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The self-assembly of the title dinuclear complex, namely (μ-p-phenylenediamine-N,N,N′,N′-tetraacetato)bis[aqua(1,10-phenanthroline)nickel(II)] dodecahydrate, [Ni2(C14H12N2O8)(C12H8N2)2(H2O)2]·12H2O, through intricate noncovalent interactions results in a two-dimensional sheet-like structure. The dimer lies about an inversion centre at the centre of the p-phenylenediamine ring. Uncoordinated water molecules form one-dimensional chains in which cyclic water tetramers act as two types of building blocks. The water molecules play a significant role in the stabilization of the three-dimensional supramolecular framework. Intramolecular `aryl–metal chelate ring' π–π interactions are also observed.
Supporting information
CCDC reference: 651562
All reagents were commercial grade materials, used as received. H4dbta was obtained by the direct reaction of p-phenylenediamine with sodium chloroacetate in alkaline aqueous solution. Elemental analyses were determined on an Elementar Vario EL elemental analyser. IR spectra were measured as KBr pellets on a Perkin–Elmer spectrophotometer in the 4000–400 cm−1 region.
The detailed preparation of (I) is as follows. 1,10-Phenanthroline (1.5 mmol) and nickel nitrate (1 mmol) were dissolved in water (20 ml) and the solution was refluxed for 1.5 h. After filtration, the solution was added to H4dbta (0.5 mmol) in water (10 ml), and the mixture was refluxed for 4 h, filtered and left to stand at room temperature. Blue single crystals of (I) were obtained after 12 h (yield 48% based on Ni). Analysis, calculated for C38H56N6Ni2O22: C 42.80, H 5.29, N 7.88; found: C 43.11, H 5.44, N 7.86%. Selected IR frequencies (KBr, ν, cm−1): 3466 (vs), 3400 (vs), 1623 (s), 1519 (m), 1431 (m), 1385 (m), 1328 (m), 1272 (m), 1208 (m), 1151 (m), 906 (m), 871 (m), 858 (m).
H atoms attached to C atoms were placed in geometrically idealized positions, with Csp2—H = 0.93 Å and Csp3—H = 0.97 Å, and refined with Uiso(H) = 1.2Ueq(C). H atoms attached to O atoms were located in a difference Fourier map and refined as riding in their as-found positions, with Uiso(H) = 1.5Ueq(O). The O—H distances are in the range 0.762–0.853 Å.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).
µ-
p-phenylenediamine-
N,
N,
N',
N'-tetraacetato- bis[aqua(1,10-phenanthroline)nickel(II)]
top
Crystal data top
[Ni2(C14H12N2O8)(C12H8N2)2(H2O)2]·12H2O | Z = 1 |
Mr = 1066.31 | F(000) = 558 |
Triclinic, P1 | Dx = 1.506 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2082 (7) Å | Cell parameters from 645 reflections |
b = 10.3481 (7) Å | θ = 2.8–22.5° |
c = 12.4101 (8) Å | µ = 0.89 mm−1 |
α = 91.336 (1)° | T = 183 K |
β = 108.426 (1)° | Block, blue |
γ = 107.536 (1)° | 0.28 × 0.25 × 0.19 mm |
V = 1175.71 (14) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4092 independent reflections |
Radiation source: fine-focus sealed tube | 3613 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −12→9 |
Tmin = 0.777, Tmax = 0.849 | k = −12→12 |
6344 measured reflections | l = −11→14 |
Refinement top
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.1519P] where P = (Fo2 + 2Fc2)/3 |
4092 reflections | (Δ/σ)max = 0.002 |
307 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
[Ni2(C14H12N2O8)(C12H8N2)2(H2O)2]·12H2O | γ = 107.536 (1)° |
Mr = 1066.31 | V = 1175.71 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.2082 (7) Å | Mo Kα radiation |
b = 10.3481 (7) Å | µ = 0.89 mm−1 |
c = 12.4101 (8) Å | T = 183 K |
α = 91.336 (1)° | 0.28 × 0.25 × 0.19 mm |
β = 108.426 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4092 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3613 reflections with I > 2σ(I) |
Tmin = 0.777, Tmax = 0.849 | Rint = 0.016 |
6344 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.32 e Å−3 |
4092 reflections | Δρmin = −0.21 e Å−3 |
307 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Ni1 | 0.24698 (3) | 0.20513 (3) | 0.12975 (2) | 0.01974 (10) | |
N1 | 0.32658 (19) | 0.15431 (17) | 0.00485 (15) | 0.0219 (4) | |
N2 | 0.4609 (2) | 0.23217 (17) | 0.22986 (15) | 0.0235 (4) | |
N3 | 0.28895 (18) | 0.42482 (16) | 0.11306 (14) | 0.0192 (4) | |
O1 | 0.16863 (18) | 0.01076 (15) | 0.16068 (14) | 0.0357 (4) | |
H1A | 0.1019 | −0.0528 | 0.1110 | 0.054* | |
H1B | 0.2117 | −0.0241 | 0.2168 | 0.054* | |
O2 | 0.19289 (17) | 0.27094 (14) | 0.26139 (13) | 0.0274 (4) | |
O3 | 0.22254 (19) | 0.45257 (16) | 0.37774 (13) | 0.0341 (4) | |
O4 | 0.05353 (15) | 0.18899 (14) | 0.00605 (13) | 0.0246 (3) | |
O5 | −0.05917 (17) | 0.30612 (15) | −0.11608 (13) | 0.0308 (4) | |
O6 | 0.4096 (2) | 0.1036 (2) | 0.56415 (17) | 0.0563 (5) | |
H6A | 0.3846 | 0.1748 | 0.5657 | 0.084* | |
H6B | 0.3703 | 0.0569 | 0.4981 | 0.084* | |
O7 | 0.32015 (19) | 0.33440 (17) | 0.58451 (14) | 0.0418 (4) | |
H7A | 0.3020 | 0.3741 | 0.5250 | 0.063* | |
H7B | 0.2402 | 0.2901 | 0.5934 | 0.063* | |
O8 | 0.6859 (2) | 0.08154 (17) | 0.64381 (15) | 0.0436 (5) | |
H8A | 0.7474 | 0.1571 | 0.6416 | 0.065* | |
H8B | 0.6008 | 0.0858 | 0.6182 | 0.065* | |
O9 | 0.0137 (2) | 0.07804 (18) | 0.36227 (16) | 0.0479 (5) | |
H9A | 0.0706 | 0.1266 | 0.3312 | 0.072* | |
H9B | 0.0226 | 0.1223 | 0.4241 | 0.072* | |
O10 | 0.0444 (2) | 0.18741 (18) | 0.58790 (17) | 0.0511 (5) | |
H10A | 0.0230 | 0.1192 | 0.6106 | 0.077* | |
H10B | 0.0101 | 0.2348 | 0.6124 | 0.077* | |
O11 | 0.0946 (2) | 0.6558 (2) | 0.33375 (15) | 0.0507 (5) | |
H11A | 0.0699 | 0.6543 | 0.2611 | 0.076* | |
H11B | 0.1255 | 0.5888 | 0.3521 | 0.076* | |
C1 | 0.2576 (3) | 0.1115 (2) | −0.10633 (19) | 0.0283 (5) | |
H1 | 0.1545 | 0.0904 | −0.1356 | 0.034* | |
C2 | 0.3300 (3) | 0.0959 (2) | −0.1825 (2) | 0.0347 (6) | |
H2 | 0.2766 | 0.0649 | −0.2615 | 0.042* | |
C3 | 0.4774 (3) | 0.1258 (2) | −0.1417 (2) | 0.0370 (6) | |
H3 | 0.5280 | 0.1173 | −0.1925 | 0.044* | |
C4 | 0.5556 (3) | 0.1695 (2) | −0.0238 (2) | 0.0310 (5) | |
C5 | 0.4738 (2) | 0.1814 (2) | 0.04599 (19) | 0.0234 (5) | |
C6 | 0.5460 (2) | 0.2224 (2) | 0.16695 (19) | 0.0241 (5) | |
C7 | 0.7089 (3) | 0.1980 (2) | 0.0271 (3) | 0.0390 (6) | |
H7 | 0.7642 | 0.1897 | −0.0199 | 0.047* | |
C8 | 0.7774 (3) | 0.2367 (2) | 0.1409 (3) | 0.0430 (7) | |
H8 | 0.8800 | 0.2554 | 0.1723 | 0.052* | |
C9 | 0.6977 (3) | 0.2500 (2) | 0.2152 (2) | 0.0334 (6) | |
C10 | 0.7605 (3) | 0.2873 (3) | 0.3340 (3) | 0.0467 (7) | |
H10 | 0.8626 | 0.3068 | 0.3707 | 0.056* | |
C11 | 0.6743 (3) | 0.2954 (3) | 0.3970 (2) | 0.0489 (8) | |
H11 | 0.7161 | 0.3202 | 0.4777 | 0.059* | |
C12 | 0.5249 (3) | 0.2671 (2) | 0.34218 (19) | 0.0339 (6) | |
H12 | 0.4663 | 0.2730 | 0.3871 | 0.041* | |
C13 | 0.3969 (2) | 0.46920 (19) | 0.05752 (17) | 0.0187 (4) | |
C14 | 0.5453 (2) | 0.5237 (2) | 0.11799 (17) | 0.0207 (4) | |
H14 | 0.5781 | 0.5414 | 0.1992 | 0.025* | |
C15 | 0.3537 (2) | 0.4473 (2) | −0.06187 (17) | 0.0203 (4) | |
H15 | 0.2526 | 0.4117 | −0.1056 | 0.024* | |
C16 | 0.3298 (2) | 0.4904 (2) | 0.23157 (18) | 0.0238 (5) | |
H16A | 0.3121 | 0.5793 | 0.2297 | 0.029* | |
H16B | 0.4351 | 0.5075 | 0.2724 | 0.029* | |
C17 | 0.2402 (2) | 0.3983 (2) | 0.29523 (18) | 0.0248 (5) | |
C18 | 0.1443 (2) | 0.4323 (2) | 0.04394 (18) | 0.0220 (5) | |
H18A | 0.1586 | 0.5043 | −0.0064 | 0.026* | |
H18B | 0.0991 | 0.4604 | 0.0963 | 0.026* | |
C19 | 0.0392 (2) | 0.2997 (2) | −0.02968 (18) | 0.0222 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.02224 (16) | 0.01726 (15) | 0.01987 (16) | 0.00570 (11) | 0.00798 (11) | 0.00295 (10) |
N1 | 0.0267 (10) | 0.0170 (9) | 0.0226 (9) | 0.0081 (7) | 0.0084 (8) | 0.0021 (7) |
N2 | 0.0286 (10) | 0.0185 (9) | 0.0219 (10) | 0.0081 (8) | 0.0060 (8) | 0.0027 (7) |
N3 | 0.0211 (9) | 0.0172 (8) | 0.0189 (9) | 0.0040 (7) | 0.0085 (7) | 0.0024 (7) |
O1 | 0.0433 (10) | 0.0193 (8) | 0.0304 (9) | 0.0018 (7) | 0.0014 (8) | 0.0064 (7) |
O2 | 0.0370 (9) | 0.0211 (8) | 0.0302 (9) | 0.0075 (7) | 0.0212 (7) | 0.0060 (6) |
O3 | 0.0532 (11) | 0.0329 (9) | 0.0276 (9) | 0.0188 (8) | 0.0240 (8) | 0.0061 (7) |
O4 | 0.0218 (8) | 0.0181 (7) | 0.0295 (8) | 0.0042 (6) | 0.0050 (7) | 0.0025 (6) |
O5 | 0.0270 (9) | 0.0313 (9) | 0.0288 (9) | 0.0096 (7) | 0.0021 (7) | 0.0051 (7) |
O6 | 0.0590 (13) | 0.0688 (14) | 0.0498 (12) | 0.0335 (11) | 0.0182 (10) | 0.0038 (10) |
O7 | 0.0396 (11) | 0.0455 (11) | 0.0351 (10) | 0.0105 (8) | 0.0085 (8) | 0.0095 (8) |
O8 | 0.0428 (11) | 0.0412 (10) | 0.0428 (11) | 0.0158 (9) | 0.0066 (9) | 0.0119 (8) |
O9 | 0.0554 (12) | 0.0402 (10) | 0.0474 (11) | 0.0016 (9) | 0.0297 (10) | 0.0087 (9) |
O10 | 0.0653 (13) | 0.0432 (11) | 0.0669 (13) | 0.0231 (10) | 0.0462 (11) | 0.0177 (10) |
O11 | 0.0756 (14) | 0.0608 (12) | 0.0300 (10) | 0.0444 (11) | 0.0158 (10) | 0.0086 (9) |
C1 | 0.0382 (14) | 0.0205 (11) | 0.0239 (12) | 0.0072 (10) | 0.0097 (10) | 0.0009 (9) |
C2 | 0.0563 (17) | 0.0241 (12) | 0.0251 (12) | 0.0095 (11) | 0.0190 (12) | 0.0019 (10) |
C3 | 0.0594 (18) | 0.0249 (12) | 0.0416 (15) | 0.0156 (12) | 0.0349 (14) | 0.0100 (11) |
C4 | 0.0412 (14) | 0.0175 (11) | 0.0454 (15) | 0.0126 (10) | 0.0259 (12) | 0.0108 (10) |
C5 | 0.0290 (12) | 0.0138 (10) | 0.0317 (12) | 0.0086 (9) | 0.0140 (10) | 0.0059 (9) |
C6 | 0.0263 (12) | 0.0145 (10) | 0.0333 (13) | 0.0082 (9) | 0.0106 (10) | 0.0076 (9) |
C7 | 0.0379 (15) | 0.0289 (13) | 0.0657 (19) | 0.0151 (11) | 0.0337 (14) | 0.0147 (12) |
C8 | 0.0261 (13) | 0.0310 (13) | 0.079 (2) | 0.0136 (11) | 0.0220 (14) | 0.0163 (14) |
C9 | 0.0265 (13) | 0.0221 (12) | 0.0493 (16) | 0.0105 (10) | 0.0068 (11) | 0.0092 (11) |
C10 | 0.0294 (15) | 0.0433 (16) | 0.0547 (18) | 0.0132 (12) | −0.0041 (13) | 0.0069 (13) |
C11 | 0.0506 (18) | 0.0470 (16) | 0.0308 (15) | 0.0154 (14) | −0.0098 (13) | 0.0018 (12) |
C12 | 0.0424 (15) | 0.0339 (13) | 0.0222 (12) | 0.0147 (11) | 0.0047 (11) | 0.0040 (10) |
C13 | 0.0213 (11) | 0.0135 (10) | 0.0232 (11) | 0.0043 (8) | 0.0110 (9) | 0.0046 (8) |
C14 | 0.0238 (11) | 0.0185 (10) | 0.0171 (10) | 0.0044 (9) | 0.0056 (9) | 0.0025 (8) |
C15 | 0.0180 (11) | 0.0186 (10) | 0.0201 (11) | 0.0025 (8) | 0.0040 (9) | 0.0030 (8) |
C16 | 0.0288 (12) | 0.0198 (10) | 0.0231 (11) | 0.0045 (9) | 0.0127 (9) | 0.0002 (9) |
C17 | 0.0290 (12) | 0.0273 (12) | 0.0223 (12) | 0.0129 (10) | 0.0106 (10) | 0.0050 (9) |
C18 | 0.0228 (11) | 0.0197 (10) | 0.0267 (12) | 0.0082 (9) | 0.0110 (9) | 0.0049 (9) |
C19 | 0.0199 (11) | 0.0255 (11) | 0.0241 (12) | 0.0072 (9) | 0.0114 (10) | 0.0032 (9) |
Geometric parameters (Å, º) top
Ni1—O1 | 2.0232 (15) | C1—H1 | 0.9500 |
Ni1—O4 | 2.0389 (14) | C2—C3 | 1.360 (4) |
Ni1—O2 | 2.0452 (15) | C2—H2 | 0.9500 |
Ni1—N2 | 2.0718 (18) | C3—C4 | 1.412 (3) |
Ni1—N1 | 2.0869 (18) | C3—H3 | 0.9500 |
Ni1—N3 | 2.2104 (16) | C4—C5 | 1.406 (3) |
N1—C1 | 1.329 (3) | C4—C7 | 1.422 (4) |
N1—C5 | 1.361 (3) | C5—C6 | 1.435 (3) |
N2—C12 | 1.326 (3) | C6—C9 | 1.407 (3) |
N2—C6 | 1.360 (3) | C7—C8 | 1.351 (4) |
N3—C13 | 1.445 (3) | C7—H7 | 0.9500 |
N3—C16 | 1.481 (3) | C8—C9 | 1.438 (4) |
N3—C18 | 1.482 (3) | C8—H8 | 0.9500 |
O1—H1A | 0.8499 | C9—C10 | 1.400 (4) |
O1—H1B | 0.8499 | C10—C11 | 1.367 (4) |
O2—C17 | 1.268 (3) | C10—H10 | 0.9500 |
O3—C17 | 1.244 (3) | C11—C12 | 1.393 (4) |
O4—C19 | 1.270 (2) | C11—H11 | 0.9500 |
O5—C19 | 1.235 (3) | C12—H12 | 0.9500 |
O6—H6A | 0.8501 | C13—C14 | 1.387 (3) |
O6—H6B | 0.8502 | C13—C15 | 1.397 (3) |
O7—H7A | 0.8500 | C14—C15i | 1.384 (3) |
O7—H7B | 0.8500 | C14—H14 | 0.9500 |
O8—H8A | 0.8499 | C15—C14i | 1.384 (3) |
O8—H8B | 0.8409 | C15—H15 | 0.9500 |
O9—H9A | 0.8447 | C16—C17 | 1.528 (3) |
O9—H9B | 0.8492 | C16—H16A | 0.9900 |
O10—H10A | 0.7615 | C16—H16B | 0.9900 |
O10—H10B | 0.7868 | C18—C19 | 1.518 (3) |
O11—H11A | 0.8543 | C18—H18A | 0.9900 |
O11—H11B | 0.8520 | C18—H18B | 0.9900 |
C1—C2 | 1.405 (3) | | |
| | | |
O1—Ni1—O4 | 91.80 (6) | N1—C5—C6 | 117.14 (19) |
O1—Ni1—O2 | 88.91 (6) | C4—C5—C6 | 119.7 (2) |
O4—Ni1—O2 | 95.11 (6) | N2—C6—C9 | 123.1 (2) |
O1—Ni1—N2 | 94.61 (7) | N2—C6—C5 | 116.90 (19) |
O4—Ni1—N2 | 168.58 (7) | C9—C6—C5 | 120.0 (2) |
O2—Ni1—N2 | 94.45 (7) | C8—C7—C4 | 121.4 (2) |
O1—Ni1—N1 | 95.16 (7) | C8—C7—H7 | 119.3 |
O4—Ni1—N1 | 90.10 (6) | C4—C7—H7 | 119.3 |
O2—Ni1—N1 | 173.29 (6) | C7—C8—C9 | 121.1 (2) |
N2—Ni1—N1 | 79.93 (7) | C7—C8—H8 | 119.4 |
O1—Ni1—N3 | 165.10 (7) | C9—C8—H8 | 119.4 |
O4—Ni1—N3 | 82.02 (6) | C10—C9—C6 | 117.0 (2) |
O2—Ni1—N3 | 78.22 (6) | C10—C9—C8 | 124.4 (2) |
N2—Ni1—N3 | 93.85 (6) | C6—C9—C8 | 118.6 (2) |
N1—Ni1—N3 | 98.38 (6) | C11—C10—C9 | 119.7 (2) |
C1—N1—C5 | 117.81 (19) | C11—C10—H10 | 120.2 |
C1—N1—Ni1 | 129.74 (16) | C9—C10—H10 | 120.2 |
C5—N1—Ni1 | 112.21 (14) | C10—C11—C12 | 119.6 (3) |
C12—N2—C6 | 117.9 (2) | C10—C11—H11 | 120.2 |
C12—N2—Ni1 | 128.95 (17) | C12—C11—H11 | 120.2 |
C6—N2—Ni1 | 112.91 (14) | N2—C12—C11 | 122.7 (3) |
C13—N3—C16 | 116.41 (16) | N2—C12—H12 | 118.6 |
C13—N3—C18 | 112.93 (16) | C11—C12—H12 | 118.6 |
C16—N3—C18 | 109.21 (16) | C14—C13—C15 | 117.39 (19) |
C13—N3—Ni1 | 109.17 (12) | C14—C13—N3 | 122.72 (18) |
C16—N3—Ni1 | 104.08 (12) | C15—C13—N3 | 119.68 (18) |
C18—N3—Ni1 | 103.94 (11) | C15i—C14—C13 | 121.04 (19) |
Ni1—O1—H1A | 124.1 | C15i—C14—H14 | 119.5 |
Ni1—O1—H1B | 124.7 | C13—C14—H14 | 119.5 |
H1A—O1—H1B | 109.1 | C14i—C15—C13 | 121.56 (19) |
C17—O2—Ni1 | 117.66 (14) | C14i—C15—H15 | 119.2 |
C19—O4—Ni1 | 116.21 (13) | C13—C15—H15 | 119.2 |
H6A—O6—H6B | 111.7 | N3—C16—C17 | 110.22 (16) |
H7A—O7—H7B | 109.1 | N3—C16—H16A | 109.6 |
H8A—O8—H8B | 110.0 | C17—C16—H16A | 109.6 |
H9A—O9—H9B | 109.7 | N3—C16—H16B | 109.6 |
H10A—O10—H10B | 106.7 | C17—C16—H16B | 109.6 |
H11A—O11—H11B | 108.5 | H16A—C16—H16B | 108.1 |
N1—C1—C2 | 123.0 (2) | O3—C17—O2 | 125.0 (2) |
N1—C1—H1 | 118.5 | O3—C17—C16 | 118.07 (19) |
C2—C1—H1 | 118.5 | O2—C17—C16 | 116.94 (18) |
C3—C2—C1 | 119.1 (2) | N3—C18—C19 | 114.48 (16) |
C3—C2—H2 | 120.5 | N3—C18—H18A | 108.6 |
C1—C2—H2 | 120.5 | C19—C18—H18A | 108.6 |
C2—C3—C4 | 120.1 (2) | N3—C18—H18B | 108.6 |
C2—C3—H3 | 119.9 | C19—C18—H18B | 108.6 |
C4—C3—H3 | 119.9 | H18A—C18—H18B | 107.6 |
C5—C4—C3 | 116.8 (2) | O5—C19—O4 | 124.43 (19) |
C5—C4—C7 | 119.2 (2) | O5—C19—C18 | 118.16 (18) |
C3—C4—C7 | 124.0 (2) | O4—C19—C18 | 117.26 (18) |
N1—C5—C4 | 123.2 (2) | | |
| | | |
O1—Ni1—N1—C1 | 83.81 (18) | C3—C4—C5—N1 | −0.6 (3) |
O4—Ni1—N1—C1 | −8.01 (18) | C7—C4—C5—N1 | −179.04 (19) |
N2—Ni1—N1—C1 | 177.59 (19) | C3—C4—C5—C6 | 178.64 (18) |
N3—Ni1—N1—C1 | −89.96 (18) | C7—C4—C5—C6 | 0.2 (3) |
O1—Ni1—N1—C5 | −102.05 (14) | C12—N2—C6—C9 | −1.3 (3) |
O4—Ni1—N1—C5 | 166.13 (14) | Ni1—N2—C6—C9 | 173.70 (16) |
N2—Ni1—N1—C5 | −8.27 (13) | C12—N2—C6—C5 | 178.59 (18) |
N3—Ni1—N1—C5 | 84.18 (14) | Ni1—N2—C6—C5 | −6.5 (2) |
O1—Ni1—N2—C12 | −83.36 (19) | N1—C5—C6—N2 | −0.7 (3) |
O4—Ni1—N2—C12 | 152.7 (3) | C4—C5—C6—N2 | 179.95 (18) |
O2—Ni1—N2—C12 | 5.90 (19) | N1—C5—C6—C9 | 179.10 (18) |
N1—Ni1—N2—C12 | −177.8 (2) | C4—C5—C6—C9 | −0.2 (3) |
N3—Ni1—N2—C12 | 84.36 (19) | C5—C4—C7—C8 | −0.2 (3) |
O1—Ni1—N2—C6 | 102.38 (14) | C3—C4—C7—C8 | −178.5 (2) |
O4—Ni1—N2—C6 | −21.6 (4) | C4—C7—C8—C9 | 0.3 (4) |
O2—Ni1—N2—C6 | −168.37 (14) | N2—C6—C9—C10 | 0.9 (3) |
N1—Ni1—N2—C6 | 7.94 (13) | C5—C6—C9—C10 | −178.9 (2) |
N3—Ni1—N2—C6 | −89.90 (14) | N2—C6—C9—C8 | −179.96 (19) |
O1—Ni1—N3—C13 | −174.9 (2) | C5—C6—C9—C8 | 0.2 (3) |
O4—Ni1—N3—C13 | −108.65 (13) | C7—C8—C9—C10 | 178.8 (2) |
O2—Ni1—N3—C13 | 154.40 (13) | C7—C8—C9—C6 | −0.2 (3) |
N2—Ni1—N3—C13 | 60.64 (13) | C6—C9—C10—C11 | −0.1 (4) |
N1—Ni1—N3—C13 | −19.73 (13) | C8—C9—C10—C11 | −179.2 (2) |
O1—Ni1—N3—C16 | 60.2 (3) | C9—C10—C11—C12 | −0.3 (4) |
O4—Ni1—N3—C16 | 126.42 (13) | C6—N2—C12—C11 | 0.8 (3) |
O2—Ni1—N3—C16 | 29.46 (13) | Ni1—N2—C12—C11 | −173.18 (18) |
N2—Ni1—N3—C16 | −64.29 (13) | C10—C11—C12—N2 | −0.1 (4) |
N1—Ni1—N3—C16 | −144.67 (13) | C16—N3—C13—C14 | 25.5 (3) |
O1—Ni1—N3—C18 | −54.1 (3) | C18—N3—C13—C14 | 153.00 (18) |
O4—Ni1—N3—C18 | 12.10 (12) | Ni1—N3—C13—C14 | −91.91 (19) |
O2—Ni1—N3—C18 | −84.86 (13) | C16—N3—C13—C15 | −159.83 (18) |
N2—Ni1—N3—C18 | −178.61 (13) | C18—N3—C13—C15 | −32.3 (2) |
N1—Ni1—N3—C18 | 101.02 (13) | Ni1—N3—C13—C15 | 82.77 (18) |
O1—Ni1—O2—C17 | 169.24 (16) | C15—C13—C14—C15i | −1.2 (3) |
O4—Ni1—O2—C17 | −99.04 (16) | N3—C13—C14—C15i | 173.65 (18) |
N2—Ni1—O2—C17 | 74.70 (16) | C14—C13—C15—C14i | 1.2 (3) |
N3—Ni1—O2—C17 | −18.31 (15) | N3—C13—C15—C14i | −173.81 (18) |
O1—Ni1—O4—C19 | 168.62 (15) | C13—N3—C16—C17 | −156.71 (17) |
O2—Ni1—O4—C19 | 79.55 (15) | C18—N3—C16—C17 | 74.0 (2) |
N2—Ni1—O4—C19 | −67.2 (4) | Ni1—N3—C16—C17 | −36.54 (19) |
N1—Ni1—O4—C19 | −96.21 (15) | Ni1—O2—C17—O3 | −176.24 (17) |
N3—Ni1—O4—C19 | 2.24 (15) | Ni1—O2—C17—C16 | 1.7 (2) |
C5—N1—C1—C2 | −1.3 (3) | N3—C16—C17—O3 | −155.87 (19) |
Ni1—N1—C1—C2 | 172.56 (15) | N3—C16—C17—O2 | 26.1 (3) |
N1—C1—C2—C3 | −0.1 (3) | C13—N3—C18—C19 | 94.7 (2) |
C1—C2—C3—C4 | 1.1 (3) | C16—N3—C18—C19 | −134.06 (18) |
C2—C3—C4—C5 | −0.8 (3) | Ni1—N3—C18—C19 | −23.46 (19) |
C2—C3—C4—C7 | 177.5 (2) | Ni1—O4—C19—O5 | 167.57 (17) |
C1—N1—C5—C4 | 1.7 (3) | Ni1—O4—C19—C18 | −16.9 (2) |
Ni1—N1—C5—C4 | −173.25 (15) | N3—C18—C19—O5 | −155.30 (19) |
C1—N1—C5—C6 | −177.62 (18) | N3—C18—C19—O4 | 28.9 (3) |
Ni1—N1—C5—C6 | 7.5 (2) | | |
Symmetry code: (i) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O5ii | 0.85 | 1.83 | 2.665 (2) | 164 |
O11—H11B···O3 | 0.85 | 1.93 | 2.772 (2) | 169 |
O10—H10A···O9iii | 0.76 | 2.02 | 2.758 (3) | 164 |
O10—H10B···O11iv | 0.79 | 2.00 | 2.789 (3) | 175 |
O9—H9B···O10 | 0.85 | 2.05 | 2.882 (3) | 167 |
O9—H9A···O2 | 0.84 | 2.04 | 2.874 (2) | 170 |
O8—H8A···O11v | 0.85 | 2.05 | 2.896 (3) | 170 |
O8—H8B···O6 | 0.84 | 1.92 | 2.761 (3) | 177 |
O7—H7A···O3 | 0.85 | 2.05 | 2.887 (2) | 170 |
O7—H7B···O10 | 0.85 | 1.94 | 2.781 (3) | 171 |
O6—H6B···O8vi | 0.85 | 2.06 | 2.887 (3) | 165 |
O6—H6A···O7 | 0.85 | 1.99 | 2.834 (3) | 174 |
O1—H1B···O8vi | 0.85 | 1.93 | 2.773 (2) | 173 |
O1—H1A···O5vii | 0.85 | 2.53 | 3.102 (2) | 126 |
O1—H1A···O4vii | 0.85 | 1.93 | 2.776 (2) | 177 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1; (vii) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Ni2(C14H12N2O8)(C12H8N2)2(H2O)2]·12H2O |
Mr | 1066.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 10.2082 (7), 10.3481 (7), 12.4101 (8) |
α, β, γ (°) | 91.336 (1), 108.426 (1), 107.536 (1) |
V (Å3) | 1175.71 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.28 × 0.25 × 0.19 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.777, 0.849 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6344, 4092, 3613 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.083, 1.06 |
No. of reflections | 4092 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.21 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O5i | 0.85 | 1.83 | 2.665 (2) | 164 |
O11—H11B···O3 | 0.85 | 1.93 | 2.772 (2) | 169 |
O10—H10A···O9ii | 0.76 | 2.02 | 2.758 (3) | 164 |
O10—H10B···O11iii | 0.79 | 2.00 | 2.789 (3) | 175 |
O9—H9B···O10 | 0.85 | 2.05 | 2.882 (3) | 167 |
O9—H9A···O2 | 0.84 | 2.04 | 2.874 (2) | 170 |
O8—H8A···O11iv | 0.85 | 2.05 | 2.896 (3) | 170 |
O8—H8B···O6 | 0.84 | 1.92 | 2.761 (3) | 177 |
O7—H7A···O3 | 0.85 | 2.05 | 2.887 (2) | 170 |
O7—H7B···O10 | 0.85 | 1.94 | 2.781 (3) | 171 |
O6—H6B···O8v | 0.85 | 2.06 | 2.887 (3) | 165 |
O6—H6A···O7 | 0.85 | 1.99 | 2.834 (3) | 174 |
O1—H1B···O8v | 0.85 | 1.93 | 2.773 (2) | 173 |
O1—H1A···O5vi | 0.85 | 2.53 | 3.102 (2) | 126 |
O1—H1A···O4vi | 0.85 | 1.93 | 2.776 (2) | 177 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) −x, −y, −z. |
Geometry of hydrogen bonds in the water chain (Å, °) topD-H···A | D-H | H···A | D···A | D-H···A |
O6-H6A···O7 | 0.85 | 1.99 | 2.834 (3) | 174 |
O7-H7B···O10 | 0.85 | 1.94 | 2.781 (3) | 171 |
O8-H8A···O11i | 0.85 | 2.05 | 2.896 (3) | 170 |
O8-H8B···O6 | 0.84 | 1.92 | 2.761 (3) | 177 |
O9-H9B···O10 | 0.85 | 2.05 | 2.882 (3) | 167 |
O10-H10A···O9ii | 0.76 | 2.02 | 2.758 (3) | 164 |
O10-H10B···O11iii | 0.79 | 2.00 | 2.789 (3) | 175 |
O6-H6B···O8iv | 0.85 | 2.06 | 2.887 (3) | 165 |
Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x, −y, −z + 1; (iii) −x, −y + 1, −z + 1; (iv) −x + 1, −y, −z + 1. |
Geometry of hydrogen bonds between the water chain and adjacent sheet (Å, °) topD-H···A | D-H | H···A | D···A | D-H···A |
O1-H1B···O8i | 0.85 | 1.93 | 2.773 (2) | 173 |
O7-H7A···O3 | 0.85 | 2.05 | 2.887 (2) | 170 |
O9-H9A···O2 | 0.84 | 2.04 | 2.874 (3) | 170 |
O11-H11B···O3 | 0.85 | 1.93 | 2.772 (2) | 169 |
O11-H11A···O5ii | 0.85 | 1.83 | 2.665 (2) | 164 |
Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x, −y + 1, −z. |
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Water is one of the most challenging targets in biology and chemistry. In these fields, intense study is currently devoted to a variety of water clusters and low-dimensional polymeric water/ice assemblies (Chacko & Saenger, 1981; Ludwig & Appelhagen, 2005; Moorthy et al., 2002; Wei et al., 2006; Zabel et al., 1986). The number of different water clusters, including dimer (Chand & Bharadwaj, 1998; Manikumari et al., 2002), tetramer (Beobide et al., 2006; Lakshminarayanan et al., 2005; Supriya & Das, 2003), pentamer (Infantes & Motherwell, 2002; Ma et al., 2004a), hexamer (Zhang, Fang & Wu et al., 2005), octamer (Atwood et al., 2001; Blanton et al., 1999), decamer (Barbour et al., 2000, 1998), dodecamer (Neogi et al., 2004), tetradecamer (Ghosh et al., 2005), hexadecamer (Ghosh & Bharadwaj, 2004) and octadecamer (Raghuraman et al., 2003), and infinite one- (Neogi & Bharadwaj, 2005) and two-dimensional (Janiak & Scharman, 2002; Ma et al., 2004b; Zhang, Lin, Huang & Chen, 2005) polymers, has increased dramatically in the past decade. Crystal engineering provides a powerful tool to reveal the nature of the interactions between water molecules. Investigation suggests that the water molecule is one of the key factors in the formation of organic or metal–organic supramolecular frameworks in which water molecules are encapsulated as guests. The work presented here reports the structural architectural system of hydrogen bonding and π–π stacking interactions which assemble the title complex, [Ni2(dbta)(phen)2(H2O)2].12H2O, (I), in which interesting polymeric water chains are found.
Compound (I) consists of two NiII cations, two 1,10-phenanthroline (phen) ligands, one p-phenylenediamine-N,N,N',N'-tetraacetate (dbta) ligand, two coordinated water molecules and 12 uncoordinated solvent water molecules. Each metal ion is six-coordinated in a slightly distorted octahedral geometry, with equatorial coordination by two carboxylate O atoms from dbta and two N atoms from phen. The axial sites are occupied by an aqua O atom and an N atom from dbta (Table 1).
The complex displays a zigzag-like shape (Fig. 1). In this arrangement, the phenyl ring of dbta is fixed between two phen rings, similar to the mixed-ligand Ni or Co complexes (Hao, Li, Chen & Zhang, 2006; Hao, Li, Chen, Zhang et al., 2006). The dimer is symmetrical. The centroid-to-centroid distance between the Ni–(N-heterocyclic) chelate ring and the phenyl ring is 3.45 Å and the dihedral angle between the planes of these rings is 19.3°. These parameters suggest that there are intramolecular `metal-chelate ring–aromatic ring' π–π interactions. These structural features can be viewed as evidence of metalloaromaticity (Castiñeiras et al., 2002; Masui, 2001). Weak intra- and intermolecular π–π stacking interactions between phenyl rings (3.53–3.69 Å) (Fig. 2), accompanied by double hydrogen bonds between the coordinated water molecule and a carboxylate O atom of an adjacent complex [O1···O4(−x, −y, −z) = 2.776 (2) Å and O1—H1A···O4 176.63°], connect the complexes to form a two-dimensional sheet.
Uncoordinated solvent water molecules are trapped in the host framework as infinite parallel chains. A closer view of the water chain is depicted in Fig. 3, and important bond distances and angles related to the water chain are given in Table 2. The primary parts of chain are two tetrameric cyclic rings formed by atoms O6 and O8 and their symmetry-related atoms O6i and O8i (ring A), and by atoms O9 and O10 and their symmetry-related atoms O9iii and O10iii (ring B). It is interesting that the cyclic water tetramer can provide a model for understanding liquid water and ice in theoretical and experimental studies (Ludwig, 2001; Herbert & Head-Gordon, 2006). The H and O atoms involved in these rings are almost coplanar. The configurations of the cyclic water tetramers, rings A and B, are uudd (Long et al., 2004; Ugalde et al., 2000). For ring A, the H atoms on atoms O6 and O8 not included in the ring are 0.43 and 0.76 Å above the ring, respectively, while the H atoms of atoms O6i and O8i are 0.43 and 0.76 Å below the ring, respectively. For ring B, the H atoms on atoms O9 and O10iii are 0.46 and 0.40 Å above the ring, respectively, while the H atoms on atoms O9iii and O10 are 0.46 and 0.40 Å below the ring, respectively. In the ring, each water molecule acts as both hydrogen-bond donor and acceptor. Water molecules containing atoms O8, O10 and O11 are tetrahedrally connected by means of four hydrogen-bonding interactions and atoms O6, O7 and O9 are involved in three hydrogen bonds. As a building block, the planar water tetramer ring A exhibits a side-linking pattern and ring B exhibits a diagonal-linking pattern. Atoms O7 and O11iv bridge rings A and B to form a chain via hydrogen bonds [O6···O7 = 2.834 (3) Å and O6—H6A···O7 = 173.63°; O7···O10 = 2.781 (3) Å and O7—H7B···O10 = 171.02°; O8i···O11iv = 2.896 (3) Å and O8i—H8Ai···O11iv = 170.14°; O10iii···O11iv = 2.789 (3) Å and O10iii—H10iiiB···O11iv = 174.92°; for symmetry codes, see the caption to Fig. 3].
The water chains are gathered between the two-dimensional sheets by means of hydrogen bonds involving the coordinated water and the dbta ligand O atoms (Fig. 4, Table 3).
The broad IR band of (I) centred around 3466 and 3400 cm−1 can be attributed to the O—H stretching frequency of the coordinated water molecules and water tetramer (Zuhayra et al., 2006).