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Acta Cryst. (2008). E64, m1399    [ doi:10.1107/S1600536808032571 ]

Tetrakis[tris(2,2'-bi-1H-benzimidazole)nickel(II)] bis(phosphate) sulfate

C.-S. Ling and L. Yan

Abstract top

The title compound, [Ni(C14H10N4)3]4(PO4)2(SO4), consists of [Ni(C14H10N4)3]2+ complex cations (.3. symmetry) and disordered anions ({\overline 4} symmetry) with occupancy factors of two-thirds for PO43- and one-third for SO42-. The Ni2+ centre is chelated by three bidentate 2,2'-bi-1H-benzimidazole molecules in a distorted octahedral coordination. N-H...O hydrogen bonds consolidate the building units into a framework structure.

Comment top

More attentions have been paid to metal-organic coordination compounds (MOCCs) because of their potential applications in gas absorption and separation, catalysis, nonlinear optics, luminescence and magnetism (Kitagawa & Matsuda 2007, Maspoch et al. 2007). In the field of coordination chemistry, the N,N-bidentate ligands, such as 2,2'-bipyridine, 1,10-phenanthroline and their derivatives act as versatile ligands owing to the stable coordination configuration in the bidentate N-donors chelating manner. Herein, we report the title compound (I).

The title compound (I) consists of four [Ni(C14H10N4)3]2+ complex cations, one [SO4]2- and two [PO4]3- anions. In the mlecular structure, the Ni2+ centre is coordinated by six N atoms from three bidentate 1H,1'H-2,2'-bi-1H-benzimidazole molecules (Fig.1). The 1H,1'H-2,2'-bi-1H-benzimidazole ligand was prepared in situ and coordinated to the Ni2+ cations in hydrothermal reaction. Additionally, the [SO4]2- and [PO4]3- anions statistically distribute in one position with 1/3 probability for S and 2/3 probability for P atoms. The environment of the Ni2+ caion is in a distorted octahedral geometry with the Ni—N distances ranging from 2.088 (3) to 2.122 (3) Å (Table 1).

In addition, the [Ni(C14H10N4)3]2+ complex cations, [SO4]2- and [PO4]3- anions in the complexes are linked together via many N—H···O hydrogen bonds resulting in a three-dimensional structural frameworks (Fig.2 and Table 2).

Related literature top

For the potential applications of metal–organic coordination compounds in gas absorption and separation, catalysis, nonlinear optics, luminescence and magnetism, see: Kitagawa & Matsuda (2007); Maspoch et al. (2007).

Experimental top

All reagents were commercially available and of analytical grade. The mixture of NiSO4.6H2O, H3PO4, oxalic acid, and 1,2-diaminobenzene in the mole ratio of 1: 1.5: 6: 6 was dissolved in 25 ml H2O, which was heated in a Teflon-lined steel autoclave inside a programmable electric furnace at 393 K for five days. After cooling the autoclave to room temperature, green block crystals of (I) were obtained.

Refinement top

H atoms were treated as riding, with C—H = 0.93 Å and N—H = 0.86 Å, and were refined as riding with Uiso(H) = 1.2Ueq(N and C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity.
[Figure 2] Fig. 2. Three-dimensional structure of (I). Displacement ellipsoids are drawn at the 50% probability level. For clarity, H atoms not involved in hydrogen bonds are omitted.
Tetrakis[tris(2,2'-bi-1H-benzimidazole)nickel(II)] bis(phosphate) sulfate top
Crystal data top
[Ni(C14H10N4)3]4(PO4)2(SO4)Dx = 1.423 Mg m−3
Mr = 3331.96Mo Kα radiation, λ = 0.71073 Å
Cubic, I43dCell parameters from 3375 reflections
Hall symbol: I -4bd 2c 3θ = 2.3–19.2°
a = 24.964 (7) ŵ = 0.59 mm−1
V = 15558 (8) Å3T = 296 K
Z = 4Block, green
F(000) = 68720.32 × 0.27 × 0.23 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2551 independent reflections
Radiation source: fine-focus sealed tube1782 reflections with I > 2σ(I)
graphiteRint = 0.066
φ and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −30→11
Tmin = 0.834, Tmax = 0.876k = −30→29
20222 measured reflectionsl = −21→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0528P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2551 reflectionsΔρmax = 0.61 e Å−3
177 parametersΔρmin = −0.20 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1182 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.02 (2)
Crystal data top
[Ni(C14H10N4)3]4(PO4)2(SO4)Z = 4
Mr = 3331.96Mo Kα radiation
Cubic, I43dµ = 0.59 mm−1
a = 24.964 (7) ÅT = 296 K
V = 15558 (8) Å30.32 × 0.27 × 0.23 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2551 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		1782 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.876Rint = 0.066
20222 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.61 e Å−3
S = 1.01Δρmin = −0.20 e Å−3
2551 reflectionsAbsolute structure: Flack (1983), 1182 Friedel pairs
177 parametersFlack parameter: −0.02 (2)
0 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.564621 (16)0.435379 (16)−0.064621 (16)0.0428 (2)
P10.75000.62501.00000.0427 (4)0.67
S10.75000.62501.00000.0427 (4)0.33
N10.64773 (10)0.44469 (11)−0.06574 (11)0.0443 (6)
N20.71668 (10)0.50117 (12)−0.06248 (11)0.0498 (7)
H2B0.73400.5309−0.06040.060*
N30.56297 (10)0.42828 (11)0.02009 (10)0.0444 (6)
N40.55652 (11)0.37290 (12)0.08942 (11)0.0502 (7)
H4B0.55380.34350.10720.060*
C10.69498 (13)0.41559 (13)−0.06917 (13)0.0462 (8)
C20.70405 (15)0.36114 (16)−0.07434 (15)0.0594 (9)
H20.67580.3370−0.07630.071*
C30.75637 (17)0.34409 (18)−0.07642 (16)0.0744 (13)
H30.76380.3077−0.07970.089*
C40.79858 (16)0.3808 (2)−0.07359 (16)0.0707 (12)
H40.83350.3679−0.07500.085*
C50.79104 (13)0.43383 (18)−0.06895 (15)0.0627 (10)
H50.81970.4576−0.06700.075*
C60.73810 (12)0.45147 (14)−0.06724 (14)0.0473 (8)
C70.66286 (13)0.49523 (14)−0.06164 (13)0.0443 (8)
C80.56226 (15)0.45873 (13)0.06673 (14)0.0487 (9)
C90.56566 (17)0.51278 (15)0.07424 (15)0.0645 (11)
H90.56810.53630.04550.077*
C100.5653 (2)0.53090 (18)0.12671 (19)0.0848 (13)
H100.56720.56750.13330.102*
C110.5623 (2)0.49628 (19)0.16920 (17)0.0863 (14)
H110.56270.51020.20370.104*
C120.55859 (18)0.44183 (18)0.16272 (14)0.0698 (11)
H120.55620.41860.19170.084*
C130.55865 (13)0.42369 (14)0.11042 (13)0.0489 (8)
C140.55946 (13)0.37792 (14)0.03571 (13)0.0443 (8)
O10.77314 (11)0.59036 (9)0.95604 (10)0.0629 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0428 (2)0.0428 (2)0.0428 (2)−0.00140 (19)−0.00140 (19)0.00140 (19)
P10.0469 (6)0.0341 (9)0.0469 (6)0.0000.0000.000
S10.0469 (6)0.0341 (9)0.0469 (6)0.0000.0000.000
N10.0386 (14)0.0485 (17)0.0458 (16)0.0000 (13)−0.0006 (13)0.0019 (15)
N20.0447 (17)0.0543 (18)0.0503 (17)−0.0083 (14)−0.0009 (14)−0.0019 (15)
N30.0432 (16)0.0445 (16)0.0456 (15)0.0006 (15)−0.0046 (13)−0.0007 (13)
N40.0552 (19)0.0518 (18)0.0436 (17)−0.0046 (14)−0.0034 (14)0.0093 (14)
C10.049 (2)0.0486 (19)0.0411 (18)0.0030 (16)−0.0031 (17)−0.0036 (15)
C20.054 (2)0.060 (2)0.065 (2)0.0073 (18)−0.0023 (19)−0.0042 (19)
C30.064 (3)0.076 (3)0.084 (3)0.024 (2)−0.003 (2)−0.009 (2)
C40.045 (2)0.097 (4)0.070 (3)0.021 (2)−0.002 (2)−0.014 (2)
C50.0439 (19)0.083 (3)0.061 (3)0.000 (2)−0.0050 (18)−0.016 (3)
C60.0417 (19)0.064 (2)0.0366 (18)0.0018 (16)−0.0048 (16)−0.0077 (17)
C70.044 (2)0.048 (2)0.0410 (19)−0.0065 (15)−0.0027 (15)−0.0012 (16)
C80.049 (2)0.052 (2)0.0449 (19)0.0051 (16)−0.0042 (18)−0.0057 (16)
C90.092 (3)0.050 (2)0.051 (2)−0.002 (2)−0.009 (2)−0.0036 (17)
C100.124 (4)0.065 (3)0.066 (3)0.006 (3)−0.010 (3)−0.013 (2)
C110.133 (4)0.077 (3)0.049 (3)0.001 (3)−0.013 (3)−0.017 (2)
C120.093 (3)0.074 (3)0.042 (2)−0.006 (3)−0.005 (2)0.001 (2)
C130.050 (2)0.055 (2)0.0423 (19)−0.0009 (18)−0.0050 (16)−0.0006 (16)
C140.0315 (18)0.053 (2)0.049 (2)−0.0032 (16)−0.0021 (15)0.0045 (17)
O10.0818 (18)0.0455 (15)0.0616 (17)−0.0077 (13)0.0150 (14)−0.0033 (12)
Geometric parameters (Å, °) top
Ni1—N12.088 (3)C1—C61.401 (5)
Ni1—N1i2.088 (3)C2—C31.375 (5)
Ni1—N1ii2.088 (3)C2—H20.9300
Ni1—N3ii2.122 (3)C3—C41.398 (6)
Ni1—N32.122 (3)C3—H30.9300
Ni1—N3i2.122 (3)C4—C51.342 (6)
P1—O1iii1.512 (3)C4—H40.9300
P1—O1iv1.512 (3)C5—C61.394 (4)
P1—O11.512 (3)C5—H50.9300
P1—O1v1.512 (3)C7—C14ii1.435 (5)
N1—C71.321 (4)C8—C91.365 (5)
N1—C11.388 (4)C8—C131.401 (5)
N2—C71.352 (4)C9—C101.386 (6)
N2—C61.356 (4)C9—H90.9300
N2—H2B0.8600C10—C111.370 (6)
N3—C141.319 (4)C10—H100.9300
N3—C81.391 (4)C11—C121.372 (6)
N4—C141.349 (4)C11—H110.9300
N4—C131.373 (4)C12—C131.382 (5)
N4—H4B0.8600C12—H120.9300
C1—C21.384 (5)C14—C7i1.435 (5)
N1—Ni1—N1i95.67 (10)C1—C2—H2121.2
N1—Ni1—N1ii95.67 (10)C2—C3—C4120.7 (4)
N1i—Ni1—N1ii95.67 (10)C2—C3—H3119.6
N1—Ni1—N3ii78.84 (10)C4—C3—H3119.6
N1i—Ni1—N3ii170.67 (9)C5—C4—C3123.0 (4)
N1ii—Ni1—N3ii92.40 (9)C5—C4—H4118.5
N1—Ni1—N392.40 (9)C3—C4—H4118.5
N1i—Ni1—N378.84 (10)C4—C5—C6116.6 (4)
N1ii—Ni1—N3170.67 (9)C4—C5—H5121.7
N3ii—Ni1—N393.75 (9)C6—C5—H5121.7
N1—Ni1—N3i170.67 (9)N2—C6—C5131.7 (3)
N1i—Ni1—N3i92.40 (9)N2—C6—C1106.6 (3)
N1ii—Ni1—N3i78.84 (10)C5—C6—C1121.7 (3)
N3ii—Ni1—N3i93.75 (9)N1—C7—N2112.8 (3)
N3—Ni1—N3i93.75 (9)N1—C7—C14ii118.2 (3)
O1iii—P1—O1iv110.22 (17)N2—C7—C14ii128.9 (3)
O1iii—P1—O1109.10 (9)C9—C8—N3130.9 (3)
O1iv—P1—O1109.10 (9)C9—C8—C13121.0 (3)
O1iii—P1—O1v109.10 (9)N3—C8—C13108.1 (3)
O1iv—P1—O1v109.10 (9)C8—C9—C10116.9 (4)
O1—P1—O1v110.22 (17)C8—C9—H9121.6
C7—N1—C1105.2 (3)C10—C9—H9121.6
C7—N1—Ni1112.9 (2)C11—C10—C9121.7 (4)
C1—N1—Ni1141.9 (2)C11—C10—H10119.1
C7—N2—C6107.0 (3)C9—C10—H10119.1
C7—N2—H2B126.5C10—C11—C12122.5 (4)
C6—N2—H2B126.5C10—C11—H11118.7
C14—N3—C8105.8 (3)C12—C11—H11118.7
C14—N3—Ni1112.0 (2)C11—C12—C13115.8 (4)
C8—N3—Ni1142.1 (2)C11—C12—H12122.1
C14—N4—C13107.0 (3)C13—C12—H12122.1
C14—N4—H4B126.5N4—C13—C12131.5 (3)
C13—N4—H4B126.5N4—C13—C8106.4 (3)
C2—C1—N1131.2 (3)C12—C13—C8122.1 (3)
C2—C1—C6120.4 (3)N3—C14—N4112.7 (3)
N1—C1—C6108.4 (3)N3—C14—C7i117.7 (3)
C3—C2—C1117.6 (4)N4—C14—C7i129.5 (3)
C3—C2—H2121.2
N1i—Ni1—N1—C7−168.5 (2)C2—C1—C6—N2179.6 (3)
N1ii—Ni1—N1—C795.2 (3)N1—C1—C6—N20.3 (4)
N3ii—Ni1—N1—C73.9 (2)C2—C1—C6—C5−1.8 (5)
N3—Ni1—N1—C7−89.5 (3)N1—C1—C6—C5178.9 (3)
N3i—Ni1—N1—C741.7 (7)C1—N1—C7—N20.4 (4)
N1i—Ni1—N1—C111.1 (4)Ni1—N1—C7—N2−179.9 (2)
N1ii—Ni1—N1—C1−85.2 (3)C1—N1—C7—C14ii177.6 (3)
N3ii—Ni1—N1—C1−176.5 (4)Ni1—N1—C7—C14ii−2.6 (4)
N3—Ni1—N1—C190.1 (4)C6—N2—C7—N1−0.2 (4)
N3i—Ni1—N1—C1−138.6 (6)C6—N2—C7—C14ii−177.1 (3)
N1—Ni1—N3—C14−100.0 (2)C14—N3—C8—C9178.8 (4)
N1i—Ni1—N3—C14−4.7 (2)Ni1—N3—C8—C9−4.5 (7)
N1ii—Ni1—N3—C1449.9 (7)C14—N3—C8—C130.5 (4)
N3ii—Ni1—N3—C14−178.9 (2)Ni1—N3—C8—C13177.2 (3)
N3i—Ni1—N3—C1487.1 (3)N3—C8—C9—C10−178.2 (4)
N1—Ni1—N3—C883.5 (4)C13—C8—C9—C100.0 (6)
N1i—Ni1—N3—C8178.8 (4)C8—C9—C10—C110.7 (7)
N1ii—Ni1—N3—C8−126.7 (6)C9—C10—C11—C12−1.0 (8)
N3ii—Ni1—N3—C84.5 (4)C10—C11—C12—C130.6 (8)
N3i—Ni1—N3—C8−89.5 (3)C14—N4—C13—C12−178.1 (4)
C7—N1—C1—C2−179.6 (4)C14—N4—C13—C80.8 (4)
Ni1—N1—C1—C20.7 (7)C11—C12—C13—N4178.7 (4)
C7—N1—C1—C6−0.4 (4)C11—C12—C13—C80.0 (6)
Ni1—N1—C1—C6180.0 (3)C9—C8—C13—N4−179.3 (3)
N1—C1—C2—C3−179.6 (3)N3—C8—C13—N4−0.8 (4)
C6—C1—C2—C31.2 (5)C9—C8—C13—C12−0.3 (6)
C1—C2—C3—C4−0.3 (6)N3—C8—C13—C12178.2 (4)
C2—C3—C4—C5−0.2 (6)C8—N3—C14—N40.0 (4)
C3—C4—C5—C6−0.3 (6)Ni1—N3—C14—N4−177.9 (2)
C7—N2—C6—C5−178.5 (4)C8—N3—C14—C7i−177.4 (3)
C7—N2—C6—C10.0 (4)Ni1—N3—C14—C7i4.8 (3)
C4—C5—C6—N2179.5 (4)C13—N4—C14—N3−0.5 (4)
C4—C5—C6—C11.3 (6)C13—N4—C14—C7i176.5 (3)
Symmetry codes: (i) −z+1/2, −x+1, y−1/2; (ii) −y+1, z+1/2, −x+1/2; (iii) −z+7/4, −y+5/4, x+1/4; (iv) z−1/4, −y+5/4, −x+7/4; (v) −x+3/2, y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O1vi0.861.962.766 (4)156
N2—H2B···O1vii0.861.822.675 (4)170
Symmetry codes: (vi) x−1/4, −z+5/4, −y+3/4; (vii) x, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4B···O1i0.861.962.766 (4)156
N2—H2B···O1ii0.861.822.675 (4)170
Symmetry codes: (i) x−1/4, −z+5/4, −y+3/4; (ii) x, y, z−1.
Acknowledgements top

This work was supported by the Basic Research Foundation for Natural Science of Henan University.

references
References top

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Maspoch, D., Ruiz-Molina, D. & Veciana, J. (2007). Chem. Soc. Rev. 36, 770–818.

Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.