tetrakis(hydrogen phthalate) tetrahydrate and coordination ... - CiteSeerX

metal-organic compounds Acta Crystallographica Section C

Crystal Structure Communications ISSN 0108-2701

Dirubidium hexaaquacobalt(II) tetrakis(hydrogen phthalate) tetrahydrate and coordination modes of the hydrogen phthalate anion Dejan Poleti* and Jelena Rogan Department of General and Inorganic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia Correspondence e-mail: [email protected]

metal cation and a transition metal cation. Actually, the first such complex, K2[Ni(H2O)6](Hpht)44H2O, (II), was reported some years ago (Biagini Cingi et al., 1984), and was recently described again by Wu et al. (2009), who appeared to be unaware of the previous publication. Meanwhile, the structures of two very similar complexes, K2[Co(H2O)6](Hpht)44H2O, (III) (Furmanova et al., 2000), and K2[Co0.76Ni0.24(H2O)6](Hpht)44H2O, (IV) (Muthu et al., 2012a), were described. Thus, (II), (III) and (IV), together with Rb2[Co(H2O)6](Hpht)44H2O, (I), and the caesium analogue Cs2[Co(H2O)6](Hpht)44H2O, (V), presented here, form a short series of five heterocation complexes with identical general formula and the same crystal structure. These types of complex show good transparency for visible light and have recently been mentioned as potential nonlinear optic and electro-optic materials (Muthu et al., 2012a,b).

Received 1 May 2013 Accepted 17 June 2013

The title compound, Rb2[Co(H2O)6](C8H5O4)44H2O, consists of nearly regular octahedral [Co(H2O)6]2+ cations with the CoII cations on the inversion centre (special position 2a), Rb+ cations, hydrogen phthalate (Hpht) anions and disordered water molecules. The Rb+ cation is surrounded by nine O atoms from Hpht anions and water molecules, with a strongly deformed pentagonal–bipyramidal geometry and one apex split into three positions. The crystal packing is governed by numerous hydrogen bonds involving all water molecules and Hpht anions. In this way, layers parallel to the ab plane are formed, with the aromatic rings of the Hpht anions esentially directed along the c axis. While Hpht anions form the outer part of the layers, disordered water molecules and Rb+ cations alternate with [Co(H2O)6]2+ cations in the inner parts. The only interactions between the layers are van der Waals forces between the atoms of the aromatic rings. A search of the Cambridge Structural Database for coordination modes and types of hydrogen-bonding interaction of the Hpht anion showed that, when uncoordinated Hpht anions are present, compounds with intermolecular hydrogen bonds are more numerous than compounds with intramolecular hydrogen bonds. For coordinated Hpht anions, chelating and bridging anions are almost equally common, while monodentate anions are relatively scarce. The same coordination modes appear for Hpht anions with or without intramolecular hydrogen bonds, although intramolecular hydrogen bonds are less common. Keywords: crystal structure; hexaaquacobalt(II); hydrogen phthalate anion; rubidium salt.

1. Introduction The title compound, dirubidium hexaaquacobalt(II) tetrakis(hydrogen phthalate) tetrahydrate, (I), belongs to the rare class of complexes containing hydrogen phthalate anions (Hpht) and a combination of two metal cations, i.e. an alkali Acta Cryst. (2013). C69

In the report of Biagini Cingi et al. (1984), one uncoordinated water molecule is split over two close positions, while another has an extremely high displacement parameter [B = ˚ 2]. Later, both solvent water molecules were 13.2 (2) A described as disordered (Furmanova et al., 2000; Muthu et al., 2012a). Therefore, although (I) was obtained unintentionally during attempts to prepare a mixed-cation complex with pht2 and not Hpht anions, we decided to perform the crystal structure analysis in order to resolve ambiguity about uncoordinated water molecules and to test the influence of increasing alkali cation size on the structure and properties. Since crystals of Cs2[Co(H2O)6](Hpht)44H2O, (V), were of poor quality, only the space group and unit-cell parameters were determined in a preliminary experiment: P21/c, a = ˚ , = 96.09 (19) and 10.05 (4), b = 6.78 (6) and c = 30.69 (9) A 3 ˚ V = 2080 (17) A . These data suggested isostructurality with (I)–(IV), although an unexpected slightly smaller unit-cell volume with respect to (I) was observed.

2. Experimental 2.1. Synthesis and crystallization

The title compounds were crystallized from a dilute (0.1 M) aqueous solution containing Co2+, pht2 and Rb+/ Cs+ ions in the molar ratio 1:2:2. The initial pH of the solution was 4.5. Suitable single crystals were obtained by slow evaporation under ambient conditions after approximately five months. The IR spectra confirmed the presence of Hpht anions and a great similarity between (I), (II) and (V).

doi:10.1107/S0108270113016788

# 2013 International Union of Crystallography

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metal-organic compounds Table 1 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)

Rb2[Co(H2O)6](C8H5O4)44H2O 1070.51 Monoclinic, P21/c 295 10.3408 (5), 6.8658 (3), 30.0660 (17) 97.743 (5) 2115.16 (18) 2 Mo K 2.78 0.48 0.23 0.15

Data collection Diffractometer Absorption correction

Oxford Gemini S diffractometer Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) 0.690, 1.000 9648, 4326, 3305

Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A

0.033 0.625

Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment

0.056, 0.115, 1.07 4326 317 8 H atoms treated by a mixture of independent and constrained refinement 0.54, 0.67

˚ 3) max, min (e A

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), Mercury (Macrae et al., 2008), ATOMS (Dowty, 2006), publCIF (Westrip, 2010) and PARST (Nardelli, 1995).

Figure 1 Part of the crystal structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are plotted at the 50% probability level. The two crystallographically independent Hpht anions are labelled A and B. H atoms have been omitted for clarity. [Symmetry codes: (i) x + 1, y, z + 1; (ii) x + 2, y, z + 1; (iii) x + 2, y + 1, z + 1; (viii) x 1, y, z.]

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically and refined as riding, with C—H = ˚ and Uiso(H) = 1.2Ueq(C). The initial positions of the 0.93 A remaining H atoms were calculated using the program HYDROGEN (Nardelli, 1999) and were then refined isotro˚ . The pically, with O—H bond lengths restrained to 0.85 (1) A exceptions were the H atoms of the disordered water molecules (O12 and O13), which were added to the structural model in the final cycles of refinement with fixed coordinates and Uiso(H) values of 1.5Ueq(O). The site-occupation factors of the major positions of the disordered water molecules refined to 0.69 (2) and 0.604 (8) for O12B and O13B, respectively, while the atomic displacement ellipsoids for the two positions of each water molecule were constrained to be equal.

3. Results and discussion The general structural characteristics of (I) (Figs. 1 and 2) are in accordance with previous descriptions (Biagini Cingi et al., 1984; Furmanova et al., 2000; Muthu et al., 2012a). Atom Co1 is located on the inversion centre (special position 2a) and the octahedral [Co(H2O)6]2+ cation is close to regular, with minor orthorhombic deformations (Table 1). As shown in Fig. 2, in the crystal packing of (I) there are ‘sandwich’ layers parallel to (001). Rb+ and [Co(H2O)6]2+

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Rb2[Co(H2O)6](C8H5O4)44H2O

cations, together with uncoordinated water molecules, are concentrated in the inner layer, while Hpht anions make up the outer part of the layers. Thus, between the layers only weak van der Waals interactions exist and perfect crystal cleavage could be expected. There are two different Hpht anions (A and B; Fig. 1). In anion A, the dihedral angle between the aromatic ring and the –COO group is 69.5 (2) , while the dihedral angle between the aromatic ring and the –COOH group is 23.8 (2) ; in anion B, the corresponding dihedral angles are 74.2 (2) and 24.3 (3) , respectively. Hpht anions are connected in columns parallel to the b axis (Fig. 2) by relatively short hydrogen bonds (Table 2). All these findings are quite common when there are intermolecular hydrogen bonds present between Hpht anions (Langkilde et al., 2004; Biagini Cingi et al., 1984). Atom Rb1 is surrounded by nine O atoms, five from Hpht anions and four from water molecules, with Rb—O distances ˚ (Table 1). The correranging from 2.783 (9) to 3.391 (3) A sponding polyhedron can be described as a deformed pentagonal bipyramid, with atoms O4, O5, O10ii, O12B and O13B in the equatorial plane, and one apex split into three positions occupied by atoms O8, O12Bi and O13Ai (symmetry codes are as given in Fig. 1). A bond-valence calculation (Wills, 2011) yielded a quite acceptable sum value of 1.07 valence units. The coordination number (CN) of the Rb atom in (I) is higher than Acta Cryst. (2013). C69

metal-organic compounds Table 2 ˚ ). Selected bond lengths (A Rb1—O12B Rb1—O8 Rb1—O12A Rb1—O4 Rb1—O9 Rb1—O13Bi Rb1—O13Ai Rb1—O13B Rb1—O5

2.783 (9) 2.860 (3) 2.93 (2) 2.973 (3) 3.041 (3) 3.127 (9) 3.155 (14) 3.189 (10) 3.252 (3)

Rb1—O12Bi Rb1—O10ii Co1—O11 Co1—O11iii Co1—O9iii Co1—O9 Co1—O10iii Co1—O10

3.259 (16) 3.391 (3) 2.063 (3) 2.063 (3) 2.088 (3) 2.088 (3) 2.121 (3) 2.121 (3)

Symmetry codes: (i) x þ 1; y; z þ 1; (ii) x þ 2; y; z þ 1; (iii) x þ 2, y þ 1; z þ 1.

in other Rb-containing Hpht compounds, viz. RbHpht (Smith, 1975b) and Rb[H(Hpht)2]2H2O (Ku¨ppers, 1977) have CN = 7 and 8, respectively. However, since water molecules O12 and O13 are statistically disordered over two positions in an approximate 13:23 ratio for O atoms labelled A and B, respectively (Fig. 1), an alternative view of the Rb coordination polyhedra can be given. If the water molecules are classified as bridging (darker shading in Fig. 1) and terminal (lighter shading in Fig. 1), then two thirds of the centrosymmetrically related Rb+ cations are bridged by water molecules to form Rb2(H2O)4 units; these Rb+ cations are surrounded by nine O atoms. The remaining one third of the Rb+ cations have only seven nearest neighbours, involving terminal water molecules O12A and O13A. In this manner, the real structure would be a combination of these two extremes, and the depiction obtained by X-ray diffraction is just an average of them. As expected, the Rb—O distances in (I) are longer than the K—O distances in complexes (II)–(IV), which range between ˚ . However, the CN for K+ is only 8, while about 2.64 and 3.31 A ˚ . This distinction can the ninth O atom is at a distance of 3.5 A be easily explained by the different radii of K+ and Rb+ cations (Shannon, 1976). It is remarkable that, with increasing ionic radius, the distance between pairs of disordered water mol˚ in (III) and ecules decreases; they are about 0.85 and 1.30 A ˚ ˚ for (IV), but only 0.70 (3) A for O12A O12B and 0.90 (2) A O13A O13B in (I). As mentioned at the beginning, disorder of water molecules is common for this group of complexes and it was simply not completely resolved in the case of (II) (Biagini Cingi et al., 1984). In (I), the two Rb polyhedra described above alternate with [Co(H2O)6]2+ octahedra in the inner part of the layers (Fig. 2), where there are also numerous hydrogen bonds (Table 2). A great similarity in unit-cell dimensions and crystal packing between (I)–(V) and [Co(H2O)6](Hpht)2 (Adiwidjaja et al., 1978) should be emphasized. For example, the unit-cell volumes of [Co(H2O)6](Hpht)2 and (I) are quite similar ˚ 3, respectively]. This is because [2014.1 (5) and 2115.16 (18) A every second Co octahedron in [Co(H2O)6](Hpht)2 is simply replaced by two Rb polyhedra in (I). The Rb Rb distance in ˚ , which is comparable with the K K (I) is 4.4218 (7) A ˚ ) in (III) (Furmanova et al., 2000) and distances (about 4.45 A (IV) (Muthu et al., 2012a). With respect to other hydrogen benzenedicarboxylate anions, such as hydrogen iso- and terephthalate, the Hpht Acta Cryst. (2013). C69

Figure 2 A projection of (I), along the b axis, showing the crystal packing and the hydrogen bonding between Hpht anions (dashed lines). For emphasis, [Co(H2O)6]2+ octahedra are also shown.

anion with its –COO and –COOH groups in an ortho position is special because intramolecular hydrogen bonding is possible. As a consequence, compounds containing Hpht anions can be classified into two main groups, viz. with or without intramolecular hydrogen bonds. In the latter case, Hpht anions are usually connected in infinite chains, as also found in (I). In both cases, the hydrogen bonds are short and strong, but typically shorter if they are intramolecular (2.35– ˚ ). These are the main conclusions from 2.40 versus 2.50–2.60 A a recent study by Langkilde et al. (2004). However, that study was limited, in a way, focusing only on the classification of the hydrogen bonds and the geometry of the Hpht anions. Therefore, we also did a search of the Cambridge Structural Database (CSD, Version 5.33; Allen, 2002), concentrating on the coordination modes of Hpht anions in addition to the type of hydrogen bonding. The search involved alkali and alkaline earth metal (AM) salts, and transition and inner transition metal (TM) complexes. Two compounds containing NH4+ and (CH3)4N+ cations and one Tl+ salt were also included, due to their expected similarity with AM cations. The CSD survey resulted in 64 unique compounds with 90 Hpht anions overall. As in (I)–(V), some compounds contain two crystallographically and/or chemically different Hpht Poleti and Rogan


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metal-organic compounds anions. They could be all uncoordinated, like in (I)–(V), both coordinated and uncoordinated, as in [Mn2(Hpht)2(phen)4](Hpht)22H2O (phen is 1,10-phenanthroline; Ma et al., 2004) and [Mn2(Hpht)2(phen)4](Hpht)26H2O (Yang et al., 2005), or coordinated in different ways, as in [Zn(Hpht)2(4,40 -bpy)] (4,40 -bpy is 4,40 -bipyridine; Tang et al., 2004). All types of hydrogen bonds can be further classified as symmetrical, as in

[Co(H2O)6](Hpht)2 (Ku¨ppers, 1990) and [Cd(Hpht)2(4,40 bpy)]n (Wang et al., 2005), or asymmetrical, which is observed more frequently. These two types were not treated separately due to the well known uncertainty in the H-atom coordinates in most cases. When uncoordinated Hpht anions with intramolecular hydrogen bonds are present, sometimes interesting Hpht H2O Hpht chains can be found, instead of

Figure 3 Coordination modes of Hpht anions, with numbers showing the appearance of each coordination mode (AM = alkali and alkaline earth metals and TM = transition metals). (a) AM: Askarinejad & Morsali (2006); Bats, Schuckmann & Fuess (1978); Hu et al. (2004); Jessen (1990); Kariuki & Jones (1989); Li et al. (2003); Okaya (1965); Smith (1975a,b,c, 1977). TM: Adiwidjaja et al. (1978); Babb et al. (2003); Baca et al. (2003); Biagini Cingi et al. (1984); Furmanova et al. (2000); Kariuki & Jones (1993); Muthu et al. (2012a); Tomic´ et al. (1996); Zhao et al. (2002). Complexes (I) and (V) described in this study are also accounted for. (b) AM: Gonschorek & Ku¨ppers (1975); Kariuki & Jones (1989); Ku¨ppers (1978); Ku¨ppers et al. (1981); Langkilde et al. (2004). TM: Baca et al. (2005); Cingi et al. (1977); Ku¨ppers (1990); Ma et al. (2004); Poleti et al. (1999); Sharma et al. (2005); Yang et al. (2005); Zhu et al. (2010). (c) Benedict et al. (2004); Ku¨ppers (1977). (d) Adiwidjaja & Ku¨ppers (1976); Babb et al. (2003); Bermejo et al. (1999); Tang et al. (2004). (e) Marsh (2009). (f) Sun et al. (2011). (g) Gerbeleu et al. (1999); Tang et al. (2004). (h) Bartl & Ku¨ppers (1980). (i) Baca et al. (2003, 2005). (j) Chen et al. (2001); Li et al. (2000); Ma et al. (2004); Poleti et al. (1999); Yang et al. (2005). (k) Escuer et al. (1997). (l) Bats, Kallel & Fuess (1978); Rodrigues et al. (1999). (m) Bermejo et al. (1999); Wang et al. (2005). (n) Sun et al. (2011). (o) Escuer et al. (1997).

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metal-organic compounds Table 3 ˚ , ). Hydrogen-bond geometry (A D—H A

D—H

H A

D A

D—H A

O3—H31 O5 O7—H7 O2iv O9—H9A O1v O9—H9B O6ii O10—H10A O6 O10—H10B O1vi O11—H11A O8vii O11—H11B O5 O12A—H12A O2v O12A—H12B O4i O12B—H12C O2v O12B—H12D O4i O13A—H13A O8i O13A—H13B O11v O13B—H13C O2v O13B—H13D O13Bv

0.85 (4) 0.85 (5) 0.85 (4) 0.85 (4) 0.85 (3) 0.84 (3) 0.84 (5) 0.85 (4) 0.86 0.84 0.86 0.86 0.87 0.84 0.87 0.88

1.73 (4) 1.70 (5) 1.89 (4) 1.82 (4) 1.85 (3) 1.98 (4) 2.17 (5) 1.88 (4) 2.11 2.57 1.98 2.18 2.02 2.38 2.32 2.05

2.572 (5) 2.548 (4) 2.701 (4) 2.654 (4) 2.691 (4) 2.794 (4) 3.008 (5) 2.708 (5) 2.78 (2) 3.39 (2) 2.84 (1) 3.02 (1) 2.73 (1) 3.00 (2) 3.111 (9) 2.75 (1)

175 (5) 177 (5) 160 (4) 167 (4) 171 (3) 161 (3) 175 (4) 164 (4) 134 163 169 163 138 132 151 136

Symmetry codes: (i) x þ 1; y; z þ 1; (ii) x þ 2; y; z þ 1; (iv) x; y 1; z; (v) x þ 1; y þ 1; z þ 1; (vi) x þ 1; y; z; (vii) x; y þ 1; z.

Hpht Hpht chains, as in [M(1-MeIm)6](Hpht)22H2O (M = Co or Ni; 1-MeIm is 1-methylimidazole; Baca et al., 2004). The results of the CSD search are summarized in Fig. 3. The compounds containing AM, ammonium or Tl+ cations are regarded as ionic salts. When uncoordinated Hpht anions are considered, those with intermolecular hydrogen bonds are more numerous, regardless of the cations present. Previously, Langkilde et al. (2004) found a nearly equal distribution of the two bond types, but the present survey is more reliable since it involves a greater number of compounds with duplicated structures excluded. Also, it can be concluded that the presence of different AM or TM cations has no significant influence on the types of hydrogen bonds. A good example is [Co(H2O)6](Hpht)2, which appears as three polymorphs, two of them (Adiwidjaja et al., 1978; Kariuki & Jones, 1993) with intermolecular and one (Ku¨ppers, 1990) with intramolecular hydrogen bonds. This suggests that the stabilities of the different Hpht conformations are similar. Two special cases are K[H(Hpht)2]2H2O (Benedict et al., 2004) and Rb[H(Hpht)2]2H2O (Ku¨ppers, 1977) containing the so-called hydrogen diphthalate anion (Fig. 3, Type 1 III), which can be described as a proton-bound hydrogen phthalate dimer. If compounds containing TM cations are compared, coordinated Hpht anions are slightly more common than uncoordinated ones. Thus, the presence of the –COOH group has no strong influence on the coordination ability of Hpht anions. Fig. 3 also shows a somewhat unexpected diversity of coordination modes of Hpht anions, which can be from mono- to tetradentate, and also bridging or chelating. Extreme examples are the Hpht anions in [Ag2(cnpy)2(Hpht)2] (cnpy is 4-cyanopyridine; Sun et al., 2011) and the Hpht anion in {[Cu(Hpht)(N3)]H2O}n (Escuer et al., 1997), where only protonated O atoms are uncoordinated and Hpht acts as an endo–exo (i.e. 1,2,4) and a mono-endo-exo (i.e. 1,1,3,4) bridge, respectively. Chelating and bridging Hpht anions are almost equally common, while monodentate Hpht anions are relatively scarce. The same coordination modes appear for Hpht anions with or without intramolecular hydrogen bonds, Acta Cryst. (2013). C69

although those with intramolecular ones are generally less common (compare the corresponding Type I and II modes in Fig. 3), as was concluded for uncoordinated Hpht anions. Finally, some interesting hydrogen-bond motifs should be mentioned. In [Mn2(Hpht)2(phen)4](ClO4)22H2O (Ma et al., 2004), dimeric complex units make pseudo-chains due to intermolecular hydrogen bonds in the form of centrosymmetric R22 (8) pseudo-rings (Bernstein et al., 1995) characteristic of carboxylic acids. In the above-mentioned [Ag2(cnpy)2(Hpht)2], the complex units also form pseudo-dimers, but in this case much larger R22 (14) pseudo-rings exist (Fig. 3, Type 2.1 III). This work was supported financially by the Ministry for Education, Science and Technological Development of the Republic of Serbia (grant No. 45007). We are indebted to Dr Tamara Ðord-evic´ for help with drawing Fig. 2. Supplementary data for this paper are available from the IUCr electronic archives (Reference: WQ3035). Services for accessing these data are described at the back of the journal.

References Adiwidjaja, G. & Ku¨ppers, H. (1976). Acta Cryst. B32, 1571–1574. Adiwidjaja, G., Rossmanith, E. & Ku¨ppers, H. (1978). Acta Cryst. B34, 3079– 3083. Allen, F. H. (2002). Acta Cryst. B58, 380–388. Askarinejad, A. & Morsali, A. (2006). J. Coord. Chem. 59, 997–1005. Babb, J. E. V., Burrows, A. D., Harrington, R. W. & Mahon, M. F. (2003). Polyhedron, 22, 673–686. Baca, S. G., Filippova, I. G., Ambrus, C., Gdaniec, M., Simonov, Y. A., Gerbeleu, N., Gherco, O. A. & Decurtins, S. (2005). Eur. J. Inorg. Chem. pp. 3118–3130. Baca, S. G., Filippova, I. G., Gherco, O. A., Gdaniec, M., Simonov, Y. A., Gerbeleu, N. V., Franz, P., Basler, R. & Decurtins, S. (2004). Inorg. Chim. Acta, 357, 3419–3429. Baca, S. G., Simonov, Y., Gdaniec, M., Gerbeleu, N., Filippova, I. G. & Timco, G. A. (2003). Inorg. Chem. Commun. 6, 685–689. Bartl, H. & Ku¨ppers, H. (1980). Z. Kristallogr. 152, 161–167. Bats, J. W., Kallel, A. & Fuess, H. (1978). Acta Cryst. B34, 1705–1707. Bats, J. W., Schuckmann, W. & Fuess, H. (1978). Acta Cryst. B34, 2627–2628. Benedict, J. B., Bullard, T., Kaminsky, W. & Kahr, B. (2004). Acta Cryst. C60, m551–m553. Bermejo, M. R., Fondo, M., Garcia-Deibe, A., Gonzalez, A. M., Sousa, A., Sanmartin, J., McAuliffe, C. A., Pritchard, R. G., Watkinson, M. & Lukov, V. (1999). Inorg. Chim. Acta, 293, 210–217. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. Biagini Cingi, M., Manotti Lanfredi, A. M. & Tiripicchio, A. (1984). Acta Cryst. C40, 56–58. Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Chen, C., Zhu, H., Huang, D., Wen, T., Liu, Q., Liao, D. & Cui, J. (2001). Inorg. Chim. Acta, 320, 159–166. Cingi, M. B., Lanfredi, A. M. M., Tiripicchio, A. & Camellini, M. T. (1977). Acta Cryst. B33, 3772–3777. Dowty, E. (2006). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA. Escuer, A., Vicente, R., Mautner, F. A. & Goher, M. A. S. (1997). Inorg. Chem. 36, 1233–1236. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Furmanova, N. G., Eremina, T. A., Okhrimenko, T. M. & Kuznetsov, V. A. (2000). Crystallogr. Rep. 45, 771–774. Gerbeleu, N. V., Simonov, Yu. A., Timko, G. A., Bourosh, P. N., Lipkovskii, J., Baka, S. G., Saburov, D. I. & Mazus, M. D. (1999). Russ. J. Inorg. Chem. 44, 1191–1204. Gonschorek, W. & Ku¨ppers, H. (1975). Acta Cryst. B31, 1068–1072. Poleti and Rogan


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metal-organic compounds Hu, M., Geng, C., Li, S., Liu, Z., Jiang, Y. & Zhang, G. (2004). Acta Cryst. E60, m1713–m1715. Jessen, S. M. (1990). Acta Cryst. C46, 1513–1515. Kariuki, B. M. & Jones, W. (1989). Acta Cryst. C45, 1297–1299. Kariuki, B. M. & Jones, W. (1993). Acta Cryst. C49, 2100–2102. Ku¨ppers, H. (1977). Z. Kristallogr. 146, 269–280. Ku¨ppers, H. (1978). Acta Cryst. B34, 3763–3765. Ku¨ppers, H. (1990). Z. Kristallogr. 192, 97–102. ˚ . & Olovsson, I. (1981). Acta Cryst. B37, 1203–1207. Ku¨ppers, H., Kvick, A Langkilde, A., Madsen, D. & Larsen, S. (2004). Acta Cryst. B60, 502–511. Li, L., Liao, D., Jiang, Z. & Yan, S. (2000). Polyhedron, 19, 2529–2532. Li, Y.-F., Zhang, T.-L., Zhang, J.-G. & Yu, K.-B. (2003). Z. Naturforsch. Teil B, 58, 1171–1175. Ma, C., Wang, W., Zhang, X., Chen, C., Liu, Q., Zhu, H., Liao, D. & Li, L. (2004). Eur. J. Inorg. Chem. pp. 3522–3532. Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Marsh, R. E. (2009). Acta Cryst. B65, 782–783. Muthu, M., Bhagavannarayana, G. & Meenakashisundarama, S. P. (2012a). Solid State Sci. 14, 1355–1360. Muthu, M., Bhagavannarayana, G. & Meenakashisundarama, S. P. (2012b). Spectrochim. Acta Part A, 92, 289–294. Nardelli, M. (1995). J. Appl. Cryst. 28, 659. Nardelli, M. (1999). J. Appl. Cryst. 32, 563–571. Okaya, Y. (1965). Acta Cryst. 19, 879–882. Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.

6 of 6

Poleti and Rogan


Poleti, D., Karanovic´, L., Bogdanovic´, G. A. & Spasojevic´-de Bire´, A. (1999). Acta Cryst. C55, 2061–2063. Rodrigues, B. L., Costa, M. D. D. & Fernandes, N. G. (1999). Acta Cryst. C55, 1997–2000. Shannon, R. D. (1976). Acta Cryst. A32, 751–767. Sharma, R. P., Bala, R., Sharma, R., Kariuki, B. M., Rychlewska, U. & Warzajtis, B. (2005). J. Mol. Struct. 748, 143–151. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Smith, R. A. (1975a). Acta Cryst. B31, 2345–2347. Smith, R. A. (1975b). Acta Cryst. B31, 2347–2348. Smith, R. A. (1975c). Acta Cryst. B31, 2508–2509. Smith, R. A. (1977). Acta Cryst. B33, 1594–1596. Sun, D., Wei, Z.-H., Yang, C.-F., Wang, D.-F., Zhang, N., Huang, R.-B. & Zhang, L.-S. (2011). CrystEngComm, 13, 1591–1601. Tang, E., Dai, Y.-M. & Lin, S. (2004). Acta Cryst. C60, m433–m434. Tomic´, Z., Prelesnik, B., Karanovic´, L. & Poleti, D. (1996). J. Serb. Chem. Soc. 61, 97–106. Wang, X., Qin, Ch., Wang, E. & Xu, L. (2005). J. Mol. Struct. 737, 49–54. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Wills, A. S. (2011). VALIST. Program available from https://dl.dropbox.com/u/ 8933134/Website/Site/Software/Software.html. Wu, W., Xie, J.-M. & Xuan, Y.-W. (2009). Z. Anorg. Allg. Chem. 635, 351– 354. Yang, J.-M., Zhou, Z.-H., Zhang, H., Wan, H.-L. & Lu, S.-J. (2005). Inorg. Chim. Acta, 358, 1841–1849. Zhao, J.-S., Zhang, R.-L., Su, B.-Y., Gu, A.-P., He, S.-Y., Xue, G.-L., Liu, J.-N., Dou, J.-M. & Wang, D.-Q. (2002). Acta Chim. Sin. 60, 2069–2073. Zhu, H.-L., Zhang, J. & Lin, J.-L. (2010). Acta Cryst. E66, m185.


supplementary materials

supplementary materials Acta Cryst. (2013). C69 [doi:10.1107/S0108270113016788]

Dirubidium hexaaquacobalt(II) tetrakis(hydrogen phthalate) tetrahydrate and coordination modes of the hydrogen phthalate anion Dejan Poleti and Jelena Rogan Computing details Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012); molecular graphics: Mercury (Macrae et al., 2008) and ATOMS (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and PARST (Nardelli, 1995). Dirubidium hexaaquacobalt(II) tetrakis(hydrogen phthalate) tetrahydrate Crystal data Rb2[Co(H2O)6](C8H5O4)4·4H2O Mr = 1070.51 Monoclinic, P21/c Hall symbol: -P 2ybc a = 10.3408 (5) Å b = 6.8658 (3) Å c = 30.0660 (17) Å β = 97.743 (5)° V = 2115.16 (18) Å3 Z=2

F(000) = 1082 Dx = 1.681 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3513 reflections θ = 3.0–28.9° µ = 2.78 mm−1 T = 295 K Prismatic, pink 0.48 × 0.23 × 0.15 mm

Data collection Oxford Gemini S diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 16.3280 pixels mm-1 φ and ω scans Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) Tmin = 0.690, Tmax = 1.000

9648 measured reflections 4326 independent reflections 3305 reflections with I > 2σ(I) Rint = 0.033 θmax = 26.4°, θmin = 3.3° h = −8→12 k = −8→6 l = −37→32

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.056 wR(F2) = 0.115 S = 1.07 4326 reflections 317 parameters


8 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: difference Fourier map

sup-1

supplementary materials H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0392P)2 + 2.5644P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 0.54 e Å−3 Δρmin = −0.66 e Å−3

Special details Experimental. Absorption correction: CrysAlisPro (Oxford Diffraction, 2010). (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. 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 > 2sigma(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)

Rb1 Co1 O1 O2 O3 H31 O4 O5 O6 O7 H7 O8 O9 H9A H9B O10 H10A H10B O11 H11A H11B O12A H12A H12B O12B H12C H12D O13A H13A H13B O13B

x

y

z

Uiso*/Ueq

Occ. (