Bis[μ2-1-(2-carb­oxy­benzo­yl)thio­semi­carbazide(3−)]hexa­pyridine­trinickel(II) pyridine monosolvate monohydrate

Cao, F.; Li, L.; Li, D.

doi:10.1107/S1600536811048367

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1803

https://doi.org/10.1107/S1600536811048367

Open

access

Bis[μ₂-1-(2-carboxybenzoyl)thiosemicarbazide(3−)]hexapyridinetrinickel(II) pyridine monosolvate monohydrate

Fan Cao,^a Leilei Li ^a and Dacheng Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 7 November 2011; accepted 15 November 2011; online 23 November 2011)

The reaction of Ni(OAc)₂·4H₂O with 1-(2-carboxybenzoyl)thiosemicarbazide (H₃L) produces the title complex, [Ni₃(C₉H₆N₃O₃S)₂(C₅H₅N)₆]·C₅H₅N·2H₂O, which contains an linear array of three Ni^II atoms. The asymmetric unit contains half of the complex molecule, a water molecule and a half-molecule of pyridine. The central Ni^II atom, located on a crystallographic inversion centre, has an octahedral N₄O₂ environment. The other two Ni^II atoms have a square-pyramidal N₃OS environment, each bridged to the central Ni^II atom via the L³⁻ group. The carboxylate groups coordinate to the metal atoms in a monodentate fashion. The water molecule is linked to the complex molecule via O—H⋯O hydrogen bonds. The molecules further assemble into a one-dimensional network parallel to [001] via intermolecular N—H⋯O hydrogen bonds.

Related literature

For related structures and the synthesis of the 1-(2-carboxybenzoyl)thiosemicarbazide ligand, see: Shen et al. (1997 ).

Experimental

Crystal data

[Ni₃(C₉H₆N₃O₃S)₂(C₅H₅N)₆]·C₅H₅N·2H₂O
M_r = 1238.32
Monoclinic, C 2/c
a = 34.490 (3) Å
b = 8.8510 (7) Å
c = 17.8941 (16) Å
β = 90.912 (1)°
V = 5461.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 293 K
0.38 × 0.33 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.666, T_max = 0.844
13285 measured reflections
4808 independent reflections
2586 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.105
S = 0.99
4808 reflections
359 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱ	0.86	2.10	2.913 (4)	158
N3—H3B⋯O3ⁱⁱ	0.86	2.13	2.975 (5)	168
O4—H4C⋯O2	0.85	2.41	3.088 (5)	137
O4—H4D⋯O3	0.85	2.35	3.020 (5)	136
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048367/vm2135sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048367/vm2135Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title complex contains a half complex, a water molecule and a half pyridine molecule (symmetry codes to generate second half of complex and pyridine are -x + 1/2,-y + 1/2,-z + 1 and -x, y, -z + 1/2, respectively). The three nickel atoms are linked together linearly by two µ₂- bridged L groups. The central Ni2 atom is in a six-coordinated octahedral geometry with two pyridine molecules in axial positions and two amido-carbonyl oxygen atoms and two nitrogen atoms in the equatorial plane. The terminal Ni1 atom is coordinated in a trigonal-bipyramidal geometry composed of two nitrogen atoms from two pyridine molecules, one sulfur atom from the thiourea, one amido-carbonyl nitrogen atom, as well as one oxygen atom from the carboxylate. Thus, the carbonyl oxygen O1 and amine nitrogen N2 atoms of one ligand are bound to Ni2 forming a five-membered chelate ring, while the benzoyloxy oxygen O2, amine nitrogen N1 and sulfydryl sulfur S1 atoms are bound to terminal Ni1 atom forming a five-membered chelate ring and a seven-membered ring. The special position of the central Ni atom generates the linear organization of the three Ni atoms. The molecules further assemble into a one-dimensional network via intermolecular N—H···O hydrogen bonds (Table 1).

Related literature top

For related structures and the synthesis of the 1-(2-carboxybenzoyl)thiosemicarbazide ligand, see: Shen et al. (1997).

Experimental top

The title compound, [Ni₃L₂(Py)₆].Py.H₂O, was synthesized by the reaction of 3 mmol Ni(OAc)₂.4H₂O and 2 mmol 1-(2-carboxybenzoyl) thiosemicarbazide (H3L, synthesis described in Shen et al., 1997) in 10 ml methanol and 5 ml pyridine. The solution was stired for 6 hours. After slow evaporation of the solution over one month, deep red crystals suitable for X-ray diffraction were obtained. (yield 42.3%, m.p. 534-538 K).

Structure description top

For related structures and the synthesis of the 1-(2-carboxybenzoyl)thiosemicarbazide ligand, see: Shen et al. (1997).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids (symmetry codes to generate second half of complex and pyridine are -x + 1/2,-y + 1/2,-z + 1 and -x, y, -z + 1/2, respectively).

Bis[µ₂-1-(2-carboxybenzoyl)thiosemicarbazide(3-)]hexapyridinetrinickel(II) pyridine monosolvate monohydrate top

Crystal data top

[Ni₃(C₉H₆N₃O₃S)₂(C₅H₅N)₆]·C₅H₅N·2H₂O	F(000) = 2560
M_r = 1238.32	D_x = 1.506 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1906 reflections
a = 34.490 (3) Å	θ = 2.3–23.5°
b = 8.8510 (7) Å	µ = 1.17 mm⁻¹
c = 17.8941 (16) Å	T = 293 K
β = 90.912 (1)°	Block, black
V = 5461.9 (8) Å³	0.38 × 0.33 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4808 independent reflections
Radiation source: fine-focus sealed tube	2586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −40→32
T_min = 0.666, T_max = 0.844	k = −10→10
13285 measured reflections	l = −18→21

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.032P)²] where P = (F_o² + 2F_c²)/3
4808 reflections	(Δ/σ)_max < 0.001
359 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Ni₃(C₉H₆N₃O₃S)₂(C₅H₅N)₆]·C₅H₅N·2H₂O	V = 5461.9 (8) Å³
M_r = 1238.32	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 34.490 (3) Å	µ = 1.17 mm⁻¹
b = 8.8510 (7) Å	T = 293 K
c = 17.8941 (16) Å	0.38 × 0.33 × 0.15 mm
β = 90.912 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4808 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2586 reflections with I > 2σ(I)
T_min = 0.666, T_max = 0.844	R_int = 0.073
13285 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 0.99	Δρ_max = 0.65 e Å⁻³
4808 reflections	Δρ_min = −0.47 e Å⁻³
359 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.112323 (15)	0.26236 (7)	0.43526 (3)	0.03118 (19)
Ni2	0.2500	0.2500	0.5000	0.0262 (2)
S1	0.11994 (3)	0.37106 (14)	0.55102 (7)	0.0381 (3)
N1	0.17092 (9)	0.2355 (4)	0.44216 (18)	0.0268 (8)
N2	0.19160 (9)	0.2959 (4)	0.50367 (19)	0.0267 (9)
N3	0.18838 (10)	0.4244 (4)	0.61357 (19)	0.0389 (10)
H3A	0.2132	0.4211	0.6176	0.058*
H3B	0.1750	0.4680	0.6476	0.058*
N4	0.05243 (11)	0.3042 (5)	0.4317 (2)	0.0410 (11)
N5	0.10345 (10)	0.0358 (4)	0.4379 (2)	0.0381 (10)
N6	0.25781 (10)	0.4472 (4)	0.4275 (2)	0.0323 (9)
O1	0.22954 (8)	0.1319 (3)	0.41037 (15)	0.0287 (7)
O2	0.11502 (9)	0.3467 (4)	0.33229 (17)	0.0438 (9)
O3	0.15374 (11)	0.4067 (4)	0.2398 (2)	0.0701 (12)
C1	0.17038 (12)	0.3613 (5)	0.5543 (2)	0.0275 (11)
C2	0.19307 (12)	0.1557 (5)	0.3982 (2)	0.0277 (11)
C3	0.14056 (14)	0.3153 (6)	0.2833 (3)	0.0432 (13)
C4	0.17538 (11)	0.0773 (5)	0.3323 (2)	0.0263 (10)
C5	0.15244 (12)	0.1517 (5)	0.2784 (2)	0.0327 (11)
C6	0.13875 (14)	0.0710 (7)	0.2166 (3)	0.0513 (14)
H6	0.1241	0.1200	0.1799	0.062*
C7	0.14671 (16)	−0.0802 (7)	0.2094 (3)	0.0591 (16)
H7	0.1369	−0.1337	0.1686	0.071*
C8	0.16930 (15)	−0.1533 (6)	0.2626 (3)	0.0574 (16)
H8	0.1746	−0.2559	0.2579	0.069*
C9	0.18387 (13)	−0.0729 (5)	0.3224 (3)	0.0391 (12)
H9	0.1999	−0.1215	0.3572	0.047*
C10	0.02994 (14)	0.2411 (6)	0.4830 (3)	0.0618 (16)
H10	0.0414	0.1777	0.5184	0.074*
C11	−0.00927 (16)	0.2651 (8)	0.4862 (4)	0.078 (2)
H11	−0.0237	0.2186	0.5232	0.094*
C12	−0.02678 (17)	0.3547 (8)	0.4363 (4)	0.081 (2)
H12	−0.0534	0.3716	0.4379	0.098*
C13	−0.00470 (17)	0.4215 (7)	0.3825 (4)	0.076 (2)
H13	−0.0159	0.4851	0.3469	0.091*
C14	0.03455 (15)	0.3917 (6)	0.3827 (3)	0.0557 (15)
H14	0.0493	0.4364	0.3457	0.067*
C15	0.12039 (13)	−0.0501 (6)	0.4910 (3)	0.0475 (14)
H15	0.1316	−0.0021	0.5321	0.057*
C16	0.12199 (16)	−0.2043 (7)	0.4878 (4)	0.0645 (17)
H16	0.1335	−0.2595	0.5264	0.077*
C17	0.10612 (17)	−0.2764 (6)	0.4261 (4)	0.0678 (18)
H17	0.1077	−0.3808	0.4214	0.081*
C18	0.08817 (15)	−0.1917 (6)	0.3723 (3)	0.0560 (16)
H18	0.0766	−0.2378	0.3309	0.067*
C19	0.08739 (13)	−0.0390 (6)	0.3799 (3)	0.0428 (13)
H19	0.0750	0.0171	0.3427	0.051*
C20	0.27422 (15)	0.5707 (6)	0.4541 (3)	0.0625 (17)
H20	0.2822	0.5715	0.5040	0.075*
C21	0.28014 (16)	0.6987 (6)	0.4121 (4)	0.0709 (19)
H21	0.2917	0.7836	0.4335	0.085*
C22	0.26900 (14)	0.6994 (6)	0.3394 (3)	0.0495 (14)
H22	0.2727	0.7842	0.3096	0.059*
C23	0.25230 (16)	0.5732 (7)	0.3113 (3)	0.0612 (16)
H23	0.2443	0.5695	0.2614	0.073*
C24	0.24728 (15)	0.4514 (6)	0.3566 (3)	0.0562 (15)
H24	0.2357	0.3658	0.3361	0.067*
O4	0.07741 (10)	0.5704 (5)	0.2203 (2)	0.0882 (13)
H4C	0.0751	0.5189	0.2601	0.106*
H4D	0.0999	0.5533	0.2036	0.106*
N8	0.0000	0.8034 (18)	0.2500	0.172 (5)
C25	0.0223 (3)	0.8744 (16)	0.2004 (7)	0.159 (5)
H25	0.0367	0.8213	0.1657	0.191*
C26	0.0227 (5)	1.0234 (17)	0.2033 (11)	0.222 (10)
H26	0.0394	1.0749	0.1719	0.266*
C27	0.0000	1.106 (3)	0.2500	0.28 (3)
H27	0.0000	1.2110	0.2500	0.339*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0281 (3)	0.0351 (4)	0.0305 (4)	0.0010 (3)	0.0041 (3)	0.0008 (3)
Ni2	0.0239 (4)	0.0297 (5)	0.0251 (5)	−0.0005 (4)	0.0025 (3)	−0.0042 (4)
S1	0.0323 (7)	0.0486 (8)	0.0336 (7)	0.0086 (6)	0.0070 (5)	−0.0043 (6)
N1	0.024 (2)	0.037 (2)	0.0192 (19)	0.0002 (18)	0.0037 (15)	−0.0073 (18)
N2	0.027 (2)	0.030 (2)	0.023 (2)	−0.0005 (16)	0.0031 (17)	−0.0047 (18)
N3	0.034 (2)	0.053 (3)	0.030 (2)	0.001 (2)	0.0039 (18)	−0.016 (2)
N4	0.032 (2)	0.050 (3)	0.041 (3)	−0.002 (2)	0.004 (2)	0.000 (2)
N5	0.036 (2)	0.045 (3)	0.034 (3)	−0.006 (2)	0.0023 (19)	0.001 (2)
N6	0.031 (2)	0.033 (2)	0.033 (2)	0.0000 (18)	0.0058 (18)	0.002 (2)
O1	0.0252 (18)	0.0301 (18)	0.0309 (18)	0.0012 (14)	0.0002 (13)	−0.0051 (15)
O2	0.041 (2)	0.056 (2)	0.034 (2)	0.0098 (17)	0.0117 (16)	0.0110 (18)
O3	0.083 (3)	0.064 (3)	0.065 (3)	0.010 (2)	0.036 (2)	0.034 (2)
C1	0.032 (3)	0.026 (3)	0.025 (3)	0.006 (2)	0.003 (2)	−0.005 (2)
C2	0.029 (3)	0.023 (3)	0.031 (3)	−0.006 (2)	0.002 (2)	0.004 (2)
C3	0.035 (3)	0.058 (4)	0.036 (3)	−0.001 (3)	−0.004 (3)	0.009 (3)
C4	0.024 (3)	0.034 (3)	0.021 (3)	−0.004 (2)	0.0070 (19)	−0.009 (2)
C5	0.029 (3)	0.046 (3)	0.023 (3)	−0.006 (2)	0.007 (2)	−0.002 (2)
C6	0.051 (4)	0.072 (4)	0.031 (3)	−0.010 (3)	−0.003 (2)	0.000 (3)
C7	0.068 (4)	0.074 (5)	0.035 (4)	−0.017 (3)	0.000 (3)	−0.029 (3)
C8	0.061 (4)	0.050 (4)	0.062 (4)	0.002 (3)	−0.001 (3)	−0.029 (3)
C9	0.039 (3)	0.039 (3)	0.039 (3)	0.003 (2)	0.005 (2)	−0.015 (3)
C10	0.036 (3)	0.082 (5)	0.068 (4)	0.007 (3)	0.007 (3)	0.016 (4)
C11	0.036 (4)	0.108 (6)	0.092 (5)	0.007 (4)	0.020 (3)	0.017 (4)
C12	0.030 (4)	0.100 (6)	0.115 (6)	0.014 (4)	0.012 (4)	0.000 (5)
C13	0.044 (4)	0.092 (5)	0.093 (5)	0.021 (4)	−0.009 (4)	0.014 (4)
C14	0.041 (3)	0.062 (4)	0.065 (4)	0.003 (3)	0.002 (3)	0.010 (3)
C15	0.051 (4)	0.053 (4)	0.039 (3)	−0.007 (3)	0.000 (3)	0.004 (3)
C16	0.070 (4)	0.045 (4)	0.078 (5)	0.001 (3)	0.000 (3)	0.022 (3)
C17	0.078 (5)	0.027 (3)	0.099 (5)	−0.007 (3)	0.019 (4)	0.001 (4)
C18	0.051 (4)	0.048 (4)	0.069 (4)	−0.018 (3)	0.007 (3)	−0.014 (3)
C19	0.035 (3)	0.046 (4)	0.047 (4)	−0.009 (2)	0.005 (2)	−0.004 (3)
C20	0.080 (4)	0.048 (4)	0.059 (4)	−0.016 (3)	−0.018 (3)	0.005 (3)
C21	0.085 (5)	0.043 (4)	0.084 (5)	−0.025 (3)	−0.019 (4)	0.014 (4)
C22	0.053 (4)	0.043 (4)	0.053 (4)	0.002 (3)	0.013 (3)	0.018 (3)
C23	0.076 (4)	0.066 (4)	0.042 (4)	−0.009 (3)	0.001 (3)	0.006 (3)
C24	0.083 (4)	0.051 (4)	0.035 (3)	−0.021 (3)	0.003 (3)	0.004 (3)
O4	0.077 (3)	0.111 (4)	0.076 (3)	0.015 (3)	0.011 (2)	0.011 (3)
N8	0.155 (14)	0.194 (17)	0.164 (15)	0.000	−0.023 (10)	0.000
C25	0.157 (12)	0.174 (12)	0.146 (11)	−0.012 (11)	−0.020 (8)	0.040 (11)
C26	0.253 (18)	0.17 (2)	0.23 (2)	−0.107 (18)	−0.143 (14)	0.094 (17)
C27	0.46 (6)	0.10 (2)	0.28 (5)	0.000	−0.29 (4)	0.000

Geometric parameters (Å, º) top

Ni1—O2	1.992 (3)	C9—H9	0.9300
Ni1—N5	2.029 (4)	C10—C11	1.371 (6)
Ni1—N1	2.037 (3)	C10—H10	0.9300
Ni1—N4	2.099 (4)	C11—C12	1.332 (8)
Ni1—S1	2.2953 (13)	C11—H11	0.9300
Ni2—O1	2.032 (3)	C12—C13	1.371 (8)
Ni2—O1ⁱ	2.032 (3)	C12—H12	0.9300
Ni2—N2ⁱ	2.057 (3)	C13—C14	1.379 (6)
Ni2—N2	2.057 (3)	C13—H13	0.9300
Ni2—N6	2.194 (4)	C14—H14	0.9300
Ni2—N6ⁱ	2.194 (4)	C15—C16	1.367 (7)
S1—C1	1.742 (4)	C15—H15	0.9300
N1—C2	1.311 (5)	C16—C17	1.380 (7)
N1—N2	1.408 (4)	C16—H16	0.9300
N2—C1	1.309 (5)	C17—C18	1.361 (7)
N3—C1	1.342 (5)	C17—H17	0.9300
N3—H3A	0.8600	C18—C19	1.359 (6)
N3—H3B	0.8600	C18—H18	0.9300
N4—C14	1.317 (6)	C19—H19	0.9300
N4—C10	1.334 (6)	C20—C21	1.377 (7)
N5—C19	1.343 (5)	C20—H20	0.9300
N5—C15	1.343 (5)	C21—C22	1.351 (7)
N6—C24	1.314 (5)	C21—H21	0.9300
N6—C20	1.317 (6)	C22—C23	1.350 (6)
O1—C2	1.290 (4)	C22—H22	0.9300
O2—C3	1.283 (5)	C23—C24	1.362 (7)
O3—C3	1.216 (5)	C23—H23	0.9300
C2—C4	1.492 (5)	C24—H24	0.9300
C3—C5	1.508 (6)	O4—H4C	0.8501
C4—C9	1.374 (6)	O4—H4D	0.8498
C4—C5	1.402 (6)	N8—C25ⁱⁱ	1.338 (11)
C5—C6	1.392 (6)	N8—C25	1.338 (11)
C6—C7	1.373 (7)	C25—C26	1.320 (16)
C6—H6	0.9300	C25—H25	0.9300
C7—C8	1.381 (7)	C26—C27	1.366 (19)
C7—H7	0.9300	C26—H26	0.9300
C8—C9	1.374 (6)	C27—C26ⁱⁱ	1.366 (19)
C8—H8	0.9300	C27—H27	0.9300

O2—Ni1—N5	113.67 (15)	C6—C7—H7	119.9
O2—Ni1—N1	92.23 (13)	C8—C7—H7	119.9
N5—Ni1—N1	91.89 (14)	C9—C8—C7	119.3 (5)
O2—Ni1—N4	88.08 (14)	C9—C8—H8	120.3
N5—Ni1—N4	91.52 (15)	C7—C8—H8	120.3
N1—Ni1—N4	176.13 (14)	C4—C9—C8	121.6 (5)
O2—Ni1—S1	132.18 (10)	C4—C9—H9	119.2
N5—Ni1—S1	114.10 (12)	C8—C9—H9	119.2
N1—Ni1—S1	83.98 (10)	N4—C10—C11	123.3 (5)
N4—Ni1—S1	92.95 (11)	N4—C10—H10	118.4
O1—Ni2—O1ⁱ	180.000 (1)	C11—C10—H10	118.4
O1—Ni2—N2ⁱ	101.60 (12)	C12—C11—C10	120.1 (6)
O1ⁱ—Ni2—N2ⁱ	78.40 (12)	C12—C11—H11	120.0
O1—Ni2—N2	78.40 (12)	C10—C11—H11	120.0
O1ⁱ—Ni2—N2	101.60 (12)	C11—C12—C13	118.5 (6)
N2ⁱ—Ni2—N2	180.000 (1)	C11—C12—H12	120.8
O1—Ni2—N6	89.26 (13)	C13—C12—H12	120.8
O1ⁱ—Ni2—N6	90.74 (13)	C12—C13—C14	118.2 (6)
N2ⁱ—Ni2—N6	90.51 (13)	C12—C13—H13	120.9
N2—Ni2—N6	89.49 (13)	C14—C13—H13	120.9
O1—Ni2—N6ⁱ	90.74 (13)	N4—C14—C13	124.3 (5)
O1ⁱ—Ni2—N6ⁱ	89.25 (13)	N4—C14—H14	117.9
N2ⁱ—Ni2—N6ⁱ	89.49 (13)	C13—C14—H14	117.9
N2—Ni2—N6ⁱ	90.51 (13)	N5—C15—C16	123.6 (5)
N6—Ni2—N6ⁱ	180.000 (1)	N5—C15—H15	118.2
C1—S1—Ni1	96.29 (15)	C16—C15—H15	118.2
C2—N1—N2	112.4 (3)	C15—C16—C17	118.6 (5)
C2—N1—Ni1	127.9 (3)	C15—C16—H16	120.7
N2—N1—Ni1	119.5 (2)	C17—C16—H16	120.7
C1—N2—N1	115.3 (3)	C18—C17—C16	118.8 (5)
C1—N2—Ni2	131.9 (3)	C18—C17—H17	120.6
N1—N2—Ni2	112.6 (2)	C16—C17—H17	120.6
C1—N3—H3A	120.0	C19—C18—C17	119.1 (5)
C1—N3—H3B	120.0	C19—C18—H18	120.5
H3A—N3—H3B	120.0	C17—C18—H18	120.5
C14—N4—C10	115.7 (4)	N5—C19—C18	124.0 (5)
C14—N4—Ni1	125.1 (4)	N5—C19—H19	118.0
C10—N4—Ni1	119.2 (4)	C18—C19—H19	118.0
C19—N5—C15	115.9 (4)	N6—C20—C21	123.5 (5)
C19—N5—Ni1	122.0 (3)	N6—C20—H20	118.3
C15—N5—Ni1	120.8 (3)	C21—C20—H20	118.3
C24—N6—C20	115.9 (4)	C22—C21—C20	119.2 (5)
C24—N6—Ni2	124.0 (3)	C22—C21—H21	120.4
C20—N6—Ni2	120.2 (3)	C20—C21—H21	120.4
C2—O1—Ni2	112.0 (3)	C23—C22—C21	117.9 (5)
C3—O2—Ni1	126.4 (3)	C23—C22—H22	121.0
N2—C1—N3	118.3 (4)	C21—C22—H22	121.0
N2—C1—S1	124.6 (3)	C22—C23—C24	119.4 (5)
N3—C1—S1	117.1 (3)	C22—C23—H23	120.3
O1—C2—N1	124.3 (4)	C24—C23—H23	120.3
O1—C2—C4	116.3 (4)	N6—C24—C23	124.2 (5)
N1—C2—C4	119.3 (4)	N6—C24—H24	117.9
O3—C3—O2	124.1 (5)	C23—C24—H24	117.9
O3—C3—C5	119.8 (5)	H4C—O4—H4D	107.3
O2—C3—C5	116.0 (4)	C25ⁱⁱ—N8—C25	124 (2)
C9—C4—C5	119.1 (4)	C26—C25—N8	116.7 (19)
C9—C4—C2	117.8 (4)	C26—C25—H25	121.6
C5—C4—C2	123.1 (4)	N8—C25—H25	121.6
C6—C5—C4	119.1 (5)	C25—C26—C27	123 (3)
C6—C5—C3	116.8 (4)	C25—C26—H26	118.3
C4—C5—C3	124.1 (4)	C27—C26—H26	118.3
C7—C6—C5	120.6 (5)	C26ⁱⁱ—C27—C26	115 (3)
C7—C6—H6	119.7	C26ⁱⁱ—C27—H27	122.3
C5—C6—H6	119.7	C26—C27—H27	122.3
C6—C7—C8	120.2 (5)

O2—Ni1—S1—C1	−83.36 (19)	N1—N2—C1—N3	−178.5 (3)
N5—Ni1—S1—C1	93.57 (18)	Ni2—N2—C1—N3	6.7 (6)
N1—Ni1—S1—C1	4.19 (18)	N1—N2—C1—S1	2.2 (5)
N4—Ni1—S1—C1	−173.44 (18)	Ni2—N2—C1—S1	−172.6 (2)
O2—Ni1—N1—C2	−58.4 (4)	Ni1—S1—C1—N2	−4.9 (4)
N5—Ni1—N1—C2	55.3 (4)	Ni1—S1—C1—N3	175.8 (3)
N4—Ni1—N1—C2	−153 (2)	Ni2—O1—C2—N1	−5.8 (5)
S1—Ni1—N1—C2	169.4 (4)	Ni2—O1—C2—C4	178.4 (3)
O2—Ni1—N1—N2	127.7 (3)	N2—N1—C2—O1	1.4 (6)
N5—Ni1—N1—N2	−118.6 (3)	Ni1—N1—C2—O1	−172.8 (3)
N4—Ni1—N1—N2	33 (2)	N2—N1—C2—C4	177.1 (3)
S1—Ni1—N1—N2	−4.5 (3)	Ni1—N1—C2—C4	2.8 (6)
C2—N1—N2—C1	−172.1 (4)	Ni1—O2—C3—O3	−143.0 (4)
Ni1—N1—N2—C1	2.7 (4)	Ni1—O2—C3—C5	40.6 (6)
C2—N1—N2—Ni2	3.7 (4)	O1—C2—C4—C9	45.9 (5)
Ni1—N1—N2—Ni2	178.48 (16)	N1—C2—C4—C9	−130.1 (4)
O1—Ni2—N2—C1	169.9 (4)	O1—C2—C4—C5	−130.6 (4)
O1ⁱ—Ni2—N2—C1	−10.1 (4)	N1—C2—C4—C5	53.4 (6)
N2ⁱ—Ni2—N2—C1	34 (81)	C9—C4—C5—C6	0.3 (6)
N6—Ni2—N2—C1	−100.7 (4)	C2—C4—C5—C6	176.7 (4)
N6ⁱ—Ni2—N2—C1	79.3 (4)	C9—C4—C5—C3	178.9 (4)
O1—Ni2—N2—N1	−5.0 (2)	C2—C4—C5—C3	−4.7 (7)
O1ⁱ—Ni2—N2—N1	175.0 (2)	O3—C3—C5—C6	−70.0 (6)
N2ⁱ—Ni2—N2—N1	−141 (81)	O2—C3—C5—C6	106.5 (5)
N6—Ni2—N2—N1	84.3 (3)	O3—C3—C5—C4	111.4 (6)
N6ⁱ—Ni2—N2—N1	−95.7 (3)	O2—C3—C5—C4	−72.1 (6)
O2—Ni1—N4—C14	−15.1 (4)	C4—C5—C6—C7	1.7 (7)
N5—Ni1—N4—C14	−128.8 (4)	C3—C5—C6—C7	−177.0 (5)
N1—Ni1—N4—C14	80 (2)	C5—C6—C7—C8	−1.7 (8)
S1—Ni1—N4—C14	117.0 (4)	C6—C7—C8—C9	−0.3 (8)
O2—Ni1—N4—C10	166.0 (4)	C5—C4—C9—C8	−2.4 (7)
N5—Ni1—N4—C10	52.4 (4)	C2—C4—C9—C8	−179.0 (4)
N1—Ni1—N4—C10	−99 (2)	C7—C8—C9—C4	2.4 (8)
S1—Ni1—N4—C10	−61.9 (4)	C14—N4—C10—C11	−0.6 (8)
O2—Ni1—N5—C19	−22.5 (4)	Ni1—N4—C10—C11	178.3 (4)
N1—Ni1—N5—C19	−115.8 (3)	N4—C10—C11—C12	0.3 (10)
N4—Ni1—N5—C19	66.1 (4)	C10—C11—C12—C13	−0.1 (10)
S1—Ni1—N5—C19	160.0 (3)	C11—C12—C13—C14	0.3 (10)
O2—Ni1—N5—C15	143.8 (3)	C10—N4—C14—C13	0.9 (8)
N1—Ni1—N5—C15	50.5 (4)	Ni1—N4—C14—C13	−178.0 (4)
N4—Ni1—N5—C15	−127.7 (4)	C12—C13—C14—N4	−0.8 (9)
S1—Ni1—N5—C15	−33.7 (4)	C19—N5—C15—C16	0.5 (7)
O1—Ni2—N6—C24	4.2 (4)	Ni1—N5—C15—C16	−166.6 (4)
O1ⁱ—Ni2—N6—C24	−175.8 (4)	N5—C15—C16—C17	1.4 (8)
N2ⁱ—Ni2—N6—C24	105.8 (4)	C15—C16—C17—C18	−2.5 (8)
N2—Ni2—N6—C24	−74.2 (4)	C16—C17—C18—C19	1.8 (8)
N6ⁱ—Ni2—N6—C24	168 (100)	C15—N5—C19—C18	−1.2 (7)
O1—Ni2—N6—C20	−175.2 (4)	Ni1—N5—C19—C18	165.7 (4)
O1ⁱ—Ni2—N6—C20	4.8 (4)	C17—C18—C19—N5	0.1 (8)
N2ⁱ—Ni2—N6—C20	−73.6 (4)	C24—N6—C20—C21	0.5 (8)
N2—Ni2—N6—C20	106.4 (4)	Ni2—N6—C20—C21	179.9 (4)
N6ⁱ—Ni2—N6—C20	−11 (100)	N6—C20—C21—C22	−0.5 (9)
O1ⁱ—Ni2—O1—C2	132 (100)	C20—C21—C22—C23	0.2 (8)
N2ⁱ—Ni2—O1—C2	−174.4 (3)	C21—C22—C23—C24	0.1 (8)
N2—Ni2—O1—C2	5.6 (3)	C20—N6—C24—C23	−0.2 (8)
N6—Ni2—O1—C2	−84.0 (3)	Ni2—N6—C24—C23	−179.5 (4)
N6ⁱ—Ni2—O1—C2	96.0 (3)	C22—C23—C24—N6	−0.2 (9)
N5—Ni1—O2—C3	−63.3 (4)	C25ⁱⁱ—N8—C25—C26	2.2 (9)
N1—Ni1—O2—C3	29.7 (4)	N8—C25—C26—C27	−4.6 (18)
N4—Ni1—O2—C3	−154.1 (4)	C25—C26—C27—C26ⁱⁱ	2.4 (10)
S1—Ni1—O2—C3	113.6 (4)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.10	2.913 (4)	158
N3—H3B···O3ⁱⁱⁱ	0.86	2.13	2.975 (5)	168
O4—H4C···O2	0.85	2.41	3.088 (5)	137
O4—H4D···O3	0.85	2.35	3.020 (5)	136

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (iii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni₃(C₉H₆N₃O₃S)₂(C₅H₅N)₆]·C₅H₅N·2H₂O
M_r	1238.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	34.490 (3), 8.8510 (7), 17.8941 (16)
β (°)	90.912 (1)
V (Å³)	5461.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.38 × 0.33 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.666, 0.844
No. of measured, independent and observed [I > 2σ(I)] reflections	13285, 4808, 2586
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.105, 0.99
No. of reflections	4808
No. of parameters	359
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.47

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.86	2.10	2.913 (4)	158
N3—H3B···O3ⁱⁱ	0.86	2.13	2.975 (5)	168
O4—H4C···O2	0.85	2.41	3.088 (5)	137
O4—H4D···O3	0.85	2.35	3.020 (5)	136

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y+1, z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 20671048, 21041002) and the Shandong Province Higher School Science and Technology Plan Projects (No. J10LB61).

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, X., Wu, D. & Huang, X. (1997). Polyhedron, 16, 1477–1482. CSD CrossRef CAS Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.