Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020764/lh2376sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020764/lh2376Isup2.hkl |
CCDC reference: 651377
All reagents and solvents were used as obtained without further purification. EGTB [EGTB = (µ2-N,N,N',N'- tetrakis(Benzimidazol-2-ylmethyl)-3,6-dioxaoctane-1,8-diamine] was prepared according to literature procedure (Hendriks et al., 1982). The title organic salt was obtained unexpectedly by reacting EGTB with Fe(NO3).6H2O (molar ratio: 1/2). The mixture was stirred for half an hour at 70° and then filtered. The resulting pale-yellow solution was kept in air for one week. Crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel.
All H atoms bonded to carbon atoms were placed in calculated positions with C–H=0.97 Å(methylene) and 0.93 Å(aromatic), Uiso(H) = 1.2Ueq(C). H atoms bonded to imine N atoms were located from the difference maps and the N—H distance were refined freely without any constraints, but their Uiso(H) values were set 1.2 times Ueq of their carrier atoms.
As part of our continuing studies on the ligands or metal complexes containing multi-benzimidazole groups (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005), we report here the crystal structure of a related compound, (I), which was obtained unexpectedly by reacting µ2-N,N, N', N'-tetrakis(Benzimidazol-2-ylmethyl)- 3,6- dioxaoctane-1,8-diamine (EGTB) with Fe(NO3).6H2O in H2O solution.
In the aymmetric unit of (I) (Fig. 1), the cation lies across an inversion center in space group of P21/c. The two terminal benzimidazoles rings on one side of the cation are effectively planar with the dihedral angle of only 0.75 (1)°.
All imine N atoms in the benzimidazole groups of are protonated foming a tetracation. Two nitrate anions lie to the inner side of the two end-on benzimidazole groups, forming the four nearly symmetric intra-molecular hydrogen bonds (Table 1). However, the other two anions lie at the outside of the two benzimidazole groups, linking the adjacent cations into a two-dimensional network running parallel the (100) direction. These networks are further joined by the C7–H···O7i (symmetry code as in Table 1) hydrogen bonds, forming a three-dimensional framework (Fig.2). In addition, the supramolecular aggregation is augmented by π-π stacking interactions between the aromatic rings C5—C10 and C13—C18, respectively. The two phenyl rings which lie in the molecules at (x,y,z) and (-x,1 - y,-z), respectively, are almost parallel with the dihedral angle of only 1.36 (1)°, the ring centroid separation of 3.682 (2) Å and the interpalanar spacing of ca 3.404 Å.
We have already published some crystal structures tha are related to the title compound (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005).
For related literature, see: Hendriks et al. (1982).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
C38H44N10O24+·4(NO3−) | F(000) = 964 |
Mr = 920.87 | Dx = 1.439 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2223 reflections |
a = 8.4296 (6) Å | θ = 2.4–19.9° |
b = 17.6744 (12) Å | µ = 0.11 mm−1 |
c = 14.279 (1) Å | T = 294 K |
β = 92.421 (1)° | Block, colourless |
V = 2125.5 (3) Å3 | 0.20 × 0.12 × 0.10 mm |
Z = 2 |
Bruker SMART APEX CCD area-detector diffractometer | 4642 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 2655 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
0.3° wide ω exposures scans | θmax = 27.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −10→10 |
Tmin = 0.975, Tmax = 0.989 | k = −19→22 |
23482 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0744P)2 + 0.3238P] where P = (Fo2 + 2Fc2)/3 |
4642 reflections | (Δ/σ)max < 0.001 |
310 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C38H44N10O24+·4(NO3−) | V = 2125.5 (3) Å3 |
Mr = 920.87 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.4296 (6) Å | µ = 0.11 mm−1 |
b = 17.6744 (12) Å | T = 294 K |
c = 14.279 (1) Å | 0.20 × 0.12 × 0.10 mm |
β = 92.421 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 4642 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2655 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.989 | Rint = 0.067 |
23482 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.169 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.29 e Å−3 |
4642 reflections | Δρmin = −0.19 e Å−3 |
310 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2091 (3) | 0.53564 (19) | 0.38291 (19) | 0.0604 (8) | |
H1A | 0.2269 | 0.5895 | 0.3759 | 0.072* | |
H1B | 0.1398 | 0.5284 | 0.4347 | 0.072* | |
C2 | 0.1299 (3) | 0.50482 (16) | 0.29426 (18) | 0.0481 (7) | |
H2A | 0.1247 | 0.4502 | 0.3006 | 0.058* | |
H2B | 0.0214 | 0.5233 | 0.2911 | 0.058* | |
C3 | 0.2078 (3) | 0.60132 (15) | 0.1804 (2) | 0.0516 (7) | |
H3A | 0.2777 | 0.6079 | 0.1287 | 0.062* | |
H3B | 0.2532 | 0.6287 | 0.2339 | 0.062* | |
C4 | 0.0490 (3) | 0.63386 (16) | 0.15382 (17) | 0.0439 (6) | |
C5 | −0.2006 (3) | 0.64709 (15) | 0.10256 (16) | 0.0402 (6) | |
C6 | −0.3564 (3) | 0.63661 (16) | 0.06912 (18) | 0.0482 (7) | |
H6 | −0.3976 | 0.5887 | 0.0562 | 0.058* | |
C7 | −0.4458 (3) | 0.70087 (19) | 0.05621 (18) | 0.0538 (8) | |
H7 | −0.5505 | 0.6964 | 0.0337 | 0.065* | |
C8 | −0.3840 (3) | 0.77308 (17) | 0.07599 (19) | 0.0550 (8) | |
H8 | −0.4491 | 0.8152 | 0.0670 | 0.066* | |
C9 | −0.2306 (3) | 0.78310 (16) | 0.10818 (18) | 0.0510 (7) | |
H9 | −0.1892 | 0.8310 | 0.1205 | 0.061* | |
C10 | −0.1396 (3) | 0.71858 (15) | 0.12152 (17) | 0.0420 (6) | |
C11 | 0.3475 (3) | 0.48165 (16) | 0.1873 (2) | 0.0505 (7) | |
H11A | 0.4223 | 0.4907 | 0.2395 | 0.061* | |
H11B | 0.3932 | 0.5013 | 0.1310 | 0.061* | |
C12 | 0.3205 (3) | 0.39871 (16) | 0.17669 (17) | 0.0453 (7) | |
C13 | 0.2109 (3) | 0.28778 (17) | 0.14316 (17) | 0.0481 (7) | |
C14 | 0.1108 (4) | 0.22818 (18) | 0.11782 (19) | 0.0564 (8) | |
H14 | 0.0065 | 0.2361 | 0.0964 | 0.068* | |
C15 | 0.1746 (4) | 0.15673 (19) | 0.1262 (2) | 0.0666 (9) | |
H15 | 0.1120 | 0.1153 | 0.1088 | 0.080* | |
C16 | 0.3291 (5) | 0.1445 (2) | 0.1598 (2) | 0.0759 (10) | |
H16 | 0.3664 | 0.0951 | 0.1657 | 0.091* | |
C17 | 0.4284 (4) | 0.2034 (2) | 0.1844 (2) | 0.0676 (9) | |
H17 | 0.5324 | 0.1952 | 0.2063 | 0.081* | |
C18 | 0.3663 (3) | 0.27573 (17) | 0.17529 (18) | 0.0508 (7) | |
C19 | 0.4248 (3) | 0.52156 (19) | 0.49117 (19) | 0.0605 (8) | |
H19A | 0.3520 | 0.5113 | 0.5404 | 0.073* | |
H19B | 0.4468 | 0.5754 | 0.4907 | 0.073* | |
N1 | 0.1992 (2) | 0.52134 (12) | 0.20352 (14) | 0.0427 (5) | |
N2 | −0.0788 (2) | 0.59601 (14) | 0.12376 (15) | 0.0450 (6) | |
H2 | −0.084 (3) | 0.5449 (17) | 0.1178 (18) | 0.054* | |
N3 | 0.0169 (3) | 0.70765 (14) | 0.15369 (15) | 0.0465 (6) | |
H3 | 0.085 (3) | 0.7437 (16) | 0.1678 (18) | 0.056* | |
N4 | 0.4296 (3) | 0.34628 (16) | 0.19490 (16) | 0.0548 (7) | |
H4 | 0.516 (4) | 0.3587 (17) | 0.218 (2) | 0.066* | |
N5 | 0.1875 (3) | 0.36534 (14) | 0.14572 (15) | 0.0456 (6) | |
H5 | 0.106 (3) | 0.3912 (16) | 0.1281 (19) | 0.055* | |
N6 | 0.7793 (3) | 0.37255 (17) | 0.32131 (19) | 0.0621 (7) | |
O1 | 0.3557 (2) | 0.49900 (11) | 0.40309 (12) | 0.0566 (5) | |
O2 | 0.6974 (3) | 0.42656 (14) | 0.29412 (17) | 0.0876 (8) | |
O3 | 0.8884 (3) | 0.37929 (14) | 0.38036 (19) | 0.0902 (8) | |
O4 | 0.7453 (3) | 0.30882 (15) | 0.28733 (18) | 0.0908 (8) | |
N7 | −0.2022 (3) | 0.41060 (15) | 0.06511 (16) | 0.0546 (6) | |
O5 | −0.3230 (2) | 0.44713 (13) | 0.04530 (17) | 0.0787 (7) | |
O6 | −0.0836 (2) | 0.44321 (12) | 0.10178 (17) | 0.0766 (7) | |
O7 | −0.1903 (3) | 0.34285 (14) | 0.0487 (2) | 0.0942 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0578 (18) | 0.075 (2) | 0.0474 (17) | 0.0142 (16) | −0.0083 (13) | −0.0031 (15) |
C2 | 0.0402 (14) | 0.0546 (18) | 0.0488 (16) | 0.0041 (13) | −0.0059 (12) | 0.0025 (13) |
C3 | 0.0405 (14) | 0.0479 (18) | 0.0652 (18) | −0.0094 (12) | −0.0127 (13) | 0.0071 (14) |
C4 | 0.0427 (14) | 0.0443 (18) | 0.0442 (15) | −0.0071 (12) | −0.0053 (11) | 0.0033 (12) |
C5 | 0.0433 (14) | 0.0412 (16) | 0.0360 (13) | 0.0016 (12) | 0.0003 (11) | 0.0054 (11) |
C6 | 0.0455 (14) | 0.0530 (18) | 0.0455 (15) | −0.0055 (13) | −0.0057 (12) | 0.0012 (13) |
C7 | 0.0441 (15) | 0.070 (2) | 0.0469 (16) | 0.0052 (15) | −0.0040 (12) | 0.0087 (14) |
C8 | 0.0589 (18) | 0.055 (2) | 0.0504 (17) | 0.0157 (15) | −0.0009 (14) | 0.0098 (14) |
C9 | 0.0621 (18) | 0.0461 (18) | 0.0447 (16) | 0.0003 (14) | 0.0032 (13) | −0.0003 (13) |
C10 | 0.0459 (14) | 0.0434 (17) | 0.0364 (14) | 0.0002 (12) | −0.0033 (11) | 0.0027 (11) |
C11 | 0.0367 (14) | 0.062 (2) | 0.0527 (17) | −0.0006 (13) | −0.0044 (12) | 0.0033 (14) |
C12 | 0.0409 (14) | 0.0554 (19) | 0.0395 (14) | 0.0031 (13) | −0.0007 (11) | 0.0018 (13) |
C13 | 0.0538 (16) | 0.055 (2) | 0.0356 (14) | 0.0063 (14) | 0.0035 (12) | 0.0021 (13) |
C14 | 0.0645 (18) | 0.058 (2) | 0.0470 (16) | −0.0045 (16) | 0.0040 (14) | −0.0006 (14) |
C15 | 0.092 (2) | 0.052 (2) | 0.0566 (19) | −0.0009 (18) | 0.0123 (17) | 0.0033 (15) |
C16 | 0.111 (3) | 0.059 (2) | 0.058 (2) | 0.021 (2) | 0.005 (2) | 0.0032 (17) |
C17 | 0.075 (2) | 0.072 (2) | 0.0546 (19) | 0.0264 (19) | −0.0056 (16) | 0.0036 (17) |
C18 | 0.0571 (17) | 0.056 (2) | 0.0393 (15) | 0.0119 (15) | 0.0001 (12) | −0.0011 (13) |
C19 | 0.0645 (19) | 0.070 (2) | 0.0456 (17) | 0.0011 (15) | −0.0152 (14) | −0.0014 (14) |
N1 | 0.0360 (11) | 0.0454 (14) | 0.0460 (13) | −0.0016 (10) | −0.0062 (9) | 0.0050 (10) |
N2 | 0.0433 (12) | 0.0399 (13) | 0.0507 (13) | −0.0031 (11) | −0.0087 (10) | 0.0027 (11) |
N3 | 0.0482 (13) | 0.0407 (15) | 0.0499 (13) | −0.0080 (10) | −0.0078 (10) | −0.0014 (11) |
N4 | 0.0441 (13) | 0.0697 (18) | 0.0498 (14) | 0.0114 (13) | −0.0078 (11) | 0.0008 (12) |
N5 | 0.0409 (12) | 0.0483 (16) | 0.0469 (13) | 0.0074 (11) | −0.0052 (10) | −0.0007 (11) |
N6 | 0.0457 (14) | 0.066 (2) | 0.0738 (18) | 0.0063 (14) | −0.0011 (13) | 0.0094 (15) |
O1 | 0.0544 (11) | 0.0675 (14) | 0.0464 (11) | 0.0091 (10) | −0.0150 (9) | −0.0071 (9) |
O2 | 0.0809 (16) | 0.0818 (18) | 0.0986 (18) | 0.0335 (14) | −0.0129 (14) | 0.0038 (14) |
O3 | 0.0605 (14) | 0.0913 (19) | 0.116 (2) | −0.0012 (13) | −0.0352 (14) | 0.0062 (15) |
O4 | 0.0764 (16) | 0.0726 (18) | 0.121 (2) | 0.0040 (14) | −0.0302 (15) | −0.0099 (15) |
N7 | 0.0473 (14) | 0.0551 (17) | 0.0602 (15) | −0.0020 (12) | −0.0134 (11) | −0.0018 (12) |
O5 | 0.0533 (12) | 0.0746 (16) | 0.1052 (18) | 0.0111 (11) | −0.0310 (12) | −0.0085 (13) |
O6 | 0.0480 (12) | 0.0495 (13) | 0.129 (2) | −0.0029 (10) | −0.0305 (12) | −0.0134 (12) |
O7 | 0.0891 (17) | 0.0481 (15) | 0.141 (2) | 0.0016 (13) | −0.0459 (16) | −0.0181 (15) |
C1—O1 | 1.414 (3) | C12—N4 | 1.323 (3) |
C1—C2 | 1.508 (4) | C12—N5 | 1.326 (3) |
C1—H1A | 0.9700 | C13—N5 | 1.386 (4) |
C1—H1B | 0.9700 | C13—C18 | 1.386 (4) |
C2—N1 | 1.473 (3) | C13—C14 | 1.388 (4) |
C2—H2A | 0.9700 | C14—C15 | 1.376 (4) |
C2—H2B | 0.9700 | C14—H14 | 0.9300 |
C3—N1 | 1.454 (3) | C15—C16 | 1.385 (5) |
C3—C4 | 1.491 (3) | C15—H15 | 0.9300 |
C3—H3A | 0.9700 | C16—C17 | 1.374 (5) |
C3—H3B | 0.9700 | C16—H16 | 0.9300 |
C4—N2 | 1.324 (3) | C17—C18 | 1.385 (4) |
C4—N3 | 1.332 (3) | C17—H17 | 0.9300 |
C5—C10 | 1.387 (4) | C18—N4 | 1.380 (4) |
C5—C6 | 1.391 (3) | C19—O1 | 1.421 (3) |
C5—N2 | 1.391 (3) | C19—C19i | 1.491 (6) |
C6—C7 | 1.371 (4) | C19—H19A | 0.9700 |
C6—H6 | 0.9300 | C19—H19B | 0.9700 |
C7—C8 | 1.403 (4) | N2—H2 | 0.91 (3) |
C7—H7 | 0.9300 | N3—H3 | 0.87 (3) |
C8—C9 | 1.366 (4) | N4—H4 | 0.82 (3) |
C8—H8 | 0.9300 | N5—H5 | 0.86 (3) |
C9—C10 | 1.383 (4) | N6—O3 | 1.227 (3) |
C9—H9 | 0.9300 | N6—O2 | 1.231 (3) |
C10—N3 | 1.392 (3) | N6—O4 | 1.255 (3) |
C11—N1 | 1.460 (3) | N7—O7 | 1.225 (3) |
C11—C12 | 1.490 (4) | N7—O5 | 1.228 (3) |
C11—H11A | 0.9700 | N7—O6 | 1.249 (3) |
C11—H11B | 0.9700 | ||
O1—C1—C2 | 111.0 (2) | C18—C13—C14 | 121.7 (3) |
O1—C1—H1A | 109.4 | C15—C14—C13 | 116.3 (3) |
C2—C1—H1A | 109.4 | C15—C14—H14 | 121.9 |
O1—C1—H1B | 109.4 | C13—C14—H14 | 121.9 |
C2—C1—H1B | 109.4 | C14—C15—C16 | 122.1 (3) |
H1A—C1—H1B | 108.0 | C14—C15—H15 | 118.9 |
N1—C2—C1 | 119.3 (2) | C16—C15—H15 | 118.9 |
N1—C2—H2A | 107.5 | C17—C16—C15 | 121.6 (3) |
C1—C2—H2A | 107.5 | C17—C16—H16 | 119.2 |
N1—C2—H2B | 107.5 | C15—C16—H16 | 119.2 |
C1—C2—H2B | 107.5 | C16—C17—C18 | 116.9 (3) |
H2A—C2—H2B | 107.0 | C16—C17—H17 | 121.6 |
N1—C3—C4 | 112.3 (2) | C18—C17—H17 | 121.6 |
N1—C3—H3A | 109.1 | N4—C18—C17 | 132.3 (3) |
C4—C3—H3A | 109.1 | N4—C18—C13 | 106.3 (2) |
N1—C3—H3B | 109.1 | C17—C18—C13 | 121.4 (3) |
C4—C3—H3B | 109.1 | O1—C19—C19i | 108.7 (3) |
H3A—C3—H3B | 107.9 | O1—C19—H19A | 110.0 |
N2—C4—N3 | 109.4 (2) | C19i—C19—H19A | 110.0 |
N2—C4—C3 | 126.6 (3) | O1—C19—H19B | 110.0 |
N3—C4—C3 | 124.0 (2) | C19i—C19—H19B | 110.0 |
C10—C5—C6 | 121.7 (2) | H19A—C19—H19B | 108.3 |
C10—C5—N2 | 106.5 (2) | C3—N1—C11 | 112.3 (2) |
C6—C5—N2 | 131.8 (2) | C3—N1—C2 | 114.7 (2) |
C7—C6—C5 | 116.2 (3) | C11—N1—C2 | 114.7 (2) |
C7—C6—H6 | 121.9 | C4—N2—C5 | 109.0 (2) |
C5—C6—H6 | 121.9 | C4—N2—H2 | 124.5 (17) |
C6—C7—C8 | 121.9 (3) | C5—N2—H2 | 126.5 (17) |
C6—C7—H7 | 119.0 | C4—N3—C10 | 109.0 (2) |
C8—C7—H7 | 119.0 | C4—N3—H3 | 125.6 (18) |
C9—C8—C7 | 121.6 (3) | C10—N3—H3 | 125.2 (18) |
C9—C8—H8 | 119.2 | C12—N4—C18 | 109.5 (2) |
C7—C8—H8 | 119.2 | C12—N4—H4 | 119 (2) |
C8—C9—C10 | 116.8 (3) | C18—N4—H4 | 131 (2) |
C8—C9—H9 | 121.6 | C12—N5—C13 | 109.3 (2) |
C10—C9—H9 | 121.6 | C12—N5—H5 | 121.4 (19) |
C9—C10—C5 | 121.7 (2) | C13—N5—H5 | 129.3 (19) |
C9—C10—N3 | 132.2 (3) | O3—N6—O2 | 122.4 (3) |
C5—C10—N3 | 106.1 (2) | O3—N6—O4 | 120.3 (3) |
N1—C11—C12 | 111.2 (2) | O2—N6—O4 | 117.3 (3) |
N1—C11—H11A | 109.4 | C1—O1—C19 | 112.0 (2) |
C12—C11—H11A | 109.4 | N6—O2—H4 | 95.9 (8) |
N1—C11—H11B | 109.4 | N6—O4—H4 | 89.8 (8) |
C12—C11—H11B | 109.4 | O7—N7—O5 | 122.9 (2) |
H11A—C11—H11B | 108.0 | O7—N7—O6 | 117.4 (2) |
N4—C12—N5 | 108.9 (3) | O5—N7—O6 | 119.6 (3) |
N4—C12—C11 | 124.6 (2) | N7—O6—H2 | 120.4 (9) |
N5—C12—C11 | 126.5 (2) | N7—O6—H5 | 121.3 (8) |
N5—C13—C18 | 106.1 (2) | H2—O6—H5 | 117.9 (12) |
N5—C13—C14 | 132.2 (3) | ||
O1—C1—C2—N1 | −69.8 (3) | C12—C11—N1—C2 | 67.7 (3) |
N1—C3—C4—N2 | −21.2 (4) | C1—C2—N1—C3 | −60.6 (3) |
N1—C3—C4—N3 | 161.5 (2) | C1—C2—N1—C11 | 71.7 (3) |
C10—C5—C6—C7 | −0.1 (4) | N3—C4—N2—C5 | 0.2 (3) |
N2—C5—C6—C7 | 179.7 (3) | C3—C4—N2—C5 | −177.4 (3) |
C5—C6—C7—C8 | −0.3 (4) | C10—C5—N2—C4 | 0.0 (3) |
C6—C7—C8—C9 | 0.8 (4) | C6—C5—N2—C4 | −179.9 (3) |
C7—C8—C9—C10 | −0.8 (4) | N2—C4—N3—C10 | −0.3 (3) |
C8—C9—C10—C5 | 0.4 (4) | C3—C4—N3—C10 | 177.4 (2) |
C8—C9—C10—N3 | −179.2 (3) | C9—C10—N3—C4 | 179.9 (3) |
C6—C5—C10—C9 | 0.0 (4) | C5—C10—N3—C4 | 0.3 (3) |
N2—C5—C10—C9 | −179.9 (2) | N5—C12—N4—C18 | 0.0 (3) |
C6—C5—C10—N3 | 179.7 (2) | C11—C12—N4—C18 | −178.4 (2) |
N2—C5—C10—N3 | −0.1 (3) | C17—C18—N4—C12 | −178.0 (3) |
N1—C11—C12—N4 | −154.4 (2) | C13—C18—N4—C12 | 0.3 (3) |
N1—C11—C12—N5 | 27.5 (4) | N4—C12—N5—C13 | −0.3 (3) |
N5—C13—C14—C15 | −178.5 (3) | C11—C12—N5—C13 | 178.1 (2) |
C18—C13—C14—C15 | −0.1 (4) | C18—C13—N5—C12 | 0.5 (3) |
C13—C14—C15—C16 | 1.2 (4) | C14—C13—N5—C12 | 179.0 (3) |
C14—C15—C16—C17 | −1.6 (5) | C2—C1—O1—C19 | −174.0 (2) |
C15—C16—C17—C18 | 0.8 (5) | C19i—C19—O1—C1 | 177.9 (3) |
C16—C17—C18—N4 | 178.5 (3) | O3—N6—O2—H4 | −169.1 (8) |
C16—C17—C18—C13 | 0.3 (4) | O4—N6—O2—H4 | 9.7 (8) |
N5—C13—C18—N4 | −0.5 (3) | O3—N6—O4—H4 | 169.7 (8) |
C14—C13—C18—N4 | −179.2 (2) | O2—N6—O4—H4 | −9.1 (8) |
N5—C13—C18—C17 | 178.1 (2) | O7—N7—O6—H2 | 173.8 (10) |
C14—C13—C18—C17 | −0.7 (4) | O5—N7—O6—H2 | −4.6 (10) |
C4—C3—N1—C11 | 153.5 (2) | O7—N7—O6—H5 | 1.3 (10) |
C4—C3—N1—C2 | −73.1 (3) | O5—N7—O6—H5 | −177.1 (10) |
C12—C11—N1—C3 | −158.9 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O7 | 0.93 | 2.58 | 3.364 (4) | 142 |
C11—H11A···O1 | 0.97 | 2.43 | 3.094 (3) | 125 |
C6—H6···O5 | 0.93 | 2.59 | 3.379 (4) | 143 |
N4—H4···O4 | 0.82 (3) | 2.31 (3) | 2.995 (3) | 142 (3) |
N4—H4···O2 | 0.82 (3) | 2.20 (3) | 2.975 (4) | 160 (3) |
N5—H5···O6 | 0.86 (3) | 1.87 (3) | 2.719 (3) | 174 (3) |
N2—H2···O6 | 0.91 (3) | 1.81 (3) | 2.719 (3) | 177 (3) |
C7—H7···O7ii | 0.93 | 2.53 | 3.443 (4) | 166 |
N3—H3···O4iii | 0.87 (3) | 1.93 (3) | 2.789 (3) | 169 (3) |
N3—H3···O3iii | 0.87 (3) | 2.51 (3) | 3.180 (3) | 134 (2) |
Symmetry codes: (ii) −x−1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C38H44N10O24+·4(NO3−) |
Mr | 920.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.4296 (6), 17.6744 (12), 14.279 (1) |
β (°) | 92.421 (1) |
V (Å3) | 2125.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.20 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.975, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23482, 4642, 2655 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.169, 1.03 |
No. of reflections | 4642 |
No. of parameters | 310 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.19 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O7 | 0.93 | 2.58 | 3.364 (4) | 141.7 |
C11—H11A···O1 | 0.97 | 2.43 | 3.094 (3) | 125.4 |
C6—H6···O5 | 0.93 | 2.59 | 3.379 (4) | 143.4 |
N4—H4···O4 | 0.82 (3) | 2.31 (3) | 2.995 (3) | 142 (3) |
N4—H4···O2 | 0.82 (3) | 2.20 (3) | 2.975 (4) | 160 (3) |
N5—H5···O6 | 0.86 (3) | 1.87 (3) | 2.719 (3) | 174 (3) |
N2—H2···O6 | 0.91 (3) | 1.81 (3) | 2.719 (3) | 177 (3) |
C7—H7···O7i | 0.93 | 2.53 | 3.443 (4) | 166.1 |
N3—H3···O4ii | 0.87 (3) | 1.93 (3) | 2.789 (3) | 169 (3) |
N3—H3···O3ii | 0.87 (3) | 2.51 (3) | 3.180 (3) | 134 (2) |
Symmetry codes: (i) −x−1, −y+1, −z; (ii) −x+1, y+1/2, −z+1/2. |
As part of our continuing studies on the ligands or metal complexes containing multi-benzimidazole groups (Zhang et al., 2005; Li et al., 2005; Qiu et al., 2005), we report here the crystal structure of a related compound, (I), which was obtained unexpectedly by reacting µ2-N,N, N', N'-tetrakis(Benzimidazol-2-ylmethyl)- 3,6- dioxaoctane-1,8-diamine (EGTB) with Fe(NO3).6H2O in H2O solution.
In the aymmetric unit of (I) (Fig. 1), the cation lies across an inversion center in space group of P21/c. The two terminal benzimidazoles rings on one side of the cation are effectively planar with the dihedral angle of only 0.75 (1)°.
All imine N atoms in the benzimidazole groups of are protonated foming a tetracation. Two nitrate anions lie to the inner side of the two end-on benzimidazole groups, forming the four nearly symmetric intra-molecular hydrogen bonds (Table 1). However, the other two anions lie at the outside of the two benzimidazole groups, linking the adjacent cations into a two-dimensional network running parallel the (100) direction. These networks are further joined by the C7–H···O7i (symmetry code as in Table 1) hydrogen bonds, forming a three-dimensional framework (Fig.2). In addition, the supramolecular aggregation is augmented by π-π stacking interactions between the aromatic rings C5—C10 and C13—C18, respectively. The two phenyl rings which lie in the molecules at (x,y,z) and (-x,1 - y,-z), respectively, are almost parallel with the dihedral angle of only 1.36 (1)°, the ring centroid separation of 3.682 (2) Å and the interpalanar spacing of ca 3.404 Å.