Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814004280/hg5386sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536814004280/hg5386Isup2.hkl |
CCDC reference: 988599
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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).
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.
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).
[Cu(C7H3N2O6)(OH)] | F(000) = 580 |
Mr = 291.66 | Dx = 2.183 Mg m−3 |
Orthorhombic, Pna21 | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: P 2c -2n | Cell parameters from 2719 reflections |
a = 7.4665 (2) Å | θ = 5.0–74.1° |
b = 17.7858 (5) Å | µ = 3.87 mm−1 |
c = 6.6821 (2) Å | T = 100 K |
V = 887.37 (4) Å3 | Prism, blue |
Z = 4 | 0.25 × 0.20 × 0.15 mm |
Agilent SuperNova Dual diffractometer with an Atlas detector | 1324 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 1318 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.017 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 74.3°, θmin = 5.0° |
ω scan | h = −6→9 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −20→21 |
Tmin = 0.873, Tmax = 1.000 | l = −7→8 |
3156 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.05 | Δρmax = 0.45 e Å−3 |
1324 reflections | Δρmin = −0.67 e Å−3 |
155 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0078 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 360 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.06 (5) |
[Cu(C7H3N2O6)(OH)] | V = 887.37 (4) Å3 |
Mr = 291.66 | Z = 4 |
Orthorhombic, Pna21 | Cu Kα radiation |
a = 7.4665 (2) Å | µ = 3.87 mm−1 |
b = 17.7858 (5) Å | T = 100 K |
c = 6.6821 (2) Å | 0.25 × 0.20 × 0.15 mm |
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 = 1.000 | Rint = 0.017 |
3156 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 0.45 e Å−3 |
S = 1.05 | Δρmin = −0.67 e Å−3 |
1324 reflections | Absolute structure: Flack (1983), 360 Friedel pairs |
155 parameters | Absolute structure parameter: 0.06 (5) |
1 restraint |
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 | ||
Cu | 0.00521 (5) | 0.502896 (17) | 0.50002 (17) | 0.00920 (17) | |
O1 | 0.0918 (2) | 0.40286 (10) | 0.5811 (3) | 0.0146 (4) | |
O2 | 0.0673 (3) | 0.39533 (9) | 0.9179 (3) | 0.0136 (4) | |
O3 | −0.0991 (3) | 0.14441 (11) | 1.1700 (3) | 0.0155 (4) | |
O4 | −0.0088 (2) | 0.04569 (11) | 1.0096 (4) | 0.0186 (4) | |
O5 | 0.2389 (2) | 0.07033 (9) | 0.3473 (3) | 0.0141 (4) | |
O6 | 0.3041 (2) | 0.18099 (10) | 0.2336 (3) | 0.0187 (4) | |
O7 | −0.1161 (2) | 0.51396 (9) | 0.7481 (3) | 0.0105 (4) | |
H1 | −0.2242 | 0.5270 | 0.7463 | 0.016* | |
N1 | −0.0260 (3) | 0.11347 (12) | 1.0269 (4) | 0.0124 (5) | |
N2 | 0.2439 (3) | 0.13903 (11) | 0.3632 (3) | 0.0119 (4) | |
C1 | 0.0847 (3) | 0.36866 (12) | 0.7455 (4) | 0.0099 (4) | |
C2 | 0.0984 (3) | 0.28424 (13) | 0.7318 (4) | 0.0110 (5) | |
C3 | 0.0397 (4) | 0.23927 (14) | 0.8891 (4) | 0.0121 (5) | |
H3 | −0.0025 | 0.2611 | 1.0100 | 0.014* | |
C4 | 0.0445 (4) | 0.16166 (14) | 0.8649 (4) | 0.0109 (5) | |
C5 | 0.1101 (4) | 0.12656 (13) | 0.6959 (4) | 0.0108 (5) | |
H5 | 0.1135 | 0.0734 | 0.6839 | 0.013* | |
C6 | 0.1710 (3) | 0.17364 (13) | 0.5442 (4) | 0.0113 (5) | |
C7 | 0.1637 (3) | 0.25149 (13) | 0.5565 (4) | 0.0111 (5) | |
H7 | 0.2024 | 0.2819 | 0.4478 | 0.013* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0143 (3) | 0.0092 (2) | 0.0042 (3) | 0.00052 (10) | 0.00062 (13) | 0.00047 (15) |
O1 | 0.0228 (10) | 0.0118 (8) | 0.0092 (9) | 0.0025 (6) | 0.0030 (7) | 0.0015 (7) |
O2 | 0.0210 (10) | 0.0118 (8) | 0.0081 (9) | 0.0024 (7) | −0.0017 (7) | −0.0004 (7) |
O3 | 0.0177 (9) | 0.0182 (9) | 0.0105 (9) | −0.0005 (8) | 0.0047 (7) | −0.0002 (7) |
O4 | 0.0268 (11) | 0.0112 (8) | 0.0179 (10) | −0.0027 (6) | 0.0038 (8) | 0.0013 (10) |
O5 | 0.0173 (9) | 0.0119 (8) | 0.0129 (9) | 0.0024 (6) | −0.0015 (7) | −0.0019 (7) |
O6 | 0.0258 (10) | 0.0180 (9) | 0.0122 (9) | −0.0006 (7) | 0.0079 (9) | 0.0013 (8) |
O7 | 0.0124 (9) | 0.0129 (7) | 0.0061 (8) | 0.0010 (6) | −0.0013 (8) | −0.0012 (8) |
N1 | 0.0134 (10) | 0.0153 (10) | 0.0085 (12) | 0.0000 (8) | −0.0008 (8) | 0.0025 (9) |
N2 | 0.0131 (10) | 0.0150 (9) | 0.0075 (10) | 0.0030 (7) | −0.0005 (8) | −0.0006 (8) |
C1 | 0.0092 (10) | 0.0126 (11) | 0.0080 (11) | 0.0015 (8) | −0.0009 (10) | −0.0015 (10) |
C2 | 0.0111 (10) | 0.0121 (11) | 0.0099 (12) | 0.0004 (9) | −0.0028 (11) | 0.0014 (11) |
C3 | 0.0124 (11) | 0.0158 (13) | 0.0080 (12) | 0.0018 (9) | −0.0014 (10) | −0.0014 (10) |
C4 | 0.0116 (11) | 0.0130 (12) | 0.0081 (12) | −0.0019 (9) | −0.0010 (11) | 0.0033 (9) |
C5 | 0.0118 (11) | 0.0109 (11) | 0.0098 (13) | 0.0012 (9) | −0.0010 (9) | −0.0007 (9) |
C6 | 0.0113 (11) | 0.0144 (10) | 0.0081 (13) | 0.0010 (8) | −0.0022 (9) | −0.0003 (8) |
C7 | 0.0121 (11) | 0.0117 (10) | 0.0095 (12) | −0.0004 (9) | −0.0016 (9) | −0.0009 (8) |
Cu—O1 | 1.9689 (18) | O7—H1 | 0.8400 |
Cu—O7 | 1.899 (2) | N1—C4 | 1.478 (3) |
Cu—O2i | 1.9675 (18) | N2—C6 | 1.462 (3) |
Cu—O5ii | 2.5871 (18) | C1—C2 | 1.508 (3) |
Cu—O7i | 1.900 (2) | C2—C3 | 1.392 (4) |
O1—C1 | 1.257 (4) | C2—C7 | 1.396 (4) |
O2—C1 | 1.252 (3) | C3—C4 | 1.390 (4) |
O2—Cuiii | 1.9675 (18) | C3—H3 | 0.9500 |
O3—N1 | 1.231 (3) | C4—C5 | 1.380 (4) |
O4—N1 | 1.218 (3) | C5—C6 | 1.391 (3) |
O5—N2 | 1.227 (3) | C5—H5 | 0.9500 |
O6—N2 | 1.228 (3) | C6—C7 | 1.388 (3) |
O7—Cuiii | 1.900 (2) | C7—H7 | 0.9500 |
O7—Cu—O7i | 176.03 (4) | O2—C1—O1 | 128.7 (2) |
O7—Cu—O2i | 90.98 (8) | O2—C1—C2 | 116.1 (2) |
O7i—Cu—O2i | 91.02 (9) | O1—C1—C2 | 115.2 (2) |
O7—Cu—O1 | 90.57 (9) | C3—C2—C7 | 120.3 (2) |
O7i—Cu—O1 | 87.60 (8) | C3—C2—C1 | 120.3 (2) |
O2i—Cu—O1 | 176.81 (9) | C7—C2—C1 | 119.4 (2) |
O7—Cu—O5ii | 91.71 (7) | C4—C3—C2 | 118.3 (2) |
O7i—Cu—O5ii | 84.60 (8) | C4—C3—H3 | 120.8 |
O2i—Cu—O5ii | 98.13 (7) | C2—C3—H3 | 120.8 |
O1—Cu—O5ii | 84.60 (7) | C5—C4—C3 | 123.6 (2) |
C1—O1—Cu | 131.60 (17) | C5—C4—N1 | 117.6 (2) |
C1—O2—Cuiii | 129.32 (16) | C3—C4—N1 | 118.8 (2) |
Cu—O7—Cuiii | 123.32 (10) | C4—C5—C6 | 116.1 (2) |
Cu—O7—H1 | 118.3 | C4—C5—H5 | 122.0 |
Cuiii—O7—H1 | 118.3 | C6—C5—H5 | 122.0 |
O4—N1—O3 | 124.3 (2) | C7—C6—C5 | 123.0 (2) |
O4—N1—C4 | 117.8 (2) | C7—C6—N2 | 118.9 (2) |
O3—N1—C4 | 117.9 (2) | C5—C6—N2 | 118.1 (2) |
O5—N2—O6 | 123.7 (2) | C6—C7—C2 | 118.6 (2) |
O5—N2—C6 | 118.7 (2) | C6—C7—H7 | 120.7 |
O6—N2—C6 | 117.62 (19) | C2—C7—H7 | 120.7 |
O7—Cu—O1—C1 | −8.5 (2) | O4—N1—C4—C5 | 6.0 (3) |
O7i—Cu—O1—C1 | 175.0 (2) | O3—N1—C4—C5 | −173.7 (2) |
O2i—Cu—O7—Cuiii | −127.01 (11) | O4—N1—C4—C3 | −174.7 (2) |
O1—Cu—O7—Cuiii | 50.20 (11) | O3—N1—C4—C3 | 5.7 (4) |
Cuiii—O2—C1—O1 | 14.1 (4) | C3—C4—C5—C6 | −0.9 (4) |
Cuiii—O2—C1—C2 | −165.63 (15) | N1—C4—C5—C6 | 178.3 (2) |
Cu—O1—C1—O2 | −22.7 (4) | C4—C5—C6—C7 | −1.5 (3) |
Cu—O1—C1—C2 | 156.98 (16) | C4—C5—C6—N2 | 179.2 (2) |
O2—C1—C2—C3 | 19.2 (3) | O5—N2—C6—C7 | −175.1 (2) |
O1—C1—C2—C3 | −160.6 (2) | O6—N2—C6—C7 | 3.6 (3) |
O2—C1—C2—C7 | −163.4 (2) | O5—N2—C6—C5 | 4.2 (3) |
O1—C1—C2—C7 | 16.8 (3) | O6—N2—C6—C5 | −177.0 (2) |
C7—C2—C3—C4 | −1.3 (4) | C5—C6—C7—C2 | 2.4 (3) |
C1—C2—C3—C4 | 176.0 (2) | N2—C6—C7—C2 | −178.3 (2) |
C2—C3—C4—C5 | 2.3 (4) | C3—C2—C7—C6 | −0.9 (3) |
C2—C3—C4—N1 | −176.9 (2) | C1—C2—C7—C6 | −178.3 (2) |
Symmetry codes: (i) −x, −y+1, z−1/2; (ii) x−1/2, −y+1/2, z; (iii) −x, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H1···O3iv | 0.84 | 2.52 | 3.190 (3) | 137 |
O7—H1···O4iv | 0.84 | 2.57 | 3.271 (2) | 142 |
Symmetry code: (iv) −x−1/2, y+1/2, z−1/2. |
Cu—O1 | 1.9689 (18) | Cu—O5ii | 2.5871 (18) |
Cu—O7 | 1.899 (2) | Cu—O7i | 1.900 (2) |
Cu—O2i | 1.9675 (18) |
Symmetry codes: (i) −x, −y+1, z−1/2; (ii) x−1/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H1···O3iii | 0.84 | 2.52 | 3.190 (3) | 137 |
O7—H1···O4iii | 0.84 | 2.57 | 3.271 (2) | 142 |
Symmetry code: (iii) −x−1/2, y+1/2, z−1/2. |