metal-organic compounds
Bis[μ3-N′-oxidopyridine-2-carboximidamidato(2−)]bis[μ2-N′-oxidopyridine-2-carboximidamidato(1−)]tetrapyridinetetranickel(II) dinitrate
aInstitute of Cash Crops, Hubei Academy of Agricultural Science, Wuhan 430064, People's Republic of China, and bKey Laboratory of Industrial Ecology and Environmental Engineering (MOE) and State Key Laboratory of Fine Chemicals, School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, People's Republic of China
*Correspondence e-mail: xhdengyy@yahoo.com.cn
The title compound, [Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2, is a tetranuclear nickel complex containing a single-decker cation, located on an inversion center. The two unique NiII cations are N,N′,N′′,O-chelated by carboximidamidate(2−) and carboximidamidate(1−) anions, forming a distorted four-coordinate planar structure, while the other two NiII atoms are N,N′,O,O′-chelated by the same bridging ligands and two pyridine molecules, affording six-coordinated metals in an octahedral geometry. The cation is isostructural with the complex crystallized with perchlorate counter-ions in place of nitrate.
Related literature
For similar metal complexes, see: Kou et al. (2010); Papatriantafyllopoulou et al. (2008); Inglis et al. (2010); Deng & Ran (2011). For the synthesis of the ligand pyridine-2-amidoxine, see: Bernasek (1957).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell 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
10.1107/S1600536811052524/bh2397sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811052524/bh2397Isup2.hkl
The synthesis of pyridine-2-amidoxine was carried out according to literature (Bernasek, 1957). The title compound was synthesized by adding a solution of Ni(NO3)2.6H2O (290.8 mg, 1 mmol) in H2O (20 ml) to a solution of the ligand (137 mg, 1 mmol) and NaOH (80 mg, 2 mmol) in ethanol/water (3:1, 20 ml). The mixture was stirred at room temperature. The resulting precipitate was collected and dissolved in a mixture of ethanol and pyridine (3:1 v/v) at 50°C. The solution was allowed to stand in air for one day, and brown crystals were formed at the bottom of the vessel on slow evaporation of the solvent at room temperature. Yield: 56%. Anal. Calcd for C44H42N18Ni4O10: C 43.40, H 3.48, N 20.70. Found: C 43.36, H 3.53, N 20.94. IR (KBr, cm-1): ν = 3412 (w), 3268 (w), 1605 (s), 1552 (s), 1390 (very strong), 1347 (very strong), 1107 (m), 1450 (very strong), 705 (m).
H atoms were included in calculated positions with C—H = 0.93, N—H = 0.86 Å. For the terminal amine group N6, H atoms were refined freely, with restrained N—H bond lengths. Other H atoms were refined using a riding-model. Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.2 Ueq(C,N). Anisotropic displacement parameters for nitrate O atoms were restrained.
Data collection: APEX2 (Bruker, 2007); cell
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).Fig. 1. The molecular structure of the title complex, showing displacement ellipsoids at the 50% probability level. |
[Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2 | Z = 1 |
Mr = 1217.80 | F(000) = 624 |
Triclinic, P1 | Dx = 1.651 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4356 (6) Å | Cell parameters from 1738 reflections |
b = 10.7190 (8) Å | θ = 3.1–21.8° |
c = 11.2908 (9) Å | µ = 1.59 mm−1 |
α = 92.041 (6)° | T = 293 K |
β = 98.240 (5)° | Block, brown |
γ = 100.870 (5)° | 0.40 × 0.38 × 0.35 mm |
V = 1224.96 (15) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 4286 independent reflections |
Radiation source: fine-focus sealed tube | 3180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −12→12 |
Tmin = 0.569, Tmax = 0.606 | k = −12→11 |
9481 measured reflections | l = −9→13 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.042P)2 + 0.4034P] where P = (Fo2 + 2Fc2)/3 |
4286 reflections | (Δ/σ)max = 0.001 |
349 parameters | Δρmax = 0.66 e Å−3 |
8 restraints | Δρmin = −0.52 e Å−3 |
0 constraints |
[Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2 | γ = 100.870 (5)° |
Mr = 1217.80 | V = 1224.96 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.4356 (6) Å | Mo Kα radiation |
b = 10.7190 (8) Å | µ = 1.59 mm−1 |
c = 11.2908 (9) Å | T = 293 K |
α = 92.041 (6)° | 0.40 × 0.38 × 0.35 mm |
β = 98.240 (5)° |
Bruker SMART APEXII CCD area-detector diffractometer | 4286 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 3180 reflections with I > 2σ(I) |
Tmin = 0.569, Tmax = 0.606 | Rint = 0.039 |
9481 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 8 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.66 e Å−3 |
4286 reflections | Δρmin = −0.52 e Å−3 |
349 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.45373 (3) | 0.49188 (3) | 0.66926 (3) | 0.03132 (8) | |
Ni2 | 0.37394 (3) | 0.76610 (3) | 0.59280 (3) | 0.03324 (9) | |
N1 | 0.45234 (18) | 0.33873 (19) | 0.77743 (18) | 0.0346 (5) | |
N2 | 0.50204 (18) | 0.35800 (18) | 0.55758 (17) | 0.0323 (5) | |
N3 | 0.65769 (18) | 0.5669 (2) | 0.75316 (18) | 0.0364 (6) | |
N4 | 0.24626 (18) | 0.4257 (2) | 0.61209 (18) | 0.0371 (6) | |
N5 | 0.35016 (18) | 0.70397 (19) | 0.74148 (18) | 0.0340 (5) | |
N6 | 0.2507 (2) | 0.7224 (2) | 0.9124 (2) | 0.0510 (7) | |
H6B | 0.2906 (19) | 0.6662 (16) | 0.941 (2) | 0.061* | |
H6A | 0.235 (2) | 0.7699 (19) | 0.9683 (17) | 0.061* | |
N7 | 0.27188 (19) | 0.88369 (19) | 0.63555 (19) | 0.0384 (6) | |
N8 | 0.4142 (2) | 0.82419 (19) | 0.44897 (19) | 0.0419 (6) | |
H8 | 0.3973 | 0.8940 | 0.4213 | 0.050* | |
N9 | 0.2065 (2) | 0.9041 (2) | 0.1685 (2) | 0.0626 (7) | |
O1 | 0.40271 (16) | 0.60905 (16) | 0.79192 (15) | 0.0387 (5) | |
O2 | 0.45424 (15) | 0.63556 (15) | 0.55536 (14) | 0.0346 (4) | |
O3 | 0.2335 (2) | 0.9647 (2) | 0.2650 (2) | 0.0902 (8) | |
O4 | 0.1740 (3) | 0.7894 (3) | 0.1607 (3) | 0.1234 (12) | |
O5 | 0.2296 (4) | 0.9553 (3) | 0.0776 (2) | 0.1285 (11) | |
C1 | 0.4176 (3) | 0.3303 (3) | 0.8866 (2) | 0.0477 (8) | |
H1 | 0.3974 | 0.4017 | 0.9234 | 0.057* | |
C2 | 0.4105 (3) | 0.2203 (3) | 0.9472 (3) | 0.0562 (9) | |
H2 | 0.3853 | 0.2171 | 1.0229 | 0.067* | |
C3 | 0.4416 (3) | 0.1151 (3) | 0.8929 (3) | 0.0532 (9) | |
H3 | 0.4352 | 0.0390 | 0.9307 | 0.064* | |
C4 | 0.4823 (2) | 0.1235 (3) | 0.7816 (2) | 0.0410 (7) | |
H4 | 0.5067 | 0.0544 | 0.7447 | 0.049* | |
C5 | 0.4859 (2) | 0.2373 (2) | 0.7266 (2) | 0.0332 (7) | |
C6 | 0.5271 (2) | 0.2555 (2) | 0.6071 (2) | 0.0321 (6) | |
C7 | 0.7375 (2) | 0.4927 (3) | 0.8027 (3) | 0.0480 (8) | |
H7 | 0.7126 | 0.4051 | 0.7865 | 0.058* | |
C8 | 0.8551 (3) | 0.5403 (3) | 0.8767 (3) | 0.0612 (10) | |
H8A | 0.9077 | 0.4856 | 0.9101 | 0.073* | |
C9 | 0.8934 (3) | 0.6691 (3) | 0.9002 (3) | 0.0651 (11) | |
H9 | 0.9709 | 0.7033 | 0.9517 | 0.078* | |
C10 | 0.8154 (3) | 0.7466 (3) | 0.8465 (3) | 0.0587 (10) | |
H10 | 0.8405 | 0.8347 | 0.8585 | 0.070* | |
C11 | 0.6988 (2) | 0.6920 (3) | 0.7743 (3) | 0.0445 (8) | |
H11 | 0.6461 | 0.7455 | 0.7385 | 0.053* | |
C12 | 0.1604 (2) | 0.4086 (3) | 0.6893 (3) | 0.0497 (8) | |
H12 | 0.1919 | 0.4291 | 0.7703 | 0.060* | |
C13 | 0.0283 (3) | 0.3623 (3) | 0.6558 (3) | 0.0654 (10) | |
H13 | −0.0283 | 0.3513 | 0.7128 | 0.079* | |
C14 | −0.0189 (3) | 0.3328 (3) | 0.5370 (4) | 0.0708 (11) | |
H14 | −0.1084 | 0.3014 | 0.5114 | 0.085* | |
C15 | 0.0670 (3) | 0.3500 (3) | 0.4571 (3) | 0.0664 (10) | |
H15 | 0.0371 | 0.3309 | 0.3757 | 0.080* | |
C16 | 0.1994 (3) | 0.3960 (3) | 0.4975 (3) | 0.0503 (8) | |
H16 | 0.2577 | 0.4065 | 0.4419 | 0.060* | |
C17 | 0.2787 (2) | 0.7604 (2) | 0.8038 (2) | 0.0374 (7) | |
C18 | 0.2286 (2) | 0.8621 (2) | 0.7436 (2) | 0.0368 (7) | |
C19 | 0.1439 (2) | 0.9336 (3) | 0.7852 (3) | 0.0529 (9) | |
H19 | 0.1137 | 0.9175 | 0.8577 | 0.063* | |
C20 | 0.1053 (3) | 1.0286 (3) | 0.7175 (3) | 0.0617 (10) | |
H20 | 0.0498 | 1.0780 | 0.7446 | 0.074* | |
C21 | 0.1495 (3) | 1.0495 (3) | 0.6102 (3) | 0.0585 (9) | |
H21 | 0.1239 | 1.1132 | 0.5639 | 0.070* | |
C22 | 0.2319 (3) | 0.9763 (3) | 0.5708 (3) | 0.0488 (8) | |
H22 | 0.2608 | 0.9911 | 0.4975 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.03287 (15) | 0.03169 (17) | 0.03126 (17) | 0.01043 (13) | 0.00592 (13) | 0.00101 (13) |
Ni2 | 0.03572 (15) | 0.03221 (17) | 0.03383 (17) | 0.01353 (13) | 0.00404 (14) | −0.00190 (14) |
N1 | 0.0353 (10) | 0.0386 (12) | 0.0312 (11) | 0.0102 (9) | 0.0055 (9) | 0.0022 (9) |
N2 | 0.0389 (10) | 0.0305 (11) | 0.0292 (11) | 0.0082 (9) | 0.0091 (9) | 0.0017 (9) |
N3 | 0.0362 (10) | 0.0368 (11) | 0.0378 (12) | 0.0088 (9) | 0.0088 (9) | 0.0010 (10) |
N4 | 0.0353 (10) | 0.0417 (12) | 0.0359 (11) | 0.0088 (9) | 0.0094 (9) | 0.0008 (10) |
N5 | 0.0349 (10) | 0.0352 (11) | 0.0342 (11) | 0.0131 (9) | 0.0061 (9) | −0.0035 (9) |
N6 | 0.0580 (12) | 0.0633 (15) | 0.0413 (13) | 0.0282 (11) | 0.0185 (11) | 0.0009 (12) |
N7 | 0.0382 (10) | 0.0358 (11) | 0.0401 (12) | 0.0112 (9) | −0.0011 (10) | −0.0057 (10) |
N8 | 0.0565 (12) | 0.0310 (11) | 0.0451 (13) | 0.0210 (10) | 0.0133 (10) | 0.0057 (10) |
N9 | 0.0837 (15) | 0.0704 (16) | 0.0504 (15) | 0.0439 (13) | 0.0246 (13) | 0.0175 (13) |
O1 | 0.0458 (9) | 0.0395 (10) | 0.0345 (9) | 0.0176 (8) | 0.0066 (8) | 0.0013 (8) |
O2 | 0.0448 (8) | 0.0347 (9) | 0.0299 (9) | 0.0180 (7) | 0.0107 (7) | 0.0037 (7) |
O3 | 0.1267 (16) | 0.1144 (18) | 0.0461 (13) | 0.0744 (14) | 0.0053 (13) | −0.0103 (13) |
O4 | 0.151 (2) | 0.079 (2) | 0.138 (3) | −0.0138 (19) | 0.064 (2) | 0.0039 (19) |
O5 | 0.243 (3) | 0.0930 (18) | 0.0743 (17) | 0.0774 (19) | 0.044 (2) | 0.0252 (15) |
C1 | 0.0498 (14) | 0.0572 (18) | 0.0381 (15) | 0.0145 (13) | 0.0081 (13) | 0.0043 (14) |
C2 | 0.0515 (15) | 0.085 (2) | 0.0355 (15) | 0.0151 (16) | 0.0099 (13) | 0.0193 (15) |
C3 | 0.0510 (15) | 0.0552 (18) | 0.0529 (17) | 0.0102 (14) | 0.0022 (14) | 0.0224 (14) |
C4 | 0.0394 (13) | 0.0388 (15) | 0.0435 (15) | 0.0086 (12) | −0.0005 (12) | 0.0071 (12) |
C5 | 0.0303 (11) | 0.0332 (13) | 0.0347 (14) | 0.0042 (10) | 0.0028 (11) | 0.0020 (11) |
C6 | 0.0332 (11) | 0.0274 (13) | 0.0346 (13) | 0.0061 (10) | 0.0017 (11) | −0.0005 (11) |
C7 | 0.0384 (13) | 0.0400 (15) | 0.0642 (19) | 0.0097 (12) | 0.0004 (14) | 0.0037 (14) |
C8 | 0.0447 (15) | 0.0564 (18) | 0.078 (2) | 0.0122 (14) | −0.0111 (16) | 0.0107 (17) |
C9 | 0.0421 (15) | 0.068 (2) | 0.074 (2) | 0.0004 (16) | −0.0103 (16) | −0.0087 (18) |
C10 | 0.0466 (15) | 0.0435 (17) | 0.081 (2) | 0.0018 (14) | 0.0066 (16) | −0.0128 (16) |
C11 | 0.0408 (13) | 0.0436 (15) | 0.0519 (17) | 0.0136 (12) | 0.0096 (13) | 0.0020 (13) |
C12 | 0.0398 (13) | 0.0613 (18) | 0.0474 (17) | 0.0088 (13) | 0.0082 (13) | −0.0031 (15) |
C13 | 0.0443 (15) | 0.060 (2) | 0.096 (3) | 0.0107 (14) | 0.0270 (16) | −0.0007 (19) |
C14 | 0.0370 (14) | 0.0539 (19) | 0.115 (3) | 0.0073 (14) | −0.0030 (17) | −0.021 (2) |
C15 | 0.0554 (17) | 0.069 (2) | 0.066 (2) | 0.0117 (16) | −0.0144 (16) | −0.0184 (18) |
C16 | 0.0502 (15) | 0.0569 (18) | 0.0431 (16) | 0.0117 (14) | 0.0049 (13) | −0.0024 (14) |
C17 | 0.0351 (12) | 0.0359 (14) | 0.0399 (15) | 0.0069 (11) | 0.0032 (11) | −0.0039 (12) |
C18 | 0.0296 (11) | 0.0358 (14) | 0.0429 (15) | 0.0048 (11) | 0.0025 (11) | −0.0080 (12) |
C19 | 0.0429 (13) | 0.0549 (17) | 0.066 (2) | 0.0190 (13) | 0.0163 (14) | −0.0062 (15) |
C20 | 0.0542 (15) | 0.0575 (18) | 0.083 (2) | 0.0327 (14) | 0.0162 (16) | −0.0032 (17) |
C21 | 0.0596 (15) | 0.0522 (17) | 0.070 (2) | 0.0339 (13) | 0.0009 (16) | 0.0024 (16) |
C22 | 0.0548 (15) | 0.0467 (16) | 0.0481 (17) | 0.0232 (13) | 0.0015 (14) | 0.0013 (14) |
Ni1—O1 | 2.0295 (17) | C2—H2 | 0.9300 |
Ni1—O2 | 2.0410 (17) | C3—C4 | 1.383 (4) |
Ni1—N2 | 2.057 (2) | C3—H3 | 0.9300 |
Ni1—N1 | 2.080 (2) | C4—C5 | 1.386 (4) |
Ni1—N4 | 2.1435 (19) | C4—H4 | 0.9300 |
Ni1—N3 | 2.1900 (18) | C5—C6 | 1.481 (3) |
Ni2—O2 | 1.8278 (17) | C6—N8i | 1.333 (3) |
Ni2—N8 | 1.836 (2) | C7—C8 | 1.381 (4) |
Ni2—N5 | 1.860 (2) | C7—H7 | 0.9300 |
Ni2—N7 | 1.888 (2) | C8—C9 | 1.368 (4) |
N1—C1 | 1.335 (3) | C8—H8A | 0.9300 |
N1—C5 | 1.339 (3) | C9—C10 | 1.367 (4) |
N2—C6 | 1.303 (3) | C9—H9 | 0.9300 |
N2—O2i | 1.414 (3) | C10—C11 | 1.378 (4) |
N3—C11 | 1.331 (3) | C10—H10 | 0.9300 |
N3—C7 | 1.336 (3) | C11—H11 | 0.9300 |
N4—C16 | 1.321 (3) | C12—C13 | 1.367 (4) |
N4—C12 | 1.330 (3) | C12—H12 | 0.9300 |
N5—C17 | 1.306 (3) | C13—C14 | 1.366 (5) |
N5—O1 | 1.350 (3) | C13—H13 | 0.9300 |
N6—C17 | 1.360 (3) | C14—C15 | 1.354 (5) |
N6—H6B | 0.843 (15) | C14—H14 | 0.9300 |
N6—H6A | 0.851 (16) | C15—C16 | 1.380 (4) |
N7—C22 | 1.347 (3) | C15—H15 | 0.9300 |
N7—C18 | 1.373 (3) | C16—H16 | 0.9300 |
N8—C6i | 1.333 (3) | C17—C18 | 1.446 (4) |
N8—H8 | 0.8600 | C18—C19 | 1.391 (4) |
N9—O4 | 1.209 (4) | C19—C20 | 1.381 (4) |
N9—O5 | 1.214 (4) | C19—H19 | 0.9300 |
N9—O3 | 1.217 (3) | C20—C21 | 1.368 (5) |
O2—N2i | 1.414 (3) | C20—H20 | 0.9300 |
C1—C2 | 1.380 (4) | C21—C22 | 1.376 (4) |
C1—H1 | 0.9300 | C21—H21 | 0.9300 |
C2—C3 | 1.378 (4) | C22—H22 | 0.9300 |
O1—Ni1—O2 | 87.43 (7) | C2—C3—H3 | 120.2 |
O1—Ni1—N2 | 173.84 (8) | C4—C3—H3 | 120.2 |
O2—Ni1—N2 | 98.68 (7) | C3—C4—C5 | 118.3 (3) |
O1—Ni1—N1 | 95.46 (8) | C3—C4—H4 | 120.8 |
O2—Ni1—N1 | 176.94 (7) | C5—C4—H4 | 120.8 |
N2—Ni1—N1 | 78.42 (8) | N1—C5—C4 | 122.4 (2) |
O1—Ni1—N4 | 86.65 (7) | N1—C5—C6 | 115.2 (2) |
O2—Ni1—N4 | 90.52 (7) | C4—C5—C6 | 122.4 (2) |
N2—Ni1—N4 | 92.45 (8) | N2—C6—N8i | 120.5 (2) |
N1—Ni1—N4 | 88.65 (8) | N2—C6—C5 | 115.1 (2) |
O1—Ni1—N3 | 85.71 (7) | N8i—C6—C5 | 124.5 (2) |
O2—Ni1—N3 | 92.71 (7) | N3—C7—C8 | 123.0 (3) |
N2—Ni1—N3 | 94.77 (8) | N3—C7—H7 | 118.5 |
N1—Ni1—N3 | 88.52 (7) | C8—C7—H7 | 118.5 |
N4—Ni1—N3 | 171.56 (8) | C9—C8—C7 | 119.1 (3) |
O2—Ni2—N8 | 84.38 (8) | C9—C8—H8A | 120.5 |
O2—Ni2—N5 | 91.50 (8) | C7—C8—H8A | 120.5 |
N8—Ni2—N5 | 174.27 (9) | C10—C9—C8 | 118.7 (3) |
O2—Ni2—N7 | 172.23 (8) | C10—C9—H9 | 120.7 |
N8—Ni2—N7 | 100.57 (9) | C8—C9—H9 | 120.7 |
N5—Ni2—N7 | 83.96 (9) | C9—C10—C11 | 118.9 (3) |
C1—N1—C5 | 118.4 (2) | C9—C10—H10 | 120.6 |
C1—N1—Ni1 | 127.43 (19) | C11—C10—H10 | 120.6 |
C5—N1—Ni1 | 114.07 (16) | N3—C11—C10 | 123.4 (3) |
C6—N2—O2i | 109.62 (19) | N3—C11—H11 | 118.3 |
C6—N2—Ni1 | 115.76 (16) | C10—C11—H11 | 118.3 |
O2i—N2—Ni1 | 132.58 (14) | N4—C12—C13 | 123.4 (3) |
C11—N3—C7 | 116.9 (2) | N4—C12—H12 | 118.3 |
C11—N3—Ni1 | 119.41 (17) | C13—C12—H12 | 118.3 |
C7—N3—Ni1 | 122.75 (16) | C14—C13—C12 | 118.7 (3) |
C16—N4—C12 | 117.3 (2) | C14—C13—H13 | 120.7 |
C16—N4—Ni1 | 120.50 (18) | C12—C13—H13 | 120.7 |
C12—N4—Ni1 | 122.16 (16) | C15—C14—C13 | 118.7 (3) |
C17—N5—O1 | 117.4 (2) | C15—C14—H14 | 120.7 |
C17—N5—Ni2 | 116.46 (18) | C13—C14—H14 | 120.7 |
O1—N5—Ni2 | 126.15 (15) | C14—C15—C16 | 119.5 (3) |
C17—N6—H6B | 115.2 (18) | C14—C15—H15 | 120.2 |
C17—N6—H6A | 125.6 (16) | C16—C15—H15 | 120.2 |
H6B—N6—H6A | 111 (2) | N4—C16—C15 | 122.4 (3) |
C22—N7—C18 | 118.8 (2) | N4—C16—H16 | 118.8 |
C22—N7—Ni2 | 128.23 (19) | C15—C16—H16 | 118.8 |
C18—N7—Ni2 | 112.85 (17) | N5—C17—N6 | 122.5 (2) |
C6i—N8—Ni2 | 111.45 (17) | N5—C17—C18 | 113.5 (2) |
C6i—N8—H8 | 124.3 | N6—C17—C18 | 123.9 (2) |
Ni2—N8—H8 | 124.3 | N7—C18—C19 | 120.8 (3) |
O4—N9—O5 | 116.9 (3) | N7—C18—C17 | 113.1 (2) |
O4—N9—O3 | 121.9 (3) | C19—C18—C17 | 126.1 (3) |
O5—N9—O3 | 120.3 (3) | C20—C19—C18 | 119.3 (3) |
N5—O1—Ni1 | 112.62 (13) | C20—C19—H19 | 120.4 |
N2i—O2—Ni2 | 114.03 (13) | C18—C19—H19 | 120.4 |
N2i—O2—Ni1 | 127.93 (13) | C21—C20—C19 | 119.4 (3) |
Ni2—O2—Ni1 | 117.72 (8) | C21—C20—H20 | 120.3 |
N1—C1—C2 | 122.7 (3) | C19—C20—H20 | 120.3 |
N1—C1—H1 | 118.6 | C20—C21—C22 | 120.0 (3) |
C2—C1—H1 | 118.6 | C20—C21—H21 | 120.0 |
C3—C2—C1 | 118.5 (3) | C22—C21—H21 | 120.0 |
C3—C2—H2 | 120.8 | N7—C22—C21 | 121.8 (3) |
C1—C2—H2 | 120.8 | N7—C22—H22 | 119.1 |
C2—C3—C4 | 119.5 (3) | C21—C22—H22 | 119.1 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2 |
Mr | 1217.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.4356 (6), 10.7190 (8), 11.2908 (9) |
α, β, γ (°) | 92.041 (6), 98.240 (5), 100.870 (5) |
V (Å3) | 1224.96 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.40 × 0.38 × 0.35 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.569, 0.606 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9481, 4286, 3180 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.100, 1.03 |
No. of reflections | 4286 |
No. of parameters | 349 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.52 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This research was supported by the Natural Science Fund of Hubei Province (project ZRZ0140) and the National Natural Science Foundation of China (Nos. 20877013 and 20837001). The authors thank Professor Z.-M. Qiu of Hubei Academy of Agricultural Science for his valuable suggestions.
References
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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.
Transition metal compounds have been of great interest for many years. They are very important in the development of coordination chemistry. As an extension of work on the structural characterization of Ni compounds, we report here the crystal structure of a new tetranuclear nickel(II) compound.
The title compound is a tetranuclear nickel(II) complex (Fig. 1). The Ni(II) ions form a central deck, but show different coordinate ways. Two are coordinated by Npy, Nox, Nam and Oox (where the abbreviations py, ox and am are for the 2-pyridyl, oximate and deprotonated amino donor atoms, respectively), and form square planar geometry. The other two metals are coordinated by two solvent pyridine molecules and two chelating ligands, to form octahedral structures. The different coordinated-nickel(II) ions are bridged by the Oox groups. The Ni1—(N,O) bond lengths are longer than the Ni2—(N,O) bond distances. The angles are also different, as a consequence of the different coordination geometry. The cation is indeed isostructural with that found in the perchlorate complex previously reported (Kou et al., 2010). Related complexes have also been characterized (Papatriantafyllopoulou et al., 2008; Inglis et al., 2010; Deng & Ran, 2011).