[NaCl][Cu(HSeO₃)₂], NaCl-intercalated Cu(HSeO₃)₂: synthesis, crystal structure and comparison with related compounds

Abstract

NaCl][Cu(HSeO 3 ) 2 ], NaCl-intercalated Cu(HSeO 3 ) 2 : synthesis, crystal structure and comparison with related compounds Abstract: Single crystals of [NaCl][Cu(HSeO 3 ) 2 ] have been prepared by the chemical vapor transport reactions. Its crystal structure (monoclinic, C2/c, a = 13.9874(7), b = 7.2594(4), c = 9.0421(5) Å, β = 127.046(2)°, V = 732.81(7) Å 3 ) is based upon electroneutral [Cu(HSeO 3 ) 2 ] sheets formed by corner sharing between the [CuO 4 ] squares and (HSeO 3 ) groups that are parallel to the (100) plane. Each (SeO 2 OH) -group forms the O h 1 ... O2 hydrogen bond to an adjacent hydroselenite group to constitute a [(SeO 2 OH) 2 ] 2-dimer that provides additional stabilization of the copper diselenite sheet. The [Cu(HSeO 3 ) 2 ] sheets alternate with the sheets consisting of zigzag-Na-Cl-Na-Cl-chains formed by Cl atoms and disordered Na sites. The chains are parallel to the c axis. The linkage between the alternating electroneutral [Cu(HSeO 3 ) 2 ] and [NaCl] sheets is provided by the Cu-Cl and Na-O bonds. The coordination of Na is fivefold and consists of three O and two Cl atoms. [NaCl][Cu(HSeO 3 ) 2 ] is a new member of the group of compounds based upon the M(HSeO 3 ) 2 layers (M 2+ = Cu, Co, Cd). The prototype structure for this group is [Cu(HSeO 3 ) 2 ] that does not have any chemical species separating the copper hydroselenite layers. In other compounds, the interlayer space between the [Cu(HSeO 3 ) 2 ] 0 layers is occupied by structural units of different complexity. [NaCl][Cu(HSeO 3 ) 2 ] can be considered as [Cu(HSeO 3 ) 2 ] intercalated with the NaCl layers consisting of one-dimensional-Na-Cl-Na-Cl-chains.

Protonated Organic Diamines as Templates for Layered and Microporous Structures: Synthesis, Crystal Chemistry, and Structural Trends among the Compounds Formed in Aqueous Systems Transition Metal Halide or Nitrate–Diamine–Selenious Acid

“…A numerous yet sparsely addressed family of mostly inorganic compounds is formed by the "layered hydroselenites", first described by Trombe et al [9][10][11] and further extended in our studies [12][13][14][15] among compounds of copper. Later, some zinc [16], cobalt [17][18][19][20], and cadmium [21] containing species were reported.…”

“…The structures of these compounds contain quasi-planar [ M II (HSeO 3 ) 2 ] 0 layers formed by Cu 2+ cations and hydrogen-bonded dimers of HSeO 3 − anions forming a distorted quasi-square grid. The interlayer space can be either empty, as in Cu(HSeO 3 ) 2 [ 22 ], filled with water molecules, as in Cu(HSeO 3 ) 2 ·2H 2 O [ 9 ], various metal-halide [ 11 , 12 , 13 , 15 , 16 , 17 , 20 ] and metal-nitrate [ 14 ] slabs, or more complex species such as [ M II (H 2 O) 4 ][Cu(HSeO 3 ) 2 Cl 2 ] series ( M II = Mn–Zn, Fe excepted) [ 10 , 18 ] and [Co(H 2 O) 4 ][Co(HSeO 3 ) 2 Cl 2 ] [ 20 ]. It is noteworthy that the bromide analogs of the two latter compounds, as well as alkali–cobalt selenite chlorides [ 17 ], have not been reported, while within the ( A I X )[Cu(HSeO 3 ) 2 ] series ( A I = Na, K, Rb, Cs, NH 4 ) [ 13 ], as well as (Rb X )[Zn(HSeO 3 ) 2 ] [ 16 ], bromides are full structural analogs of the corresponding chlorides.…”

Exploration of Vanadate Selenites Solid Phase Space, Crystal Structures, and Polymorphism

“…Taking into account the possibility of incorporation into the crystal structure of large halides acting as scissors due to their preferred association with Pb 2+ cations, we have used both PbO and PbCl 2 precursors in order to rationalize the domain of growth and stability of the phases in competition. The pertinence of CVT techniques was confirmed in recent works, leading to the identification of six new phases in the A–Cu +/2+ –Se 4+ –O (A = Pb 2+ , Na + , K + ) system, namely, K­[Cu 5 O 2 ]­(SeO 3 ) 2 Cl 3 , K­[Cu 3 O]­(SeO 3 ) 2 Cl, Na 2 [Cu 7 O 2 ]­(SeO 3 ) 4 Cl 4 , Cu + Pb 2 Cu 9 O 4 ­(SeO 3 ) 4 Cl 7 , KCu + Pb 0.2 ­Cu 5.8 O 2 ­(SeO 3 ) 2 Cl 6 , and NaCu­(HSeO 3 ) 2 Cl . A similar method has been performed with vanadium as TM.…”

“…The vanadium redox (V 5+ , V 4+ , V 3+ ) gives even broader opportunities for the prospection of new phases. In the literature, synthesis of inorganic selenites are mainly performed using alternatively either chemical vapor transport (CVT) methods − or hydrothermal techniques due to good solubility and reactivity of (SeO 3 ) 2– anions. ,− ,, It is noteworthy that our recent systematic reinvestigation of the Pb 2+ –Ni 2+ –Se 4+ –O crystallization diagram using the hydrothermal route yielded the discovery of three previously unknown compounds, namely, α-PbM­(SeO 3 ) 2 (M 2+ = Ni, Co), β-PbNi­(SeO 3 ) 2 , and PbNi 2 ­(SeO 2 OH) 2 ­(SeO 3 ) 2 . In order to complete the rich panorama of lead vanadate selenites, we decided to reinvestigate the Pb 2+ –V–Se 4+ –O phase space in the same manner.…”

Synthesis and structural variety of first Mn and Bi selenites and selenite chlorides

“…Over the last two decades, the chemistry of selenites (Se IV ) and selenates (Se VI ) has been intensively developed [1][2][3][4][5]. Metal oxyhalides with selenite anions demonstrate a rich and diverse crystal chemistry due to the interplay between soft-soft and hard-hard interactions involving selenite groups, metals and halide ions [6][7][8][9][10][11][12]. Note, that the crystal structures of most of them consist of Cu cations.…”