Poly­[[di­aqua(μ4 squarato O,O′,O′′,O′′′)­nickel(II)] 0 71 hydrate]

(1)metal-organic papers Acta Crystallographica Section E. Structure Reports Online. Poly[[diaqua(l4-squarato-O,O0 ,O0 0 ,O0 0 0 )nickel(II)] 0.71-hydrate]. ISSN 1600-5368. Jan Greve and Christian NaÈther* Institut fuÈr Anorganische Chemie, ChristianAlbrechts-UniversitaÈt Kiel, Olshausenstraûe 40, D-24098 Kiel, Germany Correspondence e-mail: cnaether@ac.uni-kiel.de. Key indicators Single-crystal X-ray study T = 293 K Ê Mean (C±C) = 0.003 A Disorder in solvent or counterion R factor = 0.024 wR factor = 0.077 Data-to-parameter ratio = 11.9 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. # 2002 International Union of Crystallography Printed in Great Britain ± all rights reserved. Acta Cryst. (2002). E58, m653±m655. In the title compound, {[Ni(C4O4)(H2O)2]0.71H2O}n, each Ni atom is coordinated by four squarate dianions and two water molecules within a slightly distorted octahedron. The water molecules occupy general positions and the Ni atom, as well as the two crystallographically independent squarate dianions, are located in special positions. Hydrogen bonding is found between the O atoms of the squarate dianions and the water molecules. In the crystal structure, voids are found that are ®lled with disordered clathrate water molecules. The compound is isotypic with the previously reported Mn, Fe and Co compounds.. Received 11 October 2002 Accepted 15 October 2002 Online 18 October 2002. Comment Recently, we have been interested in the preparation of new coordination polymers based on transition-metal squarates and N-donor ligands, such as 4,40 -bipyridine (NaÈther et al., 2002a; Greve, 2000) or pyrazine (Greve, 2000; NaÈther & Jeû, 2001; NaÈther et al., 2002b). During the preparation of these compounds, mixtures are sometimes obtained that contain the pure metal squarate dihydrates. This is the case for the reaction of nickel chloride with squaric acid and 4,40 -bipyridine, in which crystals of the title compound, (I), are obtained as the minor phase.. The structure of (I) is isotypic with the previously reported Mn (Greve & NaÈther, 2002), Fe (NaÈther et al., 2002c) and Co compounds (Lee et al., 1996). The asymmetric unit contains half an Ni atom, quarters of two separate dianions which are located in special positions and one water molecule in a general position. One of the two crystallographically independent squarate dianions is located around a fourfold axis, whereas the second is located around a fourfold rotoinversion axis. The geometry of these two dianions is comparable. Between the water molecules and the squarate O atoms strong OÐH  O hydrogen bonding is found. The Ni atoms are coordinated by four O atoms of squarate dianions and two water molecules within a slightly distorted octahedron. Each DOI: 10.1107/S1600536802018895. Greve and NaÈther. . [Ni(C4O4)(H2O)2]0.71H2O. m653.

(2) metal-organic papers 5 ml of water in a Te¯on-lined steel autoclave at 423 K under hydrothermal conditions. After 5 d, the reaction mixture was cooled to room temperature, ®ltered and the resulting precipitate washed with water. The precipitate consists of a mixture of colourless crystals of the 4,40 -bipyridine compound poly[[diaqua(2-squarato-O,O0 )(24,40 -bipyridine)nickel(II)] hydrate] (Greve, 2000) and light-green crystals of (I). The composition of the precipitate was determined by X-ray powder diffraction. Crystal data Cell parameters from 8000 re¯ections  = 2.5±26.5  = 2.76 mmÿ1 T = 293 (2) K Block, light green 0.2  0.2  0.2 mm. [Ni(C4O4)(H2O)2]0.71H2O Mr = 218.12 Cubic, Pn3n Ê a = 16.1467 (8) A Ê3 V = 4209.7 (4) A Z = 24 Dx = 2.065 Mg mÿ3 Mo K radiation. Data collection. Figure 1. The crystal structure of the title compound, with a view of the Ni coordination, the atom labelling and displacement ellipsoids drawn at the 50% probability level [symmetry code: (i) y, x, ÿz + 12].. Rint = 0.026 max = 26.5 h = ÿ8 ! 20 k = ÿ16 ! 20 l = ÿ14 ! 16. Stoe IPDS diffractometer ' scans Absorption correction: none 7475 measured re¯ections 704 independent re¯ections 508 re¯ections with I > 2(I). Re®nement Re®nement on F 2 R[F 2 > 2(F 2)] = 0.024 wR(F 2) = 0.077 S = 1.07 704 re¯ections 59 parameters H-atom parameters constrained. w = 1/[ 2(Fo2) + (0.0348P)2 + 5.3938P] where P = (Fo2 + 2Fc2)/3 (/)max = 0.001 Ê ÿ3 max = 0.48 e A Ê ÿ3 min = ÿ0.46 e A Extinction correction: SHELXL97 Extinction coef®cient: 0.00045 (9). Table 1. Ê ,  ). Selected geometric parameters (A NiÐO3 NiÐO1 NiÐO2 C1ÐO1. 2.0206 (15) 2.0593 (16) 2.0826 (17) 1.255 (3). C1ÐC1i C2ÐO2 C2ÐC2ii. 1.460 (3) 1.253 (3) 1.466 (4). O3iiiÐNiÐO3 O3iiiÐNiÐO1 O3ÐNiÐO1 O1ÐNiÐO1iii O3iiiÐNiÐO2 O3ÐNiÐO2 O1ÐNiÐO2 O1iiiÐNiÐO2 O2ÐNiÐO2iii. 179.14 (10) 83.50 (6) 97.11 (7) 90.23 (10) 84.80 (7) 94.62 (7) 87.86 (7) 177.14 (7) 94.12 (10). O1ÐC1ÐC1i O1ÐC1ÐC1iv C1iÐC1ÐC1iv C1ÐO1ÐNi O2ÐC2ÐC2ii O2ÐC2ÐC2v C2iiÐC2ÐC2v C2ÐO2ÐNi. 133.8 (2) 136.0 (2) 90.000 (1) 134.56 (15) 133.4 (2) 136.6 (2) 89.986 (6) 136.03 (15). Symmetry codes: (i) z; y; 12 ÿ x; (ii) 1 ÿ x; 1 ÿ z; y ÿ 12; (iii) y; x; 12 ÿ z; (iv) 12 ÿ z; y; x; (v) 1 ÿ x; 12 ‡ z; 1 ÿ y.. Figure 2. The crystal structure of the title compound, viewed along the crystallographic a axis. The disordered water molecules have been omitted for clarity.. squarate dianion is connected to four Ni atoms, forming a three-dimensional coordination network, which contains cubic voids surrounded by six squarate dianions. Within these voids, additional disordered water molecules are found.. Experimental The title compound was prepared by the reaction of 0.5 mmol nickel(II) chloride, 0.5 mmol squaric acid and 0.5 mmol 4,40 -bipyridine in. m654. Greve and NaÈther. . [Ni(C4O4)(H2O)2]0.71H2O. Table 2. Ê ,  ). Hydrogen-bonding geometry (A DÐH  A iii. O3ÐH1  O1 O3ÐH2  O2iv. DÐH. H  A. D  A. DÐH  A. 0.82 0.82. 1.92 1.93. 2.724 (2) 2.730 (2). 167 164. Symmetry codes: (iii) 12 ÿ z; y; x; (iv) 1 ÿ x; 12 ‡ z; 1 ÿ y.. The H atoms of the coordinated water molecules were located in a difference Fourier map, and these molecules were re®ned as rigid Ê and ®xed groups, with idealized OÐH bond lengths of 0.82 A isotropic displacement parameters [Uiso(H) = 1.5Ueq(O)]. The two Acta Cryst. (2002). E58, m653±m655.

(3) metal-organic papers clathrate O atoms of clathrate water molecules were re®ned isotropically with variable site-occupation factors and a common displacement parameter. The site-occupation factors were re®ned to 0.38 (2) for atom O4 and 0.26 (1) for atom O5. The H atoms of these water molecules could not be located. Data collection: IPDS Program Package (Stoe & Cie, 1998); cell re®nement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXL97.. This work is supported by the state of Schleswig-Holstein. We are very grateful to Professor Dr Wolfgang Bensch for. Acta Cryst. (2002). E58, m653±m655. ®nancial support and the opportunity to use his experimental equipment.. References Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Greve, J. (2000) Diploma Thesis, University of Kiel, Germany. Greve, J. & NaÈther, C. (2002). Acta Cryst. E58, m625±m627. Lee, C.-R., Wang, C.-C. & Wang, Y. (1996). Acta Cryst. B52, 966±975. NaÈther, C., Greve, J. & Jeû, I. (2002a) Chem. Mater. In the press. NaÈther, C., Greve, J. & Jeû, I. (2002b). Z. Naturforsch. In the press. NaÈther, C., Greve, J. & Jeû, I. (2002c). Acta Cryst. E58, m507±m509. NaÈther, C. & Jeû, I. (2001). Acta Cryst. C57, 260±261. Sheldrick, G. M. (1997). SHELXS7 and SHELXL97. University of GoÈttingen, Germany. Stoe & Cie (1998). IPDS Program Package. Version 2.89. Stoe & Cie, Darmstadt, Germany.. Greve and NaÈther. . [Ni(C4O4)(H2O)2]0.71H2O. m655.

(4) supporting information. supporting information Acta Cryst. (2002). E58, m653–m655. [https://doi.org/10.1107/S1600536802018895]. Poly[[diaqua(µ4-squarato-O,O′,O′′,O′′′)nickel(II)] 0.71-hydrate] Jan Greve and Christian Näther Poly[[diaqua(µ4-squarato-O,O′,O′′,O′′′)nickel(II)] 0.71-hydrate] Crystal data [Ni(C4O4)(H2O)2]·0.71H2O Mr = 218.12 Cubic, Pn3n a = 16.1467 (8) Å V = 4209.7 (4) Å3 Z = 24 F(000) = 2632 Dx = 2.065 Mg m−3. Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8000 reflections θ = 2.5–26.5° µ = 2.76 mm−1 T = 293 K Block, light green 0.2 × 0.2 × 0.2 mm. Data collection Stoe IPDS diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ scans 7475 measured reflections 704 independent reflections. 508 reflections with I > 2σ(I) Rint = 0.026 θmax = 26.5°, θmin = 1.8° h = −8→20 k = −16→20 l = −14→16. Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.024 wR(F2) = 0.077 S = 1.07 704 reflections 59 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map. Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0348P)2 + 5.3938P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.48 e Å−3 Δρmin = −0.46 e Å−3 Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.00045 (9). Special details 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.. Acta Cryst. (2002). E58, m653–m655. sup-1.

(5) supporting information 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). Ni C1 O1 C2 O2 O3 H1 H2 O4 O5. x. y. z. Uiso*/Ueq. Occ. (<1). 0.498248 (16) 0.30983 (15) 0.38197 (10) 0.50071 (15) 0.50353 (11) 0.46163 (10) 0.4158 0.4675 0.2500 0.2982 (15). 0.498248 (16) 0.48345 (14) 0.48724 (11) 0.68953 (15) 0.61723 (10) 0.53619 (10) 0.5185 0.5845 0.6672 (15) 0.7047 (9). 0.2500 0.22750 (14) 0.19876 (10) 0.22847 (15) 0.20048 (11) 0.36349 (10) 0.3765 0.3779 0.2500 0.2007 (15). 0.0100 (2) 0.0148 (5) 0.0193 (4) 0.0173 (6) 0.0213 (5) 0.0182 (4) 0.027* 0.027* 0.132 (7)* 0.132 (7)*. 0.384 (19) 0.258 (10). Atomic displacement parameters (Å2). Ni C1 O1 C2 O2 O3. U11. U22. U33. U12. U13. U23. 0.0103 (2) 0.0131 (12) 0.0096 (8) 0.0251 (13) 0.0419 (12) 0.0193 (9). 0.0103 (2) 0.0197 (11) 0.0353 (10) 0.0135 (11) 0.0097 (8) 0.0183 (9). 0.0095 (2) 0.0115 (12) 0.0130 (9) 0.0134 (13) 0.0122 (9) 0.0170 (8). −0.00010 (13) 0.0011 (10) 0.0005 (7) −0.0014 (10) 0.0006 (7) −0.0039 (7). −0.00017 (11) −0.0005 (8) 0.0003 (7) 0.0010 (9) 0.0025 (7) 0.0070 (7). 0.00017 (11) −0.0008 (9) 0.0012 (7) 0.0013 (8) −0.0003 (7) −0.0048 (7). Geometric parameters (Å, º) Ni—O3i Ni—O3 Ni—O1 Ni—O1i Ni—O2 Ni—O2i C1—O1 C1—C1ii C1—C1iii C2—O2 C2—C2iv. 2.0206 (15) 2.0206 (15) 2.0593 (16) 2.0593 (16) 2.0826 (17) 2.0826 (17) 1.255 (3) 1.460 (3) 1.460 (3) 1.253 (3) 1.466 (4). C2—C2v O3—H1 O3—H2 O4—O5ii O4—O5iii O4—O5 O4—O5vi O5—O5vii O5—O5ii O5—O5iii. 1.466 (4) 0.8201 0.8200 1.267 (19) 1.267 (19) 1.267 (19) 1.267 (19) 1.46 (3) 1.57 (3) 1.57 (3). O3i—Ni—O3 O3i—Ni—O1 O3—Ni—O1 O3i—Ni—O1i O3—Ni—O1i. 179.14 (10) 83.50 (6) 97.11 (7) 97.11 (7) 83.50 (6). O2—C2—C2iv O2—C2—C2v C2iv—C2—C2v C2—O2—Ni Ni—O3—H1. 133.4 (2) 136.6 (2) 89.986 (6) 136.03 (15) 113.0. Acta Cryst. (2002). E58, m653–m655. sup-2.

(6) supporting information O1—Ni—O1i O3i—Ni—O2 O3—Ni—O2 O1—Ni—O2 O1i—Ni—O2 O3i—Ni—O2i O3—Ni—O2i O1—Ni—O2i O1i—Ni—O2i O2—Ni—O2i O1—C1—C1ii O1—C1—C1iii C1ii—C1—C1iii C1—O1—Ni. 90.23 (10) 84.80 (7) 94.62 (7) 87.86 (7) 177.14 (7) 94.62 (7) 84.80 (7) 177.14 (7) 87.86 (7) 94.12 (10) 133.8 (2) 136.0 (2) 90.000 (1) 134.56 (15). Ni—O3—H2 H1—O3—H2 O5ii—O4—O5iii O5ii—O4—O5 O5iii—O4—O5 O5ii—O4—O5vi O5iii—O4—O5vi O5—O4—O5vi O4—O5—O5vii O4—O5—O5ii O5vii—O5—O5ii O4—O5—O5iii O5vii—O5—O5iii O5ii—O5—O5iii. 120.9 111.3 123 (3) 76.8 (12) 76.8 (12) 76.8 (12) 76.8 (12) 123 (3) 118.5 (14) 51.6 (6) 90.7 (14) 51.6 (6) 89.3 (15) 90.000 (4). Symmetry codes: (i) y, x, −z+1/2; (ii) z, y, −x+1/2; (iii) −z+1/2, y, x; (iv) −x+1, −z+1, y−1/2; (v) −x+1, z+1/2, −y+1; (vi) −x+1/2, y, −z+1/2; (vii) −z+1/2, −y+3/2, −x+1/2.. Hydrogen-bond geometry (Å, º) D—H···A iii. O3—H1···O1 O3—H2···O2v. D—H. H···A. D···A. D—H···A. 0.82 0.82. 1.92 1.93. 2.724 (2) 2.730 (2). 167 164. Symmetry codes: (iii) −z+1/2, y, x; (v) −x+1, z+1/2, −y+1.. Acta Cryst. (2002). E58, m653–m655. sup-3.

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