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Acta Cryst. (2007). E63, m2022-m2023    [ doi:10.1107/S1600536807030978 ]

Poly[propane-1,3-diammonium [diaquatetrakis([mu]4-benzene-1,2,4,5-tetracarboxylato)nickelate(II)] hemihydrate]

H. Aghabozorg, Z. Bahrami, M. Tabatabaie, M. Ghadermazi and J. Attar Gharamaleki

Abstract top

The reaction of nickel(II) nitrate hexahydrate with the proton-transfer compound (pnH2)2(btc)·2H2O (where pn = propane-1,3-diamine and btcH4 = benzene-1,2,4,5-tetracarboxylic acid) in aqueous solution resulted in the formation of the title compound, {(C3H12N2)[Ni(C10H2O8)(H2O)2]·0.5H2O}n. Each Ni2+ ion is situated on a crystallographic twofold rotation axis and is coordinated in a distorted octahedral geometry by six O atoms [Ni-O = 2.0540 (15)-2.0804 (11) Å] from two water molecules and four btc4- ligands, which also act as bridging ligands between Ni2+ ions. In the crystal structure, intermolecular O-H...O, N-H...O and C-H...O hydrogen bonds and C-H...[pi] interactions contribute to the formation of a three-dimensional supramolecular structure. The crystal studied was an inversion twin.

Comment top

Just as there is a field of molecular chemistry based on the covalent bond, there is a field of supramolecular chemistry, the chemistry of molecular assemblies and intermolecular interactions. The importance of weak hydrogen bonds in the context of crystal engineering, molecular recognition and supramolecular chemistry have been well recognized in recent years. In this regard, we have reported cases in which proton transfer from pyridine-2,6-dicarboxylic acid (pydcH2) and benzene-1,2,4,5-tetracarboxylicacid (btcH4) to piperazine (pipz), propane-1,3-diamine and 1,10-phenanthroline (phen) resulted in the formation of novel self-assembled (pipzH2)(pydc), (pnH2)2(btc).2H2O (Aghabozorg, et al., 2007) and (phenH)4(btcH3)2(btcH2) (Aghabozorg, Ghadermazi & Gharamaleki, 2006) systems, respectively. The resulting compounds with some remaining sites as electron donors can coordinate to metallic ions (Aghabozorg, Ghasemikhah et al., 2006; Aghabozorg, Zabihiet al., 2006).

Here we report a new polymeric compound obtained from reaction of (pnH2)2(btc).2H2O with nickel(II) nitrate. The crystal structure of the title polymeric compound is shown in Fig. 1. The intermolecular hydrogen bond distances are listed in the Table. The negative charge of the anionic complex is neutralized by dicationic propane-1,3-diaminium species. According to the crystal structure of (I), the coordination around NiII is distorted octahedral. A considerable feature of the compound (I) is the presence of C—H···π stacking interactions between C—H groups of (pnH2)2+ cations and aromatic rings of (btc)4– fragments. The C—H···π distances (measured to the centre of phenyl ring) are 2.60 Å for C8—H8A···Cg1 and 2.97 Å for C7—H7A···Cg1 with the angles of 142° and 137°, respectively [Cg1 is a centroid of C1—C4/C2i/C3i; symmetry code: (i) 1/2 + x, -1/2 + y, -1/2 + z]. The most important features of the crystal structure of (I) is a number of O—H···O, N—H···O and C—H···O hydrogen bonds between (pnH2)2+ and [Ni(H2O)2(btc)]2– fragments and uncoordinated water molecules with D···A distances ranging from 2.668 (2) Å to 3.242 (2) Å (Table). Ion pairing, C—H···π stacking and van der Waals forces are also effective in the stabilization of the crystal structure, resulting in the formation of an interesting supramolecular structure (Fig. 2).

Related literature top

For details of the preparation of related proton-transfer compounds, see: Aghabozorg et al. (2007); Aghabozorg, Ghadermazi & Attar Gharamaleki (2006). For the crystal structures of related complexes, see: Aghabozorg, Ghasemikhah et al. (2006); Aghabozorg, Zabihi et al. (2006).

Experimental top

The proton-transfer compound was prepared by a reaction between propane-1,3-diamine and benzene-1,2,4,5-tetracarboxylic acid (Aghabozorg et al., 2007). Starting with a 1:1 molar ratio of the reactants in THF, a puffy white precipitate was obtained. By recrystallization in an aqueous solution, pale-yellow crystals were obtained. A solution of Ni(NO3)2.6H2O (143 mg, 0.5 mmol) in water (15 ml) was added to an aqueous solution of (pnH2)2(btc).2H2O (253 mg, 1.0 mmol) in water (15 ml) in a 1:2 molar ratio. Crystals of (I) suitable for X-ray characterization were obtained after a few days at room temperature.

Refinement top

The value of the Flack parameter of 0.412 (17) indicates that the absolute structure in this case cannot be determined unambiguously due to the specific centrosymmetric arrangement of the anionic pattern. The refinement of the structure in the centrosymmetric space group Imma gives rise to disodering of the dication.

The hydrogen atoms of coordinate water molecules and –NH3 groups were localized in difference Fourier synthesis, but placed in idealized positions (O—H 0.90 Å, N—H 0.90–0.92 Å). C-bound H atoms were placed in calculated positions (C—H 0.95–0.99 Å). The crystalline water molecule was treated as disordered between two positions related by a mirror plane with the occupancies of 0.25 (for O6) The attached H atoms were positioned geometrically (O—H 0.96, 0.97 Å). All H atoms were refined in a riding model with Uiso(H)=1.2–1.3Ueq of the parent atom.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing of (I). Hydrogen bonds are shown as dashed lines.
Poly[propane-1,3-diammonium [diaquatetrakis(µ4-benzene-1,2,4,5-tetracarboxylato)nickelate(II)] hemihydrate] top
Crystal data top
(C3H12N2)[Ni(C10H2O8)(H2O)2]·0.5H2OF000 = 892
Mr = 430.01Dx = 1.716 Mg m−3
Orthorhombic, Ima2Mo Kα radiation
λ = 0.71073 Å
Hall symbol: I 2 -2aCell parameters from 6046 reflections
a = 16.3724 (6) Åθ = 2.5–30.0º
b = 7.1673 (4) ŵ = 1.23 mm−1
c = 14.1857 (8) ÅT = 100.0 (2) K
V = 1664.63 (15) Å3Prism, colourless
Z = 40.30 × 0.30 × 0.20 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2424 independent reflections
Radiation source: fine-focus sealed tube2353 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 100.0(2) Kθmax = 30.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −23→22
Tmin = 0.710, Tmax = 0.792k = −10→10
10153 measured reflectionsl = −19→19
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.028  w = 1/[σ2(Fo2) + (0.05P)2 + 1.1P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.073(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.44 e Å−3
2424 reflectionsΔρmin = −0.24 e Å−3
132 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1113 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.412 (17)
Secondary atom site location: difference Fourier map
Crystal data top
(C3H12N2)[Ni(C10H2O8)(H2O)2]·0.5H2OV = 1664.63 (15) Å3
Mr = 430.01Z = 4
Orthorhombic, Ima2Mo Kα
a = 16.3724 (6) ŵ = 1.23 mm−1
b = 7.1673 (4) ÅT = 100.0 (2) K
c = 14.1857 (8) Å0.30 × 0.30 × 0.20 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2424 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2353 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.792Rint = 0.022
10153 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.44 e Å−3
S = 1.00Δρmin = −0.24 e Å−3
2424 reflectionsAbsolute structure: Flack (1983), 1113 Friedel pairs
132 parametersFlack parameter: 0.412 (17)
1 restraint
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)
N10.59831 (9)0.2336 (2)0.13471 (12)0.0224 (3)
H1A0.55170.25170.10070.027*
H1B0.60230.30680.18620.027*
H1C0.59820.11680.16180.027*
C70.67406 (11)0.2598 (3)0.07757 (14)0.0223 (4)
H7A0.67540.38830.05210.027*
H7B0.67370.17190.02370.027*
C80.75000.2259 (4)0.1374 (2)0.0227 (4)
H8A0.75000.09600.16110.027*
H8B0.75000.31130.19220.027*
Ni10.50000.50000.35324 (4)0.01460 (8)
O10.40867 (9)0.4393 (2)0.44765 (10)0.0196 (3)
O20.46016 (8)0.19013 (19)0.52250 (10)0.0223 (3)
O30.41573 (8)0.0581 (2)0.74825 (10)0.0186 (3)
O40.43957 (8)0.36127 (18)0.71826 (10)0.0217 (2)
O50.54310 (7)0.22702 (15)0.35648 (11)0.0198 (2)
H5A0.51960.17390.30580.024*
H5B0.52040.19360.41180.024*
C10.25000.3097 (4)0.50968 (18)0.0180 (5)
H10.25000.34990.44590.022*
C20.32398 (11)0.2805 (3)0.55610 (13)0.0166 (3)
C30.32397 (11)0.2229 (2)0.65041 (13)0.0164 (3)
C40.25000.1941 (4)0.69672 (17)0.0161 (4)
H40.25000.15440.76060.019*
C50.40460 (11)0.3053 (3)0.50457 (12)0.0179 (3)
C60.40005 (11)0.2128 (2)0.70882 (13)0.0162 (3)
O60.7040 (7)0.0338 (19)0.3588 (14)0.088 (4)0.25
H6A0.7500−0.03260.33120.105*0.50
H6B0.6575−0.02520.32980.105*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0173 (6)0.0238 (7)0.0261 (7)−0.0001 (5)0.0008 (5)−0.0031 (6)
C70.0207 (7)0.0201 (8)0.0261 (9)−0.0002 (6)0.0001 (6)−0.0003 (7)
C80.0197 (10)0.0217 (11)0.0266 (11)0.0000.000−0.0006 (9)
Ni10.01386 (12)0.01624 (12)0.01370 (12)−0.00143 (8)0.0000.000
O10.0189 (6)0.0204 (6)0.0194 (6)0.0014 (5)0.0036 (5)0.0037 (5)
O20.0193 (6)0.0244 (6)0.0233 (6)0.0033 (5)0.0031 (5)0.0027 (5)
O30.0186 (6)0.0191 (6)0.0181 (6)0.0010 (5)−0.0030 (5)0.0009 (5)
O40.0202 (5)0.0209 (6)0.0240 (6)−0.0022 (5)−0.0049 (5)0.0026 (5)
O50.0211 (5)0.0205 (5)0.0177 (5)−0.0003 (4)−0.0020 (6)−0.0010 (5)
C10.0179 (11)0.0218 (11)0.0145 (11)0.0000.0000.0021 (9)
C20.0160 (7)0.0181 (8)0.0157 (8)−0.0012 (6)0.0027 (7)0.0021 (6)
C30.0146 (7)0.0164 (7)0.0181 (8)−0.0006 (6)0.0001 (6)−0.0002 (6)
C40.0156 (10)0.0151 (10)0.0175 (12)0.0000.0000.0009 (8)
C50.0154 (7)0.0210 (8)0.0173 (8)−0.0020 (6)0.0014 (6)−0.0016 (6)
C60.0144 (7)0.0199 (8)0.0144 (7)0.0010 (6)0.0013 (6)0.0005 (6)
O60.071 (6)0.137 (10)0.055 (6)0.048 (6)−0.004 (8)−0.008 (8)
Geometric parameters (Å, °) top
N1—C71.493 (2)O2—C51.254 (2)
N1—H1A0.9121O3—C61.268 (2)
N1—H1B0.9011O4—C61.253 (2)
N1—H1C0.9210O5—H5A0.9000
C7—C81.525 (3)O5—H5B0.9011
C7—H7A0.9900C1—C21.394 (2)
C7—H7B0.9900C1—H10.9500
C8—C7i1.525 (3)C2—C31.400 (2)
C8—H8A0.9900C2—C51.519 (3)
C8—H8B0.9900C3—C41.393 (2)
Ni1—O12.0540 (15)C3—C61.498 (3)
Ni1—O3ii2.0724 (14)C4—H40.9500
Ni1—O52.0804 (11)O6—H6A0.9729
O1—C51.257 (2)O6—H6B0.9631
C7—N1—H1A112.9O5iii—Ni1—O5177.46 (10)
C7—N1—H1B107.8C5—O1—Ni1128.29 (13)
H1A—N1—H1B114.0C6—O3—Ni1v128.88 (12)
C7—N1—H1C110.0Ni1—O5—H5A103.6
H1A—N1—H1C110.4Ni1—O5—H5B97.4
H1B—N1—H1C101.0H5A—O5—H5B114.0
N1—C7—C8110.80 (16)C2vi—C1—C2120.6 (2)
N1—C7—H7A109.5C2—C1—H1119.7
C8—C7—H7A109.5C1—C2—C3119.7 (2)
N1—C7—H7B109.5C1—C2—C5120.65 (17)
C8—C7—H7B109.5C3—C2—C5119.63 (19)
H7A—C7—H7B108.1C4—C3—C2119.6 (2)
C7—C8—C7i109.3 (2)C4—C3—C6117.06 (17)
C7—C8—H8A109.8C2—C3—C6122.88 (19)
C7—C8—H8B109.8C3vi—C4—C3120.8 (2)
H8A—C8—H8B108.3C3—C4—H4119.6
O1iii—Ni1—O198.61 (9)O2—C5—O1126.49 (17)
O1—Ni1—O3ii86.64 (5)O2—C5—C2117.11 (16)
O1—Ni1—O3iv174.74 (7)O1—C5—C2116.40 (17)
O3ii—Ni1—O3iv88.12 (8)O4—C6—O3126.22 (17)
O1—Ni1—O5iii86.44 (6)O4—C6—C3116.58 (16)
O1—Ni1—O591.91 (6)O3—C6—C3117.07 (16)
O3ii—Ni1—O593.02 (6)H6A—O6—H6B103.0
O3iv—Ni1—O588.81 (6)
N1—C7—C8—C7i−178.27 (13)Ni1—O1—C5—O28.0 (3)
O1iii—Ni1—O1—C5−66.36 (16)Ni1—O1—C5—C2−171.57 (12)
O3ii—Ni1—O1—C5113.24 (18)C1—C2—C5—O2−140.7 (2)
O5iii—Ni1—O1—C5−157.75 (17)C3—C2—C5—O237.6 (2)
O5—Ni1—O1—C520.32 (17)C1—C2—C5—O139.0 (3)
C2vi—C1—C2—C3−0.6 (4)C3—C2—C5—O1−142.72 (16)
C2vi—C1—C2—C5177.70 (17)Ni1v—O3—C6—O48.7 (3)
C1—C2—C3—C40.5 (2)Ni1v—O3—C6—C3−166.96 (12)
C5—C2—C3—C4−177.8 (2)C4—C3—C6—O4−113.8 (2)
C1—C2—C3—C6−171.7 (2)C2—C3—C6—O458.6 (2)
C5—C2—C3—C610.0 (2)C4—C3—C6—O362.3 (2)
C2—C3—C4—C3vi−0.3 (3)C2—C3—C6—O3−125.31 (17)
C6—C3—C4—C3vi172.29 (15)
Symmetry codes: (i) −x+3/2, y, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, z; (iv) −x+1, y+1/2, z−1/2; (v) x, −y+1/2, z+1/2; (vi) −x+1/2, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2ii0.911.912.819 (2)174
N1—H1B···O3iv0.902.032.838 (2)149
N1—H1C···O4vii0.922.092.985 (2)163
O5—H5A···O4ii0.901.822.668 (2)156
O5—H5B···O20.901.852.731 (2)164
O6—H6B···O4vii0.962.393.321 (3)164
C7—H7A···Cg(C1-C4/C2i/C3i)viii0.992.973.757 (2)137
C8—H8A···Cg(C1-C4/C2i/C3i)ix0.992.603.433 (2)142
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, z−1/2; (vii) −x+1, y−1/2, z−1/2; (viii) x+1/2, y+1/2, z−1/2; (ix) x+1/2, y−1/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Ni1—O52.0804 (11)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.911.912.819 (2)174
N1—H1B···O3ii0.902.032.838 (2)149
N1—H1C···O4iii0.922.092.985 (2)163
O5—H5A···O4i0.901.822.668 (2)156
O5—H5B···O20.901.852.731 (2)164
O6—H6B···O4iii0.962.393.321 (3)164
C7—H7A···Cg(C1-C4/C2i/C3i)iv0.992.973.757 (2)137
C8—H8A···Cg(C1-C4/C2i/C3i)v0.992.603.433 (2)142
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, z−1/2; (iii) −x+1, y−1/2, z−1/2; (iv) x+1/2, y+1/2, z−1/2; (v) x+1/2, y−1/2, z−1/2.
Acknowledgements top

Financial support by the Islamic Azad University, Yazd Branch, and Teacher Training University is gratefully acknowledged.

references
References top

Aghabozorg, H., Ghadermazi, M. & Attar Gharamaleki, J. (2006). Acta Cryst. E62, o3174–o3176.

Aghabozorg, H., Ghadermazi, M., Sheshmani, S. & Attar Gharamaleki, J. (2007). Acta Cryst. E63, o2985–o2986.

Aghabozorg, H., Ghasemikhah, P., Soleimannejad, J., Ghadermazi, M. & Attar Gharamaleki, J. (2006). Acta Cryst. E62, m2266–m2268.

Aghabozorg, H., Zabihi, F., Ghadermazi, M., Attar Gharamaleki, J. & Sheshmani, S. (2006). Acta Cryst. E62, m2091–m2093.

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