Acta Cryst. (2009). E65, m535-m536 [ doi:10.1107/S1600536809013580 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-hydroxido-bis[(di-2-pyridylamine)nickel(II)]]--fumarato] dihydrate]The NiII ion in the one-dimensional title complex, {[Ni2(C4H2O4)(OH)2(C10H9N3)2]·2H2O}n, has a distorted square-pyramidal coordination environment formed by three O atoms from two bridging hydroxide groups and one carboxylate group of the fumarate ligand and two pyridine N atoms from a di-2-pyridylamine (dpa) ligand. Two hydroxide groups link adjacent metal centers, forming a centrosymmetric four-membered [Ni2(OH)2] ring. In the crystal structure, the H atoms of the bridging hydroxide groups form intermolecular hydrogen bonds to both water molecules. These are further linked to the uncoordinated O atoms of the carboxylate groups and the NH group of a dpa ligand to generate a three-dimensional network from the chains of the coordination polymer.
Dpa (0.20 mg,0.1 mmol), Ni(CH3COO)2 (0.28 mg, 0.12 mmol) and Na2fum (0.22 mg, 0.09 mmol), were added to a mixture (12 mL) of methanol and acetonitrile (V/V=1:5). The solution was heated and stirred for two hours and was then kept at room temperature yielding green, block-like crystals over two weeks.
All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (ring) or N—H– 0.86 Å with Uiso(H) = 1.2Ueq. H atoms of water molecule and hydroxyl group were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.83 (1) Å) with Uiso(H) = 1.5Ueq(O).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./sj2613fig1thm.gif)
| Fig. 1. Part of the structure of the title compound showing the atom-labeling scheme [symmetry codes: (i) -x, -y, -z + 2]. Displacement ellipsoids are shown at the 30% probability level. |
![[Figure 2]](./sj2613fig2thm.gif)
| Fig. 2. Partial packing diagram showing the formation of the one-dimensional zigzag chain. |
| [Ni2(C4H2O4)(OH)2(C10H9N3)2]·2H2O | Z = 1 |
| Mr = 643.92 | F(000) = 332 |
| Triclinic, P1 | Dx = 1.686 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.135 (2) Å | Cell parameters from 2216 reflections |
| b = 8.834 (3) Å | θ = 2.2–25.1° |
| c = 10.015 (3) Å | µ = 1.55 mm−1 |
| α = 70.545 (4)° | T = 298 K |
| β = 71.103 (4)° | Block, green |
| γ = 75.785 (4)° | 0.22 × 0.18 × 0.12 mm |
| V = 634.3 (3) Å3 |
| Bruker APEXII area-detector diffractometer | 2216 independent reflections |
| Radiation source: fine-focus sealed tube | 1984 reflections with I > 2σ(I) |
| graphite | Rint = 0.014 |
| φ and ω scans | θmax = 25.1°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −9→9 |
| Tmin = 0.727, Tmax = 0.836 | k = −10→9 |
| 3238 measured reflections | l = −11→11 |
| 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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.95 | w = 1/[σ2(Fo2) + (0.0374P)2 + 0.2972P] where P = (Fo2 + 2Fc2)/3 |
| 2216 reflections | (Δ/σ)max = 0.001 |
| 190 parameters | Δρmax = 0.30 e Å−3 |
| 4 restraints | Δρmin = −0.35 e Å−3 |
| [Ni2(C4H2O4)(OH)2(C10H9N3)2]·2H2O | γ = 75.785 (4)° |
| Mr = 643.92 | V = 634.3 (3) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 8.135 (2) Å | Mo Kα radiation |
| b = 8.834 (3) Å | µ = 1.55 mm−1 |
| c = 10.015 (3) Å | T = 298 K |
| α = 70.545 (4)° | 0.22 × 0.18 × 0.12 mm |
| β = 71.103 (4)° |
| Bruker APEXII area-detector diffractometer | 2216 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1984 reflections with I > 2σ(I) |
| Tmin = 0.727, Tmax = 0.836 | Rint = 0.014 |
| 3238 measured reflections | θmax = 25.1° |
| R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.063 | Δρmax = 0.30 e Å−3 |
| S = 0.95 | Δρmin = −0.35 e Å−3 |
| 2216 reflections | Absolute structure: ? |
| 190 parameters | Flack parameter: ? |
| 4 restraints | Rogers parameter: ? |
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 | ||
| Ni1 | 0.04021 (3) | 0.15037 (3) | 0.87985 (3) | 0.02129 (10) | |
| N1 | −0.0829 (2) | 0.3069 (2) | 0.73316 (19) | 0.0298 (4) | |
| N2 | −0.0529 (2) | 0.5376 (2) | 0.7868 (2) | 0.0345 (4) | |
| H2B | −0.1179 | 0.6218 | 0.8116 | 0.041* | |
| N3 | 0.1739 (2) | 0.3286 (2) | 0.85495 (19) | 0.0287 (4) | |
| O1 | 0.2311 (2) | 0.0443 (2) | 0.70594 (17) | 0.0452 (4) | |
| C12 | 0.5204 (3) | −0.0107 (3) | 0.5612 (2) | 0.0325 (5) | |
| H12 | 0.6387 | −0.0250 | 0.5576 | 0.039* | |
| O1W | 0.1972 (2) | 0.1399 (2) | 0.22330 (18) | 0.0381 (4) | |
| O4 | 0.13677 (18) | −0.00305 (18) | 1.03993 (15) | 0.0272 (3) | |
| C1 | −0.1404 (3) | 0.2457 (3) | 0.6520 (2) | 0.0369 (5) | |
| H1 | −0.1120 | 0.1347 | 0.6615 | 0.044* | |
| C2 | −0.2378 (3) | 0.3391 (3) | 0.5568 (3) | 0.0423 (6) | |
| H2 | −0.2765 | 0.2925 | 0.5039 | 0.051* | |
| C3 | −0.2782 (3) | 0.5056 (3) | 0.5407 (3) | 0.0440 (6) | |
| H3 | −0.3457 | 0.5719 | 0.4776 | 0.053* | |
| C4 | −0.2178 (3) | 0.5707 (3) | 0.6181 (3) | 0.0396 (6) | |
| H4 | −0.2429 | 0.6819 | 0.6076 | 0.048* | |
| C5 | −0.1178 (3) | 0.4688 (3) | 0.7134 (2) | 0.0304 (5) | |
| C6 | 0.1043 (3) | 0.4872 (3) | 0.8252 (2) | 0.0301 (5) | |
| C7 | 0.1878 (3) | 0.6062 (3) | 0.8296 (3) | 0.0376 (5) | |
| H7 | 0.1352 | 0.7144 | 0.8122 | 0.045* | |
| C8 | 0.3477 (3) | 0.5600 (3) | 0.8600 (3) | 0.0420 (6) | |
| H8 | 0.4049 | 0.6367 | 0.8643 | 0.050* | |
| C9 | 0.4246 (3) | 0.3974 (3) | 0.8844 (3) | 0.0393 (6) | |
| H9 | 0.5349 | 0.3642 | 0.9026 | 0.047* | |
| C10 | 0.3345 (3) | 0.2878 (3) | 0.8812 (2) | 0.0336 (5) | |
| H10 | 0.3861 | 0.1792 | 0.8978 | 0.040* | |
| C11 | 0.3878 (3) | −0.0135 (3) | 0.7062 (2) | 0.0324 (5) | |
| O2 | 0.4437 (2) | −0.0761 (2) | 0.81955 (17) | 0.0375 (4) | |
| H1WB | 0.168 (4) | 0.101 (4) | 0.169 (3) | 0.080* | |
| H1WA | 0.3066 (15) | 0.122 (4) | 0.212 (4) | 0.080* | |
| H4A | 0.231 (3) | −0.046 (4) | 0.995 (3) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.02217 (15) | 0.02005 (15) | 0.02074 (14) | −0.00466 (10) | −0.00701 (10) | −0.00218 (10) |
| N1 | 0.0313 (10) | 0.0283 (10) | 0.0282 (9) | −0.0074 (8) | −0.0095 (8) | −0.0020 (8) |
| N2 | 0.0349 (10) | 0.0271 (10) | 0.0419 (11) | 0.0016 (8) | −0.0124 (9) | −0.0125 (8) |
| N3 | 0.0310 (10) | 0.0258 (10) | 0.0280 (9) | −0.0063 (8) | −0.0081 (7) | −0.0041 (8) |
| O1 | 0.0312 (9) | 0.0669 (12) | 0.0337 (9) | 0.0070 (8) | −0.0072 (7) | −0.0209 (9) |
| C12 | 0.0292 (11) | 0.0306 (12) | 0.0344 (11) | 0.0016 (9) | −0.0073 (9) | −0.0103 (10) |
| O1W | 0.0398 (9) | 0.0352 (9) | 0.0442 (10) | −0.0011 (7) | −0.0164 (8) | −0.0153 (8) |
| O4 | 0.0272 (8) | 0.0269 (8) | 0.0266 (7) | −0.0062 (6) | −0.0091 (6) | −0.0031 (6) |
| C1 | 0.0461 (14) | 0.0333 (13) | 0.0332 (12) | −0.0124 (11) | −0.0153 (11) | −0.0025 (10) |
| C2 | 0.0474 (15) | 0.0483 (15) | 0.0354 (13) | −0.0157 (12) | −0.0177 (11) | −0.0045 (11) |
| C3 | 0.0381 (13) | 0.0496 (16) | 0.0384 (13) | −0.0048 (11) | −0.0190 (11) | 0.0024 (12) |
| C4 | 0.0355 (13) | 0.0334 (13) | 0.0412 (13) | −0.0023 (10) | −0.0114 (11) | −0.0003 (11) |
| C5 | 0.0272 (11) | 0.0302 (12) | 0.0292 (11) | −0.0058 (9) | −0.0048 (9) | −0.0041 (9) |
| C6 | 0.0345 (12) | 0.0298 (12) | 0.0243 (10) | −0.0090 (9) | −0.0044 (9) | −0.0057 (9) |
| C7 | 0.0472 (14) | 0.0295 (12) | 0.0362 (12) | −0.0086 (11) | −0.0107 (11) | −0.0078 (10) |
| C8 | 0.0496 (15) | 0.0415 (15) | 0.0423 (13) | −0.0210 (12) | −0.0125 (11) | −0.0108 (11) |
| C9 | 0.0346 (13) | 0.0443 (15) | 0.0411 (13) | −0.0139 (11) | −0.0123 (11) | −0.0066 (11) |
| C10 | 0.0308 (12) | 0.0336 (12) | 0.0348 (12) | −0.0074 (10) | −0.0083 (9) | −0.0061 (10) |
| C11 | 0.0325 (12) | 0.0312 (12) | 0.0327 (12) | −0.0020 (10) | −0.0068 (10) | −0.0118 (10) |
| O2 | 0.0350 (9) | 0.0420 (10) | 0.0322 (8) | 0.0022 (7) | −0.0102 (7) | −0.0108 (7) |
| Ni1—O4 | 1.9671 (15) | O4—Ni1i | 1.9713 (15) |
| Ni1—O4i | 1.9713 (15) | O4—H4A | 0.83 (3) |
| Ni1—N1 | 1.9984 (18) | C1—C2 | 1.364 (3) |
| Ni1—N3 | 2.0314 (18) | C1—H1 | 0.9300 |
| Ni1—O1 | 2.2232 (16) | C2—C3 | 1.392 (4) |
| Ni1—Ni1i | 2.9753 (8) | C2—H2 | 0.9300 |
| N1—C5 | 1.347 (3) | C3—C4 | 1.362 (4) |
| N1—C1 | 1.355 (3) | C3—H3 | 0.9300 |
| N2—C5 | 1.377 (3) | C4—C5 | 1.397 (3) |
| N2—C6 | 1.381 (3) | C4—H4 | 0.9300 |
| N2—H2B | 0.8600 | C6—C7 | 1.404 (3) |
| N3—C6 | 1.347 (3) | C7—C8 | 1.365 (3) |
| N3—C10 | 1.354 (3) | C7—H7 | 0.9300 |
| O1—C11 | 1.252 (3) | C8—C9 | 1.392 (4) |
| C12—C12ii | 1.313 (4) | C8—H8 | 0.9300 |
| C12—C11 | 1.499 (3) | C9—C10 | 1.364 (3) |
| C12—H12 | 0.9300 | C9—H9 | 0.9300 |
| O1W—H1WB | 0.85 (3) | C10—H10 | 0.9300 |
| O1W—H1WA | 0.840 (10) | C11—O2 | 1.263 (3) |
| O4—Ni1—O4i | 81.87 (6) | N1—C1—H1 | 118.4 |
| O4—Ni1—N1 | 173.85 (7) | C2—C1—H1 | 118.4 |
| O4i—Ni1—N1 | 94.01 (7) | C1—C2—C3 | 118.5 (2) |
| O4—Ni1—N3 | 94.06 (7) | C1—C2—H2 | 120.8 |
| O4i—Ni1—N3 | 161.16 (7) | C3—C2—H2 | 120.8 |
| N1—Ni1—N3 | 88.38 (7) | C4—C3—C2 | 119.5 (2) |
| O4—Ni1—O1 | 94.61 (6) | C4—C3—H3 | 120.3 |
| O4i—Ni1—O1 | 101.31 (7) | C2—C3—H3 | 120.3 |
| N1—Ni1—O1 | 90.68 (7) | C3—C4—C5 | 119.4 (2) |
| N3—Ni1—O1 | 97.33 (7) | C3—C4—H4 | 120.3 |
| O4—Ni1—Ni1i | 40.99 (4) | C5—C4—H4 | 120.3 |
| O4i—Ni1—Ni1i | 40.88 (4) | N1—C5—N2 | 119.92 (19) |
| N1—Ni1—Ni1i | 134.72 (5) | N1—C5—C4 | 121.6 (2) |
| N3—Ni1—Ni1i | 132.37 (5) | N2—C5—C4 | 118.5 (2) |
| O1—Ni1—Ni1i | 100.55 (5) | N3—C6—N2 | 120.05 (19) |
| C5—N1—C1 | 117.87 (19) | N3—C6—C7 | 122.1 (2) |
| C5—N1—Ni1 | 124.23 (15) | N2—C6—C7 | 117.8 (2) |
| C1—N1—Ni1 | 117.85 (15) | C8—C7—C6 | 118.8 (2) |
| C5—N2—C6 | 127.58 (19) | C8—C7—H7 | 120.6 |
| C5—N2—H2B | 116.2 | C6—C7—H7 | 120.6 |
| C6—N2—H2B | 116.2 | C7—C8—C9 | 119.6 (2) |
| C6—N3—C10 | 117.40 (19) | C7—C8—H8 | 120.2 |
| C6—N3—Ni1 | 122.94 (15) | C9—C8—H8 | 120.2 |
| C10—N3—Ni1 | 119.42 (15) | C10—C9—C8 | 118.5 (2) |
| C11—O1—Ni1 | 123.67 (14) | C10—C9—H9 | 120.8 |
| C12ii—C12—C11 | 124.0 (3) | C8—C9—H9 | 120.8 |
| C12ii—C12—H12 | 118.0 | N3—C10—C9 | 123.5 (2) |
| C11—C12—H12 | 118.0 | N3—C10—H10 | 118.2 |
| H1WB—O1W—H1WA | 112 (2) | C9—C10—H10 | 118.2 |
| Ni1—O4—Ni1i | 98.13 (6) | O1—C11—O2 | 125.1 (2) |
| Ni1—O4—H4A | 103 (2) | O1—C11—C12 | 118.0 (2) |
| Ni1i—O4—H4A | 111 (3) | O2—C11—C12 | 116.88 (19) |
| N1—C1—C2 | 123.1 (2) |
| Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O2 | 0.83 (3) | 2.07 (2) | 2.848 (2) | 158 (3) |
| O1W—H1WA···O2ii | 0.84 (1) | 1.91 (1) | 2.752 (2) | 178 (3) |
| O1W—H1WB···O4iii | 0.85 (3) | 1.92 (3) | 2.765 (2) | 172 (3) |
| N2—H2B···O1Wiv | 0.86 | 1.99 | 2.784 (3) | 153 |
| Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) −x, −y+1, −z+1. |
| Ni1—O4 | 1.9671 (15) | Ni1—N3 | 2.0314 (18) |
| Ni1—O4i | 1.9713 (15) | Ni1—O1 | 2.2232 (16) |
| Ni1—N1 | 1.9984 (18) | Ni1—Ni1i | 2.9753 (8) |
| Symmetry codes: (i) −x, −y, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O2 | 0.83 (3) | 2.07 (2) | 2.848 (2) | 158 (3) |
| O1W—H1WA···O2ii | 0.84 (1) | 1.91 (1) | 2.752 (2) | 178 (3) |
| O1W—H1WB···O4iii | 0.85 (3) | 1.92 (3) | 2.765 (2) | 172 (3) |
| N2—H2B···O1Wiv | 0.86 | 1.99 | 2.784 (3) | 153 |
| Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) −x, −y+1, −z+1. |
The author gratefully acknowledges financial support from the Youth Foundation of Lishui University, People's Republic of China (grant No. QN07014).
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Transition metal complexes with polypyridylamine ligands have diverse structures and special optical and electromagnetic properties (Cotton et al., 1998) and have aroused great interest among researchers. Multidentate amine ligands usually exhibit donor as well as acceptor properties and can be used as popular chelating ligands (Nathan & Traina, 2003). On the other hand, carboxylates are attractive as metal-binding units in coordination networks because the negative charge significantly enhances their ability to bind strongly to metal centers, a feature which undoubtedly contributes to the robust nature of the resulting materials (Liu et al., 2008). In this paper, we report the synthesis and crystal structure of the title compound (I), Figure 1.
The Ni1 atom in the title complex has a distorted square pyramidal coordination environment formed by one bidentate dpa ligand, two hydroxyl groups and one carboxylate group. The two peripheral pyridine N atoms from the dpa ligand [Ni1—N1 = 1.9984 (18)Å and Ni1—N3 =2.0314 (18) Å] and the two hydroxyl groups form the basal plane [Ni1—O4 =1.9713 (15) Å], the remaining apical position is occupied by an O atom of a carboxylate group from the fum2- ligand [Ni1—O1 =2.2232 (16) Å], Table 1. In addition, the inversion related hydroxyl groups link Ni(II) ions into a centrosymmetric [Ni2(OH)2] four-membered ring. Furthermore, the fum2- ligands bridge to an adjacent NiII linking the four-membered rings into a zigzag chain (Figure 2).
In the crystal structure, the H atoms of both water molecules and hydroxyl groups are involved in intermolecular hydrogen bonds with the O atoms of uncoordinated carboxylate groups and –NH group from dpa ligand which link the one-dimensional chains to form a three-dimensional network (Table 2).