RbHo2Cu3S5

inorganic papers

i118

Structure Reports Online

ISSN 1600-5368

RbHo

Cu

S

Jiyong Yao and James A. Ibers*

Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 153 K

Mean(Cu±S) = 0.001 AÊ

Rfactor = 0.023

wRfactor = 0.054

Data-to-parameter ratio = 17.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

Rubidium diholmium tricopper pentasul®de, RbHo2Cu3S5,

crystallizes in the orthorhombic space group Cmcm and is

isostructural with RbSm2Ag3Se5. In the asymmetric unit, the

site symmetries of atoms Rb, Cu1, and S2 aremmand those of the other atoms arem. The structure has a three-dimensional

tunnel framework, with tunnels built from HoS6 octahedra

and CuS4tetrahedra. The tunnels are ®lled with Rb atoms.

Comment

Ternary and quaternary rare-earth chalcogenides containing a combination ofd- andf-elements have been reviewed recently (Mitchell & Ibers, 2002). We report here the structure of RbHo2Cu3S5, a new member of this large family. RbHo2Cu3S5,

which has the RbSm2Ag3Se5structure type (Huang & Ibers,

2000), crystallizes in space groupCmcmof the orthorhombic

system. In the asymmetric unit (Fig. 1), the site symmetries of

atoms Rb, Cu1, and S2 aremmand those of the other atoms

arem. The structure of RbHo2Cu3S5(Fig. 2) possesses a

three-dimensional tunnel framework built from HoS6octahedra and

CuS4tetrahedra. The tunnel, comprising ten-membered rings

of six CuÐS bonds and four HoÐS bonds, is only large enough in cross-section to accommodate one Rb atom. Each Rb atom is surrounded by a bicapped trigonal prism of eight S atoms, with RbÐS separations ranging from 3.293 (1) to 3.460 (1) AÊ, comparable with those of 3.247 (2)±3.7951 (4) AÊ

in RbNd2CuS4 (Huang & Ibers, 2000). The HoÐS bond

distances range from 2.6497 (8) to 2.787 (1) AÊ, consistent with those of 2.672 (2)±2.8009 (3) AÊ in K2Ho4Cu4S9 (Yao et al.,

2003), and the CuÐS bond distances range from 2.321 (1) to 2.547 (2) AÊ, comparable with those of 2.3448 (9) to 2.534 (2) AÊ in K2Ho4Cu4S9(Yaoet al., 2003).

Received 4 August 2004 Accepted 10 August 2004 Online 21 August 2004

Figure 1

A view of the asymmetric unit of RbHo2Cu3S5, with displacement

Experimental

RbHo2Cu3S5 was obtained as yellow needles from a solid-state

reaction of Rb2S3 (1.2 mmol), Ho (Aldrich, 99%, 1.0 mmol), Cu

(Aldrich, 99.999%, 0.5 mmol), and S (Aldrich, 99.5%, 2.0 mmol). The

Rb2S3reactive ¯ux (Sunshineet al., 1987) was prepared by the

stoi-chiometric reaction of Rb (Aldrich, 98+%) and S in liquid NH3. The

reactants were loaded into a fused-silica tube under an argon

atmosphere in a glove-box. The tube was sealed under a 10ÿ4_Torr

atmosphere and then placed in a computer-controlled furnace. The sample was heated to 1173 K over a period of 25 h, kept at 1173 K for

3 d, slowly cooled at a rate of 10 K hÿ1_{to 473 K, and then cooled}

rapidly to room temperature.

Crystal data RbHo2Cu3S5

Mr= 766.25

Orthorhombic,Cmcm a= 3.9451 (11) AÊ b= 13.915 (4) AÊ c= 16.408 (5) AÊ V= 900.8 (4) AÊ3

Z= 4

Dx= 5.650 Mg mÿ3

MoKradiation Cell parameters from 4507

re¯ections

= 2.5±29.0

= 30.77 mmÿ1

T= 153 (2) K Needle, yellow

0.420.0680.030 mm

Data collection

Bruker SMART 1000 CCD diffractometer

!scans

Absorption correction: numerical face indexed

Tmin= 0.047,Tmax= 0.405

5433 measured re¯ections

673 independent re¯ections 661 re¯ections withI> 2(I) Rint= 0.050

max= 29.0

h=ÿ5!5 k=ÿ18!18 l=ÿ21!21 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.023}

wR(F2_{) = 0.054}

S= 1.39 673 re¯ections 38 parameters

w= 1/[2_(F

o2) + (0.03P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001 max= 2.37 e AÊÿ3 min=ÿ2.55 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.00404 (19)

Table 1

Selected geometric parameters (AÊ,_).

RbÐS3 3.2929 (15) RbÐS2i _{3.3410 (15)}

RbÐS1ii _{3.4604 (12)}

HoÐS2iii _{2.6497 (8)}

HoÐS3iv _{2.6957 (14)}

HoÐS1v _{2.6995 (9)}

HoÐS3vi _{2.7865 (10)}

Cu1ÐS2vii _{2.3212 (10)}

Cu1ÐS1iv _{2.5438 (14)}

Cu2ÐS1viii _{2.3641 (14)}

Cu2ÐS3v _{2.3674 (8)}

Cu2ÐS1iv _{2.5473 (15)}

S2iii_ÐHoÐS3iv _{172.13 (4)}

S2iii_ÐHoÐS1v _{92.47 (3)}

S3iv_ÐHoÐS1v _{92.89 (3)}

S1v_ÐHoÐS1vi _{93.89 (4)}

S2iii_ÐHoÐS3vi _{87.95 (4)}

S3iv_ÐHoÐS3vi _{86.50 (3)}

S1v_ÐHoÐS3vi _{178.05 (3)}

S1vi_ÐHoÐS3vi _{87.99 (3)}

S3vi_ÐHoÐS3v _{90.13 (4)}

S2vii_ÐCu1ÐS2i _{116.38 (7)}

S2i_ÐCu1ÐS1iv _{105.05 (2)}

S1iv_{ÐCu1ÐS1 120.96 (6)}

S1viii_ÐCu2ÐS3v _{108.94 (4)}

S3v_ÐCu2ÐS3vi _{112.86 (5)}

S1viii_ÐCu2ÐS1iv _{115.43 (4)}

S3v_ÐCu2ÐS1iv _{105.36 (4)} Symmetry codes: (i) xÿ1

2;yÿ12;z; (ii) 12‡x;12‡y;12ÿz; (iii) ÿx;1ÿy;1ÿz; (iv)

x;y;1

2ÿz; (v) 12ÿx;12ÿy;12‡z; (vi) ÿ12ÿx;12ÿy;12‡z; (vii) 12‡x;yÿ12;z; (viii)

ÿx;ÿy;1 2‡z.

The highest residual electron density is 0.87 AÊ from the Ho site and the deepest hole is 0.70 AÊ from this same site.

Data collection:SMART(Bruker, 2003); cell re®nement:SAINT

(Bruker, 2003); data reduction:SAINT; program(s) used to solve

structure: SHELXTL (Sheldrick, 2003); program(s) used to re®ne

structure:SHELXTL; molecular graphics:XPin SHELXTL;

soft-ware used to prepare material for publication:SHELXTL.

This research was supported by the MRSEC program of the National Science Foundation (DMR00-76097) at the Materials Research Center of Northwestern University.

References

Bruker (2003). SMART(Version 5.054) and SAINT-Plus (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.

Huang, F. Q. & Ibers, J. A. (2000).J. Solid State Chem.151, 317±322. Mitchell, K. & Ibers, J. A. (2002).Chem. Rev.102, 1929±1952.

Sheldrick, G. M. (2003).SHELXTL.DOS/Windows/NT Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.

Sunshine, S. A., Kang, D. & Ibers, J. A. (1987).J. Am. Chem. Soc.109, 6202± 6204.

Yao, J., Deng, B., Ellis, D. E. & Ibers, J. A. (2003).J. Solid State Chem.176, 5± 12.

Figure 2

supporting information

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Acta Cryst. (2004). E60, i118–i119

supporting information

Acta Cryst. (2004). E60, i118–i119 [https://doi.org/10.1107/S1600536804019786]

RbHo

Cu

S

Jiyong Yao and James A. Ibers

rubidium diholmium tricopper pentasulfide

Crystal data

RbHo2Cu3S5 Mr = 766.25

Orthorhombic, Cmcm

Hall symbol: -C 2c 2

a = 3.9451 (11) Å

b = 13.915 (4) Å

c = 16.408 (5) Å

V = 900.8 (4) Å3 Z = 4

F(000) = 1352

Dx = 5.650 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4507 reflections

θ = 2.5–29.0°

µ = 30.77 mm−1 T = 153 K Needle, yellow 0.42 × 0.07 × 0.03 mm

Data collection

Bruker 1000 CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: numerical face indexed

Tmin = 0.047, Tmax = 0.405

5433 measured reflections 673 independent reflections 661 reflections with I > 2σ(I)

Rint = 0.050

θmax = 29.0°, θmin = 2.5° h = −5→5

k = −18→18

l = −21→21

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.023} wR(F2_{) = 0.054} S = 1.39 673 reflections 38 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

w = 1/[σ2_(F

o2) + (0.03P)2]

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max = 0.001

Δρmax = 2.37 e Å−3

Δρmin = −2.55 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.00404 (19)

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Rb 0.0000 0.43385 (4) 0.2500 0.00977 (17)

Ho 0.0000 0.307904 (13) 0.593727 (13) 0.00644 (14)

Cu1 0.0000 0.15215 (6) 0.2500 0.0116 (2)

Cu2 0.0000 0.08234 (4) 0.53920 (4) 0.01149 (18) S1 0.0000 0.06208 (8) 0.11509 (7) 0.0075 (2)

S2 0.0000 0.74007 (11) 0.2500 0.0077 (3)

S3 0.0000 0.33060 (8) 0.06943 (7) 0.0075 (2)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Rb 0.0112 (3) 0.0090 (3) 0.0091 (3) 0.000 0.000 0.000 Ho 0.00684 (18) 0.00646 (17) 0.00601 (19) 0.000 0.000 −0.00007 (6) Cu1 0.0089 (4) 0.0129 (4) 0.0131 (4) 0.000 0.000 0.000 Cu2 0.0110 (3) 0.0081 (3) 0.0154 (3) 0.000 0.000 0.0008 (2) S1 0.0085 (5) 0.0058 (5) 0.0083 (5) 0.000 0.000 −0.0003 (4) S2 0.0081 (6) 0.0075 (7) 0.0074 (7) 0.000 0.000 0.000 S3 0.0081 (5) 0.0071 (4) 0.0074 (6) 0.000 0.000 0.0001 (5)

Geometric parameters (Å, º)

Rb—S3 3.2929 (15) Cu1—Hoxii _{3.2826 (7)}

Rb—S3i _{3.2929 (15) Cu1—Ho}xiii _{3.2826 (7)}

Rb—S2ii _{3.3410 (15) Cu1—Rb}ii _{3.6218 (12)}

Rb—S2iii _{3.3410 (15) Cu1—Rb}iii _{3.6218 (12)}

Rb—S1iv _{3.4604 (12) Cu2—S1}xvi _{2.3641 (14)}

Rb—S1v _{3.4604 (12) Cu2—S3}x _{2.3674 (8)}

Rb—S1vi _{3.4604 (12) Cu2—S3}xi _{2.3674 (8)}

Rb—S1vii _{3.4604 (12) Cu2—S1}i _{2.5473 (15)}

Rb—Cu1vii _{3.6219 (12) Cu2—Cu2}xvii _{2.6278 (13)}

Rb—Cu1vi _{3.6219 (12) Cu2—Ho}xiii _{3.3137 (8)}

Rb—Cu1 3.9200 (15) Cu2—Hoxii _{3.3137 (8)}

Rb—Rbviii _{3.9451 (11) Cu2—Rb}xii _{3.9883 (11)}

Ho—S2ix _{2.6497 (8) Cu2—Rb}xiii _{3.9883 (11)}

Ho—S3i _{2.6957 (14) S1—Cu2}xviii _{2.3642 (14)}

Ho—S1x _{2.6995 (9) S1—Cu2}i _{2.5473 (15)}

Ho—S1xi _{2.6995 (9) S1—Ho}xv _{2.6995 (9)}

Ho—S3xi _{2.7865 (10) S1—Ho}xiv _{2.6995 (9)}

Ho—S3x _{2.7865 (10) S1—Rb}iii _{3.4605 (12)}

supporting information

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Acta Cryst. (2004). E60, i118–i119

Ho—Cu1xii _{3.2826 (7) S2—Cu1}vi _{2.3212 (10)}

Ho—Cu1xiii _{3.2826 (7) S2—Cu1}vii _{2.3212 (10)}

Ho—Cu2xiii _{3.3137 (8) S2—Ho}xix _{2.6496 (8)}

Ho—Cu2xii _{3.3137 (8) S2—Ho}ix _{2.6497 (8)}

Ho—Hoviii _{3.9451 (11) S2—Rb}vii _{3.3410 (15)}

Cu1—S2iii _{2.3212 (10) S2—Rb}vi _{3.3410 (15)}

Cu1—S2ii _{2.3212 (10) S3—Cu2}xv _{2.3674 (8)}

Cu1—S1i _{2.5438 (14) S3—Cu2}xiv _{2.3674 (8)}

Cu1—S1 2.5438 (14) S3—Hoi _{2.6957 (14)}

Cu1—Hoxiv _{3.2825 (7) S3—Ho}xiv _{2.7864 (10)}

Cu1—Hoxv _{3.2825 (7) S3—Ho}xv _{2.7864 (10)}

S3—Rb—S3i _{128.26 (5) S3}x_—Cu2—S1i _{105.36 (4)}

S3—Rb—S2ii _{69.38 (2) S3}xi_—Cu2—S1i _{105.36 (4)}

S3i_—Rb—S2ii _{69.38 (2) Cu2}xviii_{—S1—Cu1 151.30 (6)}

S3—Rb—S2iii _{69.38 (2) Cu2}xviii_—S1—Cu2i _{64.57 (4)}

S3i_—Rb—S2iii _{69.38 (2) Cu1—S1—Cu2}i _{144.13 (5)}

S2ii_—Rb—S2iii _{72.37 (4) Cu2}xviii_—S1—Hoxv _{120.09 (4)}

S3—Rb—S1iv _{143.184 (17) Cu1—S1—Ho}xv _{77.45 (3)}

S3i_—Rb—S1iv _{69.48 (3) Cu2}i_—S1—Hoxv _{78.27 (3)}

S2ii_—Rb—S1iv _{138.82 (2) Cu2}xviii_—S1—Hoxiv _{120.09 (4)}

S2iii_—Rb—S1iv _{94.56 (2) Cu1—S1—Ho}xiv _{77.45 (3)}

S3—Rb—S1v _{143.184 (17) Cu2}i_—S1—Hoxiv _{78.27 (3)}

S3i_—Rb—S1v _{69.48 (3) Ho}xv_—S1—Hoxiv _{93.89 (4)}

S2ii_—Rb—S1v _{94.56 (2) Cu2}xviii_—S1—Rbiii _{84.19 (4)}

S2iii_—Rb—S1v _{138.82 (2) Cu1—S1—Rb}iii _{72.38 (3)}

S1iv_—Rb—S1v _{69.51 (3) Cu2}i_—S1—Rbiii _{133.86 (3)}

S3—Rb—S1vi _{69.48 (3) Ho}xv_—S1—Rbiii _{90.69 (2)}

S3i_—Rb—S1vi _{143.185 (17) Ho}xiv_—S1—Rbiii _{147.69 (4)}

S2ii_—Rb—S1vi _{94.57 (2) Cu2}xviii_—S1—Rbii _{84.19 (4)}

S2iii_—Rb—S1vi _{138.83 (2) Cu1—S1—Rb}ii _{72.38 (3)}

S1iv_—Rb—S1vi _{117.92 (4) Cu2}i_—S1—Rbii _{133.86 (3)}

S1v_—Rb—S1vi _{79.54 (4) Ho}xv_—S1—Rbii _{147.69 (4)}

S3—Rb—S1vii _{69.48 (3) Ho}xiv_—S1—Rbii _{90.69 (2)}

S3i_—Rb—S1vii _{143.185 (17) Rb}iii_—S1—Rbii _{69.50 (3)}

S2ii_—Rb—S1vii _{138.83 (2) Cu1}vi_—S2—Cu1vii _{116.38 (7)}

S2iii_—Rb—S1vii _{94.57 (2) Cu1}vi_—S2—Hoxix _{82.37 (2)}

S1iv_—Rb—S1vii _{79.54 (4) Cu1}vii_—S2—Hoxix _{82.37 (2)}

S1v_—Rb—S1vii _{117.92 (4) Cu1}vi_—S2—Hoix _{82.37 (2)}

S1vi_—Rb—S1vii _{69.51 (3) Cu1}vii_—S2—Hoix _{82.37 (2)}

S2ix_—Ho—S3i _{172.13 (4) Ho}xix_—S2—Hoix _{150.81 (6)}

S2ix_—Ho—S1x _{92.47 (3) Cu1}vi_—S2—Rbvii _{157.99 (5)}

S3i_—Ho—S1x _{92.89 (3) Cu1}vii_—S2—Rbvii _{85.62 (3)}

S2ix_—Ho—S1xi _{92.47 (3) Ho}xix_—S2—Rbvii _{101.73 (2)}

S3i_—Ho—S1xi _{92.89 (3) Ho}ix_—S2—Rbvii _{101.73 (2)}

S1x_—Ho—S1xi _{93.89 (4) Cu1}vi_—S2—Rbvi _{85.62 (3)}

S2ix_—Ho—S3xi _{87.95 (4) Cu1}vii_—S2—Rbvi _{157.99 (5)}

S1x_—Ho—S3xi _{178.05 (3) Ho}ix_—S2—Rbvi _{101.73 (2)}

S1xi_—Ho—S3xi _{87.99 (3) Rb}vii_—S2—Rbvi _{72.37 (4)}

S2ix_—Ho—S3x _{87.95 (4) Cu2}xv_—S3—Cu2xiv _{112.86 (5)}

S3i_—Ho—S3x _{86.50 (3) Cu2}xv_—S3—Hoi _{81.48 (3)}

S1x_—Ho—S3x _{87.99 (3) Cu2}xiv_—S3—Hoi _{81.48 (3)}

S1xi_—Ho—S3x _{178.05 (3) Cu2}xv_—S3—Hoxiv _{166.85 (4)}

S3xi_—Ho—S3x _{90.13 (4) Cu2}xiv_—S3—Hoxiv _{78.12 (2)}

S2iii_—Cu1—S2ii _{116.38 (7) Ho}i_—S3—Hoxiv _{93.50 (3)}

S2iii_—Cu1—S1i _{105.051 (19) Cu2}xv_—S3—Hoxv _{78.12 (2)}

S2ii_—Cu1—S1i _{105.05 (2) Cu2}xiv_—S3—Hoxv _{166.85 (4)}

S2iii_{—Cu1—S1 105.053 (19) Ho}i_—S3—Hoxv _{93.50 (3)}

S2ii_{—Cu1—S1 105.053 (19) Ho}xiv_—S3—Hoxv _{90.13 (4)}

S1i_{—Cu1—S1 120.96 (6) Cu2}xv_{—S3—Rb 88.01 (4)}

S1xvi_—Cu2—S3x _{108.94 (4) Cu2}xiv_{—S3—Rb 88.01 (4)}

S1xvi_—Cu2—S3xi _{108.94 (4) Ho}i_{—S3—Rb 160.86 (5)}

S3x_—Cu2—S3xi _{112.86 (5) Ho}xiv_{—S3—Rb 99.97 (3)}

S1xvi_—Cu2—S1i _{115.43 (4) Ho}xv_{—S3—Rb 99.97 (3)}

Symmetry codes: (i) x, y, −z+1/2; (ii) x−1/2, y−1/2, z; (iii) x+1/2, y−1/2, z; (iv) x+1/2, y+1/2, −z+1/2; (v) x−1/2, y+1/2, −z+1/2; (vi) x−1/2, y+1/2, z; (vii)

x+1/2, y+1/2, z; (viii) x+1, y, z; (ix) −x, −y+1, −z+1; (x) −x+1/2, −y+1/2, z+1/2; (xi) −x−1/2, −y+1/2, z+1/2; (xii) −x+1/2, −y+1/2, −z+1; (xiii) −x−1/2, −y+1/2, −z+1; (xiv) −x−1/2, −y+1/2, z−1/2; (xv) −x+1/2, −y+1/2, z−1/2; (xvi) −x, −y, z+1/2; (xvii) −x, −y, −z+1; (xviii) −x, −y, z−1/2; (xix) −x, −y+1,