Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110012394/sq3241sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110012394/sq3241Isup2.hkl |
CCDC reference: 779957
A mixture of NiCl2·6H2O (0.025 g, 0.1 mmol), H2acc (0.020 g, 0.1 mmol), 4,4'-bpy (0.017 g, 0.1 mmol), dimethylformamide (5 ml) and H2O (5 ml) was placed in a Teflon reactor and heated at 393 K for 24 h. After cooling to room temperature, blue [Green in CIF data - please clarify] crystals of (I) were obtained in 45% yield based on H2acc. Elemental analysis for C20H18N2O6Ni (Mr 684.0): C 35.09, H 2.63, N 4.09%; found: C 35.18, H 2.70, N 4.02%. FT–IR (KBr pellet, cm−1): 3407 (s), 1630 (s), 1577 (s), 1386 (w), 1298 (w), 1218 (w), 1113 (w), 1050 (w), 1004 (w), 931 (w), 898 (w), 704 (w), 638 (w), 544 (w), 516 (w).
All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93 (pyridine, arene) or 0.97 Å (methylene) [Uiso(H) = 1.2Ueq(C)] and O—H = 0.82 Å (water) [Uiso(H) = 1.5Ueq(O)].
The acc2− anion ligand is disordered both rotationally about the axis that includes the carboxylate C—C bonds and lengthwise, having the arene ring connected to either atom C1 or C12. That is, when the arene ring is connected to atom C1, the bond between atoms C8 and C9 represents the vinyl group, while when the arene ring is connected to atom C12, the vinyl group should be assigned to the bond between atoms C4 and C5. The disordered arene rings and C ═C bonds were refined using a rigid group model, where the atoms were fitted to two orientations of an ideal naphthalene moiety which were allowed to translate and rotate (the AFIX 116 instruction in SHELXL97; Sheldrick, 2008). The first group including atoms C4–C9 possesses the same occupancy factors, which all were distributed over two positions (unprimed and primed) with refined site occupation factors of 0.56 (1)/0.44 (1) related to the rotational disorder about the carboxylate C—C bonds. Atoms C2, C3, C10 and C11 assigned to the second group were also distributed over two positions, and they were refined with site occupation factors of 0.279 (6)/0.221 (6) due to the lengthwise disorder that flips the entire ligand. H atoms were assigned site occupation factors consistent with the parent C atoms. The disordered model still leaves several residual electron-density peaks in this region of the structure, but further modelling of the disorder was unfruitful.
Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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).
[Ni(C10H6O4)(C10H8N2)(H2O)2] | Dx = 1.483 Mg m−3 |
Mr = 441.07 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P32 | Cell parameters from 1991 reflections |
Hall symbol: P 32 | θ = 5.6–22.6° |
a = 11.261 (2) Å | µ = 1.02 mm−1 |
c = 13.495 (6) Å | T = 298 K |
V = 1482.0 (8) Å3 | Block, green |
Z = 3 | 0.32 × 0.30 × 0.26 mm |
F(000) = 684 |
Bruker SMART APEX CCD area-detector diffractometer | 3429 independent reflections |
Radiation source: fine-focus sealed tube | 2458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.736, Tmax = 0.777 | k = −13→13 |
7628 measured reflections | l = −15→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.211 | w = 1/[σ2(Fo2) + (0.1135P)2 + 3.2806P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3429 reflections | Δρmax = 1.02 e Å−3 |
324 parameters | Δρmin = −0.65 e Å−3 |
937 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (4) |
[Ni(C10H6O4)(C10H8N2)(H2O)2] | Z = 3 |
Mr = 441.07 | Mo Kα radiation |
Hexagonal, P32 | µ = 1.02 mm−1 |
a = 11.261 (2) Å | T = 298 K |
c = 13.495 (6) Å | 0.32 × 0.30 × 0.26 mm |
V = 1482.0 (8) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 3429 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2458 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 0.777 | Rint = 0.050 |
7628 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.211 | Δρmax = 1.02 e Å−3 |
S = 1.06 | Δρmin = −0.65 e Å−3 |
3429 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
324 parameters | Absolute structure parameter: 0.01 (4) |
937 restraints |
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 | Occ. (<1) | |
Ni1 | 0.89237 (9) | 0.66653 (11) | 1.16739 (12) | 0.0337 (3) | |
O1 | 0.8978 (6) | 0.6717 (7) | 1.0184 (6) | 0.042 (2) | |
O2 | 0.9894 (9) | 0.8922 (8) | 0.9802 (6) | 0.067 (2) | |
O3 | 0.8932 (6) | 0.6610 (6) | 0.3162 (7) | 0.043 (2) | |
O4 | 0.7634 (9) | 0.4409 (8) | 0.3545 (6) | 0.069 (2) | |
O5 | 0.7857 (6) | 0.4526 (6) | 1.1565 (5) | 0.0402 (16) | |
H5C | 0.7666 | 0.4421 | 1.2180 | 0.048* | |
H5D | 0.7115 | 0.4104 | 1.1238 | 0.048* | |
O6 | 0.9994 (6) | 0.8809 (6) | 1.1782 (5) | 0.0402 (17) | |
H6C | 0.9909 | 0.8916 | 1.1167 | 0.048* | |
H6D | 0.9681 | 0.9238 | 1.2109 | 0.048* | |
N1 | 0.7053 (8) | 0.6665 (10) | 1.1674 (6) | 0.0390 (17) | |
N2 | 0.0794 (8) | 0.6671 (10) | 1.1671 (6) | 0.0414 (19) | |
C1 | 0.9366 (10) | 0.7676 (12) | 0.9569 (7) | 0.052 (3) | |
C2 | 0.904 (3) | 0.564 (2) | 0.7371 (16) | 0.091 (4) | 0.221 (6) |
H2 | 0.9102 | 0.4854 | 0.7249 | 0.109* | 0.221 (6) |
C3 | 0.918 (3) | 0.614 (3) | 0.8332 (14) | 0.082 (5) | 0.221 (6) |
H3 | 0.9335 | 0.5687 | 0.8853 | 0.098* | 0.221 (6) |
C4 | 0.910 (2) | 0.731 (3) | 0.8513 (12) | 0.086 (4) | 0.442 (13) |
H4 | 0.9067 | 0.6477 | 0.8338 | 0.103* | 0.221 (6) |
C5 | 0.887 (2) | 0.798 (2) | 0.7734 (14) | 0.094 (4) | 0.442 (13) |
H5 | 0.8816 | 0.8760 | 0.7856 | 0.113* | 0.442 (13) |
C6 | 0.8734 (18) | 0.7478 (18) | 0.6774 (13) | 0.099 (4) | 0.442 (13) |
H6 | 0.8529 | 0.7910 | 0.6268 | 0.119* | 0.221 (6) |
C7 | 0.882 (2) | 0.6308 (19) | 0.6592 (13) | 0.102 (4) | 0.442 (13) |
H7 | 0.8986 | 0.5913 | 0.7125 | 0.123* | 0.221 (6) |
C8 | 0.868 (3) | 0.581 (2) | 0.5632 (14) | 0.099 (4) | 0.442 (13) |
H8 | 0.8737 | 0.5027 | 0.5510 | 0.119* | 0.442 (13) |
C9 | 0.845 (3) | 0.648 (3) | 0.4853 (12) | 0.100 (5) | 0.442 (13) |
H9 | 0.8436 | 0.7245 | 0.4969 | 0.120* | 0.221 (6) |
C10 | 0.837 (3) | 0.765 (3) | 0.5034 (14) | 0.101 (5) | 0.221 (6) |
H10 | 0.8218 | 0.8100 | 0.4513 | 0.121* | 0.221 (6) |
C11 | 0.851 (3) | 0.815 (2) | 0.5995 (16) | 0.100 (4) | 0.221 (6) |
H11 | 0.8451 | 0.8932 | 0.6116 | 0.120* | 0.221 (6) |
C2' | 0.7300 (18) | 0.5251 (19) | 0.7451 (12) | 0.102 (4) | 0.279 (6) |
H2' | 0.6482 | 0.4429 | 0.7373 | 0.122* | 0.279 (6) |
C3' | 0.773 (2) | 0.581 (2) | 0.8391 (11) | 0.097 (5) | 0.279 (6) |
H3' | 0.7195 | 0.5359 | 0.8942 | 0.117* | 0.279 (6) |
C4' | 0.895 (2) | 0.704 (2) | 0.8508 (10) | 0.087 (4) | 0.558 (13) |
H4' | 0.8208 | 0.6288 | 0.8431 | 0.105* | 0.279 (6) |
C5' | 0.9746 (18) | 0.7711 (18) | 0.7684 (12) | 0.104 (4) | 0.558 (13) |
H5' | 1.0564 | 0.8534 | 0.7763 | 0.125* | 0.558 (13) |
C6' | 0.9319 (14) | 0.7154 (15) | 0.6745 (10) | 0.098 (4) | 0.558 (13) |
H6' | 0.9795 | 0.7546 | 0.6189 | 0.118* | 0.279 (6) |
C7' | 0.8096 (14) | 0.5924 (14) | 0.6628 (10) | 0.094 (4) | 0.558 (13) |
H7' | 0.7471 | 0.5422 | 0.7140 | 0.113* | 0.279 (6) |
C8' | 0.7669 (16) | 0.5367 (16) | 0.5688 (11) | 0.099 (4) | 0.558 (13) |
H8' | 0.6851 | 0.4544 | 0.5610 | 0.119* | 0.558 (13) |
C9' | 0.8465 (19) | 0.6039 (19) | 0.4865 (10) | 0.072 (4) | 0.558 (13) |
H9' | 0.9282 | 0.6897 | 0.5013 | 0.087* | 0.279 (6) |
C10' | 0.969 (2) | 0.727 (2) | 0.4981 (11) | 0.086 (5) | 0.279 (6) |
H10' | 1.0220 | 0.7719 | 0.4431 | 0.103* | 0.279 (6) |
C11' | 1.0114 (17) | 0.7827 (18) | 0.5921 (12) | 0.089 (4) | 0.279 (6) |
H11' | 1.0933 | 0.8650 | 0.5999 | 0.107* | 0.279 (6) |
C12 | 0.8357 (9) | 0.5672 (11) | 0.3786 (7) | 0.045 (2) | |
C13 | 0.6664 (9) | 0.7090 (10) | 1.2460 (7) | 0.046 (2) | |
H13 | 0.7223 | 0.7370 | 1.3018 | 0.055* | |
C14 | 0.5459 (10) | 0.7132 (11) | 1.2481 (7) | 0.050 (2) | |
H14 | 0.5240 | 0.7480 | 1.3033 | 0.060* | |
C15 | 0.4574 (9) | 0.6653 (11) | 1.1673 (7) | 0.043 (2) | |
C16 | 0.4987 (10) | 0.6192 (11) | 1.0861 (8) | 0.051 (2) | |
H16 | 0.4427 | 0.5852 | 1.0306 | 0.062* | |
C17 | 0.6224 (9) | 0.6244 (10) | 1.0887 (7) | 0.048 (2) | |
H17 | 0.6504 | 0.5971 | 1.0326 | 0.057* | |
C18 | 0.0889 (9) | 0.5597 (10) | 1.1353 (8) | 0.048 (2) | |
H18 | 0.0090 | 0.4824 | 1.1142 | 0.058* | |
C19 | 0.2053 (9) | 0.5561 (11) | 1.1316 (7) | 0.046 (2) | |
H19 | 0.2056 | 0.4799 | 1.1053 | 0.055* | |
C20 | 0.3265 (9) | 0.6666 (10) | 1.1671 (8) | 0.043 (2) | |
C21 | 0.3180 (9) | 0.7769 (10) | 1.2033 (7) | 0.048 (2) | |
H21 | 0.3951 | 0.8522 | 1.2299 | 0.058* | |
C22 | 0.1940 (10) | 0.7748 (11) | 1.1996 (7) | 0.047 (2) | |
H22 | 0.1909 | 0.8518 | 1.2208 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0311 (6) | 0.0444 (7) | 0.0308 (5) | 0.0228 (5) | −0.0016 (5) | −0.0025 (4) |
O1 | 0.052 (5) | 0.056 (5) | 0.020 (5) | 0.030 (3) | 0.003 (3) | 0.001 (3) |
O2 | 0.102 (6) | 0.060 (5) | 0.031 (4) | 0.034 (5) | 0.009 (4) | 0.008 (3) |
O3 | 0.045 (5) | 0.047 (4) | 0.040 (6) | 0.025 (3) | −0.006 (3) | 0.000 (3) |
O4 | 0.088 (6) | 0.066 (5) | 0.032 (4) | 0.024 (4) | −0.001 (4) | 0.006 (3) |
O5 | 0.036 (3) | 0.054 (4) | 0.029 (4) | 0.022 (3) | −0.001 (2) | −0.004 (3) |
O6 | 0.041 (4) | 0.055 (4) | 0.031 (4) | 0.029 (3) | −0.002 (3) | −0.005 (3) |
N1 | 0.035 (4) | 0.054 (4) | 0.034 (4) | 0.026 (4) | −0.012 (3) | −0.017 (3) |
N2 | 0.043 (5) | 0.052 (4) | 0.034 (4) | 0.026 (4) | −0.005 (3) | −0.006 (3) |
C1 | 0.050 (6) | 0.075 (8) | 0.037 (6) | 0.035 (6) | −0.003 (4) | −0.010 (5) |
C2 | 0.106 (7) | 0.102 (7) | 0.078 (6) | 0.063 (7) | −0.005 (6) | −0.007 (6) |
C3 | 0.101 (8) | 0.097 (8) | 0.074 (6) | 0.069 (7) | 0.001 (7) | −0.015 (6) |
C4 | 0.102 (8) | 0.100 (8) | 0.072 (6) | 0.063 (7) | −0.003 (6) | −0.009 (6) |
C5 | 0.107 (8) | 0.104 (8) | 0.078 (6) | 0.057 (7) | −0.003 (6) | −0.008 (6) |
C6 | 0.107 (7) | 0.110 (7) | 0.078 (5) | 0.052 (7) | −0.011 (6) | −0.001 (5) |
C7 | 0.111 (7) | 0.108 (7) | 0.082 (5) | 0.050 (7) | −0.007 (6) | −0.014 (5) |
C8 | 0.110 (8) | 0.110 (8) | 0.081 (6) | 0.057 (7) | −0.004 (6) | −0.008 (6) |
C9 | 0.109 (8) | 0.109 (8) | 0.083 (6) | 0.054 (7) | −0.005 (7) | −0.002 (6) |
C10 | 0.113 (8) | 0.108 (8) | 0.081 (6) | 0.055 (8) | −0.007 (7) | −0.008 (7) |
C11 | 0.112 (8) | 0.107 (8) | 0.082 (6) | 0.057 (7) | −0.005 (6) | −0.007 (6) |
C2' | 0.112 (8) | 0.109 (8) | 0.082 (6) | 0.054 (7) | −0.005 (6) | −0.008 (6) |
C3' | 0.109 (8) | 0.106 (8) | 0.081 (6) | 0.057 (7) | −0.008 (7) | −0.009 (6) |
C4' | 0.103 (8) | 0.102 (8) | 0.075 (6) | 0.065 (7) | −0.003 (6) | −0.003 (6) |
C5' | 0.115 (7) | 0.109 (7) | 0.083 (6) | 0.053 (7) | −0.007 (6) | −0.008 (6) |
C6' | 0.114 (7) | 0.103 (7) | 0.085 (5) | 0.060 (7) | −0.007 (6) | −0.012 (5) |
C7' | 0.110 (7) | 0.106 (7) | 0.080 (5) | 0.064 (6) | 0.007 (6) | −0.008 (5) |
C8' | 0.110 (7) | 0.105 (7) | 0.087 (6) | 0.056 (7) | −0.010 (6) | −0.005 (6) |
C9' | 0.096 (7) | 0.089 (7) | 0.068 (6) | 0.074 (6) | −0.011 (6) | −0.004 (6) |
C10' | 0.102 (8) | 0.099 (8) | 0.076 (6) | 0.064 (7) | −0.012 (7) | −0.008 (6) |
C11' | 0.104 (7) | 0.102 (7) | 0.078 (6) | 0.063 (7) | −0.006 (6) | −0.007 (6) |
C12 | 0.041 (5) | 0.068 (7) | 0.031 (5) | 0.030 (5) | −0.001 (4) | −0.006 (5) |
C13 | 0.044 (5) | 0.071 (6) | 0.034 (5) | 0.037 (5) | −0.011 (4) | −0.013 (4) |
C14 | 0.043 (5) | 0.075 (7) | 0.039 (5) | 0.035 (5) | −0.003 (4) | −0.019 (5) |
C15 | 0.034 (5) | 0.065 (6) | 0.039 (5) | 0.031 (5) | 0.008 (4) | 0.024 (4) |
C16 | 0.051 (6) | 0.071 (7) | 0.047 (6) | 0.042 (6) | −0.014 (5) | −0.012 (5) |
C17 | 0.046 (5) | 0.068 (6) | 0.037 (5) | 0.034 (5) | −0.006 (4) | −0.017 (5) |
C18 | 0.029 (5) | 0.048 (6) | 0.065 (7) | 0.016 (4) | −0.004 (4) | −0.011 (5) |
C19 | 0.040 (5) | 0.057 (6) | 0.048 (5) | 0.030 (5) | −0.009 (4) | −0.013 (5) |
C20 | 0.028 (5) | 0.041 (5) | 0.062 (6) | 0.019 (4) | 0.004 (4) | 0.003 (4) |
C21 | 0.034 (5) | 0.055 (6) | 0.062 (6) | 0.026 (5) | −0.009 (4) | −0.022 (5) |
C22 | 0.045 (6) | 0.065 (7) | 0.044 (6) | 0.037 (5) | −0.012 (4) | −0.011 (5) |
Ni1—O3i | 2.009 (10) | C11—H6 | 0.4644 |
Ni1—O1 | 2.011 (9) | C11—H11 | 0.9300 |
Ni1—O5 | 2.091 (6) | C2'—C3' | 1.3900 |
Ni1—O6 | 2.096 (6) | C2'—C7' | 1.3900 |
Ni1—N2ii | 2.103 (7) | C2'—H2' | 0.9300 |
Ni1—N1 | 2.107 (7) | C2'—H7' | 0.4617 |
O1—C1 | 1.255 (13) | C3'—C4' | 1.3900 |
O2—C1 | 1.260 (13) | C3'—H3' | 0.9300 |
O3—C12 | 1.249 (12) | C3'—H4' | 0.5435 |
O3—Ni1iii | 2.009 (10) | C4'—C5' | 1.3900 |
O4—C12 | 1.278 (12) | C4'—H4 | 0.7441 |
O5—H5C | 0.8500 | C4'—H4' | 0.8466 |
O5—H5D | 0.8500 | C5'—C6' | 1.3900 |
O6—H6C | 0.8501 | C5'—H5' | 0.9300 |
O6—H6D | 0.8499 | C6'—C7' | 1.3900 |
N1—C13 | 1.324 (12) | C6'—C11' | 1.3900 |
N1—C17 | 1.335 (12) | C6'—H6' | 0.8993 |
N2—C22 | 1.328 (14) | C7'—C8' | 1.3900 |
N2—C18 | 1.337 (14) | C7'—H7 | 1.2113 |
N2—Ni1iv | 2.103 (7) | C7'—H7' | 0.9457 |
C1—C4 | 1.472 (19) | C8'—C9' | 1.3900 |
C1—C4' | 1.565 (16) | C8'—H8' | 0.9300 |
C2—C3 | 1.3900 | C9'—C10' | 1.3900 |
C2—C7 | 1.3900 | C9'—C12 | 1.502 (15) |
C2—H2 | 0.9300 | C9'—H9' | 0.9650 |
C2—H7 | 0.4816 | C10'—C11' | 1.3900 |
C3—C4 | 1.3900 | C10'—H9' | 0.4409 |
C3—H3 | 0.9300 | C10'—H10' | 0.9300 |
C3—H4 | 0.4641 | C11'—H6' | 0.4957 |
C4—C5 | 1.3900 | C11'—H11' | 0.9300 |
C4—H4 | 0.9462 | C13—C14 | 1.383 (12) |
C4—H4' | 1.0871 | C13—H13 | 0.9300 |
C5—C6 | 1.3900 | C14—C15 | 1.391 (14) |
C5—H5 | 0.9300 | C14—H14 | 0.9300 |
C6—C7 | 1.3900 | C15—C16 | 1.389 (14) |
C6—C11 | 1.3900 | C15—C20 | 1.481 (10) |
C6—H6 | 0.9311 | C16—C17 | 1.365 (13) |
C7—C8 | 1.3900 | C16—H16 | 0.9300 |
C7—H7 | 0.9129 | C17—H17 | 0.9300 |
C8—C9 | 1.3900 | C18—C19 | 1.332 (13) |
C8—H8 | 0.9300 | C18—H18 | 0.9300 |
C9—C10 | 1.3900 | C19—C20 | 1.394 (14) |
C9—C12 | 1.68 (2) | C19—H19 | 0.9300 |
C9—H9 | 0.8847 | C20—C21 | 1.382 (14) |
C9—H9' | 0.8356 | C21—C22 | 1.386 (12) |
C10—C11 | 1.3900 | C21—H21 | 0.9300 |
C10—H9 | 0.5072 | C22—H22 | 0.9300 |
C10—H10 | 0.9300 | ||
O3i—Ni1—O1 | 177.9 (2) | C3'—C2'—H2' | 120.0 |
O3i—Ni1—O5 | 92.5 (3) | C7'—C2'—H2' | 120.0 |
O1—Ni1—O5 | 87.4 (3) | C3'—C2'—H7' | 131.5 |
O3i—Ni1—O6 | 87.6 (2) | H2'—C2'—H7' | 108.1 |
O1—Ni1—O6 | 92.5 (3) | C4'—C3'—C2' | 120.0 |
O5—Ni1—O6 | 179.9 (4) | C2'—C3'—H4 | 104.4 |
O3i—Ni1—N2ii | 88.9 (3) | C4'—C3'—H3' | 120.0 |
O1—Ni1—N2ii | 89.0 (3) | C2'—C3'—H3' | 120.0 |
O5—Ni1—N2ii | 90.1 (3) | H4—C3'—H3' | 126.9 |
O6—Ni1—N2ii | 89.9 (3) | C2'—C3'—H4' | 119.1 |
O3i—Ni1—N1 | 91.1 (3) | H3'—C3'—H4' | 120.9 |
O1—Ni1—N1 | 90.9 (3) | C3'—C4'—C5' | 120.0 |
O5—Ni1—N1 | 90.1 (3) | C3'—C4'—C1 | 118.8 (12) |
O6—Ni1—N1 | 90.0 (3) | C5'—C4'—C1 | 121.2 (12) |
N2ii—Ni1—N1 | 179.8 (5) | C3'—C4'—H4 | 68.1 |
C1—O1—Ni1 | 132.8 (7) | C5'—C4'—H4 | 83.0 |
C12—O3—Ni1iii | 133.7 (7) | C1—C4'—H4 | 122.1 |
Ni1—O5—H5C | 93.0 | C5'—C4'—H4' | 119.4 |
Ni1—O5—H5D | 121.3 | C1—C4'—H4' | 119.3 |
H5C—O5—H5D | 108.7 | H4—C4'—H4' | 67.6 |
Ni1—O6—H6C | 93.1 | C4'—C5'—C6' | 120.0 |
Ni1—O6—H6D | 121.8 | C6'—C5'—H4 | 102.6 |
H6C—O6—H6D | 108.7 | C4'—C5'—H5' | 120.0 |
C13—N1—C17 | 117.8 (7) | C6'—C5'—H5' | 120.0 |
C13—N1—Ni1 | 120.7 (6) | H4—C5'—H5' | 130.6 |
C17—N1—Ni1 | 121.4 (6) | C5'—C6'—C7' | 120.0 |
C22—N2—C18 | 116.9 (8) | C5'—C6'—C11' | 120.0 |
C22—N2—Ni1iv | 121.1 (7) | C7'—C6'—C11' | 120.0 |
C18—N2—Ni1iv | 122.0 (7) | C5'—C6'—H7 | 88.6 |
O1—C1—O2 | 124.0 (9) | C7'—C6'—H7 | 52.4 |
O1—C1—C4 | 117.6 (13) | C11'—C6'—H7 | 129.4 |
O2—C1—C4 | 118.3 (14) | C5'—C6'—H6' | 123.6 |
O1—C1—C4' | 108.4 (11) | C7'—C6'—H6' | 116.4 |
O2—C1—C4' | 127.3 (12) | H7—C6'—H6' | 127.7 |
C3—C2—C7 | 120.0 | C8'—C7'—C6' | 120.0 |
C3—C2—H2 | 120.0 | C8'—C7'—C2' | 120.0 |
C7—C2—H2 | 120.0 | C6'—C7'—C2' | 120.0 |
C3—C2—H7 | 114.0 | C8'—C7'—H7 | 127.0 |
H2—C2—H7 | 125.9 | C6'—C7'—H7 | 62.3 |
C2—C3—C4 | 120.0 | C2'—C7'—H7 | 82.2 |
C2—C3—H3 | 120.0 | C8'—C7'—H7' | 114.3 |
C4—C3—H3 | 120.0 | C6'—C7'—H7' | 125.7 |
C2—C3—H4 | 109.4 | H7—C7'—H7' | 87.8 |
H3—C3—H4 | 129.7 | C9'—C8'—C7' | 120.0 |
C2—C3—H4' | 103.6 | C9'—C8'—H8' | 120.0 |
C4—C3—H4' | 48.9 | C7'—C8'—H8' | 120.0 |
H3—C3—H4' | 115.0 | C8'—C9'—C10' | 120.0 |
C3—C4—C5 | 120.0 | C8'—C9'—C12 | 133.1 (11) |
C3—C4—C1 | 109.7 (14) | C10'—C9'—C12 | 106.7 (11) |
C5—C4—C1 | 130.1 (14) | C8'—C9'—H9 | 97.4 |
C5—C4—H4 | 114.9 | C10'—C9'—H9 | 60.5 |
C1—C4—H4 | 115.0 | C12—C9'—H9 | 109.4 |
C3—C4—H4' | 56.5 | C8'—C9'—H9' | 114.4 |
C5—C4—H4' | 100.0 | C12—C9'—H9' | 112.4 |
C1—C4—H4' | 110.4 | H9—C9'—H9' | 58.3 |
H4—C4—H4' | 51.3 | C11'—C10'—C9' | 120.0 |
C6—C5—C4 | 120.0 | C11'—C10'—H9 | 97.9 |
C6—C5—H5 | 120.0 | C9'—C10'—H9 | 59.4 |
C4—C5—H5 | 120.0 | C11'—C10'—H9' | 107.6 |
C5—C6—C7 | 120.0 | H9—C10'—H9' | 55.1 |
C5—C6—C11 | 120.0 | C11'—C10'—H10' | 120.0 |
C7—C6—C11 | 120.0 | C9'—C10'—H10' | 120.0 |
C5—C6—H6 | 118.7 | H9—C10'—H10' | 111.8 |
C7—C6—H6 | 121.2 | H9'—C10'—H10' | 132.3 |
C5—C6—H6' | 125.6 | C10'—C11'—C6' | 120.0 |
C7—C6—H6' | 59.4 | C10'—C11'—H6' | 113.5 |
C11—C6—H6' | 85.8 | C6'—C11'—H9' | 104.6 |
H6—C6—H6' | 89.2 | H6'—C11'—H9' | 98.1 |
C8—C7—C6 | 120.0 | C10'—C11'—H11' | 120.0 |
C8—C7—C2 | 120.0 | C6'—C11'—H11' | 120.0 |
C6—C7—C2 | 120.0 | H6'—C11'—H11' | 126.5 |
C8—C7—H7 | 123.1 | H9'—C11'—H11' | 135.4 |
C6—C7—H7 | 116.9 | O3—C12—O4 | 122.9 (9) |
C8—C7—H6' | 85.0 | O3—C12—C9' | 119.0 (12) |
C6—C7—H6' | 60.8 | O4—C12—C9' | 118.1 (11) |
C2—C7—H6' | 125.2 | O3—C12—C9 | 104.7 (12) |
H7—C7—H6' | 123.1 | O4—C12—C9 | 130.9 (12) |
C8—C7—H7' | 108.2 | N1—C13—C14 | 122.4 (8) |
C6—C7—H7' | 91.0 | N1—C13—H13 | 118.8 |
C2—C7—H7' | 70.7 | C14—C13—H13 | 118.8 |
H7—C7—H7' | 71.3 | C13—C14—C15 | 119.7 (8) |
H6'—C7—H7' | 151.4 | C13—C14—H14 | 120.1 |
C7—C8—C9 | 120.0 | C15—C14—H14 | 120.1 |
C7—C8—H8 | 120.0 | C16—C15—C14 | 117.0 (7) |
C9—C8—H8 | 120.0 | C16—C15—C20 | 121.5 (8) |
C7—C8—H9' | 107.8 | C14—C15—C20 | 121.4 (9) |
H8—C8—H9' | 120.6 | C17—C16—C15 | 119.3 (9) |
C10—C9—C8 | 120.0 | C17—C16—H16 | 120.4 |
C10—C9—C12 | 130.5 (14) | C15—C16—H16 | 120.4 |
C8—C9—C12 | 109.5 (14) | N1—C17—C16 | 123.6 (9) |
C8—C9—H9 | 119.6 | N1—C17—H17 | 118.2 |
C12—C9—H9 | 130.8 | C16—C17—H17 | 118.2 |
C10—C9—H9' | 90.5 | C19—C18—N2 | 124.4 (9) |
C8—C9—H9' | 69.7 | C19—C18—H18 | 117.8 |
C12—C9—H9' | 106.2 | N2—C18—H18 | 117.8 |
H9—C9—H9' | 88.3 | C18—C19—C20 | 120.0 (9) |
C11—C10—C9 | 120.0 | C18—C19—H19 | 120.0 |
C11—C10—H9 | 119.2 | C20—C19—H19 | 120.0 |
C11—C10—H10 | 120.0 | C21—C20—C19 | 116.5 (8) |
C9—C10—H10 | 120.0 | C21—C20—C15 | 121.6 (8) |
H9—C10—H10 | 120.6 | C19—C20—C15 | 121.9 (8) |
C10—C11—C6 | 120.0 | C20—C21—C22 | 119.6 (9) |
C10—C11—H6 | 122.3 | C20—C21—H21 | 120.2 |
C10—C11—H11 | 120.0 | C22—C21—H21 | 120.2 |
C6—C11—H11 | 120.0 | N2—C22—C21 | 122.5 (10) |
H6—C11—H11 | 117.3 | N2—C22—H22 | 118.7 |
C3'—C2'—C7' | 120.0 | C21—C22—H22 | 118.7 |
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z; (iii) x, y, z−1; (iv) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···O4i | 0.85 | 1.84 | 2.681 (10) | 168 |
O5—H5D···O4v | 0.85 | 2.04 | 2.873 (9) | 169 |
O6—H6D···O2vi | 0.85 | 2.03 | 2.871 (9) | 168 |
O6—H6C···O2 | 0.85 | 1.84 | 2.679 (10) | 168 |
Symmetry codes: (i) x, y, z+1; (v) −y+1, x−y, z+2/3; (vi) −x+y+1, −x+2, z+1/3. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C10H6O4)(C10H8N2)(H2O)2] |
Mr | 441.07 |
Crystal system, space group | Hexagonal, P32 |
Temperature (K) | 298 |
a, c (Å) | 11.261 (2), 13.495 (6) |
V (Å3) | 1482.0 (8) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.32 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.736, 0.777 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7628, 3429, 2458 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.211, 1.06 |
No. of reflections | 3429 |
No. of parameters | 324 |
No. of restraints | 937 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.02, −0.65 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.01 (4) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Ni1—O3i | 2.009 (10) | Ni1—O6 | 2.096 (6) |
Ni1—O1 | 2.011 (9) | Ni1—N2ii | 2.103 (7) |
Ni1—O5 | 2.091 (6) | Ni1—N1 | 2.107 (7) |
O3i—Ni1—O5 | 92.5 (3) | O5—Ni1—N2ii | 90.1 (3) |
O1—Ni1—O5 | 87.4 (3) | O6—Ni1—N2ii | 89.9 (3) |
O3i—Ni1—O6 | 87.6 (2) | O3i—Ni1—N1 | 91.1 (3) |
O1—Ni1—O6 | 92.5 (3) | O1—Ni1—N1 | 90.9 (3) |
O5—Ni1—O6 | 179.9 (4) | O5—Ni1—N1 | 90.1 (3) |
O1—Ni1—N2ii | 89.0 (3) |
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5C···O4i | 0.85 | 1.84 | 2.681 (10) | 168.3 |
O5—H5D···O4iii | 0.85 | 2.04 | 2.873 (9) | 168.5 |
O6—H6D···O2iv | 0.85 | 2.03 | 2.871 (9) | 168.4 |
O6—H6C···O2 | 0.85 | 1.84 | 2.679 (10) | 168.0 |
Symmetry codes: (i) x, y, z+1; (iii) −y+1, x−y, z+2/3; (iv) −x+y+1, −x+2, z+1/3. |
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The construction of metal–organic assemblies has attracted increasing attention in recent years, not only for their potential applications but also due to their fascinating architectures and topologies (Ferey et al., 2005; Murray et al., 2009). Examples of some of the interesting networks of entanglement systems include polycatenation, polythreading, polyknotting and Borromean links (Batten & Robson, 1998; Batten, 2001; Carlucci, Ciani & Proserpio, 2003). Of particular interest to us is the fact that the entanglement of lower-dimensional polymeric structures can generate a structure of overall higher dimensionality, which has been classified as polycatenation. That is, the whole catenated array has a higher dimensionality than the component motifs, such as one-dimensional → two-dimensional, one-dimensional → three-dimensional and two-dimensional → three-dimensional (one-dimensional, two-dimensional and three-dimensional are one-, two- and three-dimensional, respectively). A dimensionality increase from two-dimensional layers to an overall three-dimensional entanglement can occur for systems interpenetrating in parallel or inclined fashion. Although the first two-dimensional → three-dimensional parallel interpenetration was reported over ten years ago (Liu & Tilley, 1997), such compounds are still relatively rare (Blatov et al., 2004; Baburin et al., 2005; Guo et al., 2009).
The (4,4) and (6,3) nets are the most common two-dimensional topologies, which are inclined to interpenetrate when large four- or six-membered rings are formed, or when the network shows undulating features, or both. For the former case, three possible arrangements of interpenetrating sheets have been observed in the examples reported to date: parallel–parallel (p-p), parallel–diagonal (p-d) and diagonal–diagonal (d-d), depending on how the networks orient and penetrate through each other (Zaworotko, 2001; Herbstein, 2001; Biradha et al., 2000). The majority of them, however, consist of two identical sets of two-dimensional parallel layers, spanning two different stacking directions. Only a limited number of networks have been found that contain more than two sets of differently oriented layers (Kondo et al., 2000; Carlucci, Ciani, Proserpio & Rizzato, 2003; Chen et al., 2006; Zhuang et al., 2007) since this possibility was first predicted (Batten & Robson, 1998).
Meanwhile, chiral units and homochiral interactions between them would be crucial to the synthesis of chiral interpenetrating structures through spontaneous resolution upon crystallization without any chiral auxiliary (Gao et al., 2004; Bai et al., 2005). 4,4'-Bipyridine (4,4'-bpy), which only possesses the ideal achiral geometry of D2h symmetry without any twist between the two pyridyl rings, would easily become chiral once if there were any twist in the molecule. This kind of ligand is a potential source of chiral units which may be induced into a chiral configuration by coordination bonds or hydrogen bonds (Cotton et al., 2003; Mukherjee et al., 2004). Here, we report the title coordination compound, [Ni(acc)2(4,4'-bpy)(H2O)2]n, (I) (H2acc is 4-carboxycinnamic acid), which features an unusual chiral three-dimensional threefold polycatenating network self-assembled from inclined interpenetration of two-dimensional (4,4) layer motifs.
Compound (I) crystallizes in the noncentrosymmetric hexagonal space group P32, and the asymmetric unit is composed of one NiII centre, one acc2− anion, one 4,4'-bpy molecule and two coordinated water molecules (Fig. 1). The NiII centre adopts an octahedral coordination geometry, with two carboxylate O atoms from different acc2− anions and two N atoms from two 4,4'-bpy ligands in the equatorial plane, and two aqua O atoms occupying the axial positions. The acc2− anion is significantly disordered (see below) and adopts a bis(monodentate) bridging mode, linking two NiII centres. The NiII centres are linked by acc2− anions and 4,4'-bpy ligands into a two-dimensional grid in the ac plane (Fig. 2), with dimensions of 13.49 (6) × 11.26 (2) Å based on the separation of the metal ions.
As expected, the large dimensions of these two-dimensional grids allow them to interpenetrate in an extensive and unusual fashion (Fig. 3a). Each two-dimensional grid interpenetrates two adjacent ones, and these three different sets are parallel to the crystallographic c axis, displaying relative rotations about this axis of 120° as required by the symmetry. This network is highly unusual in that the three stacking sheets occur along three coplanar directions, and the interlocking mode can be described as parallel–parallel–parallel (p-p-p) with the same `density of catenation' (2/2/2) (Carlucci, Ciani, Proserpio & Rizzato, 2003). Each grid is surrounded by four other grids to form triangular interspaces (Fig. 3b), in which the coordinated water molecules O5 and O6 form O—H···O hydrogen bonds with the uncoordinated carboxylate O atoms O4 and O2, respectively, resulting a right-handed helical chain (Fig. 4 and Table 2). These interactions, to some extent, stabilize the whole special interpenetration mode.
To the best of our knowledge, only a few compounds are known to contain three sets of (4,4) nets. The first two, [Pt(HL)2L2]·2H2O (HL is isonicotinic acid) and [Fe(bpb)2(NCS)2]·0.5MeOH [bpb is 1,4-bis(4-pyridyl)butadiyne], are both three-dimensional networks containing three sets of (4,4) layers stacked in three `perpendicular' directions (Aakeroy et al., 1999; Moliner et al., 2000). Structures with three sets in coplanar directions, however, were only reported very recently, namely [Ni(cpoa)(4,4'-bpy)(H2O)2] (H2cpoa is 4-carboxyphenoxy acetic acid; Chen et al., 2006), [Ni(L)(4,4'-bpy)(H2O)2] (H2L is trans,trans-muconic acid; Zhuang et al., 2007) and [Ni6(bpe)10(H2O)16](SO4)6.xH2O] [bpe is bis(4-pyridyl)ethane] (Carlucci, Ciani, Proserpio & Rizzato, 2003). The first two examples are very similar to (I), with the same three sets interpenetrating each other, while the third is different in that one rectangular net and two sets of square nets interpenetrate in inclined mode with the density of catenation of (2/4/4). The compound we report thus represents one of the very limited examples of a two-dimensional → three-dimensional polycatenating framework generated by inclined (4,4) nets.
Another fascinating feature of the title compound is the introduction of chirality into the structure by spontaneous resolution upon crystallization. The two pyridine rings of 4,4'-bpy are twisted out of the plane with a dihedral angle of 44.6 (5)°, nearly twice the twist seen in similar structures (Chen et al., 2006). The 4,4'-bpy ligand thus adopts a large twisted chiral configuration and introduces chirality into the NiII–4,4'-bpy chains, the two-dimensional homochiral sheets and finally the three-dimensional framework. Interactions between the 4,4'-bpy molecules of the different nets contribute to reinforcement of the three-dimensional framework. Two C—H groups (C14—H14 and C16—H16) in one pyridyl ring of the 4,4'-bpy in a given sheet have C—H···π interactions with the centroid Cg of the other pyridyl ring of a neighbouring sheet containing atom N2 (Fig. 5). The C···Cg distances and the C—H···Cg angle are in the ranges 3.76 (1)–3.77 (1) Å and 164.2 (7)–166.2 (7)°, respectively.