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Acta Cryst. (2007). E63, m2517    [ doi:10.1107/S1600536807042705 ]

1,1'-[1,4-Phenylenebis(methylene)]dipyridinium hexacyanidoferrate(II) octahydrate

M.-S. Tang, Y.-J. Wu, X.-C. Liu, C.-X. Du and Y.-Y. Niu

Abstract top

The structure of the title complex, (C18H18N2)2[Fe(CN)6]·8H2O, comprises two 1,1'-[1,4-phenylenebis(methylene)]dipyridinium cations, one octahedral [Fe(CN)6]4- anion and eight solvent water molecules (four in the asymmetric unit); the anion and both cations are located on inversion centres. Extensive O-H...O and O-H...N hydrogen bonding involving all components of the structure leads to a three-dimensional array.

Comment top

Organo-inorganic hybrid compounds containing hexacyanoferrate(II) anions have been the subject of numerous investigations, in which the cations used to balance the charges are mainly metal complex or alkyammonium (Razak et al., 2000; Marsh, 1995; Kuchár et al., 2004; Overgaard et al., 2005; Sakai et al., 2004). In this work we present the crystal structure of a novel compound with 1,1'-(1,4-phenylenebis(methylene))dipyridinium cations.

The crystal structure of the title compound, ((C18H18N2)2+)2[Fe(CN)6].4 H2O, has been determined by single-crystal X-ray diffraction. It consists of discrete 1,1'-(1,4-phenylenebis(methylene))dipyridinium cations and hexacyanoferrate(II) anions. The site symmetry of the cations as well as the anion is −1. The structure comprises (C18H18N2)2+ cations, [Fe(CN)6]4− anions and water molecules in the ratio 2:1:8 (Figs. 1 and 2). The anions show the expected octahedral coordination with only minor deviations from the ideal geometry. By contrast, the conformations of the cations differ slightly. Extensive hydrogen bonding is found in the crystal structure involving all constituents, shown in Table 1.

Related literature top

For related literature, see: Razak et al. (2000); Marsh (1995); Kuchár et al. (2004); Overgaard et al. (2005); Sakai et al. (2004).

Experimental top

All chemicals were used as purchased from Jinan Henghua Sci. and Tec·Co., Ltd. The salt was synthesized from the reaction of 1,1'-(1,4-phenylenebis(methylene))dipyridinium dichloride (0.067 g, 0.2 mmol) in methanol (5 ml) and K4[Fe(CN)6](0.037 g, 0.1 mmol) in DMF (10 ml). The mixture was set aside for the formation of pink crystals in 43% yield after several days. Anal. Calc. for C42H52FeN10O8: C 57.21, H 5.90, N 15.89, Fe 6.36%; Found: C 57.24, H 5.96, N 15.92, Fe 6.39%.

Refinement top

All H atoms on C atoms were generated geometrically and refined as riding atoms with C—H= 0.93Å and Uiso(H)= 1.2 Ueq(C). The H atoms of the water molecule were located in a difference Fourier map.

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound except the second cation, displacement ellipsoids drawn at the 50% probability level. Unlabeled atoms in the anion are related to labeled atoms by −x, −y, −z. Unlabeled atoms in the dication are related to labeled atoms by −x, 1 − y, 1 − z.
[Figure 2] Fig. 2. The molecular structure of the second cation in the title compound, displacement ellipsoids drawn at the 50% probability level. Unlabeled atoms are related to labeled atoms by 1 − x, 1 − y, 1 − z.
1,1'-[1,4-Phenylenebis(methylene)]dipyridinium hexacyanidoferrate(II) octahydrate top
Crystal data top
(C18H18N2)2[Fe(CN)6]·8H2OZ = 1
Mr = 880.79F000 = 464
Triclinic, P1Dx = 1.309 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.4119 (14) ÅCell parameters from 2267 reflections
b = 10.7164 (16) Åθ = 2.3–22.2º
c = 12.321 (3) ŵ = 0.40 mm−1
α = 104.955 (2)ºT = 291 (2) K
β = 101.123 (3)ºBlock, red
γ = 104.538 (2)º0.33 × 0.25 × 0.14 mm
V = 1117.2 (4) Å3
Data collection top
Bruker APEX II CCD
diffractometer		5049 independent reflections
Radiation source: fine-focus sealed tube3739 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 291(2) Kθmax = 27.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −12→12
Tmin = 0.881, Tmax = 0.946k = −13→13
9731 measured reflectionsl = −16→16
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)] = 0.057H-atom parameters constrained
wR(F2) = 0.176  w = 1/[σ2(Fo2) + (0.1P)2 + 0.2979P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
5049 reflectionsΔρmax = 0.99 e Å−3
277 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C18H18N2)2[Fe(CN)6]·8H2Oγ = 104.538 (2)º
Mr = 880.79V = 1117.2 (4) Å3
Triclinic, P1Z = 1
a = 9.4119 (14) ÅMo Kα
b = 10.7164 (16) ŵ = 0.40 mm−1
c = 12.321 (3) ÅT = 291 (2) K
α = 104.955 (2)º0.33 × 0.25 × 0.14 mm
β = 101.123 (3)º
Data collection top
Bruker APEX II CCD
diffractometer		5049 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		3739 reflections with I > 2σ(I)
Tmin = 0.881, Tmax = 0.946Rint = 0.028
9731 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057277 parameters
wR(F2) = 0.176H-atom parameters constrained
S = 1.00Δρmax = 0.99 e Å−3
5049 reflectionsΔρmin = −0.37 e Å−3
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 > 2sigma(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*/Ueq
Fe10.00000.00000.00000.03288 (18)
O10.7215 (4)0.9269 (4)0.4988 (3)0.1141 (12)
H1W0.74190.88980.43650.171*
H2W0.80490.98830.54370.171*
O20.3687 (3)0.6379 (3)0.9271 (4)0.1295 (17)
H3W0.33860.69190.89920.194*
H4W0.38550.66010.99780.194*
O30.2842 (4)0.3630 (3)0.8512 (3)0.1001 (11)
H5W0.28980.44380.86490.150*
H6W0.27620.33700.90800.150*
O40.8906 (3)0.8455 (3)0.3470 (2)0.0822 (8)
H7W0.95770.89120.32540.123*
H8W0.83530.77500.29310.123*
N10.1041 (3)0.0368 (3)0.2623 (2)0.0555 (7)
N20.1551 (3)−0.2203 (3)−0.0605 (3)0.0539 (7)
N30.2958 (3)0.2186 (2)0.0181 (2)0.0505 (6)
N40.2605 (2)0.8518 (2)0.6697 (2)0.0403 (5)
N50.3193 (4)0.5603 (3)0.2302 (3)0.0634 (8)
C10.0670 (3)0.0243 (3)0.1630 (3)0.0394 (6)
C20.0958 (3)−0.1385 (3)−0.0374 (2)0.0370 (6)
C30.1839 (3)0.1364 (3)0.0117 (2)0.0368 (6)
C40.3744 (4)0.8100 (3)0.6387 (3)0.0608 (9)
H40.35480.74580.56600.073*
C50.5183 (4)0.8608 (3)0.7125 (4)0.0658 (10)
H50.59600.83000.69090.079*
C60.5478 (4)0.9575 (3)0.8186 (3)0.0559 (8)
H60.64560.99340.86970.067*
C70.4304 (4)1.0007 (3)0.8485 (3)0.0529 (7)
H70.44851.06710.91970.063*
C80.2873 (3)0.9451 (3)0.7729 (3)0.0434 (6)
H80.20750.97290.79370.052*
C90.1039 (3)0.7955 (3)0.5867 (3)0.0528 (8)
H9A0.10410.82960.52100.063*
H9B0.03280.82620.62580.063*
C100.0523 (3)0.6421 (3)0.5428 (2)0.0409 (6)
C110.0583 (3)0.5669 (3)0.6188 (2)0.0478 (7)
H110.09710.61120.69890.057*
C120.0068 (3)0.4262 (3)0.5759 (3)0.0468 (7)
H120.01190.37680.62770.056*
C130.1762 (5)0.4854 (4)0.1682 (3)0.0637 (9)
H130.14980.39090.14150.076*
C140.0686 (5)0.5463 (4)0.1439 (3)0.0693 (10)
H14−0.03130.49360.10200.083*
C150.1083 (6)0.6844 (5)0.1813 (4)0.0768 (12)
H150.03630.72660.16240.092*
C160.2515 (7)0.7601 (5)0.2454 (5)0.0936 (15)
H160.27800.85460.27230.112*
C170.3593 (5)0.6973 (4)0.2714 (4)0.0854 (13)
H170.45820.74880.31670.102*
C180.4348 (5)0.4928 (5)0.2578 (4)0.0792 (12)
H18A0.52850.53800.24280.095*
H18B0.39790.39880.20720.095*
C190.4677 (4)0.4967 (3)0.3827 (3)0.0597 (9)
C200.3580 (4)0.4261 (4)0.4245 (4)0.0694 (10)
H200.26140.37560.37440.083*
C210.3904 (4)0.4300 (4)0.5399 (4)0.0695 (10)
H210.31480.38190.56600.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0296 (3)0.0293 (3)0.0410 (3)0.0110 (2)0.0117 (2)0.0101 (2)
O10.113 (3)0.149 (3)0.092 (2)0.054 (3)0.034 (2)0.041 (2)
O20.0580 (17)0.0456 (15)0.264 (5)0.0241 (14)0.034 (2)0.017 (2)
O30.136 (3)0.0579 (17)0.083 (2)0.0022 (17)0.0086 (19)0.0265 (15)
O40.098 (2)0.0815 (19)0.0659 (16)0.0213 (16)0.0246 (15)0.0272 (14)
N10.0516 (15)0.0710 (18)0.0459 (15)0.0230 (14)0.0159 (12)0.0167 (13)
N20.0530 (15)0.0417 (13)0.0740 (18)0.0253 (12)0.0230 (13)0.0162 (12)
N30.0433 (14)0.0393 (13)0.0664 (17)0.0064 (11)0.0217 (12)0.0146 (12)
N40.0338 (11)0.0313 (11)0.0500 (13)0.0069 (9)0.0106 (10)0.0076 (10)
N50.071 (2)0.0630 (18)0.0653 (18)0.0276 (16)0.0330 (16)0.0190 (15)
C10.0301 (13)0.0362 (13)0.0520 (17)0.0126 (11)0.0152 (12)0.0096 (12)
C20.0341 (13)0.0338 (13)0.0419 (14)0.0075 (11)0.0113 (11)0.0128 (11)
C30.0377 (14)0.0330 (13)0.0426 (14)0.0160 (11)0.0134 (11)0.0103 (11)
C40.0478 (18)0.0495 (18)0.070 (2)0.0133 (15)0.0224 (16)−0.0086 (16)
C50.0376 (16)0.0519 (19)0.097 (3)0.0148 (14)0.0224 (17)0.0027 (18)
C60.0379 (16)0.0449 (17)0.074 (2)0.0060 (13)0.0036 (15)0.0178 (16)
C70.0514 (18)0.0505 (17)0.0479 (17)0.0148 (15)0.0080 (14)0.0068 (14)
C80.0426 (15)0.0424 (15)0.0481 (16)0.0185 (12)0.0164 (13)0.0115 (13)
C90.0417 (16)0.0412 (16)0.0606 (19)0.0090 (13)−0.0005 (14)0.0068 (14)
C100.0331 (13)0.0364 (14)0.0456 (15)0.0064 (11)0.0065 (11)0.0083 (12)
C110.0484 (17)0.0473 (16)0.0341 (14)0.0069 (13)0.0045 (12)0.0041 (12)
C120.0483 (16)0.0457 (16)0.0423 (15)0.0094 (13)0.0079 (13)0.0164 (13)
C130.083 (3)0.062 (2)0.0497 (19)0.029 (2)0.0216 (18)0.0148 (16)
C140.077 (3)0.086 (3)0.054 (2)0.032 (2)0.0230 (18)0.028 (2)
C150.099 (3)0.085 (3)0.084 (3)0.048 (3)0.051 (3)0.052 (2)
C160.119 (4)0.055 (2)0.132 (4)0.031 (3)0.065 (4)0.046 (3)
C170.079 (3)0.064 (2)0.111 (4)0.008 (2)0.043 (3)0.026 (2)
C180.075 (3)0.099 (3)0.070 (2)0.047 (2)0.028 (2)0.014 (2)
C190.0532 (19)0.0539 (19)0.069 (2)0.0274 (16)0.0202 (17)0.0031 (16)
C200.0454 (19)0.064 (2)0.080 (3)0.0104 (17)0.0081 (18)0.0056 (19)
C210.0481 (19)0.069 (2)0.092 (3)0.0179 (17)0.0256 (19)0.023 (2)
Geometric parameters (Å, °) top
Fe1—C1i1.913 (3)C7—H70.9300
Fe1—C11.913 (3)C8—H80.9300
Fe1—C3i1.918 (3)C9—C101.507 (4)
Fe1—C31.918 (3)C9—H9A0.9700
Fe1—C21.926 (3)C9—H9B0.9700
Fe1—C2i1.926 (3)C10—C12ii1.384 (4)
O1—H1W0.8495C10—C111.386 (4)
O1—H2W0.8608C11—C121.382 (4)
O2—H3W0.8253C11—H110.9300
O2—H4W0.8141C12—C10ii1.384 (4)
O3—H5W0.8245C12—H120.9300
O3—H6W0.8266C13—C141.362 (5)
O4—H7W0.8282C13—H130.9300
O4—H8W0.8319C14—C151.360 (6)
N1—C11.168 (4)C14—H140.9300
N2—C21.157 (3)C15—C161.345 (7)
N3—C31.165 (3)C15—H150.9300
N4—C81.332 (4)C16—C171.384 (7)
N4—C41.344 (4)C16—H160.9300
N4—C91.495 (4)C17—H170.9300
N5—C131.336 (5)C18—C191.497 (5)
N5—C171.349 (5)C18—H18A0.9700
N5—C181.484 (5)C18—H18B0.9700
C4—C51.362 (5)C19—C21iii1.380 (5)
C4—H40.9300C19—C201.384 (5)
C5—C61.370 (5)C20—C211.383 (6)
C5—H50.9300C20—H200.9300
C6—C71.377 (4)C21—C19iii1.380 (5)
C6—H60.9300C21—H210.9300
C7—C81.366 (4)
C1i—Fe1—C1180.0 (3)N4—C9—H9A109.4
C1i—Fe1—C3i90.61 (11)C10—C9—H9A109.4
C1—Fe1—C3i89.39 (11)N4—C9—H9B109.4
C1i—Fe1—C389.39 (11)C10—C9—H9B109.4
C1—Fe1—C390.61 (11)H9A—C9—H9B108.0
C3i—Fe1—C3180.00 (18)C12ii—C10—C11118.8 (3)
C1i—Fe1—C289.07 (11)C12ii—C10—C9119.5 (3)
C1—Fe1—C290.93 (11)C11—C10—C9121.6 (3)
C3i—Fe1—C289.95 (10)C12—C11—C10120.2 (3)
C3—Fe1—C290.05 (10)C12—C11—H11119.9
C1i—Fe1—C2i90.93 (11)C10—C11—H11119.9
C1—Fe1—C2i89.07 (11)C11—C12—C10ii120.9 (3)
C3i—Fe1—C2i90.05 (10)C11—C12—H12119.5
C3—Fe1—C2i89.95 (10)C10ii—C12—H12119.5
C2—Fe1—C2i180.0 (2)N5—C13—C14120.5 (4)
H1W—O1—H2W106.4N5—C13—H13119.7
H3W—O2—H4W113.0C14—C13—H13119.7
H5W—O3—H6W112.1C15—C14—C13119.6 (4)
H7W—O4—H8W111.5C15—C14—H14120.2
C8—N4—C4120.3 (3)C13—C14—H14120.2
C8—N4—C9119.9 (2)C16—C15—C14120.1 (4)
C4—N4—C9119.7 (3)C16—C15—H15120.0
C13—N5—C17120.7 (4)C14—C15—H15120.0
C13—N5—C18120.1 (3)C15—C16—C17119.9 (4)
C17—N5—C18119.2 (4)C15—C16—H16120.0
N1—C1—Fe1178.2 (3)C17—C16—H16120.0
N2—C2—Fe1178.8 (2)N5—C17—C16119.2 (4)
N3—C3—Fe1179.5 (3)N5—C17—H17120.4
N4—C4—C5120.8 (3)C16—C17—H17120.4
N4—C4—H4119.6N5—C18—C19111.5 (3)
C5—C4—H4119.6N5—C18—H18A109.3
C4—C5—C6119.6 (3)C19—C18—H18A109.3
C4—C5—H5120.2N5—C18—H18B109.3
C6—C5—H5120.2C19—C18—H18B109.3
C5—C6—C7118.9 (3)H18A—C18—H18B108.0
C5—C6—H6120.5C21iii—C19—C20117.6 (4)
C7—C6—H6120.5C21iii—C19—C18120.9 (4)
C8—C7—C6119.5 (3)C20—C19—C18121.4 (4)
C8—C7—H7120.2C21—C20—C19120.8 (3)
C6—C7—H7120.2C21—C20—H20119.6
N4—C8—C7120.8 (3)C19—C20—H20119.6
N4—C8—H8119.6C19iii—C21—C20121.6 (4)
C7—C8—H8119.6C19iii—C21—H21119.2
N4—C9—C10111.1 (2)C20—C21—H21119.2
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H2W···N1iii0.862.482.955 (5)115
O2—H3W···N2iv0.832.242.812 (4)127
O3—H6W···N3v0.832.102.876 (4)157
O4—H7W···N1vi0.832.213.029 (4)168
O4—H8W···O3iii0.831.912.729 (4)168
O4—H8W···O3iii0.831.912.729 (4)168
O4—H7W···N1vi0.832.213.029 (4)168
O3—H6W···N3v0.832.102.876 (4)157
O3—H5W···O20.821.912.702 (4)161
O2—H3W···N2iv0.832.242.812 (4)127
O1—H2W···N1iii0.862.482.955 (5)115
O1—H1W···O40.852.012.792 (5)152
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z+1; (v) x, y, z+1; (vi) x+1, y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H2W···N1i0.862.482.955 (5)115
O2—H3W···N2ii0.832.242.812 (4)127
O3—H6W···N3iii0.832.102.876 (4)157
O4—H7W···N1iv0.832.213.029 (4)168
O4—H8W···O3i0.831.912.729 (4)168
O4—H8W···O3i0.831.912.729 (4)168
O4—H7W···N1iv0.832.213.029 (4)168
O3—H6W···N3iii0.832.102.876 (4)157
O3—H5W···O20.821.912.702 (4)161
O2—H3W···N2ii0.832.242.812 (4)127
O1—H2W···N1i0.862.482.955 (5)115
O1—H1W···O40.852.012.792 (5)152
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z+1; (iii) x, y, z+1; (iv) x+1, y+1, z.
Acknowledgements top

The authors thank the National Natural Science Foundation (No. 20671083), the Henan Province Excellent Young Foundation (No. 0612002800), and Jinan Henghua Science and Technology Co. Ltd for supporting this work. We also thank Luoyang Normal College for the diffraction measurements.

references
References top

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Sakai, K., Uchida, Y., Kajiwara, T. & Ito, T. (2004). Acta Cryst. C60, m65–m68.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.