Crystal structure and electrical resistance property of Rb_0.21(H₂O)_yWS₂

Rb_0.21(H₂O)_yWS₂, rubidium hydrate di­thio­tungstate, is a new quasi two-dimensional sulfide. Its crystal structure consists of ordered WS₂ layers, separated by disordered Rb⁺ ions and water mol­ecules. All atomic sites are located on mirror planes. The WS₂ layers are composed of edge-sharing [WS₆] octa­hedra and extend parallel to (001). The presence of structural water was revealed by thermogravimetry, but the position and exact amount could not be determined in the present study. The temperature dependence of the electrical resistance indicates that Rb_0.21(H₂O)_yWS₂ is semiconducting between 80–300 K.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](W-S) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.050
• wR factor = 0.124
• Data-to-parameter ratio = 10.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT077_ALERT_4_C Unitcell Contains Non-integer Number of Atoms ..     Please Check
PLAT260_ALERT_2_C Large Average Ueq of Residue Including       Rb4      0.143 Check
PLAT260_ALERT_2_C Large Average Ueq of Residue Including       Rb5      0.168 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.593          7 Report
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.79A   From W1              2.28 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.82A   From W1              2.15 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.83A   From W1              2.09 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  1.31A   From S2              2.08 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.93A   From W1              1.93 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.79A   From W1              1.87 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  1.27A   From S3             -1.62 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  1.43A   From S3             -1.56 eA-3

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT068_ALERT_1_G Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.10 Report
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )       100% Note
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  3  )       100% Note
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2 Note
              Rb2
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3 Note
              Rb0.40
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        87% Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          7 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  12 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  12 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).

rubidium hydrate dithiotungstate

Crystal data

Rb0.21(H2O)yWS2	F(000) = 237
Mr = 277.23	Dx = 5.345 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.703 (3) Å	Cell parameters from 68 reflections
b = 3.2524 (18) Å	θ = 3.9–23.0°
c = 9.423 (5) Å	µ = 39.25 mm^−1
β = 99.724 (16)°	T = 298 K
V = 172.27 (16) Å^3	Plate, black
Z = 2	0.05 × 0.03 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer	327 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.030
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θmax = 24.9°, θmin = 2.2°
Tmin = 0.251, Tmax = 0.674	h = −6→6
1167 measured reflections	k = −3→3
352 independent reflections	l = −11→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters not defined
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.1024P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.124	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 2.45 e Å^−3
352 reflections	Δρmin = −1.66 e Å^−3
33 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	0.19782 (11)	0.7500	1.00615 (8)	0.0371 (5)
S2	0.3744 (9)	0.2500	0.8600 (6)	0.0376 (12)
S3	0.1409 (10)	0.2500	1.1850 (6)	0.0401 (12)
Rb4	0.21 (4)	−0.2500	0.534 (6)	0.14 (6)	0.14 (7)
Rb5	0.38 (2)	−0.2500	0.525 (8)	0.17 (2)	0.20 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.0319 (7)	0.0374 (7)	0.0423 (7)	0.000	0.0073 (4)	0.000
S2	0.034 (2)	0.038 (3)	0.041 (3)	0.000	0.007 (2)	0.000
S3	0.041 (3)	0.039 (3)	0.041 (3)	0.000	0.008 (2)	0.000
Rb4	0.28 (14)	0.12 (4)	0.04 (2)	0.000	0.06 (4)	0.000
Rb5	0.18 (6)	0.24 (6)	0.08 (3)	0.000	0.01 (3)	0.000

Geometric parameters (Å, º)

W1—S3^i	2.403 (4)	Rb4—Rb5	0.99 (10)
W1—S3	2.403 (4)	Rb4—Rb4^x	2.9 (3)
W1—S3^ii	2.408 (5)	Rb4—Rb4^xi	2.9 (3)
W1—S2	2.454 (4)	Rb4—Rb5^xii	3.0 (3)
W1—S2^i	2.454 (4)	Rb4—Rb5^xiii	3.0 (3)
W1—S2^iii	2.550 (5)	Rb4—Rb4^i	3.252 (2)
W1—W1^ii	2.7678 (15)	Rb4—Rb4^v	3.2524 (19)
W1—W1^iv	2.7678 (15)	Rb4—Rb5^i	3.40 (3)
S2—W1^v	2.454 (4)	Rb4—Rb5^v	3.40 (3)
S2—W1^iii	2.550 (5)	Rb4—S2^v	3.47 (7)
S2—Rb4	3.47 (7)	Rb4—S3^vii	3.58 (11)
S2—Rb4^i	3.47 (7)	Rb5—Rb5^xii	2.23 (19)
S2—Rb5^i	3.56 (8)	Rb5—Rb5^xiii	2.23 (19)
S2—Rb5	3.56 (8)	Rb5—Rb4^xii	3.0 (3)
S3—W1^v	2.403 (4)	Rb5—Rb4^xiii	3.0 (3)
S3—W1^ii	2.408 (5)	Rb5—Rb5^i	3.2524 (18)
S3—Rb5^vi	3.53 (6)	Rb5—Rb5^v	3.2524 (18)
S3—Rb4^vii	3.58 (11)	Rb5—Rb4^v	3.40 (3)
S3—Rb4^viii	3.63 (4)	Rb5—Rb4^i	3.40 (3)
S3—Rb4^ix	3.63 (4)	Rb5—S3^vi	3.53 (6)
S3—Rb5^viii	3.64 (5)	Rb5—S2^v	3.56 (8)
S3—Rb5^ix	3.64 (5)
S3^i—W1—S3	85.18 (18)	Rb5^xii—Rb4—Rb5^i	40 (3)
S3^i—W1—S3^ii	109.76 (14)	Rb5^xiii—Rb4—Rb5^i	106 (4)
S3—W1—S3^ii	109.76 (14)	Rb4^i—Rb4—Rb5^i	16.9 (16)
S3^i—W1—S2	163.5 (2)	Rb4^v—Rb4—Rb5^i	163.1 (16)
S3—W1—S2	93.55 (13)	Rb5—Rb4—Rb5^v	73.1 (16)
S3^ii—W1—S2	86.20 (17)	Rb4^x—Rb4—Rb5^v	71 (3)
S3^i—W1—S2^i	93.55 (13)	Rb4^xi—Rb4—Rb5^v	140 (7)
S3—W1—S2^i	163.5 (2)	Rb5^xii—Rb4—Rb5^v	106 (4)
S3^ii—W1—S2^i	86.20 (17)	Rb5^xiii—Rb4—Rb5^v	40 (3)
S2—W1—S2^i	82.99 (18)	Rb4^i—Rb4—Rb5^v	163.1 (16)
S3^i—W1—S2^iii	83.36 (18)	Rb4^v—Rb4—Rb5^v	16.9 (16)
S3—W1—S2^iii	83.36 (18)	Rb5^i—Rb4—Rb5^v	146 (3)
S3^ii—W1—S2^iii	161.7 (2)	Rb5—Rb4—S2^v	87 (10)
S2—W1—S2^iii	80.13 (16)	Rb4^x—Rb4—S2^v	91.3 (12)
S2^i—W1—S2^iii	80.13 (16)	Rb4^xi—Rb4—S2^v	124 (4)
S3^i—W1—W1^ii	102.78 (13)	Rb5^xii—Rb4—S2^v	108 (5)
S3—W1—W1^ii	54.97 (13)	Rb5^xiii—Rb4—S2^v	79 (2)
S3^ii—W1—W1^ii	54.79 (10)	Rb4^i—Rb4—S2^v	118.0 (6)
S2—W1—W1^ii	89.78 (11)	Rb4^v—Rb4—S2^v	62.0 (6)
S2^i—W1—W1^ii	140.78 (13)	Rb5^i—Rb4—S2^v	116 (4)
S2^iii—W1—W1^ii	136.53 (8)	Rb5^v—Rb4—S2^v	62 (2)
S3^i—W1—W1^iv	54.97 (13)	Rb5—Rb4—S2	87 (10)
S3—W1—W1^iv	102.78 (13)	Rb4^x—Rb4—S2	124 (4)
S3^ii—W1—W1^iv	54.79 (10)	Rb4^xi—Rb4—S2	91.3 (12)
S2—W1—W1^iv	140.78 (13)	Rb5^xii—Rb4—S2	79 (2)
S2^i—W1—W1^iv	89.78 (11)	Rb5^xiii—Rb4—S2	108 (5)
S2^iii—W1—W1^iv	136.53 (8)	Rb4^i—Rb4—S2	62.0 (6)
W1^ii—W1—W1^iv	71.96 (5)	Rb4^v—Rb4—S2	118.0 (6)
W1^v—S2—W1	82.99 (18)	Rb5^i—Rb4—S2	62 (2)
W1^v—S2—W1^iii	99.87 (16)	Rb5^v—Rb4—S2	116 (4)
W1—S2—W1^iii	99.87 (16)	S2^v—Rb4—S2	56.0 (12)
W1^v—S2—Rb4	96.3 (15)	Rb5—Rb4—S3^vii	138 (10)
W1—S2—Rb4	137 (3)	Rb4^x—Rb4—S3^vii	68 (4)
W1^iii—S2—Rb4	122 (3)	Rb4^xi—Rb4—S3^vii	68 (4)
W1^v—S2—Rb4^i	137 (3)	Rb5^xii—Rb4—S3^vii	133.8 (12)
W1—S2—Rb4^i	96.3 (15)	Rb5^xiii—Rb4—S3^vii	133.8 (12)
W1^iii—S2—Rb4^i	122 (3)	Rb4^i—Rb4—S3^vii	90.000 (2)
Rb4—S2—Rb4^i	56.0 (12)	Rb4^v—Rb4—S3^vii	90.000 (1)
W1^v—S2—Rb5^i	150.1 (12)	Rb5^i—Rb4—S3^vii	102.5 (13)
W1—S2—Rb5^i	105.1 (13)	Rb5^v—Rb4—S3^vii	102.5 (12)
W1^iii—S2—Rb5^i	106.8 (18)	S2^v—Rb4—S3^vii	56.3 (7)
Rb4—S2—Rb5^i	57.9 (7)	S2—Rb4—S3^vii	56.3 (7)
Rb4^i—S2—Rb5^i	16.1 (18)	Rb4—Rb5—Rb5^xii	132 (4)
W1^v—S2—Rb5	105.1 (13)	Rb4—Rb5—Rb5^xiii	132 (4)
W1—S2—Rb5	150.1 (12)	Rb5^xii—Rb5—Rb5^xiii	94 (10)
W1^iii—S2—Rb5	106.8 (18)	Rb4—Rb5—Rb4^xii	146 (2)
Rb4—S2—Rb5	16.1 (18)	Rb5^xii—Rb5—Rb4^xii	14.3 (18)
Rb4^i—S2—Rb5	57.9 (7)	Rb5^xiii—Rb5—Rb4^xii	80 (8)
Rb5^i—S2—Rb5	54.4 (14)	Rb4—Rb5—Rb4^xiii	146 (2)
W1^v—S3—W1	85.18 (18)	Rb5^xii—Rb5—Rb4^xiii	80 (8)
W1^v—S3—W1^ii	70.24 (14)	Rb5^xiii—Rb5—Rb4^xiii	14.3 (18)
W1—S3—W1^ii	70.24 (14)	Rb4^xii—Rb5—Rb4^xiii	66 (7)
W1^v—S3—Rb5^vi	111.4 (15)	Rb4—Rb5—Rb5^i	90.00 (5)
W1—S3—Rb5^vi	111.4 (16)	Rb5^xii—Rb5—Rb5^i	43 (5)
W1^ii—S3—Rb5^vi	178 (2)	Rb5^xiii—Rb5—Rb5^i	137 (5)
W1^v—S3—Rb4^vii	132.7 (12)	Rb4^xii—Rb5—Rb5^i	57 (3)
W1—S3—Rb4^vii	132.7 (11)	Rb4^xiii—Rb5—Rb5^i	123 (3)
W1^ii—S3—Rb4^vii	94 (3)	Rb4—Rb5—Rb5^v	90.00 (10)
Rb5^vi—S3—Rb4^vii	83.2 (13)	Rb5^xii—Rb5—Rb5^v	137 (5)
W1^v—S3—Rb4^viii	159 (2)	Rb5^xiii—Rb5—Rb5^v	43 (5)
W1—S3—Rb4^viii	109.0 (6)	Rb4^xii—Rb5—Rb5^v	123 (3)
W1^ii—S3—Rb4^viii	129 (3)	Rb4^xiii—Rb5—Rb5^v	57 (3)
Rb5^vi—S3—Rb4^viii	49 (5)	Rb5^i—Rb5—Rb5^v	180.00 (7)
Rb4^vii—S3—Rb4^viii	47 (5)	Rb4—Rb5—Rb4^v	73.1 (17)
W1^v—S3—Rb4^ix	109.0 (6)	Rb5^xii—Rb5—Rb4^v	153 (5)
W1—S3—Rb4^ix	159 (2)	Rb5^xiii—Rb5—Rb4^v	60 (6)
W1^ii—S3—Rb4^ix	129 (3)	Rb4^xii—Rb5—Rb4^v	140 (3)
Rb5^vi—S3—Rb4^ix	49 (5)	Rb4^xiii—Rb5—Rb4^v	74 (4)
Rb4^vii—S3—Rb4^ix	47 (5)	Rb5^i—Rb5—Rb4^v	163.1 (16)
Rb4^viii—S3—Rb4^ix	53.3 (7)	Rb5^v—Rb5—Rb4^v	16.9 (16)
W1^v—S3—Rb5^viii	147.5 (16)	Rb4—Rb5—Rb4^i	73.1 (16)
W1—S3—Rb5^viii	103.9 (12)	Rb5^xii—Rb5—Rb4^i	60 (6)
W1^ii—S3—Rb5^viii	142.2 (16)	Rb5^xiii—Rb5—Rb4^i	153 (5)
Rb5^vi—S3—Rb5^viii	36 (3)	Rb4^xii—Rb5—Rb4^i	74 (4)
Rb4^vii—S3—Rb5^viii	61 (4)	Rb4^xiii—Rb5—Rb4^i	140 (3)
Rb4^viii—S3—Rb5^viii	15.7 (16)	Rb5^i—Rb5—Rb4^i	16.9 (16)
Rb4^ix—S3—Rb5^viii	55.8 (6)	Rb5^v—Rb5—Rb4^i	163.1 (16)
W1^v—S3—Rb5^ix	103.9 (12)	Rb4^v—Rb5—Rb4^i	146 (3)
W1—S3—Rb5^ix	147.5 (16)	Rb4—Rb5—S3^vi	125 (9)
W1^ii—S3—Rb5^ix	142.2 (16)	Rb5^xii—Rb5—S3^vi	75 (3)
Rb5^vi—S3—Rb5^ix	36 (3)	Rb5^xiii—Rb5—S3^vi	75 (3)
Rb4^vii—S3—Rb5^ix	61 (4)	Rb4^xii—Rb5—S3^vi	67 (4)
Rb4^viii—S3—Rb5^ix	55.8 (6)	Rb4^xiii—Rb5—S3^vi	67 (4)
Rb4^ix—S3—Rb5^ix	15.7 (16)	Rb5^i—Rb5—S3^vi	90.000 (5)
Rb5^viii—S3—Rb5^ix	53.0 (8)	Rb5^v—Rb5—S3^vi	90.000 (2)
Rb5—Rb4—Rb4^x	141 (2)	Rb4^v—Rb5—S3^vi	100 (3)
Rb5—Rb4—Rb4^xi	141 (2)	Rb4^i—Rb5—S3^vi	100 (3)
Rb4^x—Rb4—Rb4^xi	69 (9)	Rb4—Rb5—S2^v	77 (8)
Rb5—Rb4—Rb5^xii	34 (2)	Rb5^xii—Rb5—S2^v	128 (3)
Rb4^x—Rb4—Rb5^xii	157 (2)	Rb5^xiii—Rb5—S2^v	87 (3)
Rb4^xi—Rb4—Rb5^xii	107.5 (14)	Rb4^xii—Rb5—S2^v	123 (3)
Rb5—Rb4—Rb5^xiii	34 (2)	Rb4^xiii—Rb5—S2^v	92.3 (10)
Rb4^x—Rb4—Rb5^xiii	107.5 (13)	Rb5^i—Rb5—S2^v	117.2 (7)
Rb4^xi—Rb4—Rb5^xiii	157 (2)	Rb5^v—Rb5—S2^v	62.8 (7)
Rb5^xii—Rb4—Rb5^xiii	66 (7)	Rb4^v—Rb5—S2^v	59.7 (19)
Rb5—Rb4—Rb4^i	90.00 (5)	Rb4^i—Rb5—S2^v	112 (3)
Rb4^x—Rb4—Rb4^i	125 (5)	S3^vi—Rb5—S2^v	55.4 (8)
Rb4^xi—Rb4—Rb4^i	55 (5)	Rb4—Rb5—S2	77 (8)
Rb5^xii—Rb4—Rb4^i	57 (3)	Rb5^xii—Rb5—S2	87 (3)
Rb5^xiii—Rb4—Rb4^i	123 (3)	Rb5^xiii—Rb5—S2	128 (3)
Rb5—Rb4—Rb4^v	90.000 (19)	Rb4^xii—Rb5—S2	92.3 (10)
Rb4^x—Rb4—Rb4^v	55 (5)	Rb4^xiii—Rb5—S2	123 (3)
Rb4^xi—Rb4—Rb4^v	125 (5)	Rb5^i—Rb5—S2	62.8 (7)
Rb5^xii—Rb4—Rb4^v	123 (3)	Rb5^v—Rb5—S2	117.2 (7)
Rb5^xiii—Rb4—Rb4^v	57 (3)	Rb4^v—Rb5—S2	112 (3)
Rb4^i—Rb4—Rb4^v	180.00 (10)	Rb4^i—Rb5—S2	59.7 (19)
Rb5—Rb4—Rb5^i	73.1 (16)	S3^vi—Rb5—S2	55.4 (8)
Rb4^x—Rb4—Rb5^i	140 (7)	S2^v—Rb5—S2	54.4 (14)
Rb4^xi—Rb4—Rb5^i	71 (3)

Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+2, −z+2; (v) x, y−1, z; (vi) −x+1, −y, −z+2; (vii) −x, −y, −z+2; (viii) x, y+1, z+1; (ix) x, y, z+1; (x) −x, −y−1, −z+1; (xi) −x, −y, −z+1; (xii) −x+1, −y, −z+1; (xiii) −x+1, −y−1, −z+1.