Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The reaction of Ni(CH3COO)2·4H2O, 5-nitro-1,3-benzene­di­carboxylic acid (H2nmbdc), 1,10-phenanthroline and water under hydro­thermal conditions yields the first reported two-dimensional nickel coordination polymer with water- and carboxyl­ate-bridged dimeric units, viz. [Ni2(C8H3NO6)2(C12H8N2)2(H2O)]n. The coordination polyhedron of the NiII ion in the title structure is an octahedron defined by an N2O4 donor set. The water mol­ecule is positioned on a mirror plane and the 5-nitro-1,3-benzene­di­carboxylate group is located on a twofold axis. Two types of nmbdc2− coordination mode are observed: one is a bis-monodentate mode, μ2-nmbdc2−, and the other is a bis-bridging mode, μ4-nmbdc2−. The dimeric unit in the title compound is similar to the structural moiety in urease. In the two-dimensional framework in the title compound, strong stacking interactions between benzene rings (μ2-nmbdc2− and μ4-nmbdc2−) and 1,10-phenanthroline ligands are observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104023431/av1206sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104023431/av1206Isup2.hkl
Contains datablock I

CCDC reference: 244112

Comment top

Binuclear nickel units with both bridged water and carboxylate ligands have been found to be important structural moieties in some metalloenzymes, such as urease; these units? can catalyze the hydrolysis of urease to form ammonia and carbamate (Person et al., 1997; Jabri et al., 1995). Recently, several binuclear complexes were prepared as models for urease, in order to explore the nature of urea hydrolysis (Sung et al., 2001; Barrios & Lippard, 1999; Barrios & Lippard, 2000). However, only a few such nickel binuclear carboxylate complexes whave been structurally characterized, and all of these complexes were synthesized using ligands with one carboxyl group. In the present study, we use a dicarboxylate (5-nitro-1,3-benzenedicarboxylic acid, H2nmbdc) to prepare the first reported two-dimensional compound with a µ2-H2O dimeric motifs, namely [Ni2(H2O)(nmbdc)2(phen)2]n, (I).

Compound (I) consists of a two-dimensional NiII complex in which the Ni atom has a six-coordinate geometry completed by two N atoms from one 1,10-phenanthroline group, one O atom from a coordinated water molecule and three O atoms from three nmbdc2− ligands (Fig. 1 and Table 1). The water molecule occupies a special position in the mirror plane, and the 5-nitro-1,3-benzenedicarboxylate group occupies a special position on a twofold axis. There are two nmbdc2− coordination modes in the title compound; one is a bis-monodentate mode, namely µ2-nmbdc2−, and the other is a bis-bridging mode, namely µ4-nmbdc2−. The basic motif in the two-dimensional framework is a dimeric unit, [Ni22-H2O)(phen)22-nmbdc)24-nmbdc)2], in which the water molecule bridges two Ni atoms, with an Ni···Ni distance of 3.5042 (8) Å; this value agrees well with the Ni···Ni distance observed in urease (3.5 Å).

In general, a binuclear unit constructed from bridged carboxylate groups has four carboxyl groups around two metal centers, with short metal–metal distances, and a paddle-wheel motif is expected (Braqun et al., 2001; Li et al., 1998; Gao et al., 2003). In the title compound, the dimeric unit comprises two bridged and two monodentate carboxyl groups. The bridged water molecule and intramolecular hydrogen bonds assemble the monodentate carboxyl groups into pseudo-bridging linkers. Therefore, the dimeric motif in (I) could be considered as a pseudo-paddle-wheel motif; even nmbdc2− ligands are roughly parallel (the dihedral angle is 6.19 °). This dimeric motif in (I) is found in several reported binuclear water-bridged nickel complexes, such as [Ni22-H2O)(OOCC(CH3)3)22-OOCC(CH3)3)2(2,2'-bipy)2], (II) (Eremenko et al., 1999). The difference between the coordination geometries in (I) and (II) is the orientation of the carboxylate ligands wit respect to the Ni atoms.

In the two-dimensional framework in (I) (Fig. 2), the [Ni(µ4-nmbdc)] building blocks form a one-dimensional chain (Fig. 3a), while the [Ni(µ2-nmbdc)] blocks form dimeric species; the dmeric units are held together by µ2-H2O molecules and extend into a one-dimensional chain (Fig. 3 b). The combination of [Ni(µ4-nmbdc)] and [Ni(µ2-nmbdc)(µ2-H2O)] units leads to the assembly of a two-dimensional architecture. The Ni···Ni separations in these two one-dimensional chains are 8.7326 (8), 10.2223 (5), 10.5166 (8) and 10.5884 (8) Å, respectively.

Two complexes based on the M2+/phen/H2nmbdc system were by Zhou et al. (2004). The copper compound, [Cu(nmbdc)(phen)]2, (III), is a two-dimensional network with a square-pyramidal copper center, in which the nmbdc2− ligand has a µ3-bridging monoatomic monodentate coordination mode. The cobalt compound, [Co2(nmbdc)2(phen)2]n(IV), is a one-dimensional chain and the nmbdc2− ligand has a chelating-bridging coordination mode. The µ2-nmbdc2− and µ2-nmbdc2− coordination modes in (I) create a new assembly compared with the topologies of (III) and (IV). Moreover, in (I), the ability of the water molecule to serve as a bridge for two NiII ions seems to be both an unexpected and a remarkable phenomenon, accounting for the absence of coordination water molecules in (III) and (IV).

Intramolecular hydrogen bonds exist between water molecules and uncoordinated carboxylate O atoms [O7W···O2 = 2.509 (2) Å]. There are abundant strong ππ interactions in the two-dimensional network. As well as a ππ stacking interaction (3.23 Å) between µ2-nmbdc2− and µ4-nmbdc2− ligands in the dimeric motif, ππ stacking interactions exist between pairs of µ2-nmbdc2− and neighboring µ4-nmbdc2− ligands???. Moreover, ππ stacking of phen ligands among neighboring dimeric motifs is observed (3.48 and 3.60 Å).

Experimental top

A mixture of Ni(CH3COO)2·4H2O (0.0376 g,0.15 mmol), 5-nitro-1,3-benzenedicaroxylic acid (0.0318 g, 0.15 mmol), 1,10-phenanthroline (0.0304 g, 0.15 mmol) and water (10 ml) in a molar ratio of ca 1:1:1:3700 was sealed in to a 25 ml Teflon-lined stainless-steel reactor and heated at 453 K for 72 h. After cooling, plate-like blue crystals of (I) were collected by filtration. Analysis calculated for C40H46N6Ni2O13: C 51.70, H 2.65, N 9.19%; found: C 51.64, H 2.70, N 9.36%. Weight loss in the temperature range 574–637 K corresponds to the release of the water molecule (calculated 1.97%, found 1.73%).

Refinement top

H atoms attached to the benzne ring were positioned geometrically and treated as riding, with C—H distances of 0.93 Å and Uiso(H) values of 1.2Ueq(parent). Water H atoms were found in a difference Fourier map and included in the refinement with an O—H distance restraint (0.85 Å) and with Uiso(H) set at 0.05 Å2.

Computing details top

Data collection: SMART (Bruker,1997); cell refinement: SMART; data reduction: SHELXTL (Bruker,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. An ORTEP-3 diagram (Farrugia, 1997) of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The atom labeled with a hash (#) is at the symmetry position (1/2 − x, 1 − y, z).
[Figure 2] Fig. 2. A view of the two-dimensional framework. Phen ligands, nitro groups and H atoms have been omitted for clarity.
[Figure 3] Fig. 3. (a) A view of the one-dimensional chain constructed from [Ni(µ4-nmbdc)] building blocks. (b) A view of the one-dimensional chain constructed from [Ni(µ2-nmbdc)(µ2-H2O)] building blocks. H atoms and nitro groups have been omitted for clarity.
Poly[[µ2-aqua-bis[(1,10-phenanthroline)copper(II)]-di-µ24-5-nitro- 1,3-benzenedicarboxylato] top
Crystal data top
[Cu2(C8H3NO6)2(C12H8N2)2(H2O)]Dx = 1.724 Mg m3
Mr = 914.03Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnnaCell parameters from 3176 reflections
a = 29.5645 (13) Åθ = 2.6–50.4°
b = 18.0613 (7) ŵ = 1.15 mm1
c = 6.5961 (3) ÅT = 293 K
V = 3522.1 (3) Å3Plate, blue
Z = 40.54 × 0.45 × 0.06 mm
F(000) = 1864
Data collection top
Bruker SMART CCD area-detector
diffractometer
3176 independent reflections
Radiation source: fine-focus sealed tube2953 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2335
Tmin = 0.575, Tmax = 0.934k = 2121
17323 measured reflectionsl = 77
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.039P)2 + 7.1492P]
where P = (Fo2 + 2Fc2)/3
3176 reflections(Δ/σ)max = 0.001
282 parametersΔρmax = 0.38 e Å3
1 restraintΔρmin = 0.33 e Å3
Crystal data top
[Cu2(C8H3NO6)2(C12H8N2)2(H2O)]V = 3522.1 (3) Å3
Mr = 914.03Z = 4
Orthorhombic, PnnaMo Kα radiation
a = 29.5645 (13) ŵ = 1.15 mm1
b = 18.0613 (7) ÅT = 293 K
c = 6.5961 (3) Å0.54 × 0.45 × 0.06 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3176 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2953 reflections with I > 2σ(I)
Tmin = 0.575, Tmax = 0.934Rint = 0.034
17323 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0481 restraint
wR(F2) = 0.108H-atom parameters constrained
S = 1.15Δρmax = 0.38 e Å3
3176 reflectionsΔρmin = 0.33 e Å3
282 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
Ni10.306836 (13)0.52748 (2)0.99129 (6)0.02044 (14)
O10.34417 (7)0.44444 (12)0.8217 (4)0.0303 (5)
O20.28576 (8)0.38532 (13)0.6797 (4)0.0345 (6)
O30.49061 (9)0.19494 (15)0.8146 (5)0.0481 (7)
O40.27473 (7)0.61324 (11)1.1358 (3)0.0241 (5)
O50.20897 (7)0.55445 (11)1.1890 (4)0.0266 (5)
O60.07096 (9)0.69074 (16)1.2370 (5)0.0494 (7)
N10.36813 (9)0.53974 (13)1.1381 (4)0.0236 (6)
N20.33847 (9)0.60372 (14)0.7961 (4)0.0243 (6)
N30.47096 (13)0.25000.75000.0318 (10)
N40.09075 (13)0.75001.25000.0294 (9)
C10.32311 (12)0.6383 (2)0.6334 (6)0.0352 (8)
H10.29240.63560.60360.042*
C20.35140 (14)0.6789 (2)0.5043 (6)0.0467 (10)
H20.33930.70290.39210.056*
C30.39653 (13)0.6832 (2)0.5424 (6)0.0417 (9)
H30.41550.70930.45560.050*
C40.41405 (12)0.64771 (19)0.7145 (5)0.0315 (8)
C50.46118 (13)0.6477 (2)0.7675 (6)0.0401 (9)
H50.48170.67230.68470.048*
C60.47613 (12)0.6129 (2)0.9343 (6)0.0405 (9)
H60.50690.61320.96310.049*
C70.44580 (11)0.5754 (2)1.0689 (6)0.0337 (8)
C80.45863 (13)0.5397 (2)1.2492 (7)0.0432 (10)
H80.48890.53921.28820.052*
C90.42694 (14)0.5060 (2)1.3670 (6)0.0441 (10)
H90.43550.48191.48570.053*
C100.38160 (12)0.50766 (19)1.3086 (5)0.0316 (8)
H100.36010.48561.39200.038*
C110.39953 (11)0.57365 (17)1.0208 (5)0.0256 (7)
C120.38359 (11)0.60936 (17)0.8385 (5)0.0248 (7)
C130.32519 (11)0.38840 (16)0.7474 (5)0.0217 (7)
C140.35205 (10)0.31691 (16)0.7441 (4)0.0204 (6)
C150.39883 (10)0.31726 (17)0.7455 (5)0.0222 (7)
H150.41480.36160.74340.027*
C160.42136 (15)0.25000.75000.0223 (9)
C170.32898 (15)0.25000.75000.0206 (9)
H170.29750.25000.75000.025*
C180.23344 (10)0.61052 (16)1.1809 (5)0.0208 (7)
C190.20974 (10)0.68353 (16)1.2238 (4)0.0184 (6)
C200.16264 (10)0.68355 (17)1.2263 (4)0.0201 (6)
H200.14650.63961.21230.024*
C210.14037 (14)0.75001.25000.0207 (9)
C220.23292 (14)0.75001.25000.0200 (9)
H220.26440.75001.25000.024*
O70.25000.50000.8224 (5)0.0215 (7)
H7A0.2631 (13)0.4662 (17)0.754 (6)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0182 (2)0.0144 (2)0.0287 (2)0.00080 (15)0.00051 (17)0.00021 (16)
O10.0256 (12)0.0184 (11)0.0469 (15)0.0009 (9)0.0012 (11)0.0075 (11)
O20.0290 (13)0.0280 (13)0.0466 (15)0.0085 (10)0.0109 (12)0.0131 (11)
O30.0285 (14)0.0495 (16)0.066 (2)0.0140 (12)0.0081 (14)0.0011 (15)
O40.0192 (11)0.0160 (11)0.0372 (13)0.0006 (8)0.0023 (10)0.0055 (9)
O50.0261 (12)0.0157 (11)0.0379 (13)0.0051 (9)0.0047 (10)0.0068 (10)
O60.0250 (14)0.0504 (17)0.073 (2)0.0125 (12)0.0024 (14)0.0099 (15)
N10.0271 (14)0.0134 (12)0.0304 (15)0.0024 (10)0.0013 (12)0.0026 (11)
N20.0202 (14)0.0182 (13)0.0344 (15)0.0029 (10)0.0013 (12)0.0016 (12)
N30.023 (2)0.036 (2)0.036 (2)0.0000.0000.0103 (19)
N40.019 (2)0.042 (3)0.028 (2)0.0000.0000.0054 (18)
C10.0295 (19)0.0343 (19)0.042 (2)0.0009 (16)0.0045 (16)0.0107 (17)
C20.043 (2)0.051 (2)0.045 (2)0.0053 (19)0.0012 (19)0.022 (2)
C30.039 (2)0.045 (2)0.041 (2)0.0131 (18)0.0067 (18)0.0118 (18)
C40.0283 (18)0.0310 (18)0.035 (2)0.0087 (15)0.0094 (15)0.0052 (15)
C50.031 (2)0.046 (2)0.044 (2)0.0139 (17)0.0106 (18)0.0056 (18)
C60.0185 (18)0.052 (2)0.051 (2)0.0082 (16)0.0010 (17)0.007 (2)
C70.0256 (18)0.0324 (19)0.043 (2)0.0028 (15)0.0026 (16)0.0092 (17)
C80.0291 (19)0.044 (2)0.056 (3)0.0026 (17)0.017 (2)0.001 (2)
C90.044 (2)0.042 (2)0.046 (2)0.0048 (19)0.020 (2)0.0096 (19)
C100.036 (2)0.0260 (18)0.0326 (19)0.0066 (15)0.0043 (16)0.0019 (15)
C110.0217 (16)0.0205 (16)0.0347 (18)0.0049 (13)0.0020 (14)0.0062 (14)
C120.0232 (17)0.0189 (15)0.0323 (18)0.0037 (13)0.0058 (14)0.0053 (13)
C130.0272 (17)0.0168 (15)0.0212 (15)0.0012 (13)0.0037 (14)0.0018 (12)
C140.0239 (16)0.0210 (16)0.0162 (15)0.0001 (13)0.0021 (13)0.0025 (12)
C150.0269 (17)0.0173 (15)0.0225 (16)0.0058 (13)0.0013 (13)0.0020 (12)
C160.018 (2)0.028 (2)0.021 (2)0.0000.0000.0028 (18)
C170.018 (2)0.028 (2)0.016 (2)0.0000.0000.0037 (17)
C180.0218 (16)0.0187 (16)0.0219 (16)0.0020 (12)0.0031 (13)0.0010 (12)
C190.0200 (15)0.0164 (15)0.0187 (15)0.0000 (12)0.0007 (12)0.0001 (12)
C200.0192 (15)0.0213 (16)0.0198 (15)0.0056 (12)0.0000 (13)0.0007 (12)
C210.018 (2)0.029 (2)0.015 (2)0.0000.0000.0022 (18)
C220.017 (2)0.021 (2)0.022 (2)0.0000.0000.0009 (18)
O70.0221 (16)0.0163 (15)0.0260 (17)0.0044 (12)0.0000.000
Geometric parameters (Å, º) top
Ni1—O5i2.027 (2)C5—C61.341 (6)
Ni1—O42.052 (2)C5—H50.9300
Ni1—N12.067 (3)C6—C71.432 (5)
Ni1—O72.0762 (17)C6—H60.9300
Ni1—N22.104 (3)C7—C81.405 (6)
Ni1—O12.172 (2)C7—C111.405 (5)
O1—C131.257 (4)C8—C91.361 (6)
O2—C131.250 (4)C8—H80.9300
O3—N31.228 (3)C9—C101.395 (5)
O4—C181.257 (4)C9—H90.9300
O5—C181.246 (4)C10—H100.9300
O6—N41.223 (3)C11—C121.443 (5)
N1—C101.326 (4)C13—C141.516 (4)
N1—C111.355 (4)C14—C151.383 (4)
N2—C11.322 (4)C14—C171.388 (4)
N2—C121.367 (4)C15—C161.386 (4)
N3—C161.466 (6)C15—H150.9300
N4—C211.467 (6)C17—H170.9300
C1—C21.400 (5)C18—C191.520 (4)
C1—H10.9300C19—C201.393 (4)
C2—C31.360 (6)C19—C221.393 (4)
C2—H20.9300C20—C211.378 (4)
C3—C41.402 (5)C20—H200.9300
C3—H30.9300C22—H220.9300
C4—C121.400 (5)O7—H7A0.85 (3)
C4—C51.437 (5)
O5i—Ni1—O498.38 (9)C1—C2—H2119.9
O5i—Ni1—N188.80 (10)C2—C3—C4119.1 (3)
O4—Ni1—N196.15 (9)C2—C3—H3120.5
O5i—Ni1—O789.08 (9)C4—C3—H3120.5
O4—Ni1—O793.17 (7)C12—C4—C3117.5 (3)
N1—Ni1—O7170.65 (8)C12—C4—C5118.8 (3)
O5i—Ni1—N2166.85 (10)C3—C4—C5123.7 (3)
O4—Ni1—N289.76 (10)C6—C5—C4121.3 (3)
N1—Ni1—N280.04 (10)C6—C5—H5119.4
O7—Ni1—N2100.83 (10)C4—C5—H5119.4
O5i—Ni1—O186.81 (9)C5—C6—C7121.6 (3)
O4—Ni1—O1174.63 (9)C5—C6—H6119.2
N1—Ni1—O182.52 (9)C7—C6—H6119.2
O7—Ni1—O188.27 (8)C8—C7—C11116.4 (3)
N2—Ni1—O184.89 (10)C8—C7—C6124.9 (3)
O5i—Ni1—Ni1ii114.87 (7)C11—C7—C6118.7 (4)
O4—Ni1—Ni1ii28.77 (6)C9—C8—C7120.2 (4)
N1—Ni1—Ni1ii73.63 (7)C9—C8—H8119.9
O7—Ni1—Ni1ii115.450 (19)C7—C8—H8119.9
N2—Ni1—Ni1ii68.70 (7)C8—C9—C10119.6 (4)
O1—Ni1—Ni1ii146.80 (6)C8—C9—H9120.2
O5i—Ni1—Ni1iii110.76 (7)C10—C9—H9120.2
O4—Ni1—Ni1iii13.03 (6)N1—C10—C9122.1 (3)
N1—Ni1—Ni1iii92.13 (7)N1—C10—H10118.9
O7—Ni1—Ni1iii97.14 (3)C9—C10—H10118.9
N2—Ni1—Ni1iii76.84 (7)N1—C11—C7123.2 (3)
O1—Ni1—Ni1iii161.60 (6)N1—C11—C12117.0 (3)
Ni1ii—Ni1—Ni1iii19.326 (4)C7—C11—C12119.7 (3)
O5i—Ni1—Ni1iv59.92 (7)N2—C12—C4123.0 (3)
O4—Ni1—Ni1iv149.34 (6)N2—C12—C11117.1 (3)
N1—Ni1—Ni1iv104.12 (7)C4—C12—C11119.9 (3)
O7—Ni1—Ni1iv67.032 (13)O2—C13—O1126.3 (3)
N2—Ni1—Ni1iv116.01 (7)O2—C13—C14116.5 (3)
O1—Ni1—Ni1iv35.52 (6)O1—C13—C14117.2 (3)
Ni1ii—Ni1—Ni1iv174.612 (10)C15—C14—C17119.7 (3)
Ni1iii—Ni1—Ni1iv160.569 (4)C15—C14—C13121.3 (3)
O5i—Ni1—Ni1v26.04 (7)C17—C14—C13118.9 (3)
O4—Ni1—Ni1v124.40 (6)C14—C15—C16118.5 (3)
N1—Ni1—Ni1v87.15 (7)C14—C15—H15120.8
O7—Ni1—Ni1v86.94 (3)C16—C15—H15120.8
N2—Ni1—Ni1v144.75 (7)C15—C16—C15iv122.5 (4)
O1—Ni1—Ni1v60.82 (6)C15—C16—N3118.7 (2)
Ni1ii—Ni1—Ni1v138.189 (9)C15iv—C16—N3118.7 (2)
Ni1iii—Ni1—Ni1v136.774 (8)C14—C17—C14iv121.1 (4)
Ni1iv—Ni1—Ni1v36.422 (3)C14—C17—H17119.4
C13—O1—Ni1122.0 (2)C14iv—C17—H17119.4
C18—O4—Ni1121.98 (19)O5—C18—O4127.3 (3)
C18—O5—Ni1i134.4 (2)O5—C18—C19115.4 (3)
C10—N1—C11118.4 (3)O4—C18—C19117.2 (3)
C10—N1—Ni1127.9 (2)C20—C19—C22119.4 (3)
C11—N1—Ni1112.4 (2)C20—C19—C18117.6 (3)
C1—N2—C12117.8 (3)C22—C19—C18123.0 (3)
C1—N2—Ni1130.8 (2)C21—C20—C19118.6 (3)
C12—N2—Ni1110.9 (2)C21—C20—H20120.7
O3iv—N3—O3123.5 (4)C19—C20—H20120.7
O3iv—N3—C16118.2 (2)C20ii—C21—C20122.9 (4)
O3—N3—C16118.2 (2)C20ii—C21—N4118.5 (2)
O6—N4—O6ii122.8 (4)C20—C21—N4118.5 (2)
O6—N4—C21118.6 (2)C19—C22—C19ii121.1 (4)
O6ii—N4—C21118.6 (2)C19—C22—H22119.5
N2—C1—C2122.4 (3)C19ii—C22—H22119.5
N2—C1—H1118.8Ni1—O7—Ni1i115.11 (15)
C2—C1—H1118.8Ni1—O7—H7A95 (3)
C3—C2—C1120.2 (4)Ni1i—O7—H7A119 (3)
C3—C2—H2119.9
Symmetry codes: (i) x+1/2, y+1, z; (ii) x, y+3/2, z+5/2; (iii) x+1/2, y+1/2, z+5/2; (iv) x, y+1/2, z+3/2; (v) x, y+1/2, z+5/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7A···O10.85 (3)2.47 (4)2.959 (2)117 (3)
O7—H7A···O20.85 (3)1.68 (2)2.509 (2)163 (4)

Experimental details

Crystal data
Chemical formula[Cu2(C8H3NO6)2(C12H8N2)2(H2O)]
Mr914.03
Crystal system, space groupOrthorhombic, Pnna
Temperature (K)293
a, b, c (Å)29.5645 (13), 18.0613 (7), 6.5961 (3)
V3)3522.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.15
Crystal size (mm)0.54 × 0.45 × 0.06
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.575, 0.934
No. of measured, independent and
observed [I > 2σ(I)] reflections
17323, 3176, 2953
Rint0.034
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.108, 1.15
No. of reflections3176
No. of parameters282
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.33

Computer programs: SMART (Bruker,1997), SMART, SHELXTL (Bruker,1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Ni1—O5i2.027 (2)Ni1—O72.0762 (17)
Ni1—O42.052 (2)Ni1—N22.104 (3)
Ni1—N12.067 (3)Ni1—O12.172 (2)
O5i—Ni1—O498.38 (9)N1—Ni1—N280.04 (10)
O5i—Ni1—N188.80 (10)O7—Ni1—N2100.83 (10)
O4—Ni1—N196.15 (9)O5i—Ni1—O186.81 (9)
O5i—Ni1—O789.08 (9)O4—Ni1—O1174.63 (9)
O4—Ni1—O793.17 (7)N1—Ni1—O182.52 (9)
N1—Ni1—O7170.65 (8)O7—Ni1—O188.27 (8)
O5i—Ni1—N2166.85 (10)N2—Ni1—O184.89 (10)
O4—Ni1—N289.76 (10)
Symmetry code: (i) x+1/2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7A···O10.85 (3)2.47 (4)2.959 (2)117 (3)
O7—H7A···O20.85 (3)1.680 (16)2.509 (2)163 (4)
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds