.36025 (7)	0.80512 (7)	0.13303 (6)	0.02260 (7)
C8	0.78344 (7)	1.04004 (6)	0.10149 (5)	0.01543 (5)
C9	0.85770 (7)	1.01847 (6)	0.22901 (5)	0.01637 (6)
C1	0.39412 (5)	0.70371 (5)	0.45894 (4)	0.01113 (4)
C6	0.73909 (8)	0.73712 (6)	−0.08601 (6)	0.01998 (7)
C3	0.59827 (5)	0.80096 (5)	0.48744 (5)	0.01285 (5)
C4	0.31959 (6)	0.75788 (6)	0.22885 (5)	0.01458 (5)
C7	0.72268 (7)	0.89780 (6)	−0.05724 (5)	0.01598 (6)
C2	0.26083 (5)	0.69056 (5)	0.33871 (5)	0.01142 (4)
C5	0.81473 (8)	0.72133 (6)	0.04519 (6)	0.01914 (7)
H7	0.6700 (18)	0.9073 (16)	−0.1419 (15)	0.030 (3)*
H9	0.8994 (18)	1.1037 (16)	0.3354 (15)	0.031 (3)*
H8	0.7728 (17)	1.1529 (15)	0.1262 (14)	0.026 (3)*
H5	0.8283 (19)	0.6188 (17)	0.0356 (16)	0.036 (3)*
H3	0.9162 (17)	0.8506 (15)	0.2800 (15)	0.029 (3)*
H6	0.6977 (19)	0.6320 (16)	−0.1946 (15)	0.033 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.00772 (2)	0.00913 (2)	0.00989 (2)	0.00302 (2)	0.00179 (2)	0.00487 (2)
S1	0.00868 (3)	0.01653 (4)	0.01342 (3)	0.00398 (3)	0.00212 (2)	0.00929 (3)
S2	0.00935 (3)	0.01618 (4)	0.01432 (3)	0.00400 (3)	0.00190 (2)	0.00988 (3)
N3	0.01878 (13)	0.01813 (12)	0.01231 (10)	0.00877 (11)	0.00203 (9)	0.00755 (10)
N1	0.01059 (10)	0.01991 (13)	0.01920 (13)	0.00246 (10)	0.00283 (9)	0.01042 (11)
N2	0.02243 (17)	0.0300 (2)	0.02538 (18)	0.01021 (15)	0.00966 (14)	0.02128 (17)
C8	0.01803 (14)	0.01354 (12)	0.01387 (12)	0.00697 (11)	0.00232 (10)	0.00560 (10)
C9	0.01966 (15)	0.01592 (13)	0.01138 (11)	0.00804 (12)	0.00205 (10)	0.00427 (10)
C1	0.00929 (10)	0.01148 (10)	0.01210 (10)	0.00327 (8)	0.00250 (8)	0.00583 (9)
C6	0.0276 (2)	0.01572 (14)	0.01277 (13)	0.01071 (14)	−0.00166 (13)	0.00312 (11)
C3	0.01000 (10)	0.01383 (11)	0.01360 (11)	0.00323 (9)	0.00278 (9)	0.00668 (10)
C4	0.01382 (12)	0.01655 (13)	0.01683 (13)	0.00575 (10)	0.00490 (10)	0.01094 (11)
C7	0.01927 (15)	0.01563 (13)	0.01231 (12)	0.00771 (11)	0.00069 (10)	0.00605 (10)
C2	0.01045 (10)	0.01195 (10)	0.01283 (11)	0.00404 (8)	0.00295 (8)	0.00703 (9)
C5	0.02529 (19)	0.01543 (13)	0.01567 (14)	0.01035 (13)	−0.00013 (13)	0.00583 (11)

Geometric parameters (Å, º)

Ni—S2^i	2.1685 (2)	N2—C4	1.1572 (6)
Ni—S2	2.1685 (2)	C8—C9	1.3751 (6)
Ni—S1	2.1702 (2)	C8—C7	1.3855 (6)
Ni—S1^i	2.1702 (2)	C1—C2	1.3673 (5)
S1—C1	1.7288 (4)	C1—C3	1.4228 (5)
S2—C2	1.7329 (4)	C6—C5	1.3773 (6)
N3—C9	1.3401 (6)	C6—C7	1.3870 (6)
N3—C5	1.3438 (6)	C4—C2	1.4190 (5)
N1—C3	1.1582 (5)
S2^i—Ni—S2	180.0	C2—C1—C3	120.41 (3)
S2^i—Ni—S1	87.723 (5)	C2—C1—S1	120.59 (3)
S2—Ni—S1	92.277 (5)	C3—C1—S1	119.00 (3)
S2^i—Ni—S1^i	92.277 (5)	C5—C6—C7	119.03 (4)
S2—Ni—S1^i	87.723 (5)	N1—C3—C1	177.73 (4)
S1—Ni—S1^i	180.0	N2—C4—C2	176.61 (5)
C1—S1—Ni	103.172 (13)	C8—C7—C6	120.02 (4)
C2—S2—Ni	103.165 (13)	C1—C2—C4	121.96 (3)
C9—N3—C5	122.79 (4)	C1—C2—S2	120.54 (3)
C9—C8—C7	119.07 (4)	C4—C2—S2	117.44 (3)
N3—C9—C8	119.63 (4)	N3—C5—C6	119.44 (4)

Symmetry code: (i) −x, −y+1, −z+1.

(CCDC_1525430)

Crystal data

C13H6N5NiS4	F(000) = 844
Mr = 419.18	Dx = 1.775 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.1805 (10) Å	Cell parameters from 16292 reflections
b = 6.3567 (5) Å	θ = 1.4–50.0°
c = 17.0872 (7) Å	µ = 1.77 mm^−1
β = 116.837 (5)°	T = 100 K
V = 1568.20 (17) Å^3	Block, black
Z = 4	0.45 × 0.20 × 0.20 mm

Data collection

CCD area detector diffractometer	14166 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 50.0°, θmin = 1.4°
Absorption correction: multi-scan sadabs	h = −34→30
Tmin = 0.503, Tmax = 0.718	k = 0→13
16292 measured reflections	l = 0→36
16292 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 0.3858P] where P = (Fo^2 + 2Fc^2)/3
S = 1.28	(Δ/σ)max = 0.005
16292 reflections	Δρmax = 1.16 e Å^−3
233 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.633099 (5)	0.513914 (13)	0.503857 (5)	0.00990 (2)
S1	0.718112 (11)	0.79137 (3)	0.544576 (10)	0.01244 (3)
S2	0.712140 (12)	0.35970 (3)	0.627215 (10)	0.01296 (3)
S3	0.547816 (12)	0.67530 (3)	0.383680 (11)	0.01362 (3)
S4	0.551011 (11)	0.23250 (3)	0.462853 (10)	0.01241 (2)
N1	0.92449 (6)	1.01174 (12)	0.72942 (5)	0.02236 (12)
N2	0.90642 (5)	0.45331 (12)	0.84827 (4)	0.01999 (11)
N3	0.33551 (5)	0.59238 (12)	0.17317 (4)	0.01947 (10)
N4	0.33876 (5)	0.03446 (11)	0.26528 (4)	0.01799 (10)
N5	0.79905 (4)	0.42283 (10)	0.41538 (4)	0.01507 (8)
C1	0.79871 (4)	0.73158 (10)	0.64971 (4)	0.01219 (8)
C2	0.79550 (4)	0.54197 (10)	0.68679 (4)	0.01214 (8)
C3	0.86802 (5)	0.88515 (11)	0.69516 (4)	0.01519 (9)
C4	0.85810 (5)	0.49211 (11)	0.77552 (4)	0.01438 (9)
C5	0.46594 (4)	0.49220 (10)	0.32538 (4)	0.01209 (8)
C6	0.46731 (4)	0.29523 (10)	0.36044 (4)	0.01181 (8)
C7	0.39438 (5)	0.54811 (11)	0.24117 (4)	0.01397 (8)
C8	0.39751 (5)	0.14632 (10)	0.31021 (4)	0.01361 (8)
C9	0.83363 (5)	0.61377 (12)	0.41451 (4)	0.01628 (10)
C10	0.90564 (5)	0.69132 (12)	0.48989 (5)	0.01650 (10)
C11	0.94043 (5)	0.56886 (12)	0.56549 (4)	0.01594 (9)
C12	0.90282 (5)	0.37159 (12)	0.56416 (5)	0.01640 (10)
C13	0.83052 (5)	0.30060 (11)	0.48721 (5)	0.01598 (9)
H5	0.7589 (14)	0.377 (3)	0.3702 (13)	0.044 (5)*
H9	0.8064 (11)	0.686 (3)	0.3608 (10)	0.022 (3)*
H10	0.9300 (11)	0.822 (3)	0.4884 (10)	0.024 (4)*
H11	0.9889 (11)	0.619 (3)	0.6170 (10)	0.022 (4)*
H12	0.9231 (11)	0.289 (3)	0.6118 (11)	0.028 (4)*
H13	0.8000 (11)	0.173 (3)	0.4804 (10)	0.026 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00930 (3)	0.00994 (3)	0.00919 (3)	−0.00020 (2)	0.00306 (2)	0.00023 (2)
S1	0.01238 (5)	0.01092 (5)	0.01078 (5)	−0.00086 (4)	0.00237 (4)	0.00100 (4)
S2	0.01365 (6)	0.01206 (5)	0.01092 (5)	−0.00128 (4)	0.00355 (4)	0.00170 (4)
S3	0.01339 (6)	0.01110 (5)	0.01224 (5)	−0.00157 (4)	0.00213 (4)	0.00189 (4)
S4	0.01259 (5)	0.01033 (5)	0.01108 (5)	−0.00061 (4)	0.00250 (4)	0.00100 (4)
N1	0.0226 (3)	0.0185 (2)	0.0175 (2)	−0.0063 (2)	0.0016 (2)	−0.00205 (19)
N2	0.0224 (3)	0.0204 (2)	0.01152 (18)	0.0050 (2)	0.00265 (18)	0.00101 (17)
N3	0.0194 (2)	0.0209 (3)	0.01223 (18)	0.0054 (2)	0.00189 (17)	0.00140 (17)
N4	0.0193 (2)	0.0153 (2)	0.01413 (19)	−0.00428 (18)	0.00287 (17)	−0.00127 (16)
N5	0.01448 (19)	0.0163 (2)	0.01198 (17)	−0.00194 (16)	0.00377 (15)	−0.00159 (15)
C1	0.01210 (19)	0.01172 (18)	0.01064 (17)	−0.00004 (15)	0.00327 (15)	−0.00042 (14)
C2	0.01242 (19)	0.01241 (19)	0.01012 (17)	0.00051 (15)	0.00379 (15)	0.00010 (14)
C3	0.0153 (2)	0.0135 (2)	0.01250 (19)	−0.00137 (17)	0.00243 (17)	−0.00094 (16)
C4	0.0156 (2)	0.0145 (2)	0.01048 (18)	0.00201 (17)	0.00363 (16)	0.00012 (15)
C5	0.01187 (19)	0.01124 (18)	0.01108 (17)	0.00041 (14)	0.00334 (15)	0.00051 (14)
C6	0.01184 (19)	0.01056 (18)	0.01126 (17)	−0.00020 (14)	0.00366 (15)	−0.00051 (14)
C7	0.0144 (2)	0.0131 (2)	0.01178 (18)	0.00169 (16)	0.00358 (16)	0.00031 (15)
C8	0.0141 (2)	0.01194 (19)	0.01217 (18)	−0.00111 (16)	0.00361 (16)	−0.00065 (15)
C9	0.0166 (2)	0.0173 (2)	0.0124 (2)	−0.00179 (19)	0.00424 (18)	0.00167 (17)
C10	0.0158 (2)	0.0160 (2)	0.0151 (2)	−0.00273 (18)	0.00468 (18)	0.00024 (18)
C11	0.0137 (2)	0.0184 (2)	0.01256 (19)	−0.00119 (18)	0.00316 (17)	−0.00043 (18)
C12	0.0158 (2)	0.0177 (2)	0.0134 (2)	0.00059 (19)	0.00458 (18)	0.00261 (18)
C13	0.0162 (2)	0.0143 (2)	0.0158 (2)	−0.00127 (18)	0.00586 (18)	0.00041 (18)

Geometric parameters (Å, º)

Ni1—S2	2.1461 (2)	N5—C9	1.3394 (10)
Ni1—S4	2.1482 (2)	N5—C13	1.3435 (9)
Ni1—S3	2.1482 (2)	C1—C2	1.3736 (9)
Ni1—S1	2.1501 (2)	C1—C3	1.4239 (9)
S1—C1	1.7196 (6)	C2—C4	1.4278 (9)
S2—C2	1.7199 (7)	C5—C6	1.3839 (9)
S3—C5	1.7060 (6)	C5—C7	1.4259 (9)
S4—C6	1.7076 (6)	C6—C8	1.4258 (9)
N1—C3	1.1586 (10)	C9—C10	1.3801 (10)
N2—C4	1.1576 (9)	C10—C11	1.3910 (10)
N3—C7	1.1564 (9)	C11—C12	1.3895 (11)
N4—C8	1.1575 (9)	C12—C13	1.3829 (10)
S2—Ni1—S4	86.934 (9)	C4—C2—S2	118.02 (5)
S2—Ni1—S3	176.207 (8)	N1—C3—C1	177.62 (8)
S4—Ni1—S3	92.874 (9)	N2—C4—C2	177.60 (8)
S2—Ni1—S1	92.657 (9)	C6—C5—C7	120.62 (6)
S4—Ni1—S1	178.517 (8)	C6—C5—S3	120.53 (5)
S3—Ni1—S1	87.628 (9)	C7—C5—S3	118.82 (5)
C1—S1—Ni1	103.26 (2)	C5—C6—C8	119.12 (6)
C2—S2—Ni1	103.53 (2)	C5—C6—S4	120.34 (5)
C5—S3—Ni1	103.11 (2)	C8—C6—S4	120.54 (5)
C6—S4—Ni1	103.14 (2)	N3—C7—C5	179.12 (8)
C9—N5—C13	123.11 (6)	N4—C8—C6	175.77 (7)
C2—C1—C3	122.31 (6)	N5—C9—C10	119.61 (6)
C2—C1—S1	120.47 (5)	C9—C10—C11	118.95 (7)
C3—C1—S1	117.22 (5)	C12—C11—C10	119.94 (6)
C1—C2—C4	121.88 (6)	C13—C12—C11	119.10 (6)
C1—C2—S2	120.07 (5)	N5—C13—C12	119.27 (7)

(CCDC_1525431)

Crystal data

C18H12CuN6S4	Z = 1
Mr = 504.12	F(000) = 255
Triclinic, P1	Dx = 1.610 Mg m^−3
a = 7.5458 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0111 (7) Å	Cell parameters from 15123 reflections
c = 9.2574 (3) Å	θ = 2.5–60.0°
α = 115.334 (4)°	µ = 1.47 mm^−1
β = 95.223 (4)°	T = 100 K
γ = 108.563 (4)°	Block, dark green
V = 520.01 (5) Å^3	0.40 × 0.30 × 0.24 mm

Data collection

CCD area detector diffractometer	13925 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 60.0°, θmin = 2.5°
Absorption correction: multi-scan sadabs	h = −18→18
Tmin = 0.591, Tmax = 0.719	k = −21→19
15123 measured reflections	l = 0→22
15123 independent reflections

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 0.0689P] where P = (Fo^2 + 2Fc^2)/3
15123 reflections	(Δ/σ)max = 0.002
157 parameters	Δρmax = 0.98 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cu1	0.5000	1.0000	0.5000	0.009600 (10)
S1	0.172576 (14)	0.892888 (15)	0.419114 (13)	0.01361 (2)
S2	0.485502 (15)	0.914568 (16)	0.698811 (14)	0.01464 (2)
N1	−0.26008 (5)	0.61894 (6)	0.49164 (5)	0.01815 (6)
N2	0.13349 (8)	0.69076 (8)	0.86499 (7)	0.02447 (8)
N3	0.62647 (6)	0.64016 (5)	0.80570 (5)	0.01629 (5)
C1	0.10528 (5)	0.79684 (5)	0.54262 (4)	0.01159 (4)
C2	0.23749 (5)	0.80869 (5)	0.66343 (5)	0.01212 (4)
C3	−0.09672 (5)	0.70110 (5)	0.51590 (5)	0.01350 (4)
C4	0.17607 (6)	0.73972 (6)	0.77115 (6)	0.01590 (5)
C5	0.67251 (8)	0.77338 (6)	0.96161 (6)	0.01912 (7)
C6	0.74637 (8)	0.75487 (6)	1.09197 (6)	0.01948 (7)
C7	0.77132 (7)	0.59832 (6)	1.05847 (5)	0.01630 (5)
C8	0.72136 (7)	0.46287 (6)	0.89608 (5)	0.01623 (5)
C9	0.64875 (7)	0.48710 (6)	0.76925 (5)	0.01690 (6)
H3	0.5803 (19)	0.6538 (17)	0.7229 (17)	0.032 (3)*
H5	0.657 (2)	0.8757 (19)	0.9779 (18)	0.042 (4)*
H6	0.785 (2)	0.8507 (17)	1.2045 (16)	0.032 (3)*
H7	0.8229 (19)	0.5892 (16)	1.1457 (16)	0.028 (3)*
H8	0.7358 (18)	0.3498 (16)	0.8643 (15)	0.024 (3)*
H9	0.6146 (19)	0.4108 (17)	0.6622 (16)	0.031 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00857 (2)	0.00993 (2)	0.01061 (2)	0.003380 (10)	0.002420 (10)	0.005460 (10)
S1	0.00953 (3)	0.01944 (4)	0.01442 (3)	0.00481 (3)	0.00290 (2)	0.01107 (3)
S2	0.00991 (3)	0.02021 (4)	0.01716 (4)	0.00448 (3)	0.00241 (3)	0.01319 (3)
N1	0.01084 (10)	0.02172 (14)	0.01978 (13)	0.00237 (9)	0.00298 (9)	0.01137 (12)
N2	0.02269 (17)	0.0334 (2)	0.0279 (2)	0.00961 (16)	0.00940 (15)	0.02438 (19)
N3	0.01910 (13)	0.01829 (12)	0.01241 (10)	0.00812 (10)	0.00219 (9)	0.00812 (9)
C1	0.00968 (9)	0.01258 (10)	0.01238 (10)	0.00364 (8)	0.00285 (7)	0.00649 (8)
C2	0.01088 (10)	0.01341 (10)	0.01361 (11)	0.00430 (8)	0.00322 (8)	0.00822 (9)
C3	0.01030 (10)	0.01506 (11)	0.01385 (11)	0.00322 (8)	0.00287 (8)	0.00726 (9)
C4	0.01420 (12)	0.01936 (14)	0.01848 (14)	0.00587 (10)	0.00511 (10)	0.01325 (12)
C5	0.02549 (19)	0.01669 (14)	0.01523 (13)	0.01083 (13)	0.00121 (12)	0.00685 (11)
C6	0.02663 (19)	0.01639 (14)	0.01236 (12)	0.01003 (13)	−0.00034 (12)	0.00437 (10)
C7	0.01921 (14)	0.01589 (12)	0.01295 (11)	0.00718 (11)	0.00058 (10)	0.00681 (10)
C8	0.01911 (14)	0.01465 (12)	0.01448 (12)	0.00749 (11)	0.00287 (10)	0.00641 (10)
C9	0.02054 (15)	0.01696 (13)	0.01179 (11)	0.00805 (12)	0.00309 (10)	0.00558 (10)

Geometric parameters (Å, º)

Cu1—S1	2.2634 (2)	N3—C5	1.3436 (6)
Cu1—S1^i	2.2634 (2)	C1—C2	1.3727 (5)
Cu1—S2^i	2.2776 (1)	C1—C3	1.4284 (5)
Cu1—S2	2.2776 (1)	C2—C4	1.4236 (5)
S1—C1	1.7283 (4)	C5—C6	1.3797 (6)
S2—C2	1.7332 (4)	C6—C7	1.3882 (6)
N1—C3	1.1594 (5)	C7—C8	1.3875 (6)
N2—C4	1.1580 (6)	C8—C9	1.3801 (6)
N3—C9	1.3432 (6)
S1—Cu1—S1^i	180.0	C3—C1—S1	117.92 (3)
S1—Cu1—S2^i	89.067 (5)	C1—C2—C4	121.06 (3)
S1^i—Cu1—S2^i	90.933 (5)	C1—C2—S2	122.46 (3)
S1—Cu1—S2	90.933 (5)	C4—C2—S2	116.44 (3)
S1^i—Cu1—S2	89.067 (5)	N1—C3—C1	178.07 (5)
S2^i—Cu1—S2	180.000 (5)	N2—C4—C2	176.67 (6)
C1—S1—Cu1	102.019 (13)	N3—C5—C6	119.49 (4)
C2—S2—Cu1	101.667 (13)	C5—C6—C7	118.96 (4)
C9—N3—C5	122.97 (4)	C8—C7—C6	120.12 (4)
C2—C1—C3	119.38 (3)	C9—C8—C7	119.07 (4)
C2—C1—S1	122.70 (3)	N3—C9—C8	119.38 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

(CCDC_1525432)

Crystal data

C13H6CuN5S4	F(000) = 848
Mr = 424.01	Dx = 1.801 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.418 (4) Å	Cell parameters from 16128 reflections
b = 6.1838 (12) Å	θ = 2.3–49.9°
c = 18.165 (4) Å	µ = 1.93 mm^−1
β = 126.93 (3)°	T = 100 K
V = 1563.9 (5) Å^3	Block, dark green
Z = 4	0.22 × 0.15 × 0.13 mm

Data collection

CCD area detector diffractometer	11366 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 49.9°, θmin = 2.3°
Absorption correction: multi-scan sadabs	h = −37→0
Tmin = 0.676, Tmax = 0.787	k = 0→13
16128 measured reflections	l = −30→38
16128 independent reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0237P)^2 + 0.6927P] where P = (Fo^2 + 2Fc^2)/3
16128 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.71 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cu1	0.118064 (7)	−0.004154 (16)	0.128612 (7)	0.00966 (2)
S1	0.208665 (15)	−0.29276 (3)	0.173631 (15)	0.01371 (3)
S2	0.198386 (15)	0.16371 (3)	0.088456 (15)	0.01338 (3)
S3	0.045012 (16)	−0.15923 (4)	0.178841 (16)	0.01538 (4)
S4	0.024707 (15)	0.28010 (3)	0.079175 (16)	0.01485 (4)
N1	0.41943 (6)	−0.50598 (14)	0.19766 (7)	0.02093 (14)
N2	0.38480 (6)	0.04115 (14)	0.05365 (6)	0.01953 (13)
N3	−0.17236 (6)	−0.09488 (14)	0.16853 (6)	0.01910 (13)
N4	−0.19023 (6)	0.47762 (13)	0.06015 (6)	0.01685 (12)
N5	0.68599 (5)	0.57025 (13)	0.11604 (5)	0.01450 (11)
C1	0.28768 (5)	−0.22363 (13)	0.14921 (5)	0.01195 (11)
C2	0.28083 (5)	−0.03160 (13)	0.10902 (5)	0.01178 (11)
C3	0.36005 (6)	−0.37910 (14)	0.17397 (6)	0.01456 (12)
C4	0.33950 (6)	0.01229 (14)	0.07999 (6)	0.01406 (11)
C5	−0.04536 (5)	0.02406 (12)	0.14676 (5)	0.01148 (10)
C6	−0.05266 (5)	0.21545 (12)	0.10590 (5)	0.01121 (10)
C7	−0.11486 (6)	−0.03962 (13)	0.16009 (6)	0.01301 (11)
C8	−0.12773 (6)	0.36355 (13)	0.08049 (6)	0.01295 (11)
C9	0.64876 (6)	0.37474 (15)	0.08093 (6)	0.01608 (13)
C10	0.57815 (6)	0.29382 (15)	0.08576 (6)	0.01640 (13)
C11	0.54715 (6)	0.41706 (15)	0.12715 (6)	0.01564 (13)
C12	0.58763 (6)	0.61922 (15)	0.16332 (6)	0.01553 (12)
C13	0.65862 (6)	0.69333 (14)	0.15763 (6)	0.01510 (12)
H5	0.7277 (12)	0.620 (3)	0.1101 (11)	0.028 (4)*
H9	0.6711 (11)	0.304 (3)	0.0531 (10)	0.022 (4)*
H10	0.5527 (12)	0.160 (3)	0.0621 (11)	0.028 (4)*
H11	0.5042 (12)	0.366 (3)	0.1328 (11)	0.030 (4)*
H12	0.5678 (11)	0.702 (3)	0.1893 (11)	0.026 (4)*
H13	0.6889 (11)	0.825 (3)	0.1793 (10)	0.020 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00967 (3)	0.00956 (3)	0.01148 (3)	0.00046 (3)	0.00728 (3)	0.00073 (3)
S1	0.01342 (7)	0.01151 (7)	0.02069 (8)	0.00218 (6)	0.01264 (7)	0.00381 (6)
S2	0.01453 (7)	0.01112 (7)	0.01895 (8)	0.00095 (6)	0.01243 (7)	0.00252 (6)
S3	0.01781 (8)	0.01319 (8)	0.02272 (9)	0.00501 (6)	0.01621 (8)	0.00694 (7)
S4	0.01638 (8)	0.01206 (8)	0.02299 (9)	0.00359 (6)	0.01549 (7)	0.00563 (7)
N1	0.0203 (3)	0.0181 (3)	0.0306 (4)	0.0047 (3)	0.0186 (3)	0.0030 (3)
N2	0.0220 (3)	0.0203 (3)	0.0257 (3)	−0.0052 (3)	0.0193 (3)	−0.0042 (3)
N3	0.0197 (3)	0.0188 (3)	0.0259 (4)	−0.0061 (3)	0.0174 (3)	−0.0044 (3)
N4	0.0173 (3)	0.0158 (3)	0.0222 (3)	0.0036 (2)	0.0144 (3)	0.0019 (2)
N5	0.0142 (2)	0.0156 (3)	0.0175 (3)	−0.0019 (2)	0.0116 (2)	−0.0009 (2)
C1	0.0119 (2)	0.0115 (3)	0.0148 (3)	−0.0003 (2)	0.0093 (2)	−0.0006 (2)
C2	0.0119 (2)	0.0119 (3)	0.0143 (3)	−0.0013 (2)	0.0093 (2)	−0.0011 (2)
C3	0.0144 (3)	0.0134 (3)	0.0195 (3)	0.0008 (2)	0.0122 (3)	0.0001 (2)
C4	0.0151 (3)	0.0140 (3)	0.0168 (3)	−0.0028 (2)	0.0116 (2)	−0.0022 (2)
C5	0.0123 (2)	0.0110 (3)	0.0141 (3)	0.0000 (2)	0.0096 (2)	0.0002 (2)
C6	0.0115 (2)	0.0106 (3)	0.0136 (3)	0.0006 (2)	0.0087 (2)	0.0004 (2)
C7	0.0142 (3)	0.0119 (3)	0.0165 (3)	−0.0017 (2)	0.0112 (2)	−0.0016 (2)
C8	0.0141 (3)	0.0118 (3)	0.0157 (3)	0.0004 (2)	0.0105 (2)	0.0001 (2)
C9	0.0172 (3)	0.0165 (3)	0.0186 (3)	−0.0015 (3)	0.0129 (3)	−0.0033 (3)
C10	0.0164 (3)	0.0145 (3)	0.0194 (3)	−0.0035 (2)	0.0113 (3)	−0.0030 (3)
C11	0.0134 (3)	0.0182 (3)	0.0177 (3)	−0.0024 (2)	0.0106 (3)	−0.0005 (3)
C12	0.0155 (3)	0.0173 (3)	0.0177 (3)	−0.0006 (2)	0.0120 (3)	−0.0022 (3)
C13	0.0149 (3)	0.0135 (3)	0.0189 (3)	−0.0017 (2)	0.0112 (3)	−0.0022 (2)

Geometric parameters (Å, º)

Cu1—S3	2.1832 (4)	N5—C9	1.3386 (12)
Cu1—S4	2.1876 (5)	N5—C13	1.3455 (11)
Cu1—S1	2.1894 (5)	C1—C2	1.3611 (11)
Cu1—S2	2.1894 (4)	C1—C3	1.4263 (11)
S1—C1	1.7342 (8)	C2—C4	1.4295 (11)
S2—C2	1.7366 (8)	C5—C6	1.3617 (11)
S3—C5	1.7320 (8)	C5—C7	1.4253 (10)
S4—C6	1.7314 (8)	C6—C8	1.4269 (11)
N1—C3	1.1556 (12)	C9—C10	1.3785 (12)
N2—C4	1.1564 (11)	C10—C11	1.3876 (13)
N3—C7	1.1525 (11)	C11—C12	1.3910 (13)
N4—C8	1.1559 (11)	C12—C13	1.3795 (12)
S3—Cu1—S4	92.771 (16)	C4—C2—S2	118.08 (6)
S3—Cu1—S1	87.487 (16)	N1—C3—C1	177.05 (9)
S4—Cu1—S1	178.180 (11)	N2—C4—C2	177.09 (9)
S3—Cu1—S2	175.623 (10)	C6—C5—C7	121.47 (7)
S4—Cu1—S2	87.047 (16)	C6—C5—S3	121.37 (6)
S1—Cu1—S2	92.833 (16)	C7—C5—S3	117.07 (6)
C1—S1—Cu1	102.02 (3)	C5—C6—C8	120.10 (7)
C2—S2—Cu1	102.12 (3)	C5—C6—S4	121.33 (6)
C5—S3—Cu1	102.24 (3)	C8—C6—S4	118.52 (6)
C6—S4—Cu1	102.19 (3)	N3—C7—C5	177.95 (9)
C9—N5—C13	123.01 (7)	N4—C8—C6	177.58 (9)
C2—C1—C3	122.22 (7)	N5—C9—C10	119.53 (8)
C2—C1—S1	121.67 (6)	C9—C10—C11	119.18 (8)
C3—C1—S1	116.11 (6)	C10—C11—C12	119.85 (8)
C1—C2—C4	120.79 (7)	C13—C12—C11	119.07 (8)
C1—C2—S2	121.11 (6)	N5—C13—C12	119.35 (8)

(CCDC_1544718)

Crystal data

C18H12N6NiS4	Z = 1
Mr = 499.29	F(000) = 254
Triclinic, P1	Dx = 1.632 Mg m^−3
a = 7.4307 (2) Å	Cell parameters from 131084 reflections
b = 8.9072 (2) Å	θ = 1.5–33.3°
c = 9.2445 (2) Å	µ = 0.31 mm^−1
α = 115.167 (1)°	T = 15 K
β = 94.727 (1)°	Block, red
γ = 108.525 (1)°	0.12 × 0.09 × 0.06 mm
V = 507.94 (2) Å^3

Data collection

APEX II CCD detector diffractometer	Rint = 0.044
Radiation source: Synchrotron	θmax = 33.3°, θmin = 1.5°
DCM monochromator	h = −19→18
130961 measured reflections	k = −23→23
16291 independent reflections	l = −14→23
14895 reflections with I > 2σ(I)

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.058	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0296P)^2 + 0.0397P] where P = (Fo^2 + 2Fc^2)/3
16291 reflections	(Δ/σ)max = 0.014
157 parameters	Δρmax = 0.98 e Å^−3
0 restraints	Δρmin = −1.83 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ni	0.0000	0.5000	1.5000	0.004130 (10)
S1	0.317618 (9)	0.603163 (9)	1.579636 (9)	0.005930 (10)
S2	0.012018 (9)	0.581040 (9)	1.308949 (9)	0.006160 (10)
C1	0.39474 (3)	0.70368 (3)	1.45924 (3)	0.00597 (3)
C2	0.26156 (3)	0.69072 (3)	1.33830 (3)	0.00608 (3)
N2	0.36226 (4)	0.80414 (4)	1.13119 (4)	0.01179 (4)
C4	0.32093 (4)	0.75749 (4)	1.22776 (4)	0.00769 (3)
C3	0.59890 (3)	0.80103 (3)	1.48805 (3)	0.00709 (3)
N1	0.76412 (3)	0.88561 (4)	1.51355 (4)	0.01002 (3)
N3	0.87136 (3)	0.86159 (3)	1.19702 (3)	0.00776 (3)
C9	0.85642 (4)	1.01879 (3)	1.22929 (4)	0.00804 (3)
C8	0.78291 (4)	1.04088 (3)	1.10109 (4)	0.00795 (3)
C7	0.72426 (4)	0.89928 (3)	0.94116 (4)	0.00820 (3)
C6	0.74185 (4)	0.73830 (4)	0.91130 (4)	0.00921 (3)
C5	0.81664 (4)	0.72187 (4)	1.04315 (4)	0.00888 (3)
H5	0.8355 (16)	0.6178 (14)	1.0364 (14)	0.028 (3)*
H7	0.6677 (13)	0.9102 (12)	0.8533 (12)	0.0156 (19)*
H9	0.9024 (14)	1.1078 (12)	1.3380 (12)	0.017 (2)*
H6	0.6975 (14)	0.6343 (12)	0.8005 (12)	0.021 (2)*
H8	0.7733 (14)	1.1521 (12)	1.1242 (12)	0.021 (2)*
H3	0.9178 (14)	0.8491 (12)	1.2818 (13)	0.020 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.003240 (10)	0.004800 (10)	0.00433 (2)	0.001230 (10)	0.000740 (10)	0.002430 (10)
S1	0.00413 (2)	0.00804 (2)	0.00641 (2)	0.001820 (10)	0.001010 (10)	0.00458 (2)
S2	0.00423 (2)	0.00834 (2)	0.00659 (2)	0.001820 (10)	0.000870 (10)	0.00469 (2)
C1	0.00462 (5)	0.00688 (5)	0.00655 (8)	0.00169 (4)	0.00117 (4)	0.00376 (5)
C2	0.00514 (5)	0.00719 (6)	0.00652 (8)	0.00199 (4)	0.00134 (4)	0.00410 (6)
N2	0.01239 (8)	0.01559 (9)	0.01276 (11)	0.00559 (7)	0.00527 (6)	0.01093 (8)
C4	0.00723 (6)	0.00930 (6)	0.00842 (9)	0.00301 (5)	0.00245 (5)	0.00593 (7)
C3	0.00494 (5)	0.00825 (6)	0.00776 (9)	0.00160 (5)	0.00135 (5)	0.00428 (6)
N1	0.00528 (5)	0.01214 (7)	0.01194 (9)	0.00120 (5)	0.00150 (5)	0.00686 (7)
N3	0.00932 (6)	0.00833 (5)	0.00602 (7)	0.00381 (5)	0.00080 (5)	0.00371 (5)
C9	0.00967 (7)	0.00741 (6)	0.00595 (9)	0.00363 (5)	0.00072 (5)	0.00227 (6)
C8	0.00995 (7)	0.00691 (6)	0.00690 (9)	0.00385 (5)	0.00107 (5)	0.00301 (6)
C7	0.01037 (7)	0.00779 (6)	0.00617 (8)	0.00385 (5)	0.00045 (6)	0.00319 (6)
C6	0.01240 (8)	0.00759 (6)	0.00606 (9)	0.00445 (6)	0.00013 (6)	0.00191 (6)
C5	0.01152 (8)	0.00738 (6)	0.00766 (9)	0.00456 (6)	0.00073 (6)	0.00322 (6)

Geometric parameters (Å, º)

Ni—S1^i	2.1718	N2—C4	1.1592 (4)
Ni—S1	2.1718	C3—N1	1.1592 (3)
Ni—S2	2.1720	N3—C9	1.3457 (3)
Ni—S2^i	2.1721	N3—C5	1.3472 (4)
S1—C1	1.7308 (2)	C9—C8	1.3789 (4)
S2—C2	1.7340 (2)	C8—C7	1.3875 (4)
C1—C2	1.3704 (3)	C7—C6	1.3921 (4)
C1—C3	1.4232 (3)	C6—C5	1.3811 (4)
C2—C4	1.4202 (4)
S1^i—Ni—S1	179.999 (4)	C1—C2—C4	121.96 (2)
S1^i—Ni—S2	87.677 (3)	C1—C2—S2	120.477 (18)
S1—Ni—S2	92.324 (3)	C4—C2—S2	117.490 (17)
S1^i—Ni—S2^i	92.324 (3)	N2—C4—C2	176.58 (3)
S1—Ni—S2^i	87.676 (3)	N1—C3—C1	177.70 (3)
S2—Ni—S2^i	180.0	C9—N3—C5	122.83 (2)
C1—S1—Ni	103.123 (8)	N3—C9—C8	119.57 (3)
C2—S2—Ni	103.152 (8)	C9—C8—C7	119.06 (2)
C2—C1—C3	120.31 (2)	C8—C7—C6	120.14 (2)
C2—C1—S1	120.661 (17)	C5—C6—C7	118.96 (3)
C3—C1—S1	119.032 (17)	N3—C5—C6	119.43 (2)

Symmetry code: (i) −x, −y+1, −z+3.

(CCDC_1544719)

Crystal data

C13H6N5NiS4	F(000) = 844
Mr = 419.18	Dx = 1.793 Mg m^−3
Monoclinic, P21/c	Cell parameters from 277512 reflections
a = 16.0654 (5) Å	θ = 1.4–42.2°
b = 6.3464 (2) Å	µ = 0.40 mm^−1
c = 17.0333 (5) Å	T = 15 K
β = 116.606 (1)°	Block, black
V = 1552.77 (8) Å^3	0.21 × 0.19 × 0.09 mm
Z = 4

Data collection

APEX II CCD detector diffractometer	Rint = 0.053
Radiation source: Synchrotron	θmax = 42.2°, θmin = 1.4°
DCM monochromator	h = −48→50
276927 measured reflections	k = −19→19
49058 independent reflections	l = −50→31
42535 reflections with I > 2σ(I)

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0288P)^2 + 0.0769P] where P = (Fo^2 + 2Fc^2)/3
49058 reflections	(Δ/σ)max = 0.015
232 parameters	Δρmax = 1.16 e Å^−3
0 restraints	Δρmin = −2.76 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.633534 (1)	0.513951 (3)	0.503987 (1)	0.003500
S1	0.718564 (3)	0.792403 (8)	0.544859 (3)	0.004960 (10)
S2	0.712721 (3)	0.359276 (8)	0.627322 (3)	0.005090 (10)
S3	0.547916 (3)	0.675608 (8)	0.383834 (4)	0.005300 (10)
S4	0.551424 (3)	0.231606 (8)	0.463015 (3)	0.004960 (10)
N1	0.925259 (15)	1.01380 (3)	0.729738 (15)	0.00997 (2)
N2	0.907187 (14)	0.45322 (3)	0.848649 (13)	0.00931 (2)
N3	0.335054 (14)	0.59094 (3)	0.173195 (13)	0.00918 (2)
N4	0.338677 (13)	0.03297 (3)	0.265198 (13)	0.00865 (2)
N5	0.799300 (11)	0.42247 (3)	0.414799 (11)	0.00674 (2)
C1	0.799372 (12)	0.73248 (3)	0.649993 (12)	0.00545 (2)
C2	0.796234 (12)	0.54209 (3)	0.687055 (12)	0.00547 (2)
C3	0.868884 (13)	0.88636 (3)	0.695574 (13)	0.00677 (2)
C4	0.858835 (13)	0.49211 (3)	0.775762 (13)	0.00657 (2)
C5	0.465910 (12)	0.49175 (3)	0.325513 (12)	0.00546 (2)
C6	0.467465 (12)	0.29433 (3)	0.360625 (12)	0.00537 (2)
C7	0.394167 (13)	0.54723 (3)	0.241303 (13)	0.00644 (2)
C8	0.397552 (13)	0.14498 (3)	0.310349 (13)	0.00635 (2)
C9	0.833795 (14)	0.61461 (3)	0.414109 (14)	0.00737 (2)
C10	0.905744 (14)	0.69261 (3)	0.489726 (14)	0.00736 (2)
C11	0.940612 (14)	0.56947 (3)	0.565358 (14)	0.00723 (2)
C12	0.903043 (14)	0.37080 (3)	0.563884 (14)	0.00740 (2)
C13	0.830829 (14)	0.29974 (3)	0.486645 (14)	0.00728 (2)
H5	0.7527 (8)	0.3743 (18)	0.3677 (7)	0.042 (3)*
H9	0.8058 (6)	0.6874 (13)	0.3606 (5)	0.0152 (18)*
H10	0.9320 (6)	0.8242 (14)	0.4883 (5)	0.0159 (18)*
H11	0.9899 (6)	0.6206 (14)	0.6198 (5)	0.0158 (18)*
H12	0.9253 (6)	0.2835 (14)	0.6145 (5)	0.0152 (18)*
H13	0.8002 (6)	0.1708 (15)	0.4788 (6)	0.021 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.003060	0.003550	0.003190 (10)	−0.000190	0.000770	0.000030
S1	0.004620 (10)	0.004440 (10)	0.004340 (10)	−0.000540 (10)	0.000690 (10)	0.000440 (10)
S2	0.004950 (10)	0.004680 (10)	0.004340 (10)	−0.000730 (10)	0.000930 (10)	0.000540 (10)
S3	0.004890 (10)	0.004450 (10)	0.004750 (10)	−0.000760 (10)	0.000540 (10)	0.000600 (10)
S4	0.004670 (10)	0.004250 (10)	0.004370 (10)	−0.000450 (10)	0.000620 (10)	0.000430 (10)
N1	0.00922 (5)	0.00870 (5)	0.00902 (5)	−0.00378 (4)	0.00143 (4)	−0.00174 (4)
N2	0.00963 (5)	0.01031 (5)	0.00505 (4)	0.00198 (4)	0.00067 (3)	0.00092 (4)
N3	0.00812 (4)	0.01050 (5)	0.00566 (4)	0.00231 (4)	0.00017 (3)	0.00117 (4)
N4	0.00789 (4)	0.00780 (4)	0.00748 (5)	−0.00275 (3)	0.00098 (3)	−0.00142 (4)
N5	0.00632 (3)	0.00698 (4)	0.00541 (4)	−0.00103 (3)	0.00129 (3)	−0.00037 (3)
C1	0.00514 (4)	0.00509 (4)	0.00479 (4)	−0.00068 (3)	0.00103 (3)	−0.00003 (3)
C2	0.00531 (4)	0.00542 (4)	0.00445 (4)	−0.00031 (3)	0.00109 (3)	0.00026 (3)
C3	0.00622 (4)	0.00612 (4)	0.00611 (5)	−0.00147 (3)	0.00111 (3)	−0.00064 (3)
C4	0.00641 (4)	0.00703 (4)	0.00464 (4)	0.00051 (3)	0.00101 (3)	0.00036 (3)
C5	0.00497 (4)	0.00511 (4)	0.00477 (4)	−0.00025 (3)	0.00080 (3)	0.00036 (3)
C6	0.00495 (3)	0.00485 (4)	0.00489 (4)	−0.00054 (3)	0.00095 (3)	0.00001 (3)
C7	0.00581 (4)	0.00660 (4)	0.00495 (4)	0.00063 (3)	0.00067 (3)	0.00052 (3)
C8	0.00581 (4)	0.00584 (4)	0.00582 (4)	−0.00123 (3)	0.00119 (3)	−0.00070 (3)
C9	0.00731 (4)	0.00741 (5)	0.00588 (5)	−0.00086 (4)	0.00161 (4)	0.00088 (4)
C10	0.00720 (4)	0.00672 (4)	0.00677 (5)	−0.00133 (3)	0.00189 (4)	0.00026 (4)
C11	0.00650 (4)	0.00779 (5)	0.00578 (5)	−0.00098 (3)	0.00130 (4)	−0.00015 (4)
C12	0.00725 (4)	0.00752 (5)	0.00608 (5)	−0.00023 (4)	0.00178 (4)	0.00112 (4)
C13	0.00736 (4)	0.00633 (4)	0.00701 (5)	−0.00105 (3)	0.00221 (4)	0.00036 (4)

Geometric parameters (Å, º)

Ni1—S2	2.1451	N5—C9	1.3416 (3)
Ni1—S3	2.1475	N5—C13	1.3438 (3)
Ni1—S4	2.1479	C1—C2	1.3746 (3)
Ni1—S1	2.1498	C1—C3	1.4237 (2)
S1—C1	1.7189 (2)	C2—C4	1.4262 (3)
S2—C2	1.7201 (2)	C5—C6	1.3837 (3)
S3—C5	1.7064 (2)	C5—C7	1.4245 (3)
S4—C6	1.7066 (2)	C6—C8	1.4254 (2)
N1—C3	1.1580 (3)	C9—C10	1.3808 (3)
N2—C4	1.1584 (3)	C10—C11	1.3920 (3)
N3—C7	1.1567 (3)	C11—C12	1.3932 (3)
N4—C8	1.1575 (2)	C12—C13	1.3831 (3)
S2—Ni1—S3	176.170 (2)	C4—C2—S2	118.021 (14)
S2—Ni1—S4	86.848 (3)	N1—C3—C1	177.50 (2)
S3—Ni1—S4	92.916 (3)	N2—C4—C2	177.56 (2)
S2—Ni1—S1	92.687 (3)	C6—C5—C7	120.591 (16)
S3—Ni1—S1	87.639 (3)	C6—C5—S3	120.514 (14)
S4—Ni1—S1	178.569 (2)	C7—C5—S3	118.865 (14)
C1—S1—Ni1	103.263 (6)	C5—C6—C8	119.051 (16)
C2—S2—Ni1	103.533 (7)	C5—C6—S4	120.393 (13)
C5—S3—Ni1	103.068 (7)	C8—C6—S4	120.554 (14)
C6—S4—Ni1	103.107 (7)	N3—C7—C5	179.09 (2)
C9—N5—C13	123.100 (17)	N4—C8—C6	175.63 (2)
C2—C1—C3	122.250 (17)	N5—C9—C10	119.615 (19)
C2—C1—S1	120.465 (13)	C9—C10—C11	118.934 (19)
C3—C1—S1	117.283 (14)	C10—C11—C12	119.991 (18)
C1—C2—C4	121.908 (17)	C13—C12—C11	118.964 (19)
C1—C2—S2	120.038 (14)	N5—C13—C12	119.391 (18)