Home The crystal structure of poly[bis(N,N-dimethylformamide-κ1O)-tetrakis(μ2-cyanido-κ2C:N)dinickel(II)], C10H14N6O2Ni2
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The crystal structure of poly[bis(N,N-dimethylformamide-κ1O)-tetrakis(μ2-cyanido-κ2C:N)dinickel(II)], C10H14N6O2Ni2

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Published/Copyright: March 12, 2020

Abstract

C10H14N6O2Ni2, monoclinic, I2/m (no. 12), a = 6.7377(1) Å, b = 7.3500(1) Å, c = 14.8647(2) Å, β = 96.051(1)°, V = 732.030(18) Å3, Z = 8, Rgt(F) = 0.0314, wRref(F2) = 0.0996, T = 150.01(10) K.

CCDC no.: 1975440

The crystal structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Brown block
Size:0.2 × 0.08 × 0.05 mm
Wavelength:Cu Kα radiation (1.54184 Å)
μ:3.30 mm−1
Diffractometer, scan mode:XtaLAB AFC12, ω-scans
θmax, completeness:73.3°, >99%
N(hkl)measured, N(hkl)unique, Rint:2748, 783, 0.027
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 713
N(param)refined:71
Programs:CrysAlisPRO [1], OLEX2 [2], SHELX [3], [4]
Table 2:

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

AtomxyzUiso*/Ueq
Ni11.00000.50000.50000.0171(3)
Ni20.50000.00000.50000.0178(3)
O10.8655(3)0.50000.36693(15)0.0253(5)
N10.8040(3)0.2983(3)0.53023(13)0.0218(4)
N20.5848(4)0.50000.2681(2)0.0272(6)
C10.6917(3)0.1821(3)0.52274(15)0.0206(5)
C20.6801(5)0.50000.3500(2)0.0233(7)
H20.60400.50000.39870.028*
C30.3670(6)0.50000.2541(3)0.0405(10)
H3A0.315(6)0.50000.320(3)0.030(11)*
H3B0.329(5)0.396(5)0.217(3)0.059(10)*
C40.6906(7)0.50000.1877(3)0.0408(10)
H4A0.654(5)0.397(5)0.153(2)0.055(10)*
H4B0.828(8)0.50000.202(4)0.055(15)*

Source of materials

A mixture of Ni(NO3)2 ⋅ 6H2O (0.1 mmol, 0.030 g), 5,15-bis(4-carboxyphenyl)porphyrin (0.05 mmol, 0.023 g), N,N-dimethylformamide (4 mL), acetonitrile (2 mL) and water (1 mL) was sonicated for 30 min. Then the reaction mixture was transferred to Teflon-lined stainless steel reactor and placed in the oven. Subsequently, the temperature was kept 393 K for 3 days. After cooling to room temperature at a rate of 6 K⋅h−1, brown block crystals of the title compound were obtained as a side product. Yield: 5 mg (27%, based on Ni). Anal. Calcd. for C2.5H3.5N1.5O0.5Ni0.5 (%): C, 32.67; H, 3.84; N, 22.86. Found: C, 32.25.; H, 3.26; N, 22.43.

Experimental details

Crystallographic data collection and reduction were performed using the program CrysAlisPRO [1]. Using Olex2 [2], the structure was solved with the ShelXT [3] structure solution program and refined with the ShelXL [4] refinement package. Coordinates of some hydrogen atoms were refined without any constraints or restraints others were included using a riding model (see Suppl. Material). The Uiso values were set to be 1.5Ueq of the carrier atom for methyl hydrogen atoms and 1.2Ueq for formyl hydrogen atom.

Comment

Hofmann type complexes, as one of the longest-known cyano-bridged coordination compounds, are still extensively investigated in recent years due to their unique structures and properties [5], [6], [7], [8], [9]. Up to now, a number of Hofmann complexes, varying from two-dimensional to three-dimensional structures, have been synthesized by mediating metal ions, coordinated small molecules and guest molecules [10], [11], [12], [13], [14], [15], [16], [17], [18], [19]. However, the preparation method remains the classic solution chemistry method. To the best of our knowledge, the effective solvothermal method for preparing Hofmann complexes has not been reported so far. Fortunately, a Hofmann-DMF-type compound, [Ni(DMF)2Ni(CN)4]n (where DMF = N,N-dimethyl formamide), was unexpectedly synthesized by solvothermal method when the porphyrin-based Ni-MOFs were attempted to synthesize by assembling 5,15-bis(4-carboxyphenyl)porphyrin ligand and Ni(NO3)2. Although two isomorphous compounds have been reported [5], [6], their central metal ions and preparation method are different from those of the title compound.

The asymmetric unit of the title compound contains two Ni(II) ions with occupancies of 0.25, one cyanide ion (CN), a half DMF molecule. It is particularly worth mentioning that the coordinated CN ions derive not from the addition of the cyano compounds, but from the thermal decomposition of the solvent acetonitrile. Each Ni1 center is coordinated by four cyanide ligands in the equatorial positions and two oxygen atoms from two coordinated DMF molecules at the axial positions to form an approximately regular octahedron geometry (NiO2N4; A = −x + 2, −y + 1, −z + 1; B = −x + 2, y, −z + 1; C = x, −y + 1, z; cf. the figure). Ni1 and four coordinated nitrogen atoms are in the same plane (p1). Each Ni2 center exhibits a four-coordinated square geometry (NiC4; D = −x + 1, −y, −z + 1; E = x, −y, z; F = −x + 1, y, −z + 1; cf. the figure) by four carbon atoms from four cyanide ligands. Ni2 and four coordinated carbon atoms are also coplanar (p2). The dihedral angle between the two planes (p1 and p2) is 146.9(9)° (cf. the figure). The Ni—C, Ni—N and Ni—O bond lengths are 1.866(2), 2.0663(19) and 2.088(2) Å, respectively. The neighbouring Ni1 and Ni2 centers are connected by cyanide ligands to furnish a two-dimensional layered structure. The adjacent layers are further assembled by van-der-Waals forces to extend into a three-dimensional network structure. All bond lengths and bond angles within the title structure are in the typical ranges [20], [21].

References

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Received: 2020-01-23
Accepted: 2020-02-27
Published Online: 2020-03-12
Published in Print: 2020-06-25

©2020 Shuang-Hua Yang, published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  65. Hydrogen bonding versus packing effects in the crystal structure of 3-((1R,2S)-1-methylpyrrolidin-1-ium-2-yl)pyridin-1-ium tetraiodidozincate(II), C10H16I4ZnN2
  66. Dimerization of 2-[(2-((2-aminophenyl)thio)phenyl)amino]-cyclohepta-2,4,6-trien-1-one through hydrogen bonding, C19H16N2OS
  67. Crystal structure of 1-(4-chloro-phenyl)-7-ethoxyl-6,8-difluoro-4-oxo-1,4-dihydro-quinoline-3-carboxylic acid, C18H12ClF2NO4
  68. Crystal structure of 7-ethoxy-6,8-difluoro-4-oxo-1-pyridin-2-ylmethyl-1,4-dihydro-quinoline-3-carboxylic acid, C18H14F2N2O4
  69. Crystal structure of octahydro-7aR,8′R-dimethylspiro[isobenzofuran-4(1H), 4′ (3′H)-[1H-7,9a]methanocyclohepta[c]pyran]-1′,3, 9′ (3aH,4′aH)-trione, C20H26O5
  70. Crystal structure of bis(5-ethoxy-2-(((1-hydroxy-2-methyl-3-oxidopropan-2-yl)imino)methyl)phenolato-κ3N,O,O’)manganese(IV) – methanol (1/1), C27H38MnN2O9
  71. Crystal structure of 8a,8a′′-oxybis(8aH-8,9-dioxa-3a1λ4-aza-8aλ4-borabenzo[fg]tetracene), C34H22B2N2O5
  72. Crystal structure of bromido-triphenyl-(triphenylarsine oxide-κO)tin(IV), C36H30AsBrOSn
  73. Crystal structure of catena-poly[chlorido-(μ2-formato-κ2O:O′)-(1,10-phenathroline-κ2N,N′)copper(II)], C26H18Cl2Cu2N4O4
  74. The crystal structure of poly[(μ10-5-carboxyisophthalato-κ10O)disodium], C9H4Na2O6
  75. The crystal structure of 3,5-difluoroisonicotinic acid, C6H3F2NO2
  76. The crystal structure of ethyl-1-(N-(adamantan-1-yl)-carbamothioyl)piperidine-4-carboxylate, C19H30N2O2S
  77. Crystal structure of 5-methyl-3-phenyl-1-tosyl-1,2,3,4-tetrahydropyridine, C19H21NO2S
  78. Crystal structure of bis((3-chlorosalicylidene)-ethylenediaminato-κ4N,N′,O,O′)nickel (II), C16H12Cl2NiN2O2
  79. Crystal structure of (E)-N′-(2-chloro-6-hydroxybenzylidene)-4-hydroxybenzohydrazide — dihydrofuran-2(3H)-one (1/1), C18H17ClN2O5
  80. Crystal structure of bis((3-bromosalicylidene)-ethylenediaminato-κ4N,N′,O,O′) nickel (II), C16H12Br2NiN2O2
  81. Crystal structure of trimethylsulfoxonium tetrachloridocobaltate(II) [(CH3)3SO]2CoCl4
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