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The title complex, [Cu{μ3-O2CC6H3(NO2)2-3,5}(μ-OH)]n, features zigzag chains in which successive pairs of CuII atoms are connected by OH bridges and bidentate carboxyl­ate ligands, leading to six-membered Cu(O)(OCO)Cu rings. The zigzag chains are connected into a three-dimensional architecture by Cu—O(nitro) bonds. The coordination geometry of the CuII atom is square-pyramidal, with the axial position occupied by the nitro O atom, which forms the longer Cu—O bond. Bifurcated hy­droxy–nitro O—H...O hydrogen bonds contribute to the stability of the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814004280/hg5386sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536814004280/hg5386Isup2.hkl
Contains datablock I

CCDC reference: 988599

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.027
  • wR factor = 0.077
  • Data-to-parameter ratio = 8.5

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT915_ALERT_3_B Low Friedel Pair Coverage ...................... 43 %
Alert level C PLAT090_ALERT_3_C Poor Data / Parameter Ratio (Zmax > 18) ........ 6.22 Note PLAT975_ALERT_2_C Check Calcd Residual Density 0.87A From O7 0.41 eA-3 PLAT976_ALERT_2_C Check Calcd Residual Density 1.07A From O7 -0.64 eA-3
Alert level G PLAT004_ALERT_5_G Polymeric Structure Found with Dimension ....... 3 Info PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Why ? PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 28 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: The contribution of the authors to this submission is as follows: Biswajit Sinha (biswajitsi2006@yahoo.co.in) joint synthesis of the complex. Gopal Dey (gopalde@ymail.com) joint synthesis of the complex. Bipasa Sarkar (bipasamondal@rediffmail.com) joint synthesis of the complex. Abhijit Roy (Abhijitchem1947@yahoo.co.in) Supervisor and write-up. Seik Weng Ng (seikweng@um.edu.my) Data collection and refinement. Edward R. T. Tiekink (Edward.Tiekink@gmail.com) Final analysis and write-up. Note: the first three named students worked in a group on the synthesis.

1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Structural commentary top

The title complex was synthesised employing hydro­thermal methods, and X-ray crystallography revealed it to be three-dimensional. The crystallographic asymmetric unit comprises a CuII cation, and 3,5-di­nitro­benzoate and hydroxide anions, Fig. 1. Zigzag rows of CuII ions are aligned along the c axis (glide symmetry) with pairs of CuII ions being bridged by a hydroxide and two O atoms of the carboxyl­ate ligand leading to chains of six-membered rings. Neighbouring chains are linked via Cu—O(nitro) bonds, which are longer than the remaining Cu—O bonds, Table 1. The resulting O5 donor set defines an axially distorted square pyramidal coordination geometry, with the nitro-O atom in the axial position, as qu­anti­fied by the value of τ = 0.01 which compares to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal geometries, respectively (Addison et al., 1984). Additional stability to the architecture is provided by bifurcated O—H···O(nitro) hydrogen bonds, Table 2.

Similar strings of Cu(µ2-carboxyl­ate)(µ2-hydroxyl)Cu of varying dimensionality have been noted in other CuII structures (e.g. Chen et al., 2006; You et al., 2005; Xiao et al., 2006).

Synthesis and crystallization top

To a pulverised mixture of 3,5-di­nitro­benzoic acid (0.1688 g), Cu(NO3)2.3H2O (0.1932 g) and melamine (0.1002 g), all obtained from commercial sources in AR grade, distilled water (1.5 ml) was added. The mixture was stirred for 30 min to get a suspension. The reaction mixture was then sealed in a 10 ml Teflon-lined stainless steel autoclave and heated at 423 K for 45 h. The autoclave was subjected to natural cooling (for 5 h) to room temperature. The product containing blue crystals suitable for single crystal X-ray diffraction was collected by filtration and washed with adequate distilled water. The initial pH of the suspension was 5 and there was no apparent change in the pH when the reaction was over. The blue product was not formed in the absence of melamine which suggests that melamine acted as a base in this reaction. The product decomposed with explosion with green flashes above 553 K.

Refinement top

The H atoms were geometrically placed (O—H = 0.84 Å and C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(O, C).

Related literature top

For related CuII structures featuring Cu(µ2-carboxylate)(µ2-hydroxyl)Cu rings, see: You et al. (2005); Chen et al. (2006); Xiao et al. (2006). For additional structural analysis, see: Addison et al. (1984).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
[Figure 2] Fig. 2. A view approximately normal to the zigzag chain along the c axis in the title compound. The coordinating nitro groups from carboxylates belong to other chains are shown as "O2NC", for reasons of clarity.
[Figure 3] Fig. 3. A view of the unit-cell contents of the title compound in projection down the c axis, the axis along which the zigzag chains are propagated. The O—H···O hydrogen bonds are shown as orange dashed lines.
Poly[(µ3-3,5-dinitrobenzoato-κ3O1:O1':O3)(µ2-hydroxido-κ2O:O)copper(II)] top
Crystal data top
[Cu(C7H3N2O6)(OH)]F(000) = 580
Mr = 291.66Dx = 2.183 Mg m3
Orthorhombic, Pna21Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2c -2nCell parameters from 2719 reflections
a = 7.4665 (2) Åθ = 5.0–74.1°
b = 17.7858 (5) ŵ = 3.87 mm1
c = 6.6821 (2) ÅT = 100 K
V = 887.37 (4) Å3Prism, blue
Z = 40.25 × 0.20 × 0.15 mm
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
1324 independent reflections
Radiation source: SuperNova (Cu) X-ray Source1318 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.017
Detector resolution: 10.4041 pixels mm-1θmax = 74.3°, θmin = 5.0°
ω scanh = 69
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 2021
Tmin = 0.873, Tmax = 1.000l = 78
3156 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.2234P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.45 e Å3
1324 reflectionsΔρmin = 0.67 e Å3
155 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0078 (6)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 360 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.06 (5)
Crystal data top
[Cu(C7H3N2O6)(OH)]V = 887.37 (4) Å3
Mr = 291.66Z = 4
Orthorhombic, Pna21Cu Kα radiation
a = 7.4665 (2) ŵ = 3.87 mm1
b = 17.7858 (5) ÅT = 100 K
c = 6.6821 (2) Å0.25 × 0.20 × 0.15 mm
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
1324 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
1318 reflections with I > 2σ(I)
Tmin = 0.873, Tmax = 1.000Rint = 0.017
3156 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.077Δρmax = 0.45 e Å3
S = 1.05Δρmin = 0.67 e Å3
1324 reflectionsAbsolute structure: Flack (1983), 360 Friedel pairs
155 parametersAbsolute structure parameter: 0.06 (5)
1 restraint
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
Cu0.00521 (5)0.502896 (17)0.50002 (17)0.00920 (17)
O10.0918 (2)0.40286 (10)0.5811 (3)0.0146 (4)
O20.0673 (3)0.39533 (9)0.9179 (3)0.0136 (4)
O30.0991 (3)0.14441 (11)1.1700 (3)0.0155 (4)
O40.0088 (2)0.04569 (11)1.0096 (4)0.0186 (4)
O50.2389 (2)0.07033 (9)0.3473 (3)0.0141 (4)
O60.3041 (2)0.18099 (10)0.2336 (3)0.0187 (4)
O70.1161 (2)0.51396 (9)0.7481 (3)0.0105 (4)
H10.22420.52700.74630.016*
N10.0260 (3)0.11347 (12)1.0269 (4)0.0124 (5)
N20.2439 (3)0.13903 (11)0.3632 (3)0.0119 (4)
C10.0847 (3)0.36866 (12)0.7455 (4)0.0099 (4)
C20.0984 (3)0.28424 (13)0.7318 (4)0.0110 (5)
C30.0397 (4)0.23927 (14)0.8891 (4)0.0121 (5)
H30.00250.26111.01000.014*
C40.0445 (4)0.16166 (14)0.8649 (4)0.0109 (5)
C50.1101 (4)0.12656 (13)0.6959 (4)0.0108 (5)
H50.11350.07340.68390.013*
C60.1710 (3)0.17364 (13)0.5442 (4)0.0113 (5)
C70.1637 (3)0.25149 (13)0.5565 (4)0.0111 (5)
H70.20240.28190.44780.013*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0143 (3)0.0092 (2)0.0042 (3)0.00052 (10)0.00062 (13)0.00047 (15)
O10.0228 (10)0.0118 (8)0.0092 (9)0.0025 (6)0.0030 (7)0.0015 (7)
O20.0210 (10)0.0118 (8)0.0081 (9)0.0024 (7)0.0017 (7)0.0004 (7)
O30.0177 (9)0.0182 (9)0.0105 (9)0.0005 (8)0.0047 (7)0.0002 (7)
O40.0268 (11)0.0112 (8)0.0179 (10)0.0027 (6)0.0038 (8)0.0013 (10)
O50.0173 (9)0.0119 (8)0.0129 (9)0.0024 (6)0.0015 (7)0.0019 (7)
O60.0258 (10)0.0180 (9)0.0122 (9)0.0006 (7)0.0079 (9)0.0013 (8)
O70.0124 (9)0.0129 (7)0.0061 (8)0.0010 (6)0.0013 (8)0.0012 (8)
N10.0134 (10)0.0153 (10)0.0085 (12)0.0000 (8)0.0008 (8)0.0025 (9)
N20.0131 (10)0.0150 (9)0.0075 (10)0.0030 (7)0.0005 (8)0.0006 (8)
C10.0092 (10)0.0126 (11)0.0080 (11)0.0015 (8)0.0009 (10)0.0015 (10)
C20.0111 (10)0.0121 (11)0.0099 (12)0.0004 (9)0.0028 (11)0.0014 (11)
C30.0124 (11)0.0158 (13)0.0080 (12)0.0018 (9)0.0014 (10)0.0014 (10)
C40.0116 (11)0.0130 (12)0.0081 (12)0.0019 (9)0.0010 (11)0.0033 (9)
C50.0118 (11)0.0109 (11)0.0098 (13)0.0012 (9)0.0010 (9)0.0007 (9)
C60.0113 (11)0.0144 (10)0.0081 (13)0.0010 (8)0.0022 (9)0.0003 (8)
C70.0121 (11)0.0117 (10)0.0095 (12)0.0004 (9)0.0016 (9)0.0009 (8)
Geometric parameters (Å, º) top
Cu—O11.9689 (18)O7—H10.8400
Cu—O71.899 (2)N1—C41.478 (3)
Cu—O2i1.9675 (18)N2—C61.462 (3)
Cu—O5ii2.5871 (18)C1—C21.508 (3)
Cu—O7i1.900 (2)C2—C31.392 (4)
O1—C11.257 (4)C2—C71.396 (4)
O2—C11.252 (3)C3—C41.390 (4)
O2—Cuiii1.9675 (18)C3—H30.9500
O3—N11.231 (3)C4—C51.380 (4)
O4—N11.218 (3)C5—C61.391 (3)
O5—N21.227 (3)C5—H50.9500
O6—N21.228 (3)C6—C71.388 (3)
O7—Cuiii1.900 (2)C7—H70.9500
O7—Cu—O7i176.03 (4)O2—C1—O1128.7 (2)
O7—Cu—O2i90.98 (8)O2—C1—C2116.1 (2)
O7i—Cu—O2i91.02 (9)O1—C1—C2115.2 (2)
O7—Cu—O190.57 (9)C3—C2—C7120.3 (2)
O7i—Cu—O187.60 (8)C3—C2—C1120.3 (2)
O2i—Cu—O1176.81 (9)C7—C2—C1119.4 (2)
O7—Cu—O5ii91.71 (7)C4—C3—C2118.3 (2)
O7i—Cu—O5ii84.60 (8)C4—C3—H3120.8
O2i—Cu—O5ii98.13 (7)C2—C3—H3120.8
O1—Cu—O5ii84.60 (7)C5—C4—C3123.6 (2)
C1—O1—Cu131.60 (17)C5—C4—N1117.6 (2)
C1—O2—Cuiii129.32 (16)C3—C4—N1118.8 (2)
Cu—O7—Cuiii123.32 (10)C4—C5—C6116.1 (2)
Cu—O7—H1118.3C4—C5—H5122.0
Cuiii—O7—H1118.3C6—C5—H5122.0
O4—N1—O3124.3 (2)C7—C6—C5123.0 (2)
O4—N1—C4117.8 (2)C7—C6—N2118.9 (2)
O3—N1—C4117.9 (2)C5—C6—N2118.1 (2)
O5—N2—O6123.7 (2)C6—C7—C2118.6 (2)
O5—N2—C6118.7 (2)C6—C7—H7120.7
O6—N2—C6117.62 (19)C2—C7—H7120.7
O7—Cu—O1—C18.5 (2)O4—N1—C4—C56.0 (3)
O7i—Cu—O1—C1175.0 (2)O3—N1—C4—C5173.7 (2)
O2i—Cu—O7—Cuiii127.01 (11)O4—N1—C4—C3174.7 (2)
O1—Cu—O7—Cuiii50.20 (11)O3—N1—C4—C35.7 (4)
Cuiii—O2—C1—O114.1 (4)C3—C4—C5—C60.9 (4)
Cuiii—O2—C1—C2165.63 (15)N1—C4—C5—C6178.3 (2)
Cu—O1—C1—O222.7 (4)C4—C5—C6—C71.5 (3)
Cu—O1—C1—C2156.98 (16)C4—C5—C6—N2179.2 (2)
O2—C1—C2—C319.2 (3)O5—N2—C6—C7175.1 (2)
O1—C1—C2—C3160.6 (2)O6—N2—C6—C73.6 (3)
O2—C1—C2—C7163.4 (2)O5—N2—C6—C54.2 (3)
O1—C1—C2—C716.8 (3)O6—N2—C6—C5177.0 (2)
C7—C2—C3—C41.3 (4)C5—C6—C7—C22.4 (3)
C1—C2—C3—C4176.0 (2)N2—C6—C7—C2178.3 (2)
C2—C3—C4—C52.3 (4)C3—C2—C7—C60.9 (3)
C2—C3—C4—N1176.9 (2)C1—C2—C7—C6178.3 (2)
Symmetry codes: (i) x, y+1, z1/2; (ii) x1/2, y+1/2, z; (iii) x, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H1···O3iv0.842.523.190 (3)137
O7—H1···O4iv0.842.573.271 (2)142
Symmetry code: (iv) x1/2, y+1/2, z1/2.
Selected bond lengths (Å) top
Cu—O11.9689 (18)Cu—O5ii2.5871 (18)
Cu—O71.899 (2)Cu—O7i1.900 (2)
Cu—O2i1.9675 (18)
Symmetry codes: (i) x, y+1, z1/2; (ii) x1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H1···O3iii0.842.523.190 (3)137
O7—H1···O4iii0.842.573.271 (2)142
Symmetry code: (iii) x1/2, y+1/2, z1/2.
 

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