Inorganica Chimica Acta 403 (2013) 120–126

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Inorganica Chimica Acta

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Coordination polymers of transition metals derived from the in situnucleophilic addition of alcohols to dicyanonitrosomethanide[C(CN)2(NO)]�

0020-1693/$ - see front matter � 2013 Elsevier B.V. All rights reserved.http://dx.doi.org/10.1016/j.ica.2013.03.022

⇑ Corresponding author. Tel.: +61 399054606; fax: +61 399054597.E-mail address: stuart.batten@monash.edu (S.R. Batten).

Mohd. R. Razali a,b, Aron Urbatsch a, Glen B. Deacon a, Stuart R. Batten a,⇑a School of Chemistry, Box 23, Monash University, Victoria 3800, Australiab School of Chemical Sciences, University Science Malaysia, 11800 Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history:Available online 27 March 2013

Coordination Polymers Special Issue

Keywords:Small cyano anions4,40-BipyridineCoordination polymersCrystal structuresNucleophilic addition

The transition metal-promoted in situ nucleophilic addition of methanol and ethanol to a nitrile arm ofdicyanonitrosomethanide (dcnm) resulted in the formation of cyano[imino(methoxy)methyl]nitroso-methanide (cmnm) and cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) respectively. In the pres-ence of 4,40-bipyridine (4,40-bipy), [Ni(cmnm)2(4,40-bipy)]�½DMF (1), [Ni(cenm)2(4,40-bipy)]�EtOH (2) and[Zn(cmnm)2(4,40-bipy)]�2H2O (3) were isolated as 1D chains. When copper ions were used, a dinuclearstructure, namely [Cu2(cmnm)4(4,40-bipy)] (4) was observed. Synthesis of 1, 2 and 4 also required thepresence of CeCl3�6H2O. The cmnm ligands in complex 3 display unique coordination modes to the metalions, namely j2(N,O)Zn. Finally, the hydrogen bonding in 3 generates three interpenetrating 3D networkswith unusual bsn (or b-Sn) net topology.

� 2013 Elsevier B.V. All rights reserved.

1. Introduction

Coordination polymers have attracted wide interest owing totheir potential applications in various fields, such as in the manu-facture of porous frameworks for gas storage and the constructionof novel magnetic materials [1]. Ligand design is crucial in order toobtain the desired complexes. Polynitrile ligands have receivedparticular attention for the formation of coordination polymersowing to their potential applications [2–6]. In metal complexescontaining small cyano anions (SCAs), for example dicyanamide(dca) and tricyanomethanide (tcm), interesting magnetic proper-ties have been observed [7,8].

Our recent work has focussed on the less common SCAs, par-ticularly dicyanonitrosomethanide (dcnm), which also containsnitroso functionality. We have previously observed that the nitrilegroups of dcnm can undergo nucleophilic addition with water [9],primary alcohols [10,11] and amines [12] in the presence of tran-sition metals to give new ligands that aid in the construction ofcoordination compounds. There is also a strong impetus toincorporate dcnm derivatives into new classes of coordinationpolymers. For example, interesting magnetic properties have beenobserved for transition metal complexes of dcnm andits derivatives [13,14]. Cyanoxime-based molecules, C(CN)(@N–OH)–R, also have gathered attention in medicine where their

cytotoxici activity has aided the development of anti-cancer drugs[15–17].

The formation of the water addition product of dcnm, car-bamoylcyanonitrosomethanide (ccnm), can proceed without metalions present [18], however metals are essential for the formation ofthe alcohol addition products (Scheme 1). A notable recent exam-ple is the structure of the trinuclear copper cluster, [Cu3(cimm)2

(a3acnm)2]�6MeCN (cimm = cyano(imido(methoxy)methyl)nitros-omethanide, a3acnm = {amino(3-aminomethylphenyl)methylimi-no}methyl(cyanonitrosomethanide)), where cimm is the result ofdeprotonation of the cmnm ligand [14]. In this complex, cimmbridges to three metals in a l3-coordination mode, which is rela-tively rare for an alcohol-addition ligand.

Herein, we report structures resulting from the metal-mediatednucleophilic addition of methanol and ethanol across the nitrilearm of dcnm, which leads to the formation of 1D chain structuresin the presence of 4,40-bipyridine (4,40-bipy). Synthesis of 1, 2 and 4are noteworthy, as similar reactions without the presence oflanthanoid ions result in the formation of only mononuclear struc-tures, [TM(cmnm)2(MeOH)2] [19] (TM = Ni or Cu) and [Ni(cenm)2(-H2O)2] [11].

2. Results and discussion

The predominant binding mode of alcohol addition products ofdcnm to transition metals is bidentate chelating via their nitroso

Scheme 1. Metal-mediated nucleophilic addition of alcohols to a nitrile arm of dcnm.

M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126 121

and imine nitrogen atoms [20,21], which coordinate to the equato-rial sites of the metals in octahedral complexes, [M(cmnm)2L2].Therefore, ditopic linear co-ligands should coordinate to the vacantaxial sites of the metal ions giving rise to 1D chain complexes. Asuitable such ligand is 4,40-bipy, which has been used extensively

Fig. 1. Crystal structures of (a) [Ni(cmnm)2(4,40-bipy)]�½DMF (1) and (b) [Ni(cenm)2(4,atoms (except for the imine group) and lattice DMF and ethanol are omitted for clarity.

as a linear rod, due to the disposition of the two potentially coor-dinating N-donor atoms [22–24].

Reactions of NiCl2, Me4N(dcnm), 4,40-bipy and CeCl3�6H2O ineither methanol or ethanol yielded 1D-polymeric structures com-prising the corresponding alcohol addition products cmnm and

40-bipy)]�EtOH (2) with the thermal ellipsoids shown at 50% probability. HydrogenSymmetry elements used:(a) i = 1 � x, 1 � y, 1 � z; ii = �x � 1, �y, �z.

Table 1Selected bond lengths [Å] and angles [�] for 1a and 2.b

1Ni1–N1 2.067(5) Ni2–N4 2.068(6)Ni1–N3 2.046(5) Ni2–N6 2.062(5)Ni1–N7 2.113(5) Ni2–N8 2.109(5)N3i–Ni1–N3 180.0 N6ii–Ni2–N6 180.0N3i–Ni1–N1 101.1(2) N6ii–Ni2–N4 101.2(2)N3–Ni1–N1 78.90(2) N6–Ni2–N4 78.8(2)N1–Ni1–N1i 180.0 N4–Ni2–N4ii 180.0N3–Ni1–N7 90.77(19) N6–Ni2–N8ii 90.7(2)N1–Ni1–N7 89.56(19) N4–Ni2–N8ii 89.5(2)N7–Ni1–N7i 180.0 N8ii–Ni2–N8 180.0

2Ni1–N3 2.069(3) Ni1–N4 2.134(4)Ni1–N1 2.079(3) Ni1–N5 2.126(4)N3–Ni1–N3i 175.97(13) N1–Ni1–N5 90.57(7)N1i–Ni1–N1 178.85(13) N3–Ni1–N4 88.04(7)N3–Ni1–N1 78.64(12) N1–Ni1–N4 89.43(7)N3i–Ni1–N1 101.35(12) N5–Ni1–N4 180.0N3–Ni1–N5 91.96(7)

a Symmetry elements used: i = 1 � x, 1 � y, 1 � z; ii = �x � 1, �y, �z.b Symmetry element used: i = �x, y, 3/2 � z.

Table 2Selected bond lengths [Å] and angles [�] for 3.a

Zn1–O1 2.076(3) Zn1–N4 2.230(8)Zn1–N3 2.079(3) Zn1–N5i 2.247(8)

O1–Zn1–O1i 179.11(11) N3–Zn1–N4 92.85(13)O1–Zn1–N3 87.50(11) O1–Zn1–N5ii 89.55(13)O1i–Zn1–N3 92.46(11) N3–Zn1–N5ii 87.15(15)N3–Zn1–N3i 174.29(11) N4–Zn1–N5ii 180.0O1–Zn1–N4 90.45(13)

a Symmetry elements used: i = 1/2 � x, 1/2 � y, z; ii = x, y, z � 1.

122 M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126

cenm in [Ni(cmnm)2(4,40-bipy)]�½DMF (1) and [Ni(cenm)2(4,40-bi-py)]�EtOH (2), respectively. Plate green crystals of 2 formed fromthe reaction solution within a week. Green crystals of 1 formedafter dark green precipitates that initially deposited from theoriginal reaction solution were dissolved in DMF. Interestingly, ifthe CeCl3�6H2O was omitted, only the known [Ni(cmnm)2(MeOH)2][19] and [Ni(cenm)2(MeOH)2] [11] monomers formed. A similarphenomenon has been observed when NdCl3�6H2O andNd(NO3)3�6H2O are used, indicating that the lanthanoid is essentialin obtaining the complexes. It has been reported previously thatlanthanoids can influence the self-assembly of a complex, possiblythrough pre-coordination of the ligand, without appearing in thefinal product [11,25].

Complexes 1 and 2 are isostructural (Fig. 1), but crystallise indifferent space groups. Complex 1 crystallises in the triclinic spacegroup P�1, whilst complex 2 crystallises in the monoclinic spacegroup C2/c, possibly owing to the different solvents of crystalliza-tion. Even though one DMF molecule with half occupancy couldbe located in 1, the crystal structure possesses pores (424 Å3) con-taining highly disordered solvent that could not be satisfactorilyrefined. The SQUEEZE routine of PLATON [26] used in the treatment ofthe crystallographic data accounted for 97 electrons, which is inexcess of that which could be ascribed to the lattice solvent deter-mined by elemental analysis. Despite the difficulty in determiningcrystallographically the lattice solvents in 1 due to their high de-gree of disorder, the composition and connectivity of the 1D chainsin 1 are unambiguous (see Section 3).

The nickel atom is coordinated equatorially by two cyanometh-anide ligands (cmnm in 1, cenm in 2) via their nitroso and iminenitrogen atoms (Table 1). Two 4,40-bipy molecules coordinate tothe two remaining axial positions of the metal to form the 1Dchain. The pyridine moieties of the bridging 4,40-bipy ligands incomplexes 1 and 2 are twisted with respect to each other by ca.33� and 28�, respectively.

In a similar reaction to 1, but involving ZnCl2�4H2O and withoutany lanthanoid ions, the 1D polymer [Zn(cmnm)2(4,40-bipy)]�2H2O(3) was isolated. The coordination mode of cmnm in complex 3 isrelatively rare. It displays a syn-j2(O,N)Zn coordination mode,which has not been observed before (the common coordinationmode for cmnm is anti-j2(N,N0)TM, vide supra). In this new coordi-nation mode, the anion is in the syn conformation, with the nitrosooxygen rotated 180� from its usual orientation. The anion thenbinds to the metal centre through the nitroso oxygen (instead ofthe usual nitroso nitrogen) and imine nitrogen atoms (Table 2),forming a six-membered chelate (Fig. 2). The ‘bite’ angle of the li-gand to the metal centre is 87.50(11)�, somewhat larger than therelated angles of N1–Ni1–N3 in 1 and 2 (78.90(2)� and78.64(12)� respectively). All angles for the syn-cmnm ligand of

Fig. 2. Crystal structure of [Zn(cmnm)2(4,40-bipy)]�2H2O (3) with the thermal ellipsoidsmolecules in the lattice are omitted for clarity. Symmetry elements used: i = x, y, 1 + z;

complex 3 are larger than those of the anti-cmnm ligand. Forexample, the angle Zn1–N3–C3 is 124.51(3)�, larger than the corre-sponding Ni1–N3–C3 angle in 1 (114.20(5)�). In comparison withcomplexes 1 and 2, the donor atoms in the equatorial positionsare slightly displaced out of the average coordination plane in com-plex 3.

The structure contains intercalated water molecules that hydro-gen bond to the cmnm anions and crosslink the chains into 3D net-works. Each water hydrogen bonds to a nitroso oxygen on oneanion, and accepts a hydrogen bond from an imine of anothercmnm anion bound to the same metal. This water then, in turn,hydrogen bonds to a cmnm nitrile on an adjacent chain(Fig. 3(a)). Since there is only one unique cmnm anion, this

shown at 50% probability. Hydrogen atoms (except for the imine group) and waterii = x, y, z � 1.

Fig. 3. The hydrogen bonded networks in 3, showing: (a) the hydrogen bonding (striped bonds) between chains; (b) the bridging of each chain to four others via the hydrogenbonding; (c) a schematic representation of the 3D bsn topology – nodes represent the zinc atoms, vertical lines represent the Zn(4,40-bipy) chains, while the other bondsrepresent the hydrogen bonding between the chains (one chiral helix is highlighted); (d) the threefold interpenetration.

Table 3Selected bond lengths [Å] and angles [�] for 4.a

Cu1–N1 1.993(10) Cu2–N10 1.983(9)Cu1–N3 1.997(8) Cu2–N11 2.157(11)Cu1–N4 2.038(9) Cu3–N13 1.984(8)Cu1–N6 1.974(10) Cu3–N15 1.997(9)Cu1–N7 2.272(7) Cu3–N12 2.232(13)Cu2–N8 1.999(10)

N1–Cu1–N4 166.36(6) N10–Cu2–N10ii 161.0(5)N3–Cu1–N6 171.60(6) N8–Cu2–N11 91.5(3)N1–Cu1–N7 102.92(6) N10–Cu2–N11 99.5(3)N3–Cu1–N7 89.38(5) N13–Cu3–N13ii 171.9(5)N4–Cu1–N7 90.71(6) N15–Cu3–N15ii 177.0(5)N6–Cu1–N7 98.91(6) N13–Cu3–N12 94.0(2)N8–Cu2–N8ii 177.1(6) N15–Cu3–N12 91.5(2)

a Symmetry element used: ii = 2 � x, y, 1 � z.

M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126 123

hydrogen bonding links each chain to four others (Fig. 3(b)), togenerate a 3D net. The net has unusual bsn (or b-Sn) topology(Fig. 3(c)) [27], with the [Zn(cmnm)2]�2H2O moieties acting as 6-connecting nodes. The net contains chiral helical channels, how-ever it is also centrosymmetric, and thus there are equal numbersof each handedness. Three such nets interpenetrate in 3 (Fig. 3(d)).

The closest related structure that shows similar coordinationmodes to those in 1–3 is a structure derived from the water addi-tion ligand, ccnm and 4,40-bipy, namely [Cu(4,40-bipy)(ccnm)2]-�MeOH [9]. As in structures 1 and 2, the oxygen atoms of thenitroso groups are not involved in any coordination bonds to themetal ion. Hydrogen bonding networks are also present in thisstructure, involving the ccnm anions and intercalated methanolmolecules, leading again to interpenetrating 3D nets.

A reaction of CuCl2, Me4N(dcnm), CeCl3�6H2O and 4,40-bipy inmethanol yielded the dinuclear complex, [Cu2(cmnm)4(4,40-bipy)](4). Similar to the synthesis of 1 and 2, reactions without CeCl3-

�6H2O resulted in the well known [Cu(cmnm)2(MeOH)2] [19] with-in a few hours, as evidenced by crystallography, indicating that thelanthanoid metals again play an important role in formation ofcomplex 4.

The compound crystallises in the monoclinic space group C2with one and a half molecules in the asymmetric unit (the moleculecontaining Cu1 lies across a twofold axis). The basal positions ofeach square pyramidal copper atom are occupied by two trans

Fig. 4. (a) Molecular structure of [Cu2(cmnm)4(4,40-bipy)] (4) with ellipsoids shownat 50% probability. Hydrogen atoms are omitted except for imine groups. Symmetryelements used: i = 1 � x, y, �z; ii = 2 � x, y, 1 � z. (b) Packing diagram of 4 viewedalong the c axis.

Table 4IR frequencies of complexes 1–4.

1 2 3 4 Reported dcnm complexes [20,28–30]

v-OH n/a 3490 (m, br) 3587 (m, br) n/av-NH 3270 (m, br) 328 3(s, br) 3284 (s, br) 3277(m, br) 3288v-CN (nitrile) 2212m 2205s 2211s 2210m 2218v-CO(DMF) 1636s n/a n/a n/a n/av-C@N 1606s 1607s 1609s 1620s 1645vas-CNO 1389s 1394s 1398s 1413s 1350vs-CNO 1294m 1303m 1306s 1297s 1307v-CC 1198m 1200s 1200m 1134m 1203

124 M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126

cmnm ligands, chelating through the nitroso nitrogen and the iminegroup (Table 3). The square pyramidal CuN5 coordination sphere isthen completed by the nitrogen of 4,40-bipy, facilitating formationof dinuclear complexes (Fig. 4). While both molecules are com-posed of two Cu(cmnm)2 species bridged by a 4,40-bipyridine li-gand, they differ in the relative orientations of the cmnm ligandsat either end of the molecule. The Cu–N(py) distances were deter-mined to be in the range of 2.157(11)–2.272(7) Å, longer than thosein the equatorial plane (1.974(10)–2.038(9) Å). Intermolecular

hydrogen bonds were observed as the imine nitrogens N3 and N6act as hydrogen bond donors to the nitrile and nitroso nitrogen ofadjacent molecules, respectively.

Attempts to incorporate the 4,40-bipy ligand with the ethanoladdition product cenm in the presence of copper or zinc ions wereunsuccessful. Instead, pale yellow precipitates were observed toform once the reactants were dissolved in ethanol. IR spectra onthese precipitates showed no absorption around 2210 cm�1 thatcould attributed to the nitrile stretching.

Assignments for the main features of the IR spectra are given inTable 4. All complexes show features that can be assigned to v(NH)at 3290–3270 cm�1, broadened owing to H-bonding, with the twoethanol solvates having an additional broad v(OH) band at higherwavenumber and the DMF solvate showing features attributableto v(CO). Bands consistent with v(CN), vas(CNO), vs(CNO) andv(CC) were assigned by analogy with assignments for dcnm com-plexes made by Köhler and Hvastijová [20,28,29]. They are alsoconsistent with the assignments by Bohle [30] for dcnm salts,where theoretical calculations were used to support theseconclusions.

3. Experimental

Laboratory reagents and solvents were used without furtherpurification. Elemental analyses (C, H, N) were performed by theCampbell Analytical Laboratory, University of Otago, New Zealand.ATR-IR spectra were recorded with a Bruker Equinox 55 series FTIRspectrometer in the range 4000–500 cm�1 with a resolution of4 cm�1. Proton and 13C NMR spectra were recorded in [D6]dimethylsulphoxide on a Bruker DRX 400 instrument.

Me4N(dcnm) was prepared by a methathesis reaction betweenAg(dcnm) and Me4NCl in water. Ag(dcnm) was prepared accordingto a literature procedure [31].

3.1. [Ni(cmnm)2(4,40-bipy)]�½DMF (1)

Me4N(dcnm) (50 mg, 297 lmol) and 4,40-bipy (23 mg, 148lmmol) were dissolved in acetonitrile (5 mL). The solution mixturewas allowed to stir at 50 �C for 15 min. To the reaction solutionwas added a mixture of NiCl2 (19 mg, 148 lmol) and CeCl3�6H2O(26 mg, 74 lmol) in methanol (�3 mL), resulting in the immediateformation of a light green precipitate which then disappeared afterthree days. An amorphous dark green precipitate formed in a weekand was collected and dissolved in copious amounts of DMF. Thesolution was left to stand for slow evaporation and crystals of 1formed after a period of two months. The crystals were thenwashed with methanol and ether. Yield: 10 mg, 18%. ElementalAnal. Calc. for C22.5H31.5N9.5NiO9.5: C, 41.23; H, 4.94; N, 21.12.Found: C, 41.80; H, 4.87; N, 20.60%. The elemental analysis indi-cates the presence of four water molecules and DMF in the lattice.ATR-IR: 3270m, 2212w, 1636s, 1606s, 1389s, 1294m, 1198m,815w. The reaction without lanthanoids resulted the formation

M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126 125

of [Ni(cmnm)2(MeOH)2] [19] as determined by IR spectroscopy andunit cell determination.

3.2. [Ni(cenm)2(4,40-bipy)]�EtOH (2)

Me4N(dcnm) (50 mg, 297 lmol) and 4,40-bipy (23 mg,148 lm mol) were dissolved in acetonitrile (5 mL). The solutionmixture was allowed to stir at 50 �C for 15 minutes. To the reactionsolution was added a mixture of NiCl2 (19 mg, 148 lmol) andCeCl3�6H2O (23 mg, 74 lmol) in methanol (�3 mL), resulting inthe immediate formation of a light green precipitate which thendisappeared within three days. Crystals of 2 formed after a month,which were then separated from the precipitate and washed withethanol and ether. Yield: 20 mg, 23%. Elemental Anal. Calc. forC24H32N8NiO6: C, 49.04; H, 5.45; N, 19.07. Found: C, 49.11; H,5.41; N, 19.14%. ATR-IR: 3490m, 3283s, 2205s, 1607s, 1394s,1402s, 1303m, 1200m, 812w. The reaction without lanthanoids re-sulted the formation of [Ni(cenm)2(H2O)2] [11] as determined by IRspectroscopy and unit cell determination.

3.3. [Zn(cmnm)2(4,40-bipy)]�2H2O (3)

ZnCl2�4H2O (27 mg, 148 lmol) and Me4N(dcnm) (50 mg,297 lmol) were dissolved in methanol (8 mL) giving a yellow solu-tion. 4,40-bipy (23 mg, 148 lmol) was added to the solution, result-ing in the immediate formation of a white precipitate. Needlecrystals of 3 formed within two weeks, which then were manuallyseparated from the precipitate and washed with methanol andether. Yield: 20 mg, 27%. Elemental Anal. Calc. for C18H20N8O6Zn:C, 42.37; H, 3.92; N, 21.97. Found: C, 42.33; H, 3.85; N, 21.93%.ATR-IR: 3587m, 3284s, 2211s, 1609s, 1398s, 1306s, 1200m,812w. 1H NMR, (400 MHz) in [D6]DMSO: d = 3.49 (6H, methylcmnm), 7.84 (4H, 4,40-bipy), 8.72 (4H, 4,40-bipy). NH exchangedwith water in solution. 13C NMR, (400 MHz) in [D6]DMSO: 54.69,112.780, 121.319, 144.391, 150.471.

3.4. [Cu2(cmnm)4(4,40-bipy)] (4)

Me4N(dcnm) (50 mg, 297 lmol) and 4,40-bipy (23 mg,148 lm mol) were dissolved in acetonitrile (5 mL). The solutionwas allowed to stir at 50 �C for 15 min. To the reaction was addeda mixture of CuCl2 (19 mg, 148 lmol) and CeCl3�6H2O (26 mg,74 lmol) in methanol (�3 mL), resulting in the immediate forma-tion of a light green precipitate which then disappeared within aweek. Blue block crystals formed after a month which were thenwashed with methanol and ether. Yield: 15 mg, 25%. ElementalAnal. Calc. for C26H24Cu2N14O8: C, 43.10; H, 3.31; N, 27.07. Found:C, 43.55; H, 3.23; N, 27.15%. ATR-IR: 3277m, 2210m, 1620s, 1413s,1297s, 1134m, 878w. The reaction without lanthanoids resultedthe formation of [Cu(cmnm)2(MeOH)2] [19] as determined by IRspectroscopy and unit cell determination.

4. Crystallography details

Crystals of 1–4 were mounted in viscous hydrocarbon oil. Crys-tal data for 2 and 4 were collected using a Bruker Smart Apex X8diffractometer with Mo Ka radiation k = 0.71073 Å. Data were col-lected at 123 K, maintained using an open flow of nitrogen from anOxford Cryostreams cryostat. The data collection and integrationwere performed within the SMART and SAINT+ software programs,and corrected for Lorentz-polarisation and absorption effects usingthe Apex II program Suite [32]. Data for complexes 1 and 3 werecollected at 100(2) K at the Australian Synchrotron MX-1 beam-line. The data collection and integration were performed withinthe Blu-Ice [33] and XDS [34] software programs. Complexes 1–4

were solved by direct methods (SHELXS-97), and refined (SHELXL-97)by full matrix least-squares on all F2 data [35]. The program X-Seedwas used as a graphical SHELXL interface [36].

4.1. Crystallographic data for 1

C19.5H16.5N8.5NiO4.5: M = 510.65, green plate,0.20 � 0.20 � 0.05 mm3, triclinic, space group P�1, a = 10.975(2),b = 11.641(2), c = 13.659(3), a = 92.24(3), b = 96.77(3), c =115.10(3), V = 1561.5(5), Z = 1, qcalc = 1.086 g cm�3, F(000) = 527,20166 reflections collected, 4528 unique (Rint = 0.0535), 3462reflections observed (I > 2r(I)), R1(obs) = 0.0613, R1(all) = 0.0758,wR2(obs) = 0.1879, wR2(all) = 0.1979, GOF = 1.064, 339 parameters, 1restraint, l = 0.656 mm�1. The DMF molecule observed in the lat-tice was refined at half occupancy. The crystal contained significantpores (424 Å3) containing disordered solvent that could not be sat-isfactorily refined. The data was therefore treated with the SQUEEZE

routine of PLATON which accounted for 97 electrons per unit cell.R1(obs) and wR2(obs) before SQUEEZE = 0.1405 and 0.4289 respectively.

4.2. Crystallographic data for 2

C24H32N8NiO6: M = 587.27, green block, 0.10 � 0.05 �0.05 mm3, monoclinic, space group C2/c, a = 16.096(3),b = 11.352(2), c = 16.663(3), b = 116.40(3), V = 2727.2(9), Z = 4,qcalc = 1.430 g cm�3, F(000) = 1232, 8634 reflections collected,2375 unique (Rint = 0.0620), 2054 reflections observed (I > 2r(I)),R1(obs) = 0.0543, R1(all) = 0.0609, wR2(obs) = 0.1457, wR2(all) = 0.1508,GOF = 1.061, 181 parameters, 0 restraints, l = 0.765 mm�1.

4.3. Crystallographic data for 3

C18H20N8O6Zn: M = 509.81, yellow needle, 0.20 � 0.05� 0.05 mm3, orthorhombic, space group Fdd2, a = 12.7151(12),b = 29.843(3), c = 11.5626(11), V = 4387.5(7), Z = 8, qcalc = 1.544 -g cm�3, F(000) = 2096, Flack parameter = 0.09(2), 7920 reflectionscollected, 1739 unique (Rint = 0.0480), 1629 reflections observed(I > 2r(I)), R1(obs) = 0.0389, R1(all) = 0.0426, wR2(obs) = 0.0883,wR2(all) = 0.0889, GOF = 1.098, 161 parameters, 1 restraint,l = 1.173 mm�1.

4.4. Crystallographic data for 4

C26H24Cu2N14O8: M = 787.27, blue block, 0.20 � 0.20 �0.20 mm3, monoclinic, space group C2, a = 15.4005(19),b = 15.4356(19), c = 13.3294(17), V = 3165.22(7), Z = 4,qcalc = 1.653 g cm�3, F(000) = 1600, Flack parameter = 0.15(3),23934 reflections collected, 7118 unique (Rint = 0.0892), 5805reflections observed (I > 2r(I)), R1(obs) = 0.1020, R1(all) = 0.1165,wR2(obs) = 0.2636, wR2(all) = 0.2784, GOF = 1.094, 462 parameters, 1restraint, l = 1.416 mm�1. Refined as a four-component twin usingthe SHELX command TWIN 01010000�1�4; twin components re-fined to 0.00001, 0.09769, 0.06015.

5. Conclusions

Complexes 1, 2 and 3 contain 1D chains in which the 4,40-bipyligand is incorporated as a linker between the metal centres. Whilethe coordination mode of the alcohol addition products in 1 and 2is common, the binding mode of the cmnm ligand in 3 has not beenobserved previously. The hydrogen bond network in 3 displays theunusual bsn (or b-Sn) net topology. Structure 4 is a dinuclear com-plex, in which the two five-coordinate copper ions are connectedby 4,40-bipy.

126 M.R. Razali / Inorganica Chimica Acta 403 (2013) 120–126

Acknowledgements

We thank the Australian Research Council for funding (to SRBand GBD). The crystal structure determinations for 1 and 3 wereundertaken on the MX1 beamline at the Australian Synchrotron,Victoria, Australia. MRR thanks MOHE Malaysia and USM forsponsorship.

Appendix A. Supplementary material

CCDC 908095–908098 contains the supplementary crystallo-graphic data for 1–4. These data can be obtained free of chargefrom The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-ated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.ica.2013.03.022.

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