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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107047294/av3107sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107047294/av3107Isup2.hkl
Contains datablock I

CCDC reference: 651562

Comment top

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 ππ 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' ππ interactions. These structural features can be viewed as evidence of metalloaromaticity (Castiñeiras et al., 2002; Masui, 2001). Weak intra- and intermolecular ππ 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).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A perspective view of the zigzag-like structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms and uncoordinated water molecules have been omitted for clarity. Unlabelled atoms are related to labelled atoms by the symmetry operator ? [Please complete]
[Figure 2] Fig. 2. The intra- and intermolecular ππ interactions in (I), indicated as dashed lines.
[Figure 3] Fig. 3. The water chain in the structure of (I), showing the hydrogen-bonding environment of water molecules in the chain. Displacement ellipsoids are drawn at the 50% probability and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines [Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x + 1, −y + 1, −z + 1; (iii) −x, −y, −z + 1; (iv) x, y − 1, z.]
[Figure 4] Fig. 4. A space-filling view, along the b axis, of the one-dimensional water chains in the structure of (I).
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]·12H2OZ = 1
Mr = 1066.31F(000) = 558
Triclinic, P1Dx = 1.506 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.2082 (7) ÅCell parameters from 645 reflections
b = 10.3481 (7) Åθ = 2.8–22.5°
c = 12.4101 (8) ŵ = 0.89 mm1
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 tube3613 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ϕ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 129
Tmin = 0.777, Tmax = 0.849k = 1212
6344 measured reflectionsl = 1114
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-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 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
[Ni2(C14H12N2O8)(C12H8N2)2(H2O)2]·12H2Oγ = 107.536 (1)°
Mr = 1066.31V = 1175.71 (14) Å3
Triclinic, P1Z = 1
a = 10.2082 (7) ÅMo Kα radiation
b = 10.3481 (7) ŵ = 0.89 mm1
c = 12.4101 (8) ÅT = 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 = 0.849Rint = 0.016
6344 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.06Δρmax = 0.32 e Å3
4092 reflectionsΔρmin = 0.21 e Å3
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
xyzUiso*/Ueq
Ni10.24698 (3)0.20513 (3)0.12975 (2)0.01974 (10)
N10.32658 (19)0.15431 (17)0.00485 (15)0.0219 (4)
N20.4609 (2)0.23217 (17)0.22986 (15)0.0235 (4)
N30.28895 (18)0.42482 (16)0.11306 (14)0.0192 (4)
O10.16863 (18)0.01076 (15)0.16068 (14)0.0357 (4)
H1A0.10190.05280.11100.054*
H1B0.21170.02410.21680.054*
O20.19289 (17)0.27094 (14)0.26139 (13)0.0274 (4)
O30.22254 (19)0.45257 (16)0.37774 (13)0.0341 (4)
O40.05353 (15)0.18899 (14)0.00605 (13)0.0246 (3)
O50.05917 (17)0.30612 (15)0.11608 (13)0.0308 (4)
O60.4096 (2)0.1036 (2)0.56415 (17)0.0563 (5)
H6A0.38460.17480.56570.084*
H6B0.37030.05690.49810.084*
O70.32015 (19)0.33440 (17)0.58451 (14)0.0418 (4)
H7A0.30200.37410.52500.063*
H7B0.24020.29010.59340.063*
O80.6859 (2)0.08154 (17)0.64381 (15)0.0436 (5)
H8A0.74740.15710.64160.065*
H8B0.60080.08580.61820.065*
O90.0137 (2)0.07804 (18)0.36227 (16)0.0479 (5)
H9A0.07060.12660.33120.072*
H9B0.02260.12230.42410.072*
O100.0444 (2)0.18741 (18)0.58790 (17)0.0511 (5)
H10A0.02300.11920.61060.077*
H10B0.01010.23480.61240.077*
O110.0946 (2)0.6558 (2)0.33375 (15)0.0507 (5)
H11A0.06990.65430.26110.076*
H11B0.12550.58880.35210.076*
C10.2576 (3)0.1115 (2)0.10633 (19)0.0283 (5)
H10.15450.09040.13560.034*
C20.3300 (3)0.0959 (2)0.1825 (2)0.0347 (6)
H20.27660.06490.26150.042*
C30.4774 (3)0.1258 (2)0.1417 (2)0.0370 (6)
H30.52800.11730.19250.044*
C40.5556 (3)0.1695 (2)0.0238 (2)0.0310 (5)
C50.4738 (2)0.1814 (2)0.04599 (19)0.0234 (5)
C60.5460 (2)0.2224 (2)0.16695 (19)0.0241 (5)
C70.7089 (3)0.1980 (2)0.0271 (3)0.0390 (6)
H70.76420.18970.01990.047*
C80.7774 (3)0.2367 (2)0.1409 (3)0.0430 (7)
H80.88000.25540.17230.052*
C90.6977 (3)0.2500 (2)0.2152 (2)0.0334 (6)
C100.7605 (3)0.2873 (3)0.3340 (3)0.0467 (7)
H100.86260.30680.37070.056*
C110.6743 (3)0.2954 (3)0.3970 (2)0.0489 (8)
H110.71610.32020.47770.059*
C120.5249 (3)0.2671 (2)0.34218 (19)0.0339 (6)
H120.46630.27300.38710.041*
C130.3969 (2)0.46920 (19)0.05752 (17)0.0187 (4)
C140.5453 (2)0.5237 (2)0.11799 (17)0.0207 (4)
H140.57810.54140.19920.025*
C150.3537 (2)0.4473 (2)0.06187 (17)0.0203 (4)
H150.25260.41170.10560.024*
C160.3298 (2)0.4904 (2)0.23157 (18)0.0238 (5)
H16A0.31210.57930.22970.029*
H16B0.43510.50750.27240.029*
C170.2402 (2)0.3983 (2)0.29523 (18)0.0248 (5)
C180.1443 (2)0.4323 (2)0.04394 (18)0.0220 (5)
H18A0.15860.50430.00640.026*
H18B0.09910.46040.09630.026*
C190.0392 (2)0.2997 (2)0.02968 (18)0.0222 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02224 (16)0.01726 (15)0.01987 (16)0.00570 (11)0.00798 (11)0.00295 (10)
N10.0267 (10)0.0170 (9)0.0226 (9)0.0081 (7)0.0084 (8)0.0021 (7)
N20.0286 (10)0.0185 (9)0.0219 (10)0.0081 (8)0.0060 (8)0.0027 (7)
N30.0211 (9)0.0172 (8)0.0189 (9)0.0040 (7)0.0085 (7)0.0024 (7)
O10.0433 (10)0.0193 (8)0.0304 (9)0.0018 (7)0.0014 (8)0.0064 (7)
O20.0370 (9)0.0211 (8)0.0302 (9)0.0075 (7)0.0212 (7)0.0060 (6)
O30.0532 (11)0.0329 (9)0.0276 (9)0.0188 (8)0.0240 (8)0.0061 (7)
O40.0218 (8)0.0181 (7)0.0295 (8)0.0042 (6)0.0050 (7)0.0025 (6)
O50.0270 (9)0.0313 (9)0.0288 (9)0.0096 (7)0.0021 (7)0.0051 (7)
O60.0590 (13)0.0688 (14)0.0498 (12)0.0335 (11)0.0182 (10)0.0038 (10)
O70.0396 (11)0.0455 (11)0.0351 (10)0.0105 (8)0.0085 (8)0.0095 (8)
O80.0428 (11)0.0412 (10)0.0428 (11)0.0158 (9)0.0066 (9)0.0119 (8)
O90.0554 (12)0.0402 (10)0.0474 (11)0.0016 (9)0.0297 (10)0.0087 (9)
O100.0653 (13)0.0432 (11)0.0669 (13)0.0231 (10)0.0462 (11)0.0177 (10)
O110.0756 (14)0.0608 (12)0.0300 (10)0.0444 (11)0.0158 (10)0.0086 (9)
C10.0382 (14)0.0205 (11)0.0239 (12)0.0072 (10)0.0097 (10)0.0009 (9)
C20.0563 (17)0.0241 (12)0.0251 (12)0.0095 (11)0.0190 (12)0.0019 (10)
C30.0594 (18)0.0249 (12)0.0416 (15)0.0156 (12)0.0349 (14)0.0100 (11)
C40.0412 (14)0.0175 (11)0.0454 (15)0.0126 (10)0.0259 (12)0.0108 (10)
C50.0290 (12)0.0138 (10)0.0317 (12)0.0086 (9)0.0140 (10)0.0059 (9)
C60.0263 (12)0.0145 (10)0.0333 (13)0.0082 (9)0.0106 (10)0.0076 (9)
C70.0379 (15)0.0289 (13)0.0657 (19)0.0151 (11)0.0337 (14)0.0147 (12)
C80.0261 (13)0.0310 (13)0.079 (2)0.0136 (11)0.0220 (14)0.0163 (14)
C90.0265 (13)0.0221 (12)0.0493 (16)0.0105 (10)0.0068 (11)0.0092 (11)
C100.0294 (15)0.0433 (16)0.0547 (18)0.0132 (12)0.0041 (13)0.0069 (13)
C110.0506 (18)0.0470 (16)0.0308 (15)0.0154 (14)0.0098 (13)0.0018 (12)
C120.0424 (15)0.0339 (13)0.0222 (12)0.0147 (11)0.0047 (11)0.0040 (10)
C130.0213 (11)0.0135 (10)0.0232 (11)0.0043 (8)0.0110 (9)0.0046 (8)
C140.0238 (11)0.0185 (10)0.0171 (10)0.0044 (9)0.0056 (9)0.0025 (8)
C150.0180 (11)0.0186 (10)0.0201 (11)0.0025 (8)0.0040 (9)0.0030 (8)
C160.0288 (12)0.0198 (10)0.0231 (11)0.0045 (9)0.0127 (9)0.0002 (9)
C170.0290 (12)0.0273 (12)0.0223 (12)0.0129 (10)0.0106 (10)0.0050 (9)
C180.0228 (11)0.0197 (10)0.0267 (12)0.0082 (9)0.0110 (9)0.0049 (9)
C190.0199 (11)0.0255 (11)0.0241 (12)0.0072 (9)0.0114 (10)0.0032 (9)
Geometric parameters (Å, º) top
Ni1—O12.0232 (15)C1—H10.9500
Ni1—O42.0389 (14)C2—C31.360 (4)
Ni1—O22.0452 (15)C2—H20.9500
Ni1—N22.0718 (18)C3—C41.412 (3)
Ni1—N12.0869 (18)C3—H30.9500
Ni1—N32.2104 (16)C4—C51.406 (3)
N1—C11.329 (3)C4—C71.422 (4)
N1—C51.361 (3)C5—C61.435 (3)
N2—C121.326 (3)C6—C91.407 (3)
N2—C61.360 (3)C7—C81.351 (4)
N3—C131.445 (3)C7—H70.9500
N3—C161.481 (3)C8—C91.438 (4)
N3—C181.482 (3)C8—H80.9500
O1—H1A0.8499C9—C101.400 (4)
O1—H1B0.8499C10—C111.367 (4)
O2—C171.268 (3)C10—H100.9500
O3—C171.244 (3)C11—C121.393 (4)
O4—C191.270 (2)C11—H110.9500
O5—C191.235 (3)C12—H120.9500
O6—H6A0.8501C13—C141.387 (3)
O6—H6B0.8502C13—C151.397 (3)
O7—H7A0.8500C14—C15i1.384 (3)
O7—H7B0.8500C14—H140.9500
O8—H8A0.8499C15—C14i1.384 (3)
O8—H8B0.8409C15—H150.9500
O9—H9A0.8447C16—C171.528 (3)
O9—H9B0.8492C16—H16A0.9900
O10—H10A0.7615C16—H16B0.9900
O10—H10B0.7868C18—C191.518 (3)
O11—H11A0.8543C18—H18A0.9900
O11—H11B0.8520C18—H18B0.9900
C1—C21.405 (3)
O1—Ni1—O491.80 (6)N1—C5—C6117.14 (19)
O1—Ni1—O288.91 (6)C4—C5—C6119.7 (2)
O4—Ni1—O295.11 (6)N2—C6—C9123.1 (2)
O1—Ni1—N294.61 (7)N2—C6—C5116.90 (19)
O4—Ni1—N2168.58 (7)C9—C6—C5120.0 (2)
O2—Ni1—N294.45 (7)C8—C7—C4121.4 (2)
O1—Ni1—N195.16 (7)C8—C7—H7119.3
O4—Ni1—N190.10 (6)C4—C7—H7119.3
O2—Ni1—N1173.29 (6)C7—C8—C9121.1 (2)
N2—Ni1—N179.93 (7)C7—C8—H8119.4
O1—Ni1—N3165.10 (7)C9—C8—H8119.4
O4—Ni1—N382.02 (6)C10—C9—C6117.0 (2)
O2—Ni1—N378.22 (6)C10—C9—C8124.4 (2)
N2—Ni1—N393.85 (6)C6—C9—C8118.6 (2)
N1—Ni1—N398.38 (6)C11—C10—C9119.7 (2)
C1—N1—C5117.81 (19)C11—C10—H10120.2
C1—N1—Ni1129.74 (16)C9—C10—H10120.2
C5—N1—Ni1112.21 (14)C10—C11—C12119.6 (3)
C12—N2—C6117.9 (2)C10—C11—H11120.2
C12—N2—Ni1128.95 (17)C12—C11—H11120.2
C6—N2—Ni1112.91 (14)N2—C12—C11122.7 (3)
C13—N3—C16116.41 (16)N2—C12—H12118.6
C13—N3—C18112.93 (16)C11—C12—H12118.6
C16—N3—C18109.21 (16)C14—C13—C15117.39 (19)
C13—N3—Ni1109.17 (12)C14—C13—N3122.72 (18)
C16—N3—Ni1104.08 (12)C15—C13—N3119.68 (18)
C18—N3—Ni1103.94 (11)C15i—C14—C13121.04 (19)
Ni1—O1—H1A124.1C15i—C14—H14119.5
Ni1—O1—H1B124.7C13—C14—H14119.5
H1A—O1—H1B109.1C14i—C15—C13121.56 (19)
C17—O2—Ni1117.66 (14)C14i—C15—H15119.2
C19—O4—Ni1116.21 (13)C13—C15—H15119.2
H6A—O6—H6B111.7N3—C16—C17110.22 (16)
H7A—O7—H7B109.1N3—C16—H16A109.6
H8A—O8—H8B110.0C17—C16—H16A109.6
H9A—O9—H9B109.7N3—C16—H16B109.6
H10A—O10—H10B106.7C17—C16—H16B109.6
H11A—O11—H11B108.5H16A—C16—H16B108.1
N1—C1—C2123.0 (2)O3—C17—O2125.0 (2)
N1—C1—H1118.5O3—C17—C16118.07 (19)
C2—C1—H1118.5O2—C17—C16116.94 (18)
C3—C2—C1119.1 (2)N3—C18—C19114.48 (16)
C3—C2—H2120.5N3—C18—H18A108.6
C1—C2—H2120.5C19—C18—H18A108.6
C2—C3—C4120.1 (2)N3—C18—H18B108.6
C2—C3—H3119.9C19—C18—H18B108.6
C4—C3—H3119.9H18A—C18—H18B107.6
C5—C4—C3116.8 (2)O5—C19—O4124.43 (19)
C5—C4—C7119.2 (2)O5—C19—C18118.16 (18)
C3—C4—C7124.0 (2)O4—C19—C18117.26 (18)
N1—C5—C4123.2 (2)
O1—Ni1—N1—C183.81 (18)C3—C4—C5—N10.6 (3)
O4—Ni1—N1—C18.01 (18)C7—C4—C5—N1179.04 (19)
N2—Ni1—N1—C1177.59 (19)C3—C4—C5—C6178.64 (18)
N3—Ni1—N1—C189.96 (18)C7—C4—C5—C60.2 (3)
O1—Ni1—N1—C5102.05 (14)C12—N2—C6—C91.3 (3)
O4—Ni1—N1—C5166.13 (14)Ni1—N2—C6—C9173.70 (16)
N2—Ni1—N1—C58.27 (13)C12—N2—C6—C5178.59 (18)
N3—Ni1—N1—C584.18 (14)Ni1—N2—C6—C56.5 (2)
O1—Ni1—N2—C1283.36 (19)N1—C5—C6—N20.7 (3)
O4—Ni1—N2—C12152.7 (3)C4—C5—C6—N2179.95 (18)
O2—Ni1—N2—C125.90 (19)N1—C5—C6—C9179.10 (18)
N1—Ni1—N2—C12177.8 (2)C4—C5—C6—C90.2 (3)
N3—Ni1—N2—C1284.36 (19)C5—C4—C7—C80.2 (3)
O1—Ni1—N2—C6102.38 (14)C3—C4—C7—C8178.5 (2)
O4—Ni1—N2—C621.6 (4)C4—C7—C8—C90.3 (4)
O2—Ni1—N2—C6168.37 (14)N2—C6—C9—C100.9 (3)
N1—Ni1—N2—C67.94 (13)C5—C6—C9—C10178.9 (2)
N3—Ni1—N2—C689.90 (14)N2—C6—C9—C8179.96 (19)
O1—Ni1—N3—C13174.9 (2)C5—C6—C9—C80.2 (3)
O4—Ni1—N3—C13108.65 (13)C7—C8—C9—C10178.8 (2)
O2—Ni1—N3—C13154.40 (13)C7—C8—C9—C60.2 (3)
N2—Ni1—N3—C1360.64 (13)C6—C9—C10—C110.1 (4)
N1—Ni1—N3—C1319.73 (13)C8—C9—C10—C11179.2 (2)
O1—Ni1—N3—C1660.2 (3)C9—C10—C11—C120.3 (4)
O4—Ni1—N3—C16126.42 (13)C6—N2—C12—C110.8 (3)
O2—Ni1—N3—C1629.46 (13)Ni1—N2—C12—C11173.18 (18)
N2—Ni1—N3—C1664.29 (13)C10—C11—C12—N20.1 (4)
N1—Ni1—N3—C16144.67 (13)C16—N3—C13—C1425.5 (3)
O1—Ni1—N3—C1854.1 (3)C18—N3—C13—C14153.00 (18)
O4—Ni1—N3—C1812.10 (12)Ni1—N3—C13—C1491.91 (19)
O2—Ni1—N3—C1884.86 (13)C16—N3—C13—C15159.83 (18)
N2—Ni1—N3—C18178.61 (13)C18—N3—C13—C1532.3 (2)
N1—Ni1—N3—C18101.02 (13)Ni1—N3—C13—C1582.77 (18)
O1—Ni1—O2—C17169.24 (16)C15—C13—C14—C15i1.2 (3)
O4—Ni1—O2—C1799.04 (16)N3—C13—C14—C15i173.65 (18)
N2—Ni1—O2—C1774.70 (16)C14—C13—C15—C14i1.2 (3)
N3—Ni1—O2—C1718.31 (15)N3—C13—C15—C14i173.81 (18)
O1—Ni1—O4—C19168.62 (15)C13—N3—C16—C17156.71 (17)
O2—Ni1—O4—C1979.55 (15)C18—N3—C16—C1774.0 (2)
N2—Ni1—O4—C1967.2 (4)Ni1—N3—C16—C1736.54 (19)
N1—Ni1—O4—C1996.21 (15)Ni1—O2—C17—O3176.24 (17)
N3—Ni1—O4—C192.24 (15)Ni1—O2—C17—C161.7 (2)
C5—N1—C1—C21.3 (3)N3—C16—C17—O3155.87 (19)
Ni1—N1—C1—C2172.56 (15)N3—C16—C17—O226.1 (3)
N1—C1—C2—C30.1 (3)C13—N3—C18—C1994.7 (2)
C1—C2—C3—C41.1 (3)C16—N3—C18—C19134.06 (18)
C2—C3—C4—C50.8 (3)Ni1—N3—C18—C1923.46 (19)
C2—C3—C4—C7177.5 (2)Ni1—O4—C19—O5167.57 (17)
C1—N1—C5—C41.7 (3)Ni1—O4—C19—C1816.9 (2)
Ni1—N1—C5—C4173.25 (15)N3—C18—C19—O5155.30 (19)
C1—N1—C5—C6177.62 (18)N3—C18—C19—O428.9 (3)
Ni1—N1—C5—C67.5 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11A···O5ii0.851.832.665 (2)164
O11—H11B···O30.851.932.772 (2)169
O10—H10A···O9iii0.762.022.758 (3)164
O10—H10B···O11iv0.792.002.789 (3)175
O9—H9B···O100.852.052.882 (3)167
O9—H9A···O20.842.042.874 (2)170
O8—H8A···O11v0.852.052.896 (3)170
O8—H8B···O60.841.922.761 (3)177
O7—H7A···O30.852.052.887 (2)170
O7—H7B···O100.851.942.781 (3)171
O6—H6B···O8vi0.852.062.887 (3)165
O6—H6A···O70.851.992.834 (3)174
O1—H1B···O8vi0.851.932.773 (2)173
O1—H1A···O5vii0.852.533.102 (2)126
O1—H1A···O4vii0.851.932.776 (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
Mr1066.31
Crystal system, space groupTriclinic, 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)
V3)1175.71 (14)
Z1
Radiation typeMo Kα
µ (mm1)0.89
Crystal size (mm)0.28 × 0.25 × 0.19
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.777, 0.849
No. of measured, independent and
observed [I > 2σ(I)] reflections
6344, 4092, 3613
Rint0.016
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.083, 1.06
No. of reflections4092
No. of parameters307
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.21

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11A···O5i0.851.832.665 (2)164
O11—H11B···O30.851.932.772 (2)169
O10—H10A···O9ii0.762.022.758 (3)164
O10—H10B···O11iii0.792.002.789 (3)175
O9—H9B···O100.852.052.882 (3)167
O9—H9A···O20.842.042.874 (2)170
O8—H8A···O11iv0.852.052.896 (3)170
O8—H8B···O60.841.922.761 (3)177
O7—H7A···O30.852.052.887 (2)170
O7—H7B···O100.851.942.781 (3)171
O6—H6B···O8v0.852.062.887 (3)165
O6—H6A···O70.851.992.834 (3)174
O1—H1B···O8v0.851.932.773 (2)173
O1—H1A···O5vi0.852.533.102 (2)126
O1—H1A···O4vi0.851.932.776 (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, °) top
D-H···AD-HH···AD···AD-H···A
O6-H6A···O70.851.992.834 (3)174
O7-H7B···O100.851.942.781 (3)171
O8-H8A···O11i0.852.052.896 (3)170
O8-H8B···O60.841.922.761 (3)177
O9-H9B···O100.852.052.882 (3)167
O10-H10A···O9ii0.762.022.758 (3)164
O10-H10B···O11iii0.792.002.789 (3)175
O6-H6B···O8iv0.852.062.887 (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, °) top
D-H···AD-HH···AD···AD-H···A
O1-H1B···O8i0.851.932.773 (2)173
O7-H7A···O30.852.052.887 (2)170
O9-H9A···O20.842.042.874 (3)170
O11-H11B···O30.851.932.772 (2)169
O11-H11A···O5ii0.851.832.665 (2)164
Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x, −y + 1, −z.
 

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