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In the coordination compound poly[diaqua­([mu]2-4,4'-bipyri­dine)([mu]2-4-carboxyl­atocinnamato)nickel(II)], [Ni(C10H6O4)(C10H8N2)(H2O)2]n, both the 4-carboxylato­cinnamate and 4,4'-bipyridine (4,4'-bpy) ligands act as bidentate bridges, connecting the NiII centres in an octa­hedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates two other identical layers, thus giving a rare 2D [rightwards arrow] 3D polycatenating network (2D and 3D are two- and three-dimensional, respectively), with a mutually parallel arrangement of the layers. The chiral 4,4'-bpy ligands link the NiII centres into chiral chains, thus introducing chirality into the layer and the resulting 3D network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110012394/sq3241sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110012394/sq3241Isup2.hkl
Contains datablock I

CCDC reference: 779957

Comment top

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.

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The local coordination environment for the NiII centres in (I). Displacement ellipsoids are drawn at the 20% probability level and H atoms have been omitted for clarity. The disordered orientations of the acc2− ligand are shown as primed and unprimed atoms with open and filled bonds, respectively. [Symmetry codes: (i) x, y, 1 + z; (ii) 1 + x, y, z.]
[Figure 2] Fig. 2. The two-dimensional grid of (I) along the ac plane, constructed from acc2− anions and 4,4'-bpy ligands, connecting the NiII ions.
[Figure 3] Fig. 3. (a) A view of the three-dimensional structure of (I) along the c axis. (b) A schematic representation of the modes of inclined interpenetration by complementary (4,4) networks.
[Figure 4] Fig. 4. The left-handed hydrogen-bonded helical chains formed between the coordinated water molecules and the uncoordinated carboxylate O atoms within the triangular interspaces. The helical axes are represented by the long bars. [Symmtry codes: (i) x, y, 1 + z; (ii) 1 − y, xy, 2/3 + z; (iii) 1 − x + y, 2 − x, 1/3 + z.]
[Figure 5] Fig. 5. Weak C—H···π interactions between adjacent two-dimensional layers, viewed along the a axis. For clarity, the acc2− anions are simplified into long rods connecting the metal centres. The centroids (Cg) of the pyridyl rings of 4,4'-bpy are represented by black dots. [Symmtry codes: (i) −x + y, 1 − x, 1/3 + z; (ii) 1 − y, 1 + xy, −1/3 + z.]
poly[diaqua(µ2-4,4'-bipyridine)(µ2-4-carboxylatocinnamato)nickel(II)] top
Crystal data top
[Ni(C10H6O4)(C10H8N2)(H2O)2]Dx = 1.483 Mg m3
Mr = 441.07Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P32Cell parameters from 1991 reflections
Hall symbol: P 32θ = 5.6–22.6°
a = 11.261 (2) ŵ = 1.02 mm1
c = 13.495 (6) ÅT = 298 K
V = 1482.0 (8) Å3Block, green
Z = 30.32 × 0.30 × 0.26 mm
F(000) = 684
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3429 independent reflections
Radiation source: fine-focus sealed tube2458 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
ϕ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1312
Tmin = 0.736, Tmax = 0.777k = 1313
7628 measured reflectionsl = 1516
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.071H-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 reflectionsΔρmax = 1.02 e Å3
324 parametersΔρmin = 0.65 e Å3
937 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (4)
Crystal data top
[Ni(C10H6O4)(C10H8N2)(H2O)2]Z = 3
Mr = 441.07Mo Kα radiation
Hexagonal, P32µ = 1.02 mm1
a = 11.261 (2) ÅT = 298 K
c = 13.495 (6) Å0.32 × 0.30 × 0.26 mm
V = 1482.0 (8) Å3
Data collection top
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 = 0.777Rint = 0.050
7628 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.071H-atom parameters constrained
wR(F2) = 0.211Δρmax = 1.02 e Å3
S = 1.06Δρmin = 0.65 e Å3
3429 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
324 parametersAbsolute structure parameter: 0.01 (4)
937 restraints
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*/UeqOcc. (<1)
Ni10.89237 (9)0.66653 (11)1.16739 (12)0.0337 (3)
O10.8978 (6)0.6717 (7)1.0184 (6)0.042 (2)
O20.9894 (9)0.8922 (8)0.9802 (6)0.067 (2)
O30.8932 (6)0.6610 (6)0.3162 (7)0.043 (2)
O40.7634 (9)0.4409 (8)0.3545 (6)0.069 (2)
O50.7857 (6)0.4526 (6)1.1565 (5)0.0402 (16)
H5C0.76660.44211.21800.048*
H5D0.71150.41041.12380.048*
O60.9994 (6)0.8809 (6)1.1782 (5)0.0402 (17)
H6C0.99090.89161.11670.048*
H6D0.96810.92381.21090.048*
N10.7053 (8)0.6665 (10)1.1674 (6)0.0390 (17)
N20.0794 (8)0.6671 (10)1.1671 (6)0.0414 (19)
C10.9366 (10)0.7676 (12)0.9569 (7)0.052 (3)
C20.904 (3)0.564 (2)0.7371 (16)0.091 (4)0.221 (6)
H20.91020.48540.72490.109*0.221 (6)
C30.918 (3)0.614 (3)0.8332 (14)0.082 (5)0.221 (6)
H30.93350.56870.88530.098*0.221 (6)
C40.910 (2)0.731 (3)0.8513 (12)0.086 (4)0.442 (13)
H40.90670.64770.83380.103*0.221 (6)
C50.887 (2)0.798 (2)0.7734 (14)0.094 (4)0.442 (13)
H50.88160.87600.78560.113*0.442 (13)
C60.8734 (18)0.7478 (18)0.6774 (13)0.099 (4)0.442 (13)
H60.85290.79100.62680.119*0.221 (6)
C70.882 (2)0.6308 (19)0.6592 (13)0.102 (4)0.442 (13)
H70.89860.59130.71250.123*0.221 (6)
C80.868 (3)0.581 (2)0.5632 (14)0.099 (4)0.442 (13)
H80.87370.50270.55100.119*0.442 (13)
C90.845 (3)0.648 (3)0.4853 (12)0.100 (5)0.442 (13)
H90.84360.72450.49690.120*0.221 (6)
C100.837 (3)0.765 (3)0.5034 (14)0.101 (5)0.221 (6)
H100.82180.81000.45130.121*0.221 (6)
C110.851 (3)0.815 (2)0.5995 (16)0.100 (4)0.221 (6)
H110.84510.89320.61160.120*0.221 (6)
C2'0.7300 (18)0.5251 (19)0.7451 (12)0.102 (4)0.279 (6)
H2'0.64820.44290.73730.122*0.279 (6)
C3'0.773 (2)0.581 (2)0.8391 (11)0.097 (5)0.279 (6)
H3'0.71950.53590.89420.117*0.279 (6)
C4'0.895 (2)0.704 (2)0.8508 (10)0.087 (4)0.558 (13)
H4'0.82080.62880.84310.105*0.279 (6)
C5'0.9746 (18)0.7711 (18)0.7684 (12)0.104 (4)0.558 (13)
H5'1.05640.85340.77630.125*0.558 (13)
C6'0.9319 (14)0.7154 (15)0.6745 (10)0.098 (4)0.558 (13)
H6'0.97950.75460.61890.118*0.279 (6)
C7'0.8096 (14)0.5924 (14)0.6628 (10)0.094 (4)0.558 (13)
H7'0.74710.54220.71400.113*0.279 (6)
C8'0.7669 (16)0.5367 (16)0.5688 (11)0.099 (4)0.558 (13)
H8'0.68510.45440.56100.119*0.558 (13)
C9'0.8465 (19)0.6039 (19)0.4865 (10)0.072 (4)0.558 (13)
H9'0.92820.68970.50130.087*0.279 (6)
C10'0.969 (2)0.727 (2)0.4981 (11)0.086 (5)0.279 (6)
H10'1.02200.77190.44310.103*0.279 (6)
C11'1.0114 (17)0.7827 (18)0.5921 (12)0.089 (4)0.279 (6)
H11'1.09330.86500.59990.107*0.279 (6)
C120.8357 (9)0.5672 (11)0.3786 (7)0.045 (2)
C130.6664 (9)0.7090 (10)1.2460 (7)0.046 (2)
H130.72230.73701.30180.055*
C140.5459 (10)0.7132 (11)1.2481 (7)0.050 (2)
H140.52400.74801.30330.060*
C150.4574 (9)0.6653 (11)1.1673 (7)0.043 (2)
C160.4987 (10)0.6192 (11)1.0861 (8)0.051 (2)
H160.44270.58521.03060.062*
C170.6224 (9)0.6244 (10)1.0887 (7)0.048 (2)
H170.65040.59711.03260.057*
C180.0889 (9)0.5597 (10)1.1353 (8)0.048 (2)
H180.00900.48241.11420.058*
C190.2053 (9)0.5561 (11)1.1316 (7)0.046 (2)
H190.20560.47991.10530.055*
C200.3265 (9)0.6666 (10)1.1671 (8)0.043 (2)
C210.3180 (9)0.7769 (10)1.2033 (7)0.048 (2)
H210.39510.85221.22990.058*
C220.1940 (10)0.7748 (11)1.1996 (7)0.047 (2)
H220.19090.85181.22080.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0311 (6)0.0444 (7)0.0308 (5)0.0228 (5)0.0016 (5)0.0025 (4)
O10.052 (5)0.056 (5)0.020 (5)0.030 (3)0.003 (3)0.001 (3)
O20.102 (6)0.060 (5)0.031 (4)0.034 (5)0.009 (4)0.008 (3)
O30.045 (5)0.047 (4)0.040 (6)0.025 (3)0.006 (3)0.000 (3)
O40.088 (6)0.066 (5)0.032 (4)0.024 (4)0.001 (4)0.006 (3)
O50.036 (3)0.054 (4)0.029 (4)0.022 (3)0.001 (2)0.004 (3)
O60.041 (4)0.055 (4)0.031 (4)0.029 (3)0.002 (3)0.005 (3)
N10.035 (4)0.054 (4)0.034 (4)0.026 (4)0.012 (3)0.017 (3)
N20.043 (5)0.052 (4)0.034 (4)0.026 (4)0.005 (3)0.006 (3)
C10.050 (6)0.075 (8)0.037 (6)0.035 (6)0.003 (4)0.010 (5)
C20.106 (7)0.102 (7)0.078 (6)0.063 (7)0.005 (6)0.007 (6)
C30.101 (8)0.097 (8)0.074 (6)0.069 (7)0.001 (7)0.015 (6)
C40.102 (8)0.100 (8)0.072 (6)0.063 (7)0.003 (6)0.009 (6)
C50.107 (8)0.104 (8)0.078 (6)0.057 (7)0.003 (6)0.008 (6)
C60.107 (7)0.110 (7)0.078 (5)0.052 (7)0.011 (6)0.001 (5)
C70.111 (7)0.108 (7)0.082 (5)0.050 (7)0.007 (6)0.014 (5)
C80.110 (8)0.110 (8)0.081 (6)0.057 (7)0.004 (6)0.008 (6)
C90.109 (8)0.109 (8)0.083 (6)0.054 (7)0.005 (7)0.002 (6)
C100.113 (8)0.108 (8)0.081 (6)0.055 (8)0.007 (7)0.008 (7)
C110.112 (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)
C120.041 (5)0.068 (7)0.031 (5)0.030 (5)0.001 (4)0.006 (5)
C130.044 (5)0.071 (6)0.034 (5)0.037 (5)0.011 (4)0.013 (4)
C140.043 (5)0.075 (7)0.039 (5)0.035 (5)0.003 (4)0.019 (5)
C150.034 (5)0.065 (6)0.039 (5)0.031 (5)0.008 (4)0.024 (4)
C160.051 (6)0.071 (7)0.047 (6)0.042 (6)0.014 (5)0.012 (5)
C170.046 (5)0.068 (6)0.037 (5)0.034 (5)0.006 (4)0.017 (5)
C180.029 (5)0.048 (6)0.065 (7)0.016 (4)0.004 (4)0.011 (5)
C190.040 (5)0.057 (6)0.048 (5)0.030 (5)0.009 (4)0.013 (5)
C200.028 (5)0.041 (5)0.062 (6)0.019 (4)0.004 (4)0.003 (4)
C210.034 (5)0.055 (6)0.062 (6)0.026 (5)0.009 (4)0.022 (5)
C220.045 (6)0.065 (7)0.044 (6)0.037 (5)0.012 (4)0.011 (5)
Geometric parameters (Å, º) top
Ni1—O3i2.009 (10)C11—H60.4644
Ni1—O12.011 (9)C11—H110.9300
Ni1—O52.091 (6)C2'—C3'1.3900
Ni1—O62.096 (6)C2'—C7'1.3900
Ni1—N2ii2.103 (7)C2'—H2'0.9300
Ni1—N12.107 (7)C2'—H7'0.4617
O1—C11.255 (13)C3'—C4'1.3900
O2—C11.260 (13)C3'—H3'0.9300
O3—C121.249 (12)C3'—H4'0.5435
O3—Ni1iii2.009 (10)C4'—C5'1.3900
O4—C121.278 (12)C4'—H40.7441
O5—H5C0.8500C4'—H4'0.8466
O5—H5D0.8500C5'—C6'1.3900
O6—H6C0.8501C5'—H5'0.9300
O6—H6D0.8499C6'—C7'1.3900
N1—C131.324 (12)C6'—C11'1.3900
N1—C171.335 (12)C6'—H6'0.8993
N2—C221.328 (14)C7'—C8'1.3900
N2—C181.337 (14)C7'—H71.2113
N2—Ni1iv2.103 (7)C7'—H7'0.9457
C1—C41.472 (19)C8'—C9'1.3900
C1—C4'1.565 (16)C8'—H8'0.9300
C2—C31.3900C9'—C10'1.3900
C2—C71.3900C9'—C121.502 (15)
C2—H20.9300C9'—H9'0.9650
C2—H70.4816C10'—C11'1.3900
C3—C41.3900C10'—H9'0.4409
C3—H30.9300C10'—H10'0.9300
C3—H40.4641C11'—H6'0.4957
C4—C51.3900C11'—H11'0.9300
C4—H40.9462C13—C141.383 (12)
C4—H4'1.0871C13—H130.9300
C5—C61.3900C14—C151.391 (14)
C5—H50.9300C14—H140.9300
C6—C71.3900C15—C161.389 (14)
C6—C111.3900C15—C201.481 (10)
C6—H60.9311C16—C171.365 (13)
C7—C81.3900C16—H160.9300
C7—H70.9129C17—H170.9300
C8—C91.3900C18—C191.332 (13)
C8—H80.9300C18—H180.9300
C9—C101.3900C19—C201.394 (14)
C9—C121.68 (2)C19—H190.9300
C9—H90.8847C20—C211.382 (14)
C9—H9'0.8356C21—C221.386 (12)
C10—C111.3900C21—H210.9300
C10—H90.5072C22—H220.9300
C10—H100.9300
O3i—Ni1—O1177.9 (2)C3'—C2'—H2'120.0
O3i—Ni1—O592.5 (3)C7'—C2'—H2'120.0
O1—Ni1—O587.4 (3)C3'—C2'—H7'131.5
O3i—Ni1—O687.6 (2)H2'—C2'—H7'108.1
O1—Ni1—O692.5 (3)C4'—C3'—C2'120.0
O5—Ni1—O6179.9 (4)C2'—C3'—H4104.4
O3i—Ni1—N2ii88.9 (3)C4'—C3'—H3'120.0
O1—Ni1—N2ii89.0 (3)C2'—C3'—H3'120.0
O5—Ni1—N2ii90.1 (3)H4—C3'—H3'126.9
O6—Ni1—N2ii89.9 (3)C2'—C3'—H4'119.1
O3i—Ni1—N191.1 (3)H3'—C3'—H4'120.9
O1—Ni1—N190.9 (3)C3'—C4'—C5'120.0
O5—Ni1—N190.1 (3)C3'—C4'—C1118.8 (12)
O6—Ni1—N190.0 (3)C5'—C4'—C1121.2 (12)
N2ii—Ni1—N1179.8 (5)C3'—C4'—H468.1
C1—O1—Ni1132.8 (7)C5'—C4'—H483.0
C12—O3—Ni1iii133.7 (7)C1—C4'—H4122.1
Ni1—O5—H5C93.0C5'—C4'—H4'119.4
Ni1—O5—H5D121.3C1—C4'—H4'119.3
H5C—O5—H5D108.7H4—C4'—H4'67.6
Ni1—O6—H6C93.1C4'—C5'—C6'120.0
Ni1—O6—H6D121.8C6'—C5'—H4102.6
H6C—O6—H6D108.7C4'—C5'—H5'120.0
C13—N1—C17117.8 (7)C6'—C5'—H5'120.0
C13—N1—Ni1120.7 (6)H4—C5'—H5'130.6
C17—N1—Ni1121.4 (6)C5'—C6'—C7'120.0
C22—N2—C18116.9 (8)C5'—C6'—C11'120.0
C22—N2—Ni1iv121.1 (7)C7'—C6'—C11'120.0
C18—N2—Ni1iv122.0 (7)C5'—C6'—H788.6
O1—C1—O2124.0 (9)C7'—C6'—H752.4
O1—C1—C4117.6 (13)C11'—C6'—H7129.4
O2—C1—C4118.3 (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—C7120.0C8'—C7'—C6'120.0
C3—C2—H2120.0C8'—C7'—C2'120.0
C7—C2—H2120.0C6'—C7'—C2'120.0
C3—C2—H7114.0C8'—C7'—H7127.0
H2—C2—H7125.9C6'—C7'—H762.3
C2—C3—C4120.0C2'—C7'—H782.2
C2—C3—H3120.0C8'—C7'—H7'114.3
C4—C3—H3120.0C6'—C7'—H7'125.7
C2—C3—H4109.4H7—C7'—H7'87.8
H3—C3—H4129.7C9'—C8'—C7'120.0
C2—C3—H4'103.6C9'—C8'—H8'120.0
C4—C3—H4'48.9C7'—C8'—H8'120.0
H3—C3—H4'115.0C8'—C9'—C10'120.0
C3—C4—C5120.0C8'—C9'—C12133.1 (11)
C3—C4—C1109.7 (14)C10'—C9'—C12106.7 (11)
C5—C4—C1130.1 (14)C8'—C9'—H997.4
C5—C4—H4114.9C10'—C9'—H960.5
C1—C4—H4115.0C12—C9'—H9109.4
C3—C4—H4'56.5C8'—C9'—H9'114.4
C5—C4—H4'100.0C12—C9'—H9'112.4
C1—C4—H4'110.4H9—C9'—H9'58.3
H4—C4—H4'51.3C11'—C10'—C9'120.0
C6—C5—C4120.0C11'—C10'—H997.9
C6—C5—H5120.0C9'—C10'—H959.4
C4—C5—H5120.0C11'—C10'—H9'107.6
C5—C6—C7120.0H9—C10'—H9'55.1
C5—C6—C11120.0C11'—C10'—H10'120.0
C7—C6—C11120.0C9'—C10'—H10'120.0
C5—C6—H6118.7H9—C10'—H10'111.8
C7—C6—H6121.2H9'—C10'—H10'132.3
C5—C6—H6'125.6C10'—C11'—C6'120.0
C7—C6—H6'59.4C10'—C11'—H6'113.5
C11—C6—H6'85.8C6'—C11'—H9'104.6
H6—C6—H6'89.2H6'—C11'—H9'98.1
C8—C7—C6120.0C10'—C11'—H11'120.0
C8—C7—C2120.0C6'—C11'—H11'120.0
C6—C7—C2120.0H6'—C11'—H11'126.5
C8—C7—H7123.1H9'—C11'—H11'135.4
C6—C7—H7116.9O3—C12—O4122.9 (9)
C8—C7—H6'85.0O3—C12—C9'119.0 (12)
C6—C7—H6'60.8O4—C12—C9'118.1 (11)
C2—C7—H6'125.2O3—C12—C9104.7 (12)
H7—C7—H6'123.1O4—C12—C9130.9 (12)
C8—C7—H7'108.2N1—C13—C14122.4 (8)
C6—C7—H7'91.0N1—C13—H13118.8
C2—C7—H7'70.7C14—C13—H13118.8
H7—C7—H7'71.3C13—C14—C15119.7 (8)
H6'—C7—H7'151.4C13—C14—H14120.1
C7—C8—C9120.0C15—C14—H14120.1
C7—C8—H8120.0C16—C15—C14117.0 (7)
C9—C8—H8120.0C16—C15—C20121.5 (8)
C7—C8—H9'107.8C14—C15—C20121.4 (9)
H8—C8—H9'120.6C17—C16—C15119.3 (9)
C10—C9—C8120.0C17—C16—H16120.4
C10—C9—C12130.5 (14)C15—C16—H16120.4
C8—C9—C12109.5 (14)N1—C17—C16123.6 (9)
C8—C9—H9119.6N1—C17—H17118.2
C12—C9—H9130.8C16—C17—H17118.2
C10—C9—H9'90.5C19—C18—N2124.4 (9)
C8—C9—H9'69.7C19—C18—H18117.8
C12—C9—H9'106.2N2—C18—H18117.8
H9—C9—H9'88.3C18—C19—C20120.0 (9)
C11—C10—C9120.0C18—C19—H19120.0
C11—C10—H9119.2C20—C19—H19120.0
C11—C10—H10120.0C21—C20—C19116.5 (8)
C9—C10—H10120.0C21—C20—C15121.6 (8)
H9—C10—H10120.6C19—C20—C15121.9 (8)
C10—C11—C6120.0C20—C21—C22119.6 (9)
C10—C11—H6122.3C20—C21—H21120.2
C10—C11—H11120.0C22—C21—H21120.2
C6—C11—H11120.0N2—C22—C21122.5 (10)
H6—C11—H11117.3N2—C22—H22118.7
C3'—C2'—C7'120.0C21—C22—H22118.7
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z; (iii) x, y, z1; (iv) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5C···O4i0.851.842.681 (10)168
O5—H5D···O4v0.852.042.873 (9)169
O6—H6D···O2vi0.852.032.871 (9)168
O6—H6C···O20.851.842.679 (10)168
Symmetry codes: (i) x, y, z+1; (v) y+1, xy, z+2/3; (vi) x+y+1, x+2, z+1/3.

Experimental details

Crystal data
Chemical formula[Ni(C10H6O4)(C10H8N2)(H2O)2]
Mr441.07
Crystal system, space groupHexagonal, P32
Temperature (K)298
a, c (Å)11.261 (2), 13.495 (6)
V3)1482.0 (8)
Z3
Radiation typeMo Kα
µ (mm1)1.02
Crystal size (mm)0.32 × 0.30 × 0.26
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.736, 0.777
No. of measured, independent and
observed [I > 2σ(I)] reflections
7628, 3429, 2458
Rint0.050
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.071, 0.211, 1.06
No. of reflections3429
No. of parameters324
No. of restraints937
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.02, 0.65
Absolute structureFlack (1983), with how many Friedel pairs?
Absolute structure parameter0.01 (4)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Ni1—O3i2.009 (10)Ni1—O62.096 (6)
Ni1—O12.011 (9)Ni1—N2ii2.103 (7)
Ni1—O52.091 (6)Ni1—N12.107 (7)
O3i—Ni1—O592.5 (3)O5—Ni1—N2ii90.1 (3)
O1—Ni1—O587.4 (3)O6—Ni1—N2ii89.9 (3)
O3i—Ni1—O687.6 (2)O3i—Ni1—N191.1 (3)
O1—Ni1—O692.5 (3)O1—Ni1—N190.9 (3)
O5—Ni1—O6179.9 (4)O5—Ni1—N190.1 (3)
O1—Ni1—N2ii89.0 (3)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5C···O4i0.851.842.681 (10)168.3
O5—H5D···O4iii0.852.042.873 (9)168.5
O6—H6D···O2iv0.852.032.871 (9)168.4
O6—H6C···O20.851.842.679 (10)168.0
Symmetry codes: (i) x, y, z+1; (iii) y+1, xy, z+2/3; (iv) x+y+1, x+2, z+1/3.
 

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