research communications
ISSN 2056-9890
Crystal structure of l-4-oxidobenzoato-j2O1:O4bis[bis(1,10-phenanthroline-j2N,N0 )copper(II)] bis(4-hydroxybenzoate) 7.5-hydrate Jian-Rong Su* and Yu Li
Received 18 July 2016 Accepted 31 August 2016
Edited by W. T. A. Harrison, University of Aberdeen, Scotland Keywords: crystal structure; 4-hydroxybenzoate; 4-oxidobenzoate; 1,10-phenanthroline; copper; dinuclear complex cation. CCDC reference: 1501982
School of Pharmaceutical and Chemical Engineering, Taizhou University, People’s Republic of China. *Correspondence e-mail:
[email protected]
The title hydrated complex, [Cu2(C7H4O3)(C12H8N2)4](C7H5O3)27.5H2O, is composed of dinuclear CuII complex cations, noncoordinating 4-hydroxybenzoate anions and water molecules of crystallization. In the dinuclear complex cation, the CuII ions are bridged by a 4-oxidobenzoate ligand and thus each metal ion is five-coordinated by two chelating 1,10-phenanthroline (phen) molecules and one anionic O atom in a distorted trigonal-bipyramid geometry. In the crystal, aromatic – stacking occurs between phen rings of neighbouring dinuclear CuII complex cations, forming two-dimensional supramolecular systems parallel to (100).
Supporting information: this article has supporting information at journals.iucr.org/e
1. Chemical context In some biological systems, – stacking between aromatic rings is correlated with the elctron-transfer process (Deisenhofer & Michel, 1989). To study the effect of – stacking, the title complex, (I), incorporating 1,10-phenanthroline (phen), has been prepared and its crystal structure is presented here.
2. Structural commentary The crystal structure of (I) is composed of dinuclear CuII complex cations, noncoordinating 4-hydroxybenzoate anions and solvent water molecules, as shown in Fig. 1. The molecular structure of the dinuclear CuII complex cation is shown in Fig. 2. Two CuII atoms (Cu1 and Cu2) are bridged by one 4oxidobenzoate anion through oxido and carboxy O atoms (O53 and O51, respectively), with a Cu1—O53 bond length of ˚ and a Cu2—O51 bond length of 1.979 (3) A ˚ . Each 1.941 (3) A II Cu atom is five-coordinated, displaying a distorted trigonalbipyramidal geometry (Table 1). The Cu1 atom is coordinated by two chelating phen rings (N1, N2, N3 and N4) intersecting at an angle of 71.35 (5) . The out-of-plane Cu1—N1 and Cu— ˚ , respectively, N3 bond lengths are 2.002 (3) and 2.027 (3) A
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research communications Table 1 ˚ , ). Selected geometric parameters (A Cu1—O53 Cu1—N1 Cu1—N2 Cu1—N3 Cu1—N4
1.941 (3) 2.002 (3) 2.051 (4) 2.027 (3) 2.158 (4)
Cu2—O51 Cu2—N5 Cu2—N6 Cu2—N7 Cu2—N8
1.979 (3) 2.010 (4) 2.197 (4) 2.013 (4) 2.079 (4)
N1—Cu1—N3 O53—Cu1—N2 O53—Cu1—N4 N2—Cu1—N4 O53—Cu1—N1 O53—Cu1—N3 N1—Cu1—N2 N3—Cu1—N2 N1—Cu1—N4 N3—Cu1—N4
176.67 (15) 155.19 (14) 101.39 (14) 103.05 (15) 89.92 (14) 93.37 (14) 81.74 (14) 95.05 (15) 100.08 (14) 79.74 (15)
N5—Cu2—N7 O51—Cu2—N5 O51—Cu2—N7 O51—Cu2—N8 N5—Cu2—N8 N7—Cu2—N8 O51—Cu2—N6 N5—Cu2—N6 N7—Cu2—N6 N8—Cu2—N6
173.07 (16) 96.10 (15) 89.77 (15) 152.80 (15) 94.96 (16) 81.32 (17) 101.29 (16) 79.62 (16) 95.64 (16) 105.12 (16)
3. Supramolecular features
Figure 1 The structures of the molecular entities of (I), shown with 30% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds. H atoms have been omitted for clarity.
which are shorter than the in-plane Cu1—N2 and Cu1—N4 ˚ , respectively]. The bond lengths [2.051 (4) and 2.158 (4) A N1—Cu1—N3 bond angle is 176.67 (15) . The coordination parameters of the Cu2 atom are similar to those of the Cu1 atom. The CuII atoms display apparently different coordination patterns from the CuII complex coordinated by phen and 4-hydroxybenzoate ligands (Su et al., 2005), in which the reported complex is mononuclear, with the CuII ion being sixcoordinated by one chelating phen ligand and two chelating 4hydroxybenzoate anions through the carboxylate O atoms, resulting in an elongated octahedral geometry.
Figure 2 The molecular structure of the dinuclear CuII complex cation in (I), shown with 30% probability displacement ellipsoids. H atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds. Acta Cryst. (2016). E72, 1396–1399
In the crystal of (I), – stacking interactions occur between neighbouring phen ligands and generate a two-dimensional supramolecular system in the (100) plane, as shown in Fig. 3. The N1- and N3vii-phen [symmetry code: (vii) x, y + 12, z + 12] ligands are nearly parallel, the dihedral angle being 5.00 (11) and the shortest distance between the centroids of the ˚ . These aromatic rings (N1- and N3vii-rings) being 3.647 (3) A findings indicate – stacking between the N1- and N3vii-phen ligands of neighbouring complexes. The same is true for the N5- and C41viii-phen [symmetry code: (viii) x, y 12, z + 12] ligands, the dihedral angle being 8.48 (13) and the shortest distance between the centroids of the aromatic rings (N5- and ˚. C41viii-rings) being 3.671 (3) A The molecular packing of (I), as shown in Fig. 4, displays alternating layers along the a axis, one layer consisting of
Table 2 ˚ , ). Hydrogen-bond geometry (A D—H A
D—H
H A
D A
D—H A
O1W—H1A O53 O1W—H1B O61i O2W—H2A O61i O2W—H2B O4W ii O3W—H3A O62iii O3W—H3B O62 O4W—H4A O1W O4W—H4B O3W O5W—H5A O72 O5W—H5B O6W iv O73—H73 O8W O63—H63 O2W C3—H3 O1W i C8—H8 O6W C14—H14 O72 C21—H21 O4W ii C25—H25 O52 C33—H33 O62v C38—H38 O61iii C65—H65 O63vi C73—H71 O7W iv
0.97 1.00 0.97 0.83 1.00 1.00 1.01 0.86 0.96 0.97 0.82 0.82 0.93 0.93 0.93 0.93 0.93 0.93 0.93 0.93 0.93
1.90 1.76 1.75 2.04 1.69 1.84 1.79 1.94 1.87 1.84 2.15 1.85 2.59 2.48 2.50 2.58 2.47 2.55 2.37 2.49 2.58
2.819 (5) 2.758 (5) 2.708 (5) 2.843 (6) 2.685 (5) 2.731 (7) 2.756 (6) 2.750 (7) 2.818 (8) 2.779 (7) 2.88 (2) 2.638 (5) 3.240 (6) 3.371 (8) 3.388 (10) 3.230 (8) 3.033 (6) 3.247 (8) 3.298 (8) 3.410 (6) 3.413 (13)
157 169 169 160 172 147 160 157 169 164 148 161 127 162 159 128 119 132 172 172 149
Symmetry codes: (i) x; y þ 12; z þ 12; (ii) x þ 1; y þ 12; z þ 12; (iii) x þ 1; y; z; (iv) x; y þ 12; z 12; (v) x þ 1; y 12; z þ 12; (vi) x þ 1; y þ 1; z.
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Figure 3 The – stacking (dashed lines) between neighbouring dinuclear CuII complex cations, forming a two-dimensional supramolecular system parallel to (100). H atoms have been omitted for clarity. [Symmetry codes: (vii) x, y + 12, z + 12; (viii) x, y 12, z + 12.]
dinuclear CuII complex cations (complex-layer), the other consisting of noncoordinating 4-hydroxybenzoate anions and solvent water molecules (solvent-layer). Abundant hydrogenbonding interactions occur within the solvent-layer and among the solvent- and complex-layers (Table 2). The H atoms on
Table 3 Experimental details. Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A ( ) ˚ 3) V (A Z Radiation type (mm1) Crystal size (mm) Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters H-atom treatment
Figure 4 A packing diagram showing alternating layers along the a axis, one layer consisting of dinuclear CuII complex cations, the other consisting of noncoordinating 4-hydroxybenzoate dianions and solvent water molecules. H atoms have been omitted for clarity.
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[Cu2(C7H4O3)(C12H8N2)4](C7H5O3)27.5H2O
˚ 3) max, min (e A
[Cu2(C7H4O3)(C12H8N2)4](C7H5O3)27.5H2O 1393.33 Monoclinic, P21/c 296 22.6830 (11), 16.6644 (6), 16.8388 (6) 91.026 (3) 6364.0 (4) 4 Mo K 0.75 0.45 0.40 0.30
Xcalibur Atlas Gemini ultra Multi-scan (CrysAlis PRO; Agilent, 2014) 0.929, 1.000 27049, 11598, 7651 0.048 0.602
0.067, 0.201, 1.03 11598 861 H atoms treated by a mixture of independent and constrained refinement 0.90, 0.56
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1994), SHELXL2014 (Sheldrick, 2015) and ORTEP-3 for Windows and WinGX (Farrugia, 2012).
Acta Cryst. (2016). E72, 1396–1399
research communications O6W, O7W and O8W were not assigned in the structure, the ˚ and O8W O73 separations [O6W O7W = 2.729 (8) A ˚ 2.88 (2) A] suggest intermolecular hydrogen bonding between atoms O6W and O7W, and between O8W and O73.
4. Synthesis and crystallization Each reagent was available commercially and was of analytical grade. CuCl22H2O (0.17 g, 1 mmol), 4-hydroxybenzoic acid (0.28 g, 2 mmol), 1,10-phenanthroline (0.20 g, 1 mmol) and NaOH (0.16 g, 4 mmol) were dissolved in 20 ml water. The resulting solution was refluxed for 4 h and was then cooled to room temperature and filtered. Dark-green single crystals were obtained from the filtrate after five weeks.
5. Refinement Crystal data, data collection and structure refinement details are summarized in Table 3. The disordered water O8W atom was refined isotropically with a fixed occupacy of 0.5. Aromatic and hydroxy H atoms were placed in calculated ˚ and O—H = 0.82 A ˚ , and were positions, with C—H = 0.93 A included in the final cycles of refinement in riding mode, with
Acta Cryst. (2016). E72, 1396–1399
Uiso(H) = 1.2 and 1.5Ueq(parent), respectively. Water H atoms were located in difference Fourier map, and were refined with fixed positions and a fixed isotropic displacement parameter of ˚ 2. The H atoms of the water molecules O6W, O7W and 0.1 A O8W were not assigned. The peak corresponding to the maximum electron density in the difference Fourier map was ˚ ) to atom O8W. close (1.01 A
Acknowledgements This project was supported by Startup fund for scientific research, Taizhou University.
References Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, Oxfordshire, England. Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Deisenhofer, J. & Michel, H. (1989). EMBO J. 8, 2149–2170. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Su, J.-R., Gu, J.-M. & Xu, D.-J. (2005). Acta Cryst. E61, m244–m246.
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supporting information Acta Cryst. (2016). E72, 1396-1399
[doi:10.1107/S2056989016013943]
Crystal structure of µ-4-oxidobenzoato-κ2O1:O4-bis[bis(1,10-phenanthrolineκ2N,N′)copper(II)] bis(4-hydroxybenzoate) 7.5-hydrate Jian-Rong Su and Yu Li Computing details Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012). µ-4-Oxidobenzoato-κ2O1:O4-bis[bis(1,10-phenanthroline-κ2N,N′)copper(II)] bis(4-hydroxybenzoate) 7.5-hydrate Crystal data [Cu2(C7H4O3)(C12H8N2)4](C7H5O3)2·7.5H2O Mr = 1393.33 Monoclinic, P21/c a = 22.6830 (11) Å b = 16.6644 (6) Å c = 16.8388 (6) Å β = 91.026 (3)° V = 6364.0 (4) Å3 Z=4
F(000) = 2884 Dx = 1.454 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5425 reflections θ = 3.2–29.4° µ = 0.75 mm−1 T = 296 K Block, dark green 0.45 × 0.40 × 0.30 mm
Data collection Xcalibur Atlas Gemini ultra diffractometer Radiation source: Enhance (Mo) X-ray Source Detector resolution: 10.3592 pixels mm-1 ω scans Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) Tmin = 0.929, Tmax = 1.000
27049 measured reflections 11598 independent reflections 7651 reflections with I > 2σ(I) Rint = 0.048 θmax = 25.4°, θmin = 3.2° h = −27→24 k = −16→20 l = −16→20
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.067 wR(F2) = 0.201 S = 1.03 11598 reflections 861 parameters 0 restraints
Acta Cryst. (2016). E72, 1396-1399
Hydrogen site location: mixed H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0916P)2 + 7.0203P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.90 e Å−3 Δρmin = −0.56 e Å−3
sup-1
supporting information Special details Experimental. Absorption correction: CrysAlis PRO, Agilent Technologies, Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET) (compiled May 16 2011,17:55:39) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Cu1 Cu2 O51 O52 O53 C51 C52 H52 C53 H53 C54 C55 H55 C56 H56 C57 N1 N2 N3 N4 N5 N6 N7 N8 C1 H1 C2 H2 C3 H3 C4 C5 H5 C6 H6 C7
x
y
z
Uiso*/Ueq
0.28079 (2) 0.21227 (3) 0.25057 (16) 0.16596 (18) 0.32159 (14) 0.2467 (2) 0.2127 (2) 0.1723 0.2368 (2) 0.2130 0.2969 (2) 0.3326 (2) 0.3729 0.3070 (2) 0.3310 0.2179 (2) 0.30647 (16) 0.21591 (17) 0.25177 (17) 0.34316 (17) 0.15784 (18) 0.2601 (2) 0.26698 (18) 0.15934 (19) 0.3531 (2) 0.3779 0.3660 (2) 0.3990 0.3305 (2) 0.3391 0.2808 (2) 0.2391 (3) 0.2452 0.1913 (3) 0.1642 0.1815 (2)
0.31771 (3) −0.25364 (4) −0.1490 (2) −0.0964 (2) 0.21783 (19) −0.0085 (3) 0.0605 (3) 0.0554 0.1362 (3) 0.1807 0.1473 (3) 0.0770 (3) 0.0818 0.0013 (3) −0.0439 −0.0904 (3) 0.3111 (2) 0.3878 (2) 0.3299 (2) 0.4048 (2) −0.2504 (2) −0.3322 (2) −0.2714 (2) −0.3302 (2) 0.2736 (3) 0.2456 0.2747 (3) 0.2477 0.3153 (3) 0.3161 0.3563 (3) 0.3988 (3) 0.4020 0.4342 (3) 0.4593 0.4341 (3)
0.36174 (3) 0.35545 (3) 0.3772 (2) 0.3379 (2) 0.34046 (17) 0.3632 (3) 0.3706 (3) 0.3776 0.3678 (2) 0.3762 0.3527 (2) 0.3476 (3) 0.3403 0.3535 (3) 0.3509 0.3594 (2) 0.4759 (2) 0.4091 (2) 0.2478 (2) 0.3191 (2) 0.4483 (2) 0.4393 (2) 0.2643 (2) 0.2877 (2) 0.5068 (3) 0.4732 0.5880 (3) 0.6079 0.6377 (3) 0.6919 0.6076 (3) 0.6544 (3) 0.7091 0.6214 (3) 0.6539 0.5370 (3)
0.03912 (18) 0.04569 (19) 0.0555 (9) 0.0705 (11) 0.0449 (8) 0.0442 (11) 0.0453 (11) 0.054* 0.0423 (11) 0.051* 0.0403 (11) 0.0450 (11) 0.054* 0.0474 (12) 0.057* 0.0468 (12) 0.0388 (9) 0.0425 (9) 0.0416 (9) 0.0409 (9) 0.0439 (9) 0.0531 (11) 0.0471 (10) 0.0475 (10) 0.0452 (11) 0.054* 0.0480 (12) 0.058* 0.0517 (13) 0.062* 0.0454 (11) 0.0596 (15) 0.071* 0.0579 (14) 0.069* 0.0477 (12)
Acta Cryst. (2016). E72, 1396-1399
Occ. (
