Nb_1.30Cr_0.70S₅: a layered ternary mixed-metal sulfide

The new layered ternary sulfide, Nb_1.30Cr_0.70S₅, niobium chromium penta­sulfide, is isostructural with the solid solution Nb_1+xV_1-xS₅ and belongs to the FeNb₃Se₁₀ structure type. Each layer is composed of two unique chains of face-sharing [NbS₈] bicapped trigonal prisms (m symmetry) and edge-sharing [MS₆] (M= Nb, Cr) octa­hedra (m symmetry). One of the two metal sites is occupied by statistically disordered Nb and Cr atoms, with 0.3 and 0.7 occupancy, respectively. The chains are connected along the c axis, forming two-dimensional layers, which then stack on top of each other to complete the three dimensional structure. As a result, an undulating van der Waals gap is found between the layers.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](S-S) = 0.002 Å
• Disorder in main residue
• R factor = 0.048
• wR factor = 0.079
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   150.000
            Value of melting point given =     0.000
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S2
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S5
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S5
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S2
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S2
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      S1
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      M
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    M      M
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    S2     M
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    S5     M
PLAT711_ALERT_1_C BOND    Unknown or Inconsistent Label ..........          M
                    S5     M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S5
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S5
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S5
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S2
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      S1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      S1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S1     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S5     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S2     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    S1     M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      M      M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S1     NB1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S1     NB1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S1     NB1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S2     M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S2     M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S2     M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S5     M
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S5     NB1
PLAT712_ALERT_1_C ANGLE   Unknown or Inconsistent Label ..........          M
                    M      S5     NB1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  53 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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S1. Comment

The title compound is isostructural with FeNb₃Se₁₀ (Meerschaut et al., 1981), Cr_1.70Nb_2.30Se₁₀ (Mori et al., 1984), and the solid solution Nb_1+xV_1-xS₅ (Yun et al., 2003).

A view down the b-axis of Nb_1.30Cr_0.70S₅ shows the layered nature of the structure (Figure 1). Figure 2 shows that an individual layer is composed of two unique chains of face-sharing [NbS₈] bicapped trigonal prisms and edge-sharing [MS₆] (M= Nb, Cr) octahedra. The Nb atom is surrounded by six S atoms in a distorted trigonal-prismatic fashion. Atoms S1, S3, and S4 form an isosceles triangle, the S3—S4 distance (2.047 (2) Å) being much shorter than the other two (> 3.0 A). This short S3—S4 separation is typical of (S—S)^2- pairs (Kim & Yun, 2002). The Nb atoms are further coordinated by two additional S atoms that cap two of the rectangular faces of the trigonal prism. The Nb—S distances, ranging from 2.507 (1) to 2.607 (2) Å, are in agreement with the usual Nb—S distances found in niobium sulfides such as NbS₃ (Rijnsdorp & Jellinek, 1978). Longer Nb—S distances are observed for the capping S5 atoms. The Nb-centered bicapped trigonal prisms share their triangular faces to form a one-dimensional chain along the direction of the b-axis. Two of these chains are linked together by sharing two S1 atoms to form a double bicapped trigonal prismatic chain, [Nb₂S₈].

The M2 site, occupied by 30% of Nb and 70% of Cr, is surrounded by six S atoms in a distorted octahedral fashion. These octahedra then share their edges through atoms S2 and S5 to form a one-dimensional chain. Again, two octahedral chains are bound by sharing two S2 atoms and thus form a double chain, [M₂S₆]. In spite of the partial occupation of Nb, the M—S distances are in good agreement with that calculated from their ionic radii (2.455 Å, Shannon, 1976). This structural unit allows significant interchain zigzag metal–metal interactions, and an intermediate M—M separation (3.190 (2) Å) is found. The intrachain M—M distance, which is significantly longer than the interchain M—M distance, is the same as the repeating unit along the b-axis (3.3638 (5) Å).

These double Nb and M-centered chains are condensed together through atoms S1 and S5, and a quadruple chain of composition [Nb₂M₂S₁₂] is completed. Finally, these chains are connected along the c axis to form a two-dimensional layer, ²_∞[NbMS₅]. These layers then stack on top of each other to form the three-dimensional structure with an undulating van der Waals gap, as shown in Figure 1. There is no bonding interaction, only van der Waals forces, between these layers.

Related literature

The title compound is isostructural with FeNb₃Se₁₀ (Meerschaut et al., 1981), Cr_1.70Nb_2.30Se₁₀ (Mori et al., 1984), and Nb_1+xV_1-xS₅ (Yun et al., 2003). For the structure of a related niobium sulfide, see: Rijnsdorp & Jellinek (1978). For ionic radii, see: Shannon (1976). For related literature and background, see: Kim & Yun (2002); Gelato & Parthé (1987).

S2. Experimental

The title compound, Nb_1.30Cr_0.70S₅ was obtained from a reaction of Nb, Cr, and S in an elemental ratio of 1:1:5 in the presence of LiCl as flux. The mass ratio of reactants and flux was 1:3. The starting materials were placed in a fused-silica tube. The tube was evacuated to 0.133 Pa, sealed, and heated to 973 K at a rate of 80 K/hr, where it was kept for 7 days. The tube was cooled at a rate of 4 K/hr to 373 K and the furnace was shut off. Air- and water-stable black needle-shaped crystals were isolated after the flux was removed with water. Qualitative analysis of the crystals with an EDAX-equipped scanning electron microscope indicated the presence of Nb, Cr, and S. No other element was detected.

S3. Refinement

With the stoichiometric NbCrS₅ model, the displacement parameters for the M2 site are significantly smaller than those of the other atoms, which suggests that this site may be shared by Cr and Nb atoms. The positional and anisotropic displacement parameters (ADPs) of Nb and Cr in this site are equated by constraints. The result of the refinement was improved significantly by introducing the disordered model, and the displacement parameters became more plausible. The best fit was found when the M2 site was refined with site occupancy factors (s.o.f.) of 30% for Nb and 70% for Cr. With the composition established, the s.o.f.'s were fixed and the data were finally corrected for absorption with the use of the numerical method. The structure was standardized by means of the program STRUCTURE TIDY (Gelato & Parthé, 1987).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: locally modified version of ORTEP (Johnson, 1965); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A perspective view of Nb1.30Cr0.70S5 down the b axis showing the stacking of the layers. The M site is occupied by statistically disordered Nb(30%) and Cr(70%) atoms. Filled, gray, and open circles represent Nb, M(Nb or Cr), and S atoms, repectively. Displacement ellipsoids are drawn at the 90% probability level. [Symmetry code: (i) 1 - x, 1/2 + y, 1 - z.]
	Fig. 2. View of Nb1.30Cr0.70S5 along the a axis, showing the individual layer and the coordination around the metal atoms.

Chromium Niobium Sulfide

Crystal data

Cr0.70Nb1.30S5	F(000) = 300
Mr = 317.48	Dx = 3.956 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 3442 reflections
a = 8.7938 (14) Å	θ = 3.2–27.5°
b = 3.3638 (5) Å	µ = 5.98 mm^−1
c = 9.9565 (16) Å	T = 150 K
β = 115.193 (3)°	Needle, black
V = 266.50 (7) Å^3	0.45 × 0.11 × 0.10 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	795 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: numerical (NUMABS; Higashi, 2000)	h = −12→9
Tmin = 0.442, Tmax = 0.543	k = −4→3
1979 measured reflections	l = −13→14
889 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.048	Secondary atom site location: difference Fourier map
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0234P)^2 + 1.143P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
889 reflections	Δρmax = 1.21 e Å^−3
44 parameters	Δρmin = −1.49 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Nb1	0.77552 (8)	0.25	0.86289 (6)	0.00665 (17)
Nb2	0.06914 (12)	0.25	0.40161 (11)	0.0124 (2)	0.3
Cr2	0.06914 (12)	0.25	0.40161 (11)	0.0124 (2)	0.7
S1	0.0113 (2)	0.25	0.13327 (17)	0.0057 (3)
S2	0.1474 (2)	0.25	0.65632 (18)	0.0082 (3)
S3	0.3415 (2)	0.25	0.01649 (18)	0.0080 (3)
S4	0.4604 (2)	0.25	0.24351 (18)	0.0080 (3)
S5	0.7293 (2)	0.25	0.58889 (17)	0.0066 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nb1	0.0057 (3)	0.0112 (4)	0.0035 (3)	0	0.0024 (2)	0
Nb2	0.0076 (4)	0.0097 (5)	0.0169 (5)	0	0.0023 (4)	0
Cr2	0.0076 (4)	0.0097 (5)	0.0169 (5)	0	0.0023 (4)	0
S1	0.0078 (7)	0.0052 (8)	0.0042 (7)	0	0.0027 (6)	0
S2	0.0104 (8)	0.0070 (9)	0.0082 (7)	0	0.0050 (6)	0
S3	0.0121 (8)	0.0049 (9)	0.0073 (7)	0	0.0045 (6)	0
S4	0.0105 (8)	0.0061 (9)	0.0058 (7)	0	0.0020 (6)	0
S5	0.0087 (7)	0.0067 (8)	0.0060 (7)	0	0.0046 (6)	0

Geometric parameters (Å, º)

Nb1—S1^i	2.5067 (14)	M—M^iv	3.1898 (18)
Nb1—S1^ii	2.5067 (14)	S1—Nb1^i	2.5067 (14)
Nb1—S3^i	2.5265 (14)	S1—Nb1^ii	2.5067 (14)
Nb1—S3^ii	2.5265 (14)	S1—Nb1^vi	2.6065 (16)
Nb1—S4^ii	2.5266 (14)	S2—M^iv	2.4190 (15)
Nb1—S4^i	2.5266 (14)	S2—Nb2^v	2.4190 (15)
Nb1—S5	2.5814 (17)	S3—S4	2.047 (2)
Nb1—S1^iii	2.6065 (17)	S3—Nb1^i	2.5265 (14)
M—S2	2.328 (2)	S3—Nb1^ii	2.5265 (14)
M—S5^i	2.4159 (15)	S4—Nb1^ii	2.5266 (14)
M—S5^ii	2.4159 (15)	S4—Nb1^i	2.5266 (14)
M—S2^iv	2.4190 (15)	S5—M^i	2.4159 (15)
M—S2^v	2.4190 (15)	S5—Cr2^ii	2.4159 (15)
M—S1	2.4980 (19)	S5—M^ii	2.4159 (15)
M—M^v	3.1898 (18)
S1^i—Nb1—S1^ii	84.28 (6)	S2^iv—M—S2^v	88.10 (7)
S1^i—Nb1—S3^i	89.97 (4)	S2—M—S1	175.11 (7)
S1^ii—Nb1—S3^i	153.23 (6)	S5^i—M—S1	81.60 (6)
S1^i—Nb1—S3^ii	153.23 (6)	S5^ii—M—S1	81.60 (6)
S1^ii—Nb1—S3^ii	89.97 (4)	S2^iv—M—S1	87.92 (5)
S3^i—Nb1—S3^ii	83.47 (6)	S2^v—M—S1	87.92 (5)
S1^i—Nb1—S4^ii	158.17 (6)	S2—M—M^v	49.01 (4)
S1^ii—Nb1—S4^ii	92.00 (4)	S5^i—M—M^v	94.25 (4)
S3^i—Nb1—S4^ii	102.39 (5)	S5^ii—M—M^v	143.92 (6)
S3^ii—Nb1—S4^ii	47.79 (5)	S2^iv—M—M^v	92.63 (6)
S1^i—Nb1—S4^i	92.00 (4)	S2^v—M—M^v	46.58 (4)
S1^ii—Nb1—S4^i	158.17 (6)	S1—M—M^v	134.40 (5)
S3^i—Nb1—S4^i	47.79 (5)	S2—M—M^iv	49.01 (4)
S3^ii—Nb1—S4^i	102.39 (5)	S5^i—M—M^iv	143.92 (6)
S4^ii—Nb1—S4^i	83.47 (6)	S5^ii—M—M^iv	94.25 (4)
S1^i—Nb1—S5	78.25 (5)	S2^iv—M—M^iv	46.58 (4)
S1^ii—Nb1—S5	78.25 (5)	S2^v—M—M^iv	92.63 (6)
S3^i—Nb1—S5	126.13 (4)	S1—M—M^iv	134.40 (5)
S3^ii—Nb1—S5	126.13 (4)	M^v—M—M^iv	63.64 (4)
S4^ii—Nb1—S5	79.92 (5)	M—S1—Nb1^i	99.97 (5)
S4^i—Nb1—S5	79.92 (5)	M—S1—Nb1^ii	99.97 (5)
S1^i—Nb1—S1^iii	73.94 (5)	Nb1^i—S1—Nb1^ii	84.28 (6)
S1^ii—Nb1—S1^iii	73.94 (5)	M—S1—Nb1^vi	144.58 (8)
S3^i—Nb1—S1^iii	79.34 (5)	Nb1^i—S1—Nb1^vi	106.06 (5)
S3^ii—Nb1—S1^iii	79.34 (5)	Nb1^ii—S1—Nb1^vi	106.06 (5)
S4^ii—Nb1—S1^iii	125.68 (4)	M—S2—M^iv	84.41 (6)
S4^i—Nb1—S1^iii	125.68 (4)	M—S2—M^v	84.41 (6)
S5—Nb1—S1^iii	142.16 (6)	M^iv—S2—M^v	88.10 (7)
S2—M—S5^i	94.92 (6)	S4—S3—Nb1^i	66.11 (6)
S2—M—S5^ii	94.92 (6)	S4—S3—Nb1^ii	66.11 (6)
S5^i—M—S5^ii	88.24 (7)	Nb1^i—S3—Nb1^ii	83.47 (6)
S2—M—S2^iv	95.59 (6)	S3—S4—Nb1^ii	66.10 (6)
S5^i—M—S2^iv	169.50 (7)	S3—S4—Nb1^i	66.10 (6)
S5^ii—M—S2^iv	90.87 (4)	Nb1^ii—S4—Nb1^i	83.47 (6)
S2—M—S2^v	95.59 (6)	M^i—S5—M^ii	88.24 (7)
S5^i—M—S2^v	90.87 (4)	M^i—S5—Nb1	100.12 (5)
S5^ii—M—S2^v	169.50 (7)	M^ii—S5—Nb1	100.12 (5)

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