Home Physical Sciences Crystal structure of tris(cyano-(hydrogen tris(3,5-dimethylpyrazolyl)borate))-iron(III) 4-methoxypyridinium monohydrate, C24H32BN10O2Fe
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Crystal structure of tris(cyano-(hydrogen tris(3,5-dimethylpyrazolyl)borate))-iron(III) 4-methoxypyridinium monohydrate, C24H32BN10O2Fe

  • Zhong-Hai Ni EMAIL logo and Hao Sun
Published/Copyright: September 16, 2017

Abstract

C24H32BN10O2Fe, orthorhombic, Pca21 (no. 29), a = 19.053(4) Å, b = 9.0666(18) Å, c = 16.439(3) Å, V = 2839.8(10) Å3, Z = 4, Rgt(F) = 0.0482, wRref(F2) = 0.1194, T = 123(2) K.

CCDC no.:: 1568400

The crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Red block
Size:0.12 × 0.08 × 0.06 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:5.7 cm−1
Diffractometer, scan mode:Bruker APEXII, φ and ω-scans
2θmax, completeness:52°, >99%
N(hkl)measured, N(hkl)unique, Rint:22002, 5551, 0.083
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 3872
N(param)refined:359
Programs:Bruker [1], SHELX [2], PLATON [3]
Table 2

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

AtomxyzUiso*/Ueq
Fe10.33587(2)1.18721(6)0.25840(5)0.04476(16)
B10.3343(2)0.8469(5)0.2539(5)0.0442(10)
H10.3320(16)0.722(4)0.252(3)0.053*
C10.3191(2)1.3115(5)0.3512(3)0.0532(11)
C20.4147(2)1.3075(5)0.2299(3)0.0551(11)
C30.2791(2)1.3220(5)0.1974(3)0.0500(10)
C40.3617(2)1.0841(5)0.0802(3)0.0549(11)
C50.3677(2)0.9495(5)0.0407(3)0.0599(12)
H50.37490.9349−0.01470.072*
C60.3608(2)0.8420(5)0.0990(3)0.0558(12)
C70.3662(2)0.6764(5)0.0904(3)0.0692(14)
H7A0.40660.64160.11950.104*
H7B0.37060.65110.03390.104*
H7C0.32470.63120.11230.104*
C80.3676(3)1.2361(6)0.0426(3)0.0743(14)
H8A0.32171.27110.02830.111*
H8B0.39631.2310−0.00530.111*
H8C0.38861.30250.08110.111*
C90.45096(19)1.0750(5)0.3775(3)0.0476(10)
C100.4751(2)0.9371(5)0.4029(3)0.0557(11)
H100.51090.91970.44010.067*
C110.4365(2)0.8320(5)0.3630(3)0.0530(11)
C120.4414(3)0.6673(4)0.3659(3)0.0708(14)
H12A0.39520.62630.37230.106*
H12B0.47020.63830.41100.106*
H12C0.46170.63180.31620.106*
C130.4779(2)1.2225(5)0.4037(3)0.0621(12)
H13A0.50641.26380.36130.093*
H13B0.50561.21140.45220.093*
H13C0.43911.28700.41460.093*
C140.1860(2)1.0862(5)0.3050(2)0.0515(10)
C150.1519(2)0.9500(5)0.3124(3)0.0587(12)
H150.10480.93570.32480.070*
C160.2008(2)0.8408(5)0.2980(3)0.0548(11)
C170.1933(3)0.6764(5)0.2989(4)0.0797(16)
H17A0.20850.63700.24770.120*
H17B0.14500.65080.30790.120*
H17C0.22160.63600.34180.120*
C180.1548(2)1.2358(5)0.3164(3)0.0630(12)
H18A0.17561.28210.36300.095*
H18B0.10511.22680.32460.095*
H18C0.16361.29460.26890.095*
C190.5767(3)1.1592(6)0.1148(3)0.0681(13)
H190.55681.24960.12830.082*
C200.5432(2)1.0325(5)0.1366(3)0.0653(13)
H200.50051.03620.16410.078*
C210.5736(2)0.8971(5)0.1170(3)0.0619(12)
C220.6371(2)0.8945(5)0.0748(3)0.0665(14)
H220.65810.80570.06020.080*
C230.6679(2)1.0270(6)0.0554(4)0.0759(16)
H230.71081.02720.02840.091*
C240.5659(3)0.6335(5)0.1207(4)0.0905(19)
H24A0.56340.61730.06300.136*
H24B0.53890.55950.14830.136*
H24C0.61390.62790.13810.136*
N10.3091(2)1.3853(5)0.4071(3)0.0696(11)
N20.4644(2)1.3736(4)0.2116(3)0.0750(12)
N30.24658(19)1.4036(4)0.1596(2)0.0612(10)
N40.35136(17)1.0605(4)0.1600(2)0.0513(9)
N50.35062(17)0.9086(4)0.1703(2)0.0492(8)
N60.39866(16)1.0533(3)0.3230(2)0.0462(8)
N70.39031(16)0.9042(4)0.3148(2)0.0470(8)
N80.25457(17)1.0603(4)0.28588(19)0.0483(8)
N90.26258(16)0.9093(4)0.2814(2)0.0493(9)
N100.6376(2)1.1561(4)0.0745(3)0.0648(11)
H10A0.65751.23750.06060.078*
O10.53791(16)0.7784(4)0.1397(2)0.0781(10)
O1W0.3072(2)0.5851(4)0.5372(2)0.0781(10)
H1WB0.301(4)0.525(5)0.577(3)0.117*
H1WA0.314(3)0.531(6)0.494(3)0.117*

Source of material

The precursor Bu4N[Fe(Tp*)(CN)3] was synthesized according to the literature [4]. The title complex was obtained unexpectedly as follows: a methanol (MeOH) solution (10.0 ml) of cyanide-containing building block Bu4N[Fe(Tp*)(CN)3] (0.2 mmol) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) was subsequently added to a MeOH solution (10 ml) of Fe(ClO4)3⋅6H2O (0.1 mmol). 4-methoxy-pyridine (MP) (0.4 mmol) was subsequently added to the above mixture. The mixture was then carefully filtered and the resulting solution was kept at room temperature for about three days, producing red block crystals of the title complex with a yield of 25.0%. Elemental analysis–calculated for C24H32BN10O2Fe: C, 51.55%; H, 5.77%; N, 25.05%; found: C,51.36%, H, 5.79%; N, 24.88%.

Experimental details

The coordinates of the H atoms bound to boron atom and water molecule and pyridine nitrogen were found from difference Fourier maps and refined freely; distance restraints were used for water H atoms. All H atoms bond to C atoms were introduced using the HFIX command in the SHELX program [2], with the value of 0.93 Å or 0.96 Å for C—H bonds distances. All H atoms were allowed for as riding atoms with Uiso(H) = 1.5Ueq(methyl carrier and water) and Uiso(H) = 1.2Ueq(C, B) for all other hydrogen atoms.

Discussion

The design and synthesis of molecule-based magnetic materials have been the subject of several investigations in the past several decades because of their interesting properties and their novel molecular topological structures [5], [6], [7]. As one of the most well-known bridging groups for magnetic complexes, the cyanide ligand exhibits unique advantages for the assembly of new molecular magnetic materials, not only because the resulting structures can be easily predicted but also because mediation of magnetic coupling between (heterospin) metal centres can be expected. Up to date, a large number of cyanide-bridged complexes with interestingly magnetic properties have been obtained [8], [9], [10], [11], [12], [13]. Among the many cyanide-containing building blocks, tricyanide-containing building blocks of [Fe(Tp)(CN)3] (Tp = hydrogen tris(pyrazolyl)borate) and its derivatives have been extensively exploited for assemblying low-dimensional cyanide-bridged complexes [14]. Herein, we report the synthesis and crystal strucure of such a cyanide-containing building block, C24H32BN10O2Fe, in a solvated and monohydrate form, which was obtained serendipitously when assembling cyanide-bridged complex with alternating low-spin and high-spin Fe(III) ions.

The title compound consists of the [Fe(Tp*)(CN)3] unit, one 4-methoxypyridinium cation 4-methoxy-pyridin and one free water molecule. The [Fe(Tp*)(CN)3] unit resembles a three-bladed propeller, using Fe(III) and B atoms as the fixed points and three pyrazole rings as the paddles. The central metal Fe(III) cation of the title complex is six-coordinated by three nitrogen atoms from the capping ligand Tp* and three cyanide nitrogen atoms at the other three fac positions, forming a slightly distorted octahedral coordination geometry. The Fe—Npyrozle bond lengths are very similar and located within the 1.982(3) to 2.008(3) Å range, and are significantly longer than the Fe—Ccyanide distances (1.915(5)–1.923(5) Å). The C—Ncyanide bond distances range from 1.148(5) to 1.161(5) Å. The B—N bond distances within the Tp* ligand range from 1.517(8) to 1.552(7) Å. The Fe—C—N bond angles are nearly linear and located within the narrow range of 176.4(4)–179.6(5)°. The dihedral angles between the three pyrazole rings are different due to the presence of 4-methoxypyridinium cationic units and the above three dihedral angles are 55.3(3)°, 56.8(3)° and 67.9(3)°, respectively. O—H⋯N and N—H⋯O hydrogen bonds give rise to a zigzag one-dimensional (1D) supramolecular construct where [Fe(Tp*)(CN)3] units and protonated 4-methoxy-pyridine molecules are located at the opposite sides of the 1D chains.

Acknowledgement

This work was supported by the Fundamental Research Funds for the Central Universities (2015XKZD08).

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Received: 2017-2-7
Accepted: 2017-8-11
Published Online: 2017-9-16
Published in Print: 2017-11-27

©2017 Zhong-Hai Ni et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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  55. (E)-N-benzylidene-3-(benzylthio)-5-p-tolyl-4H-1,2,4-triazol-4-amine, C23H20N4S
  56. Crystal structure of ethyl 5-methyl-1-(pyridin-3-yl)-1H-1,2,3-triazole-4-carboxylate, C11H12N4O2
  57. Crystal structure of 5,5-difluoro-10-(4-fluorophenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2′,1′-f][1,3,2]diazaborinine - a Z′ = 3 structure, C19H18B2F3N2
  58. The crystal structure of the Matrine derivative: 12-(1H-indol-1-yl)dodecahydro-1H,5H,10H-dipyrido[2,1-f:3′,2′,1′-ij][1,6]naphthyridin-10-one hydrate, C23H29N3O
  59. The crystal structure of tris(μ2-1,3-bis(4,4,4-trifluoro-3-oxido-1-(oxo)but-2-en-1-yl)phenyl-κ4O,O′:O′′,O′′′)-bis(1,2-dimethoxyethane-κ2O,O′)dilutetium(III), C50H38F18Lu2O16
  60. The crystal structure of (Z)-2-(3-(2-(4-chlorobenzoyl)hydrazono)-2-oxoindolin-1-yl) acetic acid, C17H12ClN3O4
  61. Synthesis and crystal structure of trans-tetraqua-bis(2-(((7-hydroxy-3-(4-hydroxy-3-sulfonatophenyl)-4-oxo-4H-chromen-8-yl)methyl)ammonio)acetato-κO)cobalt(II) hexahydrate, C36H48CoN2O28S2
  62. The crystal structure of N,N-dimethyl-2,6-di-p-tolylpyrimidin-4-amine, C20H21N3
  63. The crystal structure (E)-4-methyl-N′-(2-nitrobenzylidene)benzenesulfonohydrazide, C14H13N3O4S
  64. Crystal structure of catena-poly[(μ2-1,3-bis(benzimidazol-1-yl)propane κ2N:N′)-(μ2-5-methoxyisophthalato-κ2O:O′)zinc(II)] hydrate, C26H24ZnN4O6
  65. The crystal structure of (E)-N′-(quinolin-2-ylmethylene)furan-2-carbohydrazide monohydrate, C15H13N3O3
  66. Crystal structure of 2,8-diphenyl-3,7,9-trioxa-1-azaspiro[4.5]dec-1-ene, C18H17N1O3
  67. Crystal structure of diethyl 2-(4-chlorophenyl)-1,3-dioxane-5,5-dicarboxylate, C16H19ClO6
  68. Crystal structure of 1-(carboxymethyl)-1H-benzo[d][1,2,3]triazole 3-oxide, C8H7N3O3
  69. Crystal structure of (acetylacetonato-κ2O,O′)-(2-amino-6-chlorobenzoato-κO)-oxido(1,10-phenanthroline-κ2N,N′)vanadium(IV) – trichloromethane (1/1)
  70. Crystal structure of (1E,4E)-1,5-bis(4-chlorophenyl)penta-1,4-dien-3-one, C17H12Cl2O
  71. The crystal structure of trans-dibromido-bis(pyridine-κN)platinum(II), C10H10Br2N2Pt
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