B-IncStrDB

Polymorphism in Zintl-Phases ACd₄Pn₃: The modulated structures of NaCd₄Pn₃ with Pn = P, As

Authors:

Grotz, Carolin; Baumgartner, Maximilian; Freitag, Katharina M.; Baumer, Franziska; Nilges, Tom

Journal:

Inorganic Chemistry 55 7764-7776 (2016)

DOI:

http://dx.doi.org/10.1021/acs.inorgchem.6b01233

B-IncStrDB ID: kRFQ3a9DVG5 Entry date: 2022-01-10 Last revision: 2022-02-12

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As3Cd4Na1_298

Chemical data

Structural Formula Sum: As3 Cd4 Na1 [ Help ]

Formula weight: 697.4 Da [ Help ]

Absolute configuration: . [ Help ]

Crystallographic data and experimental details

Crystal system: trigonal [ Help ]

Space group name (H-M): R -3 m [ Help ]

Space group name (Hall): -R 3 2" [ Help ]

Space group nb.: 166 [ Help ]

Symmetry operations of the space group: (Show/hide table) [ Help ]

Operation code	Operation in algebraic form
1	x,y,z
2	-y,x-y,z
3	-x+y,-x,z
4	y,x,-z
5	x-y,-y,-z
6	-x,-x+y,-z
7	-x,-y,-z
8	y,-x+y,-z
9	x-y,x,-z
10	-y,-x,z
11	-x+y,y,z
12	x,x-y,z
13	x+2/3,y+1/3,z+1/3
14	-y+2/3,x-y+1/3,z+1/3
15	-x+y+2/3,-x+1/3,z+1/3
16	y+2/3,x+1/3,-z+1/3
17	x-y+2/3,-y+1/3,-z+1/3
18	-x+2/3,-x+y+1/3,-z+1/3
19	-x+2/3,-y+1/3,-z+1/3
20	y+2/3,-x+y+1/3,-z+1/3
21	x-y+2/3,x+1/3,-z+1/3
22	-y+2/3,-x+1/3,z+1/3
23	-x+y+2/3,y+1/3,z+1/3
24	x+2/3,x-y+1/3,z+1/3
25	x+1/3,y+2/3,z+2/3
26	-y+1/3,x-y+2/3,z+2/3
27	-x+y+1/3,-x+2/3,z+2/3
28	y+1/3,x+2/3,-z+2/3
29	x-y+1/3,-y+2/3,-z+2/3
30	-x+1/3,-x+y+2/3,-z+2/3
31	-x+1/3,-y+2/3,-z+2/3
32	y+1/3,-x+y+2/3,-z+2/3
33	x-y+1/3,x+2/3,-z+2/3
34	-y+1/3,-x+2/3,z+2/3
35	-x+y+1/3,y+2/3,z+2/3
36	x+1/3,x-y+2/3,z+2/3

a: 4.4616(3) Å [ Help ]

b: 4.4616(3) Å [ Help ]

c: 33.783(3) Å [ Help ]

α: 90 ° [ Help ]

β: 90 ° [ Help ]

γ: 120 ° [ Help ]

Volume: 582.38(7) Å³ [ Help ]

Z: 3 [ Help ]

Cell determination reflection Nb.: 6126 [ Help ]

θ(min) for cell determination: 3.62 ° [ Help ]

θ(max) for cell determination: 32.27 ° [ Help ]

Cell measurement temperature: 298 K [ Help ]

μ: 23.714 mm^-1 [ Help ]

Absorption correction type: gaussian [ Help ]

Absorption correction remarks: Jana2006 [ Help ]

Minimum transmission factor: 0.0173 [ Help ]

Maximum transmission factor: 0.2693 [ Help ]

Refinement details

Total nb. of reflections: 172 [ Help ]

Nb. of observed reflections: 169 [ Help ]

Intense reflections threshold: I>3σ(I) [ Help ]

Refinement based on: Fsqd [ Help ]

R(obs): 0.0454 [ Help ]

wR(obs): 0.1097 [ Help ]

R(all): 0.0485 [ Help ]

wR(all): 0.1098 [ Help ]

S(all): 3.68 [ Help ]

S(obs): 3.71 [ Help ]

Nb. of reflections: 172 [ Help ]

Nb. of parameters: 15 [ Help ]

Number of restraints: 0 [ Help ]

Number of constraints: 0 [ Help ]

Weighting scheme: sigma [ Help ]

Weighting scheme remarks: w=1/(σ²(I)+0.0004I²) [ Help ]

Δ/σ(max): 0.0049 [ Help ]

Δ/σ(mean): 0.0017 [ Help ]

Δρ(max): 1.84 e_Å^-3 [ Help ]

Δρ(min): -2.39 e_Å^-3 [ Help ]

Extinction method: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) [ Help ]

Extinction coefficient: 1530(170) [ Help ]

Structural Information

Average Structure: (Show/hide table) [ Help ]

Atom site label	Atom symbol	z	ADP type	Uiso/equiv	Symmetry multiplicity	Occupancy	Coords from (d)iffraction or (c)alculated	Coords restraints or constraints	Disordered cluster	Disordered group
Cd1	Cd	0.09583(5)	Uani	0.0318(7)	6	1	d	.	.	.
As1	As	0.22070(5)	Uani	0.0121(7)	6	1	d	.	.	.
Cd2	Cd	0.29896(4)	Uani	0.0300(7)	6	1	d	.	.	.
Na1	Na	0.5	Uani	0.026(3)	3	1	d	.	.	.
As2	As	0	Uani	0.0157(8)	3	1	d	.	.	.

ADP components: (Show/hide table) [ Help ]

Atom site label	Atom site symbol	U11	U22	U33	U12
Cd1	Cd	0.0127(8)	0.0127(8)	0.0700(14)	0.0064(4)
As1	As	0.0098(8)	0.0098(8)	0.0165(12)	0.0049(4)
Cd2	Cd	0.0361(9)	0.0361(9)	0.0178(10)	0.0180(5)
Na1	Na	0.035(4)	0.035(4)	0.008(5)	0.018(2)
As2	As	0.0144(10)	0.0144(10)	0.0183(15)	0.0072(5)

As3Cd4Na1_130_mod

Chemical data

Structural Formula Sum: As3 Cd4 Na1 [ Help ]

Formula weight: 697.4 Da [ Help ]

Crystallographic data and experimental details

Crystal system: monoclinic [ Help ]

Superspace group name: Cm(α0γ)s [ Help ]

Symmetry operations of the superspace group: (Show/hide table) [ Help ]

Operation code	Operation in algebraic form
1	x1,x2,x3,x4
2	x1,-x2,x3,x4+1/2
3	x1+1/2,x2+1/2,x3,x4
4	x1+1/2,-x2+1/2,x3,x4+1/2

a: 7.7151(8) Å [ Help ]

b: 13.3673(10) Å [ Help ]

c: 11.5106(11) Å [ Help ]

α: 90 ° [ Help ]

β: 102.905(8) ° [ Help ]

γ: 90 ° [ Help ]

Volume: 1157.10(19) Å³ [ Help ]

Modulation dimension: 1 [ Help ]

Measured independent wave vectors: (Show/hide table) [ Help ]

Wave vector id	q_x	q_y	q_z
1	-0.018589	0.000000	0.341400

Z: 6 [ Help ]

Cell measurement temperature: 130 K [ Help ]

μ: 23.871 mm^-1 [ Help ]

Absorption correction type: gaussian [ Help ]

Absorption correction remarks: Jana2006 [ Help ]

Minimum transmission factor: 0.0253 [ Help ]

Maximum transmission factor: 0.3386 [ Help ]

Refinement details

Total nb. of reflections: 11345 [ Help ]

Nb. of observed reflections: 4609 [ Help ]

Intense reflections threshold: I>3σ(I) [ Help ]

Refinement based on: Fsqd [ Help ]

R(obs): 0.0481 [ Help ]

wR(obs): 0.1082 [ Help ]

R(all): 0.1065 [ Help ]

wR(all): 0.1270 [ Help ]

S(all): 1.35 [ Help ]

S(obs): 1.82 [ Help ]

Nb. of reflections: 11345 [ Help ]

Nb. of parameters: 194 [ Help ]

Number of restraints: 0 [ Help ]

Number of constraints: 2 [ Help ]

Weighting scheme: sigma [ Help ]

Weighting scheme remarks: w=1/(σ²(I)+0.0004I²) [ Help ]

Δ/σ(max): 0.0029 [ Help ]

Δ/σ(mean): 0.0006 [ Help ]

Δρ(max): 0.83 e_Å^-3 [ Help ]

Δρ(min): 0.00 e_Å^-3 [ Help ]

Extinction method: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) [ Help ]

Extinction coefficient: 1520(40) [ Help ]

Absolute structure remarks: 5447 of Friedel pairs used in the refinement [ Help ]

Flack parameter: 0.55(4) [ Help ]

Structural Information

Average Structure: (Show/hide table) [ Help ]

Atom site label	Atom symbol	x	y	z	ADP type	Uiso/equiv	Symmetry multiplicity	Occupancy	Coords from (d)iffraction or (c)alculated	Coords restraints or constraints	Disordered cluster	Disordered group
Cd1	Cd	0.18304(19)	0.16637(13)	0.04866(15)	Uani	0.0191(4)	4	1	d	.	.	.
Cd2	Cd	0.37447(18)	0.16657(13)	0.62437(15)	Uani	0.0185(4)	4	1	d	.	.	.
Cd3	Cd	0.6870(2)	0	0.0616(2)	Uani	0.0122(4)	2	1	d	.	.	.
Cd4	Cd	0.8806(3)	0	0.6383(2)	Uani	0.0191(6)	2	1	d	.	.	.
Cd5	Cd	0.07468(17)	0.32821(15)	0.23742(11)	Uani	0.0143(3)	4	1	d	.	.	.
Cd6	Cd	0.47674(19)	0.33765(19)	0.44323(15)	Uani	0.0193(4)	4	1	d	.	.	.
Cd7	Cd	0.0894(2)	0	0.23684(19)	Uani	0.0139(4)	2	1	d	.	.	.
Cd8	Cd	0.4913(3)	0	0.4424(2)	Uani	0.0194(5)	2	1	d	.	.	.
As1	As	0.2810(3)	0.16670(17)	0.3420(2)	Uani	0.0099(3)	4	1	d	.	.	.
As2	As	0.7793(3)	0	0.3340(2)	Uani	0.0093(7)	2	1	d	.	.	.
As3	As	0.0015(3)	0.33377(13)	0.00046(16)	Uiso	0.0096(3)	4	1	d	.	.	.
As4	As	0.0603(2)	0.16741(11)	0.67816(16)	Uani	0.0048(2)	4	1	d	.	.	.
As5	As	-0.0012(3)	0	-0.0010(3)	Uiso	0.0098(4)	2	1	d	.	.	.
As6	As	0.5583(3)	0	0.6770(2)	Uani	0.0042(3)	2	1	d	.	.	.
Na1	Na	0.2812(10)	0.3320(10)	0.8429(6)	Uiso	0.0095(6)	4	1	d	.	.	.
Na2	Na	0.2895(12)	0	0.8435(8)	Uiso	0.02	2	1	d	.	.	.

ADP components: (Show/hide table) [ Help ]

Atom site label	Atom site symbol	U11	U22	U33	U12	U13	U23
Cd1	Cd	0.0099(5)	0.0096(6)	0.0393(9)	0.0000(4)	0.0088(5)	0.0005(5)
Cd2	Cd	0.0096(5)	0.0079(6)	0.0390(9)	0.0003(4)	0.0080(5)	0.0003(6)
Cd3	Cd	0.0068(6)	0.0036(6)	0.0277(8)	0	0.0069(5)	0
Cd4	Cd	0.0077(6)	0.0016(7)	0.0505(14)	0	0.0120(7)	0
Cd5	Cd	0.0207(5)	0.0192(6)	0.0029(3)	-0.0009(4)	0.0023(3)	0.0011(4)
Cd6	Cd	0.0215(6)	0.0191(7)	0.0172(5)	0.0017(4)	0.0039(4)	0.0002(4)
Cd7	Cd	0.0169(7)	0.0204(9)	0.0034(5)	0	0.0003(5)	0
Cd8	Cd	0.0165(6)	0.0240(10)	0.0175(7)	0	0.0038(5)	0
As1	As	0.0077(4)	0.0076(6)	0.0147(6)	-0.00037(19)	0.0032(4)	-0.0004(3)
As2	As	0.0081(9)	0.0054(10)	0.0150(13)	0	0.0042(9)	0
As4	As	0.0049(3)	0.0019(3)	0.0083(4)	-0.0003(2)	0.0033(2)	0.0004(3)
As6	As	0.0043(5)	0.0019(5)	0.0072(5)	0	0.0030(3)	0

Fourier Wave Vectors (explicit: q_x,q_y,q_z or coefficients: q_1,q_2,...): (Show/hide table) [ Help ]

Wave vector code	q_1
1	1

Definition of the displacive (translational) Fourier series: (Show/hide table) [ Help ]

Modulation code	Atom site label	Displacement axis	Wave vector code
Cd1x1	Cd1	x	1
Cd1y1	Cd1	y	1
Cd1z1	Cd1	z	1
Cd2x1	Cd2	x	1
Cd2y1	Cd2	y	1
Cd2z1	Cd2	z	1
Cd5x1	Cd5	x	1
Cd5y1	Cd5	y	1
Cd5z1	Cd5	z	1
Cd6x1	Cd6	x	1
Cd6y1	Cd6	y	1
Cd6z1	Cd6	z	1
Cd7x1	Cd7	x	1
Cd7y1	Cd7	y	1
Cd7z1	Cd7	z	1
Cd8x1	Cd8	x	1
Cd8y1	Cd8	y	1
Cd8z1	Cd8	z	1
As1x1	As1	x	1
As1y1	As1	y	1
As1z1	As1	z	1
As3x1	As3	x	1
As3y1	As3	y	1
As3z1	As3	z	1
Na1x1	Na1	x	1
Na1y1	Na1	y	1
Na1z1	Na1	z	1
Na2x1	Na2	x	1
Na2y1	Na2	y	1
Na2z1	Na2	z	1

Displacive (translational) Fourier coefficients: (Show/hide table) [ Help ]

Modulation code	Cosine coefficient	Sine coefficient
Cd1x1	-0.0043(2)	-0.0001(6)
Cd1y1	-0.00032(16)	0.00041(15)
Cd1z1	-0.0145(2)	-0.0007(19)
Cd2x1	-0.0024(7)	-0.0047(4)
Cd2y1	-0.00027(15)	0.00020(15)
Cd2z1	-0.005(2)	-0.0148(7)
Cd5x1	0.0143(8)	0.0059(19)
Cd5y1	-0.0047(3)	-0.0020(7)
Cd5z1	0.00096(18)	-0.0008(2)
Cd6x1	0.0108(17)	0.0129(15)
Cd6y1	0.0038(6)	0.0043(5)
Cd6z1	0.0001(2)	0.00048(18)
Cd7x1	0	0
Cd7y1	0.0090(6)	0.0042(12)
Cd7z1	0	0
Cd8x1	0	0
Cd8y1	-0.0077(11)	-0.0083(11)
Cd8z1	0	0
As1x1	0.0029(3)	0.0016(5)
As1y1	-0.0005(2)	0.00068(17)
As1z1	0.0064(7)	0.0052(9)
As3x1	-0.00359(14)	-0.0005(5)
As3y1	0.00311(12)	-0.0001(4)
As3z1	0.0011(3)	-0.00231(18)
Na1x1	0.0055(10)	-0.0006(15)
Na1y1	0.0036(9)	0.0005(11)
Na1z1	-0.0001(6)	0.0000(8)
Na2x1	0	0
Na2y1	-0.0090(14)	0.0(13)
Na2z1	0	0

Definition of the ADP Fourier series: (Show/hide table) [ Help ]

Modulation code	Atom site label	Tensor element	Wave vector code
Cd1U111	Cd1	U11	1
Cd1U221	Cd1	U22	1
Cd1U331	Cd1	U33	1
Cd1U121	Cd1	U12	1
Cd1U131	Cd1	U13	1
Cd1U231	Cd1	U23	1
Cd2U111	Cd2	U11	1
Cd2U221	Cd2	U22	1
Cd2U331	Cd2	U33	1
Cd2U121	Cd2	U12	1
Cd2U131	Cd2	U13	1
Cd2U231	Cd2	U23	1
Cd5U111	Cd5	U11	1
Cd5U221	Cd5	U22	1
Cd5U331	Cd5	U33	1
Cd5U121	Cd5	U12	1
Cd5U131	Cd5	U13	1
Cd5U231	Cd5	U23	1
Cd7U111	Cd7	U11	1
Cd7U221	Cd7	U22	1
Cd7U331	Cd7	U33	1
Cd7U121	Cd7	U12	1
Cd7U131	Cd7	U13	1
Cd7U231	Cd7	U23	1

ADP Fourier coefficients: (Show/hide table) [ Help ]

Modulation code	Cosine coefficient	Sine coefficient
Cd1U111	0.0027(6)	-0.0004(7)
Cd1U221	0.0026(7)	-0.0001(8)
Cd1U331	0.0047(11)	0.0016(12)
Cd1U121	0.0005(5)	-0.0009(7)
Cd1U131	0.0013(7)	0.0013(6)
Cd1U231	0.0010(8)	-0.0020(10)
Cd2U111	-0.0003(6)	0.0014(5)
Cd2U221	-0.0003(8)	0.0026(6)
Cd2U331	-0.008(3)	-0.0249(15)
Cd2U121	-0.0008(6)	0.0000(5)
Cd2U131	-0.0032(10)	-0.0053(7)
Cd2U231	0.0005(9)	0.0001(7)
Cd5U111	0.0035(6)	0.0009(6)
Cd5U221	-0.0031(8)	-0.0020(8)
Cd5U331	0.0003(3)	-0.0003(3)
Cd5U121	0.0020(7)	0.0009(7)
Cd5U131	-0.0005(4)	-0.0006(3)
Cd5U231	0.0011(7)	-0.0004(7)
Cd7U111	0	0
Cd7U221	0	0
Cd7U331	0	0
Cd7U121	-0.0053(8)	-0.0023(10)
Cd7U131	0	0
Cd7U231	-0.0009(8)	-0.0004(8)

Polymorphism in Zintl-Phases ACd4Pn3: The modulated structures of NaCd4Pn3 with Pn = P, As

Grotz, Carolin; Baumgartner, Maximilian; Freitag, Katharina M.; Baumer, Franziska; Nilges, Tom

Inorganic Chemistry 55 7764-7776 (2016)

http://dx.doi.org/10.1021/acs.inorgchem.6b01233

Download CIF

Open in JSmol

As3Cd4Na1_298

Chemical data

Crystallographic data and experimental details

Refinement details

Structural Information

As3Cd4Na1_130_mod

Chemical data

Crystallographic data and experimental details

Refinement details

Structural Information

Polymorphism in Zintl-Phases ACd₄Pn₃: The modulated structures of NaCd₄Pn₃ with Pn = P, As