Synthesis and Structure of Bismuth(III)-Containing Noncentrosymmetric Phosphates, Cs₃KBi₂M₄(PO₄)₆Cl (M = Mn, Fe). Monoclinic (<i>Cc</i>) and Tetragonal (<i>P</i>4₃) Polymorphs Templated by Chlorine-Centered Cl(Bi₂Cs) Acentric Units

Single crystals of three new noncentrosymmetric (NCS) phosphates, α (<b>1</b>) and β (<b>2</b>) forms of Cs₃KBi₂Mn₄(PO₄)₆Cl and α-Cs₃KBi₂Fe₄(PO₄)₆Cl (<b>3</b>), were grown in a reactive CsCl/KCl molten-salt media. Their structures were determined by single-crystal X-ray diffraction methods showing that the α form crystallizes in the space group <i>Cc</i> (No. 9), which is in one of the 10 NCS polar crystal classes, <i>m</i> (2/<i>m</i>) while the β form crystallizes in <i>P</i>4₃ (No. 78) of another polar class, 4 (4/<i>m</i>). The unit cell parameters of the α form can be approximately correlated with that of the β form via the 3 × 3 orientation matrix [0.5, 0.5, 0; −0.5, 0.5, 0; 0, 0, 2 sin β]. The structures of these otherwise complicated phosphates exhibit two types of channels with circular and elliptical windows where the Cl-centered Cl­(Bi₂Cs) acentric unit is located. The neighboring acentric units are arranged in a parallel fashion in the α form, resulting in the monoclinic (<i>Cc</i>) lattice, but “antiparallel” in the β form, thus giving the tetragonal (<i>P</i>4₃) unit cell. <b>1</b>–<b>3</b> feature the compatible M–O–P unit that contains four crystallographically independent MO_<i>x</i> (<i>x</i> = 4, 5) polyhedra, which are connected to the Cl­(Bi₂Cs) acentric unit through one short and one long M^II···Cl bond. The compositions of <b>1</b> and <b>2</b> consist of three Mn²⁺ (d⁵) and one Mn³⁺ (d⁴) per formula unit and that of <b>3</b> has three Fe²⁺ (d⁶) and one Fe³⁺ (d⁵). Bond valence sums reveal that, in the α phase, the trivalent site adopts distorted tetrahedral M(1)³⁺O₄ coordination and, in the β phase, distorted trigonal-bipyramidal M(4)³⁺O₅. Thus far, the iron phase has only been isolated in the α form presumably because of little extra stabilization energy gain if the Fe²⁺ d⁶ ion were to occupy the M(1)­O₄ site. The possible origins pertaining to the structural differences in the α and β forms are discussed

Synthesis and Structure of Bismuth(III)-Containing Noncentrosymmetric Phosphates, Cs₃KBi₂M₄(PO₄)₆Cl (M = Mn, Fe). Monoclinic (<i>Cc</i>) and Tetragonal (<i>P</i>4₃) Polymorphs Templated by Chlorine-Centered Cl(Bi₂Cs) Acentric Units

Single crystals of three new noncentrosymmetric (NCS) phosphates, α (<b>1</b>) and β (<b>2</b>) forms of Cs₃KBi₂Mn₄(PO₄)₆Cl and α-Cs₃KBi₂Fe₄(PO₄)₆Cl (<b>3</b>), were grown in a reactive CsCl/KCl molten-salt media. Their structures were determined by single-crystal X-ray diffraction methods showing that the α form crystallizes in the space group <i>Cc</i> (No. 9), which is in one of the 10 NCS polar crystal classes, <i>m</i> (2/<i>m</i>) while the β form crystallizes in <i>P</i>4₃ (No. 78) of another polar class, 4 (4/<i>m</i>). The unit cell parameters of the α form can be approximately correlated with that of the β form via the 3 × 3 orientation matrix [0.5, 0.5, 0; −0.5, 0.5, 0; 0, 0, 2 sin β]. The structures of these otherwise complicated phosphates exhibit two types of channels with circular and elliptical windows where the Cl-centered Cl­(Bi₂Cs) acentric unit is located. The neighboring acentric units are arranged in a parallel fashion in the α form, resulting in the monoclinic (<i>Cc</i>) lattice, but “antiparallel” in the β form, thus giving the tetragonal (<i>P</i>4₃) unit cell. <b>1</b>–<b>3</b> feature the compatible M–O–P unit that contains four crystallographically independent MO_<i>x</i> (<i>x</i> = 4, 5) polyhedra, which are connected to the Cl­(Bi₂Cs) acentric unit through one short and one long M^II···Cl bond. The compositions of <b>1</b> and <b>2</b> consist of three Mn²⁺ (d⁵) and one Mn³⁺ (d⁴) per formula unit and that of <b>3</b> has three Fe²⁺ (d⁶) and one Fe³⁺ (d⁵). Bond valence sums reveal that, in the α phase, the trivalent site adopts distorted tetrahedral M(1)³⁺O₄ coordination and, in the β phase, distorted trigonal-bipyramidal M(4)³⁺O₅. Thus far, the iron phase has only been isolated in the α form presumably because of little extra stabilization energy gain if the Fe²⁺ d⁶ ion were to occupy the M(1)­O₄ site. The possible origins pertaining to the structural differences in the α and β forms are discussed

Country-level and individual-level predictors of men's support for gender equality in 42 countries

Men sometimes withdraw support for gender equality movements when their higher gender status is threatened. Here, we expand the focus of this phenomenon by examining it cross-culturally, to test if both individual- and country-level variables predict men's collective action intentions to support gender equality. We tested a model in which men's zero-sum beliefs about gender predict reduced collective action intentions via an increase in hostile sexism. Because country-level gender equality may threaten men's higher gender status, we also examined whether the path from zero-sum beliefs to collective action intentions was stronger in countries higher in gender equality. Multilevel modeling on 6,734 men from 42 countries supported the individual-level mediation model, but found no evidence of moderation by country-level gender equality. Both country-level gender equality and individual-level zero-sum thinking independently predicted reductions in men's willingness to act collectively for gender equality

Gendered Self-Views Across 62 Countries: A Test of Competing Models

Social role theory posits that binary gender gaps in agency and communion should be larger in less egalitarian countries, reflecting these countries' more pronounced sex-based power divisions. Conversely, evolutionary and self-construal theorists suggest that gender gaps in agency and communion should be larger in more egalitarian countries, reflecting the greater autonomy support and flexible self-construction processes present in these countries. Using data from 62 countries (N = 28,640), we examine binary gender gaps in agentic and communal self-views as a function of country-level objective gender equality (the Global Gender Gap Index) and subjective distributions of social power (the Power Distance Index). Findings show that in more egalitarian countries, gender gaps in agency are smaller and gender gaps in communality are larger. These patterns are driven primarily by cross-country differences in men's self-views and by the Power Distance Index (PDI) more robustly than the Global Gender Gap Index (GGGI). We consider possible causes and implications of these findings