Ln₃M_1 − δTX₇ – quasi-isostructural compounds: stereochemistry and silver-ion motion in the Ln₃Ag_1 − δGeS₇ (Ln = La–Nd, Sm, Gd–Er and Y; δ = 0.11–0.50) compounds

The crystal structures of the Ln₃Ag_1 − δGeS₇ (Ln = La–Nd, Sm, Gd–Er, Y; δ = 0.11–0.50, space group P6₃) compounds were determined by means of X-ray single-crystal diffraction and the similarities among the crystal structures of all Ln₃M_1 − δTX₇ (space group P6₃; Ln – lanthanide element, M – monovalent element; T – tetravalent element and X – S, Se) compounds deposited in the Inorganic Crystal Structure Database (ICSD) are discussed. Substitutions of each element in Ln₃M_1 − δTX₇ result in a different structural effect. On the basis of the data deposited in the ICSD the large family of the Ln₃M_1 − δTX₇ compounds was divided into three groups depending on the position of the monovalent element in the lattice. This position determines what kind of stereoisomer is present in the structure, either the ++ enantiomer or the +− diastereoisomer. Since the silver ions can occupy a different position and the energy barriers between positions are low the ions can move through the channel. It was shown that this movement is not a stochastic process but a correlated one.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED; data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

(la)

Crystal data

Ag0.82GeLa3S7	Dx = 4.875 Mg m^−3
Mr = 802.19	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 729 reflections
Hall symbol: P 6c	θ = 4.2–26.4°
a = 10.4056 (15) Å	µ = 16.91 mm^−1
c = 5.8280 (12) Å	T = 295 K
V = 546.49 (16) Å^3	Prism, dark red
Z = 2	0.09 × 0.04 × 0.03 mm
F(000) = 707

Data collection

KUMA KM-4 with area CCD detector diffractometer	743 independent reflections
Radiation source: fine-focus sealed tube	729 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.4°, θmin = 4.2°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.097, Tmax = 0.599	l = −7→7
5858 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0107P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.011	(Δ/σ)max = 0.001
wR(F^2) = 0.022	Δρmax = 0.37 e Å^−3
S = 1.04	Δρmin = −0.44 e Å^−3
743 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0042 (2)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 334 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.014 (12)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
La	0.875611 (18)	0.641442 (18)	0.24144 (6)	0.00881 (6)
Ag1	0.0000	0.0000	0.18424 (19)	0.0387 (6)	0.719 (3)
Ag2	0.0000	0.0000	0.9766 (13)	0.018 (2)	0.102 (3)
Ge1	0.3333	0.6667	0.32488 (9)	0.00826 (14)
S1	0.3333	0.6667	0.9515 (2)	0.0114 (3)
S2	0.90929 (9)	0.73775 (9)	0.72749 (15)	0.01254 (16)
S3	0.58764 (10)	0.47816 (10)	0.97462 (12)	0.00978 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La	0.00902 (10)	0.00790 (10)	0.00959 (8)	0.00429 (8)	−0.00087 (11)	−0.00073 (9)
Ag1	0.0098 (3)	0.0098 (3)	0.0966 (17)	0.00489 (16)	0.000	0.000
Ag2	0.0101 (18)	0.0101 (18)	0.034 (5)	0.0050 (9)	0.000	0.000
Ge1	0.0089 (2)	0.0089 (2)	0.0070 (2)	0.00445 (10)	0.000	0.000
S1	0.0132 (5)	0.0132 (5)	0.0078 (7)	0.0066 (3)	0.000	0.000
S2	0.0097 (4)	0.0169 (4)	0.0111 (3)	0.0066 (3)	0.0010 (4)	−0.0007 (4)
S3	0.0102 (5)	0.0084 (4)	0.0114 (3)	0.0051 (4)	0.0013 (3)	0.0011 (3)

Geometric parameters (Å, º)

La—S3^i	2.9145 (9)	Ag2—S2^xvi	2.811 (4)
La—S2^ii	2.9399 (9)	Ag2—S2^xvii	2.811 (4)
La—S2^iii	2.9452 (9)	Ag2—S2^xviii	2.811 (4)
La—S2	2.9665 (11)	Ag2—Ag2^viii	2.9140 (6)
La—S3^iv	3.0319 (9)	Ag2—Ag2^xi	2.9140 (6)
La—S3^iii	3.0732 (9)	Ag2—La^xvii	3.556 (3)
La—S1^v	3.0878 (7)	Ag2—La^xvi	3.556 (3)
La—S2^iv	3.1221 (11)	Ge1—S1^iv	2.1758 (14)
La—Ag1^vi	3.2981 (5)	Ge1—S3^ii	2.2245 (9)
La—Ag2^v	3.556 (3)	Ge1—S3^xix	2.2245 (9)
La—Ag2^vii	3.626 (3)	Ge1—S3^v	2.2245 (9)
Ag1—Ag2^iv	1.210 (7)	S1—Ge1^xv	2.1758 (14)
Ag1—Ag2^viii	1.704 (7)	S1—La^xx	3.0878 (7)
Ag1—S2^ix	2.4136 (9)	S1—La^xvi	3.0878 (7)
Ag1—S2^v	2.4136 (9)	S1—La^xxi	3.0878 (7)
Ag1—S2^x	2.4136 (9)	S2—Ag1^xvi	2.4136 (9)
Ag1—Ag1^viii	2.9140 (6)	S2—Ag2^vi	2.805 (4)
Ag1—Ag1^xi	2.9140 (6)	S2—Ag2^v	2.811 (4)
Ag1—La^xii	3.2981 (5)	S2—La^xxii	2.9399 (9)
Ag1—La^xiii	3.2981 (5)	S2—La^xxi	2.9452 (9)
Ag1—La^xiv	3.2981 (5)	S2—La^xv	3.1221 (11)
Ag2—Ag1^xv	1.210 (7)	S3—Ge1^xvi	2.2245 (9)
Ag2—Ag1^xi	1.704 (7)	S3—La^xxiii	2.9145 (9)
Ag2—S2^xiii	2.805 (4)	S3—La^xv	3.0319 (9)
Ag2—S2^xiv	2.805 (4)	S3—La^xxi	3.0732 (9)
Ag2—S2^xii	2.805 (4)
S3^i—La—S2^ii	140.33 (3)	Ag1^xi—Ag2—S2^xiii	58.84 (13)
S3^i—La—S2^iii	107.53 (2)	Ag1^xv—Ag2—S2^xiv	121.16 (13)
S2^ii—La—S2^iii	89.89 (3)	Ag1^xi—Ag2—S2^xiv	58.84 (13)
S3^i—La—S2	137.75 (2)	S2^xiii—Ag2—S2^xiv	95.64 (18)
S2^ii—La—S2	79.46 (2)	Ag1^xv—Ag2—S2^xii	121.16 (13)
S2^iii—La—S2	79.38 (2)	Ag1^xi—Ag2—S2^xii	58.84 (13)
S3^i—La—S3^iv	73.14 (3)	S2^xiii—Ag2—S2^xii	95.64 (18)
S2^ii—La—S3^iv	71.59 (2)	S2^xiv—Ag2—S2^xii	95.64 (18)
S2^iii—La—S3^iv	142.08 (3)	Ag1^xv—Ag2—S2^xvi	58.65 (13)
S2—La—S3^iv	126.57 (2)	Ag1^xi—Ag2—S2^xvi	121.35 (13)
S3^i—La—S3^iii	73.508 (19)	S2^xiii—Ag2—S2^xvi	179.8 (3)
S2^ii—La—S3^iii	145.66 (3)	S2^xiv—Ag2—S2^xvi	84.483 (14)
S2^iii—La—S3^iii	68.66 (2)	S2^xii—Ag2—S2^xvi	84.483 (14)
S2—La—S3^iii	70.65 (2)	Ag1^xv—Ag2—S2^xvii	58.65 (13)
S3^iv—La—S3^iii	140.85 (2)	Ag1^xi—Ag2—S2^xvii	121.35 (13)
S3^i—La—S1^v	70.13 (2)	S2^xiii—Ag2—S2^xvii	84.483 (14)
S2^ii—La—S1^v	112.021 (18)	S2^xiv—Ag2—S2^xvii	84.483 (14)
S2^iii—La—S1^v	148.62 (2)	S2^xii—Ag2—S2^xvii	179.8 (3)
S2—La—S1^v	82.82 (3)	S2^xvi—Ag2—S2^xvii	95.39 (18)
S3^iv—La—S1^v	68.65 (2)	Ag1^xv—Ag2—S2^xviii	58.65 (13)
S3^iii—La—S1^v	81.15 (2)	Ag1^xi—Ag2—S2^xviii	121.35 (13)
S3^i—La—S2^iv	72.98 (2)	S2^xiii—Ag2—S2^xviii	84.483 (14)
S2^ii—La—S2^iv	76.97 (2)	S2^xiv—Ag2—S2^xviii	179.8 (3)
S2^iii—La—S2^iv	76.90 (2)	S2^xii—Ag2—S2^xviii	84.483 (14)
S2—La—S2^iv	146.34 (3)	S2^xvi—Ag2—S2^xviii	95.39 (18)
S3^iv—La—S2^iv	66.96 (2)	S2^xvii—Ag2—S2^xviii	95.39 (18)
S3^iii—La—S2^iv	120.71 (2)	Ag1^xv—Ag2—Ag2^viii	180.000 (4)
S1^v—La—S2^iv	128.42 (3)	Ag1^xi—Ag2—Ag2^viii	0.000 (1)
S3^i—La—Ag1^vi	136.06 (3)	S2^xiii—Ag2—Ag2^viii	58.84 (13)
S2^ii—La—Ag1^vi	45.071 (16)	S2^xiv—Ag2—Ag2^viii	58.84 (13)
S2^iii—La—Ag1^vi	45.044 (16)	S2^xii—Ag2—Ag2^viii	58.84 (13)
S2—La—Ag1^vi	78.53 (3)	S2^xvi—Ag2—Ag2^viii	121.35 (13)
S3^iv—La—Ag1^vi	107.52 (2)	S2^xvii—Ag2—Ag2^viii	121.35 (13)
S3^iii—La—Ag1^vi	110.62 (2)	S2^xviii—Ag2—Ag2^viii	121.35 (13)
S1^v—La—Ag1^vi	152.74 (2)	Ag1^xv—Ag2—Ag2^xi	0.000 (1)
S2^iv—La—Ag1^vi	67.81 (3)	Ag1^xi—Ag2—Ag2^xi	180.000 (3)
S3^i—La—Ag2^v	157.44 (6)	S2^xiii—Ag2—Ag2^xi	121.16 (13)
S2^ii—La—Ag2^v	50.08 (5)	S2^xiv—Ag2—Ag2^xi	121.16 (13)
S2^iii—La—Ag2^v	50.05 (5)	S2^xii—Ag2—Ag2^xi	121.16 (13)
S2—La—Ag2^v	50.06 (11)	S2^xvi—Ag2—Ag2^xi	58.65 (13)
S3^iv—La—Ag2^v	121.66 (5)	S2^xvii—Ag2—Ag2^xi	58.65 (13)
S3^iii—La—Ag2^v	96.59 (6)	S2^xviii—Ag2—Ag2^xi	58.65 (13)
S1^v—La—Ag2^v	129.39 (11)	Ag2^viii—Ag2—Ag2^xi	180.000 (3)
S2^iv—La—Ag2^v	96.28 (12)	Ag1^xv—Ag2—La^xvii	112.67 (11)
Ag1^vi—La—Ag2^v	28.47 (11)	Ag1^xi—Ag2—La^xvii	67.33 (11)
S3^i—La—Ag2^vii	118.48 (10)	S2^xiii—Ag2—La^xvii	53.60 (6)
S2^ii—La—Ag2^vii	49.34 (4)	S2^xiv—Ag2—La^xvii	53.49 (6)
S2^iii—La—Ag2^vii	49.32 (4)	S2^xii—Ag2—La^xvii	126.2 (2)
S2—La—Ag2^vii	97.92 (11)	S2^xvi—Ag2—La^xvii	126.42 (3)
S3^iv—La—Ag2^vii	95.89 (7)	S2^xvii—Ag2—La^xvii	54.02 (3)
S3^iii—La—Ag2^vii	117.90 (4)	S2^xviii—Ag2—La^xvii	126.53 (3)
S1^v—La—Ag2^vii	160.202 (7)	Ag2^viii—Ag2—La^xvii	67.33 (11)
S2^iv—La—Ag2^vii	48.42 (11)	Ag2^xi—Ag2—La^xvii	112.67 (11)
Ag1^vi—La—Ag2^vii	19.39 (10)	Ag1^xv—Ag2—La^xvi	112.67 (11)
Ag2^v—La—Ag2^vii	47.861 (12)	Ag1^xi—Ag2—La^xvi	67.33 (11)
Ag2^iv—Ag1—Ag2^viii	180.000 (1)	S2^xiii—Ag2—La^xvi	126.2 (2)
Ag2^iv—Ag1—S2^ix	95.99 (3)	S2^xiv—Ag2—La^xvi	53.60 (6)
Ag2^viii—Ag1—S2^ix	84.01 (3)	S2^xii—Ag2—La^xvi	53.49 (6)
Ag2^iv—Ag1—S2^v	95.99 (3)	S2^xvi—Ag2—La^xvi	54.02 (3)
Ag2^viii—Ag1—S2^v	84.01 (3)	S2^xvii—Ag2—La^xvi	126.53 (3)
S2^ix—Ag1—S2^v	118.924 (11)	S2^xviii—Ag2—La^xvi	126.42 (3)
Ag2^iv—Ag1—S2^x	95.99 (3)	Ag2^viii—Ag2—La^xvi	67.33 (11)
Ag2^viii—Ag1—S2^x	84.01 (3)	Ag2^xi—Ag2—La^xvi	112.67 (11)
S2^ix—Ag1—S2^x	118.924 (11)	La^xvii—Ag2—La^xvi	106.09 (13)
S2^v—Ag1—S2^x	118.924 (11)	S1^iv—Ge1—S3^ii	113.10 (2)
Ag2^iv—Ag1—Ag1^viii	0.0	S1^iv—Ge1—S3^xix	113.10 (2)
Ag2^viii—Ag1—Ag1^viii	180.000 (1)	S3^ii—Ge1—S3^xix	105.61 (3)
S2^ix—Ag1—Ag1^viii	95.99 (3)	S1^iv—Ge1—S3^v	113.10 (2)
S2^v—Ag1—Ag1^viii	95.99 (3)	S3^ii—Ge1—S3^v	105.61 (3)
S2^x—Ag1—Ag1^viii	95.99 (3)	S3^xix—Ge1—S3^v	105.61 (3)
Ag2^iv—Ag1—Ag1^xi	180.0	Ge1^xv—S1—La^xx	113.36 (2)
Ag2^viii—Ag1—Ag1^xi	0.000 (1)	Ge1^xv—S1—La^xvi	113.36 (2)
S2^ix—Ag1—Ag1^xi	84.01 (3)	La^xx—S1—La^xvi	105.31 (3)
S2^v—Ag1—Ag1^xi	84.01 (3)	Ge1^xv—S1—La^xxi	113.36 (2)
S2^x—Ag1—Ag1^xi	84.01 (3)	La^xx—S1—La^xxi	105.31 (3)
Ag1^viii—Ag1—Ag1^xi	180.0	La^xvi—S1—La^xxi	105.31 (3)
Ag2^iv—Ag1—La^xii	95.80 (2)	Ag2^vi—S2—Ag2^v	62.51 (2)
Ag2^viii—Ag1—La^xii	84.20 (2)	Ag1^xvi—S2—La^xxii	75.34 (2)
S2^ix—Ag1—La^xii	168.21 (5)	Ag2^vi—S2—La^xxii	76.44 (3)
S2^v—Ag1—La^xii	59.715 (19)	Ag2^v—S2—La^xxii	78.15 (3)
S2^x—Ag1—La^xii	59.586 (19)	Ag1^xvi—S2—La^xxi	75.24 (2)
Ag1^viii—Ag1—La^xii	95.80 (2)	Ag2^vi—S2—La^xxi	76.35 (3)
Ag1^xi—Ag1—La^xii	84.20 (2)	Ag2^v—S2—La^xxi	78.06 (3)
Ag2^iv—Ag1—La^xiii	95.80 (2)	La^xxii—S2—La^xxi	149.90 (3)
Ag2^viii—Ag1—La^xiii	84.20 (2)	Ag1^xvi—S2—La	101.28 (4)
S2^ix—Ag1—La^xiii	59.586 (19)	Ag2^vi—S2—La	138.44 (13)
S2^v—Ag1—La^xiii	168.21 (5)	Ag2^v—S2—La	75.92 (13)
S2^x—Ag1—La^xiii	59.715 (19)	La^xxii—S2—La	95.97 (3)
Ag1^viii—Ag1—La^xiii	95.80 (2)	La^xxi—S2—La	95.86 (3)
Ag1^xi—Ag1—La^xiii	84.20 (2)	Ag1^xvi—S2—La^xv	112.38 (4)
La^xii—Ag1—La^xiii	118.992 (7)	Ag2^vi—S2—La^xv	75.22 (14)
Ag2^iv—Ag1—La^xiv	95.80 (2)	Ag2^v—S2—La^xv	137.74 (14)
Ag2^viii—Ag1—La^xiv	84.20 (2)	La^xxii—S2—La^xv	92.71 (2)
S2^ix—Ag1—La^xiv	59.715 (19)	La^xxi—S2—La^xv	92.61 (2)
S2^v—Ag1—La^xiv	59.586 (19)	La—S2—La^xv	146.34 (3)
S2^x—Ag1—La^xiv	168.21 (5)	Ge1^xvi—S3—La^xxiii	92.15 (3)
Ag1^viii—Ag1—La^xiv	95.80 (2)	Ge1^xvi—S3—La^xv	89.10 (3)
Ag1^xi—Ag1—La^xiv	84.20 (2)	La^xxiii—S3—La^xv	111.30 (3)
La^xii—Ag1—La^xiv	118.992 (7)	Ge1^xvi—S3—La^xxi	122.50 (3)
La^xiii—Ag1—La^xiv	118.992 (7)	La^xxiii—S3—La^xxi	139.09 (3)
Ag1^xv—Ag2—Ag1^xi	180.000 (1)	La^xv—S3—La^xxi	91.91 (2)
Ag1^xv—Ag2—S2^xiii	121.16 (13)

Symmetry codes: (i) −x+y+1, −x+1, z−1; (ii) y, −x+y+1, z−1/2; (iii) x−y+1, x, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) −x, −y, z−1/2; (ix) y−1, −x+y, z−1/2; (x) x−y, x−1, z−1/2; (xi) −x, −y, z+1/2; (xii) −y+1, x−y, z; (xiii) x−1, y−1, z; (xiv) −x+y, −x+1, z; (xv) x, y, z+1; (xvi) −x+1, −y+1, z+1/2; (xvii) y−1, −x+y, z+1/2; (xviii) x−y, x−1, z+1/2; (xix) x−y, x, z−1/2; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) −y+1, x−y, z+1.

(ce)

Crystal data

Ag0.88Ce3GeS7	Dx = 4.939 Mg m^−3
Mr = 812.30	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 704 reflections
Hall symbol: P 6c	θ = 4.2–26.4°
a = 10.3902 (15) Å	µ = 17.79 mm^−1
c = 5.8425 (12) Å	T = 295 K
V = 546.23 (16) Å^3	Prism, dark red
Z = 2	0.09 × 0.08 × 0.06 mm
F(000) = 719

Data collection

KUMA KM-4 with area CCD detector diffractometer	726 independent reflections
Radiation source: fine-focus sealed tube	704 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.4°, θmin = 4.2°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.097, Tmax = 0.599	l = −7→6
6515 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0294P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.021	(Δ/σ)max = 0.001
wR(F^2) = 0.046	Δρmax = 1.01 e Å^−3
S = 1.06	Δρmin = −0.70 e Å^−3
726 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0122 (6)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 319 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Ce	0.87483 (3)	0.64142 (3)	0.23920 (14)	0.01007 (13)
Ag1	0.0000	0.0000	0.1694 (6)	0.0391 (16)	0.783 (9)
Ag2	0.0000	0.0000	0.965 (4)	0.026 (7)	0.098 (9)
Ge1	0.3333	0.6667	0.3228 (2)	0.0100 (3)
S1	0.3333	0.6667	0.9480 (5)	0.0116 (6)
S2	0.90743 (17)	0.73512 (17)	0.7237 (4)	0.0135 (3)
S3	0.5867 (2)	0.47870 (19)	0.9745 (3)	0.0108 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ce	0.00999 (19)	0.00870 (19)	0.0116 (2)	0.00471 (14)	−0.0008 (2)	−0.0009 (2)
Ag1	0.0109 (6)	0.0109 (6)	0.096 (5)	0.0054 (3)	0.000	0.000
Ag2	0.020 (4)	0.020 (4)	0.04 (2)	0.010 (2)	0.000	0.000
Ge1	0.0102 (4)	0.0102 (4)	0.0096 (6)	0.00509 (19)	0.000	0.000
S1	0.0127 (9)	0.0127 (9)	0.0094 (16)	0.0063 (5)	0.000	0.000
S2	0.0112 (7)	0.0171 (7)	0.0126 (8)	0.0074 (6)	0.0003 (8)	−0.0016 (9)
S3	0.0113 (8)	0.0099 (8)	0.0115 (8)	0.0055 (7)	0.0014 (7)	0.0004 (6)

Geometric parameters (Å, º)

Ce—S3^i	2.9091 (18)	Ag2—S2^xvi	2.854 (13)
Ce—S2^ii	2.9425 (16)	Ag2—S2^xvii	2.854 (13)
Ce—S2^iii	2.9446 (16)	Ag2—S2^xviii	2.854 (13)
Ce—S2	2.957 (2)	Ag2—Ag2^xi	2.9212 (6)
Ce—S3^iv	3.0251 (18)	Ag2—Ag2^viii	2.9212 (6)
Ce—S3^ii	3.0758 (18)	Ag2—Ce^xviii	3.530 (9)
Ce—S1^v	3.0805 (13)	Ag2—Ce^xvi	3.530 (9)
Ce—S2^iv	3.131 (2)	Ge1—S1^iv	2.190 (3)
Ce—Ag1^vi	3.3005 (7)	Ge1—S3^iii	2.2391 (19)
Ce—Ag2^v	3.530 (9)	Ge1—S3^xix	2.2391 (19)
Ce—Ag2^vii	3.647 (11)	Ge1—S3^v	2.2391 (19)
Ag1—Ag2^iv	1.20 (2)	S1—Ge1^xv	2.190 (3)
Ag1—Ag2^viii	1.73 (2)	S1—Ce^xx	3.0805 (13)
Ag1—S2^v	2.4399 (16)	S1—Ce^xvi	3.0805 (13)
Ag1—S2^ix	2.4399 (16)	S1—Ce^xxi	3.0805 (13)
Ag1—S2^x	2.4399 (16)	S2—Ag1^xvi	2.4399 (16)
Ag1—Ag1^viii	2.9212 (6)	S2—Ag2^vi	2.799 (12)
Ag1—Ag1^xi	2.9213 (6)	S2—Ag2^v	2.854 (13)
Ag1—Ce^xii	3.3005 (7)	S2—Ce^xxi	2.9425 (16)
Ag1—Ce^xiii	3.3005 (7)	S2—Ce^xxii	2.9446 (16)
Ag1—Ce^xiv	3.3005 (7)	S2—Ce^xv	3.131 (2)
Ag2—Ag1^xv	1.20 (2)	S3—Ge1^xvi	2.2391 (19)
Ag2—Ag1^xi	1.73 (2)	S3—Ce^xxiii	2.9091 (18)
Ag2—S2^xiii	2.799 (12)	S3—Ce^xv	3.0251 (18)
Ag2—S2^xii	2.799 (12)	S3—Ce^xxi	3.0758 (18)
Ag2—S2^xiv	2.799 (12)
S3^i—Ce—S2^ii	106.58 (5)	Ag1^xi—Ag2—S2^xiii	59.8 (4)
S3^i—Ce—S2^iii	140.39 (6)	Ag1^xv—Ag2—S2^xii	120.2 (4)
S2^ii—Ce—S2^iii	90.76 (6)	Ag1^xi—Ag2—S2^xii	59.8 (4)
S3^i—Ce—S2	137.17 (5)	S2^xiii—Ag2—S2^xii	96.9 (6)
S2^ii—Ce—S2	80.01 (5)	Ag1^xv—Ag2—S2^xiv	120.2 (4)
S2^iii—Ce—S2	79.98 (5)	Ag1^xi—Ag2—S2^xiv	59.8 (4)
S3^i—Ce—S3^iv	73.73 (7)	S2^xiii—Ag2—S2^xiv	96.9 (6)
S2^ii—Ce—S3^iv	142.23 (6)	S2^xii—Ag2—S2^xiv	96.9 (6)
S2^iii—Ce—S3^iv	71.11 (5)	Ag1^xv—Ag2—S2^xvi	58.0 (4)
S2—Ce—S3^iv	126.28 (5)	Ag1^xi—Ag2—S2^xvi	122.0 (4)
S3^i—Ce—S3^ii	73.27 (3)	S2^xiii—Ag2—S2^xvi	178.2 (8)
S2^ii—Ce—S3^ii	68.46 (5)	S2^xii—Ag2—S2^xvi	84.28 (3)
S2^iii—Ce—S3^ii	145.89 (5)	S2^xiv—Ag2—S2^xvi	84.28 (3)
S2—Ce—S3^ii	70.23 (5)	Ag1^xv—Ag2—S2^xvii	58.0 (4)
S3^iv—Ce—S3^ii	140.90 (5)	Ag1^xi—Ag2—S2^xvii	122.0 (4)
S3^i—Ce—S1^v	70.19 (5)	S2^xiii—Ag2—S2^xvii	84.28 (3)
S2^ii—Ce—S1^v	148.24 (5)	S2^xii—Ag2—S2^xvii	84.28 (3)
S2^iii—Ce—S1^v	111.99 (4)	S2^xiv—Ag2—S2^xvii	178.2 (8)
S2—Ce—S1^v	82.44 (6)	S2^xvi—Ag2—S2^xvii	94.5 (6)
S3^iv—Ce—S1^v	68.73 (5)	Ag1^xv—Ag2—S2^xviii	58.0 (4)
S3^ii—Ce—S1^v	80.76 (4)	Ag1^xi—Ag2—S2^xviii	122.0 (4)
S3^i—Ce—S2^iv	72.60 (5)	S2^xiii—Ag2—S2^xviii	84.28 (3)
S2^ii—Ce—S2^iv	77.22 (5)	S2^xii—Ag2—S2^xviii	178.2 (8)
S2^iii—Ce—S2^iv	77.19 (5)	S2^xiv—Ag2—S2^xviii	84.28 (3)
S2—Ce—S2^iv	147.31 (6)	S2^xvi—Ag2—S2^xviii	94.5 (6)
S3^iv—Ce—S2^iv	66.74 (4)	S2^xvii—Ag2—S2^xviii	94.5 (6)
S3^ii—Ce—S2^iv	120.98 (5)	Ag1^xv—Ag2—Ag2^xi	0.000 (4)
S1^v—Ce—S2^iv	127.92 (6)	Ag1^xi—Ag2—Ag2^xi	180.000 (9)
S3^i—Ce—Ag1^vi	134.75 (7)	S2^xiii—Ag2—Ag2^xi	120.2 (4)
S2^ii—Ce—Ag1^vi	45.56 (3)	S2^xii—Ag2—Ag2^xi	120.2 (4)
S2^iii—Ce—Ag1^vi	45.55 (3)	S2^xiv—Ag2—Ag2^xi	120.2 (4)
S2—Ce—Ag1^vi	80.27 (7)	S2^xvi—Ag2—Ag2^xi	58.0 (4)
S3^iv—Ce—Ag1^vi	106.80 (5)	S2^xvii—Ag2—Ag2^xi	58.0 (4)
S3^ii—Ce—Ag1^vi	111.20 (5)	S2^xviii—Ag2—Ag2^xi	58.0 (4)
S1^v—Ce—Ag1^vi	153.84 (5)	Ag1^xv—Ag2—Ag2^viii	180.000 (12)
S2^iv—Ce—Ag1^vi	67.04 (7)	Ag1^xi—Ag2—Ag2^viii	0.000 (2)
S3^i—Ce—Ag2^v	156.6 (2)	S2^xiii—Ag2—Ag2^viii	59.8 (4)
S2^ii—Ce—Ag2^v	50.24 (14)	S2^xii—Ag2—Ag2^viii	59.8 (4)
S2^iii—Ce—Ag2^v	50.23 (14)	S2^xiv—Ag2—Ag2^viii	59.8 (4)
S2—Ce—Ag2^v	51.3 (4)	S2^xvi—Ag2—Ag2^viii	122.0 (4)
S3^iv—Ce—Ag2^v	121.33 (15)	S2^xvii—Ag2—Ag2^viii	122.0 (4)
S3^ii—Ce—Ag2^v	96.9 (2)	S2^xviii—Ag2—Ag2^viii	122.0 (4)
S1^v—Ce—Ag2^v	130.2 (3)	Ag2^xi—Ag2—Ag2^viii	180.000 (11)
S2^iv—Ce—Ag2^v	96.0 (4)	Ag1^xv—Ag2—Ce^xviii	111.9 (4)
Ag1^vi—Ce—Ag2^v	29.0 (3)	Ag1^xi—Ag2—Ce^xviii	68.1 (4)
S3^i—Ce—Ag2^vii	117.6 (3)	S2^xiii—Ag2—Ce^xviii	53.92 (19)
S2^ii—Ce—Ag2^vii	49.93 (13)	S2^xii—Ag2—Ce^xviii	127.9 (8)
S2^iii—Ce—Ag2^vii	49.92 (13)	S2^xiv—Ag2—Ce^xviii	53.96 (19)
S2—Ce—Ag2^vii	99.3 (3)	S2^xvi—Ag2—Ce^xviii	126.26 (12)
S3^iv—Ce—Ag2^vii	95.4 (2)	S2^xvii—Ag2—Ce^xviii	126.22 (12)
S3^ii—Ce—Ag2^vii	118.29 (11)	S2^xviii—Ag2—Ce^xviii	53.94 (6)
S1^v—Ce—Ag2^vii	160.43 (3)	Ag2^xi—Ag2—Ce^xviii	111.9 (4)
S2^iv—Ce—Ag2^vii	48.0 (3)	Ag2^viii—Ag2—Ce^xviii	68.1 (4)
Ag1^vi—Ce—Ag2^vii	19.0 (3)	Ag1^xv—Ag2—Ce^xvi	111.9 (4)
Ag2^v—Ce—Ag2^vii	48.00 (3)	Ag1^xi—Ag2—Ce^xvi	68.1 (4)
Ag2^iv—Ag1—Ag2^viii	180.000 (3)	S2^xiii—Ag2—Ce^xvi	127.9 (8)
Ag2^iv—Ag1—S2^v	97.47 (9)	S2^xii—Ag2—Ce^xvi	53.96 (19)
Ag2^viii—Ag1—S2^v	82.53 (9)	S2^xiv—Ag2—Ce^xvi	53.92 (19)
Ag2^iv—Ag1—S2^ix	97.47 (9)	S2^xvi—Ag2—Ce^xvi	53.94 (6)
Ag2^viii—Ag1—S2^ix	82.53 (9)	S2^xvii—Ag2—Ce^xvi	126.26 (12)
S2^v—Ag1—S2^ix	118.34 (4)	S2^xviii—Ag2—Ce^xvi	126.22 (12)
Ag2^iv—Ag1—S2^x	97.47 (9)	Ag2^xi—Ag2—Ce^xvi	111.9 (4)
Ag2^viii—Ag1—S2^x	82.53 (9)	Ag2^viii—Ag2—Ce^xvi	68.1 (4)
S2^v—Ag1—S2^x	118.34 (4)	Ce^xviii—Ag2—Ce^xvi	106.9 (4)
S2^ix—Ag1—S2^x	118.34 (4)	S1^iv—Ge1—S3^iii	113.33 (5)
Ag2^iv—Ag1—Ag1^viii	0.0	S1^iv—Ge1—S3^xix	113.33 (5)
Ag2^viii—Ag1—Ag1^viii	180.000 (3)	S3^iii—Ge1—S3^xix	105.35 (6)
S2^v—Ag1—Ag1^viii	97.47 (9)	S1^iv—Ge1—S3^v	113.33 (5)
S2^ix—Ag1—Ag1^viii	97.47 (9)	S3^iii—Ge1—S3^v	105.35 (6)
S2^x—Ag1—Ag1^viii	97.47 (9)	S3^xix—Ge1—S3^v	105.35 (6)
Ag2^iv—Ag1—Ag1^xi	180.0	Ge1^xv—S1—Ce^xx	113.33 (5)
Ag2^viii—Ag1—Ag1^xi	0.000 (3)	Ge1^xv—S1—Ce^xvi	113.33 (5)
S2^v—Ag1—Ag1^xi	82.53 (9)	Ce^xx—S1—Ce^xvi	105.35 (6)
S2^ix—Ag1—Ag1^xi	82.53 (9)	Ge1^xv—S1—Ce^xxi	113.33 (5)
S2^x—Ag1—Ag1^xi	82.53 (9)	Ce^xx—S1—Ce^xxi	105.35 (6)
Ag1^viii—Ag1—Ag1^xi	180.0	Ce^xvi—S1—Ce^xxi	105.35 (6)
Ag2^iv—Ag1—Ce^xii	97.09 (6)	Ag2^vi—S2—Ag2^v	62.23 (4)
Ag2^viii—Ag1—Ce^xii	82.91 (6)	Ag1^xvi—S2—Ce^xxi	74.99 (4)
S2^v—Ag1—Ce^xii	59.44 (4)	Ag2^vi—S2—Ce^xxi	75.84 (7)
S2^ix—Ag1—Ce^xii	165.44 (14)	Ag2^v—S2—Ce^xxi	77.96 (9)
S2^x—Ag1—Ce^xii	59.49 (4)	Ag1^xvi—S2—Ce^xxii	74.95 (4)
Ag1^viii—Ag1—Ce^xii	97.09 (6)	Ag2^vi—S2—Ce^xxii	75.80 (7)
Ag1^xi—Ag1—Ce^xii	82.91 (6)	Ag2^v—S2—Ce^xxii	77.93 (9)
Ag2^iv—Ag1—Ce^xiii	97.09 (6)	Ce^xxi—S2—Ce^xxii	148.99 (6)
Ag2^viii—Ag1—Ce^xiii	82.91 (6)	Ag1^xvi—S2—Ce	99.36 (10)
S2^v—Ag1—Ce^xiii	165.44 (14)	Ag2^vi—S2—Ce	137.0 (4)
S2^ix—Ag1—Ce^xiii	59.49 (4)	Ag2^v—S2—Ce	74.8 (4)
S2^x—Ag1—Ce^xiii	59.44 (4)	Ce^xxi—S2—Ce	96.12 (6)
Ag1^viii—Ag1—Ce^xiii	97.09 (6)	Ce^xxii—S2—Ce	96.08 (5)
Ag1^xi—Ag1—Ce^xiii	82.91 (6)	Ag1^xvi—S2—Ce^xv	113.33 (10)
Ce^xii—Ag1—Ce^xiii	118.50 (3)	Ag2^vi—S2—Ce^xv	75.7 (4)
Ag2^iv—Ag1—Ce^xiv	97.09 (6)	Ag2^v—S2—Ce^xv	137.9 (4)
Ag2^viii—Ag1—Ce^xiv	82.91 (6)	Ce^xxi—S2—Ce^xv	92.49 (5)
S2^v—Ag1—Ce^xiv	59.49 (4)	Ce^xxii—S2—Ce^xv	92.45 (5)
S2^ix—Ag1—Ce^xiv	59.44 (4)	Ce—S2—Ce^xv	147.31 (6)
S2^x—Ag1—Ce^xiv	165.44 (14)	Ge1^xvi—S3—Ce^xxiii	91.96 (6)
Ag1^viii—Ag1—Ce^xiv	97.09 (6)	Ge1^xvi—S3—Ce^xv	88.97 (6)
Ag1^xi—Ag1—Ce^xiv	82.91 (6)	Ce^xxiii—S3—Ce^xv	111.29 (6)
Ce^xii—Ag1—Ce^xiv	118.50 (3)	Ge1^xvi—S3—Ce^xxi	121.90 (7)
Ce^xiii—Ag1—Ce^xiv	118.50 (3)	Ce^xxiii—S3—Ce^xxi	139.74 (7)
Ag1^xv—Ag2—Ag1^xi	180.000 (3)	Ce^xv—S3—Ce^xxi	92.00 (5)
Ag1^xv—Ag2—S2^xiii	120.2 (4)

Symmetry codes: (i) −x+y+1, −x+1, z−1; (ii) x−y+1, x, z−1/2; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) −x, −y, z−1/2; (ix) y−1, −x+y, z−1/2; (x) x−y, x−1, z−1/2; (xi) −x, −y, z+1/2; (xii) −y+1, x−y, z; (xiii) x−1, y−1, z; (xiv) −x+y, −x+1, z; (xv) x, y, z+1; (xvi) −x+1, −y+1, z+1/2; (xvii) x−y, x−1, z+1/2; (xviii) y−1, −x+y, z+1/2; (xix) x−y, x, z−1/2; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) −y+1, x−y, z+1.

(pr)

Crystal data

Ag0.89GePr3S7	Dx = 5.176 Mg m^−3
Mr = 815.74	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 585 reflections
Hall symbol: P 6c	θ = 4.0–25.0°
a = 10.2290 (14) Å	µ = 19.50 mm^−1
c = 5.7760 (11) Å	T = 295 K
V = 523.39 (14) Å^3	Prism, dark red
Z = 2	0.10 × 0.09 × 0.07 mm
F(000) = 726

Data collection

KUMA KM-4 with area CCD detector diffractometer	602 independent reflections
Radiation source: fine-focus sealed tube	585 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 25.0°, θmin = 4.0°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→11
Tmin = 0.163, Tmax = 0.272	l = −6→6
5174 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0287P)^2 + 1.032P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.025	(Δ/σ)max < 0.001
wR(F^2) = 0.051	Δρmax = 1.22 e Å^−3
S = 1.09	Δρmin = −0.73 e Å^−3
602 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0145 (7)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 265 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Pr	0.87391 (5)	0.64129 (5)	0.23910 (18)	0.01118 (19)
Ag1	0.0000	0.0000	0.1692 (9)	0.027 (4)	0.49 (5)
Ag2	0.0000	0.0000	1.094 (18)	0.165 (10)	0.41 (5)
Ge1	0.3333	0.6667	0.3227 (3)	0.0104 (4)
S1	0.3333	0.6667	0.9467 (7)	0.0131 (10)
S2	0.9060 (2)	0.7345 (3)	0.7230 (5)	0.0152 (5)
S3	0.5856 (3)	0.4788 (3)	0.9755 (4)	0.0123 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr	0.0115 (3)	0.0105 (3)	0.0116 (3)	0.0055 (2)	−0.0010 (3)	−0.0008 (3)
Ag1	0.011 (2)	0.011 (2)	0.059 (9)	0.0054 (10)	0.000	0.000
Ag2	0.019 (3)	0.019 (3)	0.46 (3)	0.0097 (16)	0.000	0.000
Ge1	0.0121 (6)	0.0121 (6)	0.0071 (9)	0.0060 (3)	0.000	0.000
S1	0.0147 (14)	0.0147 (14)	0.010 (3)	0.0073 (7)	0.000	0.000
S2	0.0112 (11)	0.0187 (11)	0.0149 (12)	0.0068 (9)	−0.0001 (11)	−0.0018 (14)
S3	0.0137 (12)	0.0113 (12)	0.0122 (13)	0.0063 (11)	0.0006 (10)	−0.0001 (10)

Geometric parameters (Å, º)

Pr—S3^i	2.863 (2)	Ag2—Ag2^xi	2.8880 (6)
Pr—S2^ii	2.893 (2)	Ag2—Ag2^x	2.8880 (6)
Pr—S2^iii	2.905 (2)	Ag2—Ag1^xix	3.32 (11)
Pr—S2	2.918 (3)	Ag2—Pr^xx	3.33 (3)
Pr—S3^iv	2.980 (2)	Ag2—Pr^xxi	3.33 (3)
Pr—S1^v	3.0293 (18)	Ag2—Pr^xxii	3.33 (3)
Pr—S3^ii	3.037 (3)	Ge1—S1^iv	2.172 (4)
Pr—S2^iv	3.097 (3)	Ge1—S3^xxiii	2.217 (3)
Pr—Ag1^vi	3.2492 (9)	Ge1—S3^iii	2.217 (3)
Pr—Ag2^vii	3.33 (3)	Ge1—S3^v	2.217 (3)
Ag1—S2^viii	2.405 (2)	S1—Ge1^xxiv	2.172 (4)
Ag1—S2^v	2.405 (2)	S1—Pr^xxv	3.0293 (18)
Ag1—S2^ix	2.405 (2)	S1—Pr^xvi	3.0293 (18)
Ag1—Ag2^x	2.45 (11)	S1—Pr^xxvi	3.0293 (18)
Ag1—Ag1^xi	2.8880 (5)	S2—Ag1^xvi	2.405 (2)
Ag1—Ag1^x	2.8880 (5)	S2—Ag2^v	2.50 (3)
Ag1—Pr^xii	3.2492 (9)	S2—Pr^xxvi	2.893 (2)
Ag1—Pr^xiii	3.2492 (9)	S2—Pr^xxvii	2.905 (2)
Ag1—Pr^xiv	3.2492 (9)	S2—Pr^xxiv	3.097 (3)
Ag1—Ag2^xv	3.32 (11)	S3—Ge1^xvi	2.217 (3)
Ag2—Ag1^xi	2.45 (11)	S3—Pr^xx	2.863 (2)
Ag2—S2^xvi	2.50 (3)	S3—Pr^xxiv	2.980 (2)
Ag2—S2^xvii	2.50 (3)	S3—Pr^xxvi	3.037 (3)
Ag2—S2^xviii	2.50 (3)
S3^i—Pr—S2^ii	105.95 (7)	Ag2^x—Ag1—Ag2^xv	180.000 (15)
S3^i—Pr—S2^iii	140.58 (8)	Ag1^xi—Ag1—Ag2^xv	180.000 (5)
S2^ii—Pr—S2^iii	90.90 (9)	Ag1^x—Ag1—Ag2^xv	0.0
S3^i—Pr—S2	137.04 (7)	Pr^xii—Ag1—Ag2^xv	97.13 (10)
S2^ii—Pr—S2	80.27 (7)	Pr^xiii—Ag1—Ag2^xv	97.13 (10)
S2^iii—Pr—S2	80.07 (7)	Pr^xiv—Ag1—Ag2^xv	97.13 (10)
S3^i—Pr—S3^iv	74.12 (10)	Ag1^xi—Ag2—S2^xvi	107 (2)
S2^ii—Pr—S3^iv	142.26 (8)	Ag1^xi—Ag2—S2^xvii	107 (2)
S2^iii—Pr—S3^iv	71.10 (7)	S2^xvi—Ag2—S2^xvii	112 (2)
S2—Pr—S3^iv	126.16 (7)	Ag1^xi—Ag2—S2^xviii	107 (2)
S3^i—Pr—S1^v	70.35 (7)	S2^xvi—Ag2—S2^xviii	112 (2)
S2^ii—Pr—S1^v	148.00 (7)	S2^xvii—Ag2—S2^xviii	112 (2)
S2^iii—Pr—S1^v	112.28 (5)	Ag1^xi—Ag2—Ag2^xi	180.00 (3)
S2—Pr—S1^v	82.33 (9)	S2^xvi—Ag2—Ag2^xi	73 (2)
S3^iv—Pr—S1^v	68.85 (7)	S2^xvii—Ag2—Ag2^xi	73 (2)
S3^i—Pr—S3^ii	73.06 (5)	S2^xviii—Ag2—Ag2^xi	73 (2)
S2^ii—Pr—S3^ii	68.47 (7)	Ag1^xi—Ag2—Ag2^x	0.000 (3)
S2^iii—Pr—S3^ii	145.87 (8)	S2^xvi—Ag2—Ag2^x	107 (2)
S2—Pr—S3^ii	70.11 (7)	S2^xvii—Ag2—Ag2^x	107 (2)
S3^iv—Pr—S3^ii	140.86 (7)	S2^xviii—Ag2—Ag2^x	107 (2)
S1^v—Pr—S3^ii	80.42 (6)	Ag2^xi—Ag2—Ag2^x	180.00 (5)
S3^i—Pr—S2^iv	72.42 (7)	Ag1^xi—Ag2—Ag1^xix	180.000 (2)
S2^ii—Pr—S2^iv	77.34 (7)	S2^xvi—Ag2—Ag1^xix	73 (2)
S2^iii—Pr—S2^iv	77.16 (7)	S2^xvii—Ag2—Ag1^xix	73 (2)
S2—Pr—S2^iv	147.58 (9)	S2^xviii—Ag2—Ag1^xix	73 (2)
S3^iv—Pr—S2^iv	66.61 (6)	Ag2^xi—Ag2—Ag1^xix	0.00 (2)
S1^v—Pr—S2^iv	127.77 (9)	Ag2^x—Ag2—Ag1^xix	180.000 (8)
S3^ii—Pr—S2^iv	121.21 (7)	Ag1^xi—Ag2—Pr^xx	104.6 (18)
S3^i—Pr—Ag1^vi	134.41 (10)	S2^xvi—Ag2—Pr^xx	57.4 (6)
S2^ii—Pr—Ag1^vi	45.65 (5)	S2^xvii—Ag2—Pr^xx	148 (4)
S2^iii—Pr—Ag1^vi	45.59 (5)	S2^xviii—Ag2—Pr^xx	57.7 (6)
S2—Pr—Ag1^vi	80.43 (10)	Ag2^xi—Ag2—Pr^xx	75.4 (17)
S3^iv—Pr—Ag1^vi	106.85 (8)	Ag2^x—Ag2—Pr^xx	104.6 (18)
S1^v—Pr—Ag1^vi	154.12 (8)	Ag1^xix—Ag2—Pr^xx	75.4 (18)
S3^ii—Pr—Ag1^vi	111.23 (6)	Ag1^xi—Ag2—Pr^xxi	104.6 (18)
S2^iv—Pr—Ag1^vi	67.15 (10)	S2^xvi—Ag2—Pr^xxi	57.7 (6)
S3^i—Pr—Ag2^vii	127.8 (16)	S2^xvii—Ag2—Pr^xxi	57.4 (6)
S2^ii—Pr—Ag2^vii	46.7 (4)	S2^xviii—Ag2—Pr^xxi	148 (4)
S2^iii—Pr—Ag2^vii	46.6 (4)	Ag2^xi—Ag2—Pr^xxi	75.4 (18)
S2—Pr—Ag2^vii	87.9 (18)	Ag2^x—Ag2—Pr^xxi	104.6 (18)
S3^iv—Pr—Ag2^vii	102.5 (11)	Ag1^xix—Ag2—Pr^xxi	75.4 (18)
S1^v—Pr—Ag2^vii	158.3 (8)	Pr^xx—Ag2—Pr^xxi	113.9 (14)
S3^ii—Pr—Ag2^vii	114.3 (7)	Ag1^xi—Ag2—Pr^xxii	104.6 (18)
S2^iv—Pr—Ag2^vii	59.7 (18)	S2^xvi—Ag2—Pr^xxii	148 (4)
Ag1^vi—Pr—Ag2^vii	7.4 (18)	S2^xvii—Ag2—Pr^xxii	57.7 (6)
S2^viii—Ag1—S2^v	118.36 (6)	S2^xviii—Ag2—Pr^xxii	57.4 (6)
S2^viii—Ag1—S2^ix	118.36 (6)	Ag2^xi—Ag2—Pr^xxii	75.4 (18)
S2^v—Ag1—S2^ix	118.36 (6)	Ag2^x—Ag2—Pr^xxii	104.6 (18)
S2^viii—Ag1—Ag2^x	82.58 (14)	Ag1^xix—Ag2—Pr^xxii	75.4 (18)
S2^v—Ag1—Ag2^x	82.58 (13)	Pr^xx—Ag2—Pr^xxii	113.9 (14)
S2^ix—Ag1—Ag2^x	82.58 (13)	Pr^xxi—Ag2—Pr^xxii	113.9 (14)
S2^viii—Ag1—Ag1^xi	82.58 (13)	S1^iv—Ge1—S3^xxiii	113.47 (7)
S2^v—Ag1—Ag1^xi	82.58 (13)	S1^iv—Ge1—S3^iii	113.47 (7)
S2^ix—Ag1—Ag1^xi	82.58 (13)	S3^xxiii—Ge1—S3^iii	105.19 (8)
Ag2^x—Ag1—Ag1^xi	0.000 (10)	S1^iv—Ge1—S3^v	113.47 (7)
S2^viii—Ag1—Ag1^x	97.42 (13)	S3^xxiii—Ge1—S3^v	105.19 (8)
S2^v—Ag1—Ag1^x	97.42 (13)	S3^iii—Ge1—S3^v	105.19 (8)
S2^ix—Ag1—Ag1^x	97.42 (13)	Ge1^xxiv—S1—Pr^xxv	113.32 (8)
Ag2^x—Ag1—Ag1^x	180.000 (10)	Ge1^xxiv—S1—Pr^xvi	113.32 (8)
Ag1^xi—Ag1—Ag1^x	180.000 (1)	Pr^xxv—S1—Pr^xvi	105.37 (9)
S2^viii—Ag1—Pr^xii	165.4 (2)	Ge1^xxiv—S1—Pr^xxvi	113.32 (8)
S2^v—Ag1—Pr^xii	59.32 (5)	Pr^xxv—S1—Pr^xxvi	105.37 (9)
S2^ix—Ag1—Pr^xii	59.62 (5)	Pr^xvi—S1—Pr^xxvi	105.37 (9)
Ag2^x—Ag1—Pr^xii	82.87 (10)	Ag1^xvi—S2—Pr^xxvi	75.03 (6)
Ag1^xi—Ag1—Pr^xii	82.87 (10)	Ag2^v—S2—Pr^xxvi	75.9 (3)
Ag1^x—Ag1—Pr^xii	97.13 (10)	Ag1^xvi—S2—Pr^xxvii	74.79 (6)
S2^viii—Ag1—Pr^xiii	59.62 (5)	Ag2^v—S2—Pr^xxvii	75.7 (3)
S2^v—Ag1—Pr^xiii	165.4 (2)	Pr^xxvi—S2—Pr^xxvii	148.83 (9)
S2^ix—Ag1—Pr^xiii	59.32 (5)	Ag1^xvi—S2—Pr	99.29 (15)
Ag2^x—Ag1—Pr^xiii	82.87 (10)	Ag2^v—S2—Pr	89 (2)
Ag1^xi—Ag1—Pr^xiii	82.87 (10)	Pr^xxvi—S2—Pr	96.30 (8)
Ag1^x—Ag1—Pr^xiii	97.13 (10)	Pr^xxvii—S2—Pr	96.03 (8)
Pr^xii—Ag1—Pr^xiii	118.48 (4)	Ag1^xvi—S2—Pr^xxiv	113.13 (15)
S2^viii—Ag1—Pr^xiv	59.32 (5)	Ag2^v—S2—Pr^xxiv	123 (2)
S2^v—Ag1—Pr^xiv	59.62 (5)	Pr^xxvi—S2—Pr^xxiv	92.49 (8)
S2^ix—Ag1—Pr^xiv	165.4 (2)	Pr^xxvii—S2—Pr^xxiv	92.25 (8)
Ag2^x—Ag1—Pr^xiv	82.87 (10)	Pr—S2—Pr^xxiv	147.58 (9)
Ag1^xi—Ag1—Pr^xiv	82.87 (10)	Ge1^xvi—S3—Pr^xx	91.85 (9)
Ag1^x—Ag1—Pr^xiv	97.13 (10)	Ge1^xvi—S3—Pr^xxiv	88.84 (8)
Pr^xii—Ag1—Pr^xiv	118.48 (4)	Pr^xx—S3—Pr^xxiv	111.09 (8)
Pr^xiii—Ag1—Pr^xiv	118.48 (4)	Ge1^xvi—S3—Pr^xxvi	121.46 (10)
S2^viii—Ag1—Ag2^xv	97.42 (13)	Pr^xx—S3—Pr^xxvi	140.32 (9)
S2^v—Ag1—Ag2^xv	97.42 (14)	Pr^xxiv—S3—Pr^xxvi	92.01 (7)
S2^ix—Ag1—Ag2^xv	97.42 (13)

Symmetry codes: (i) −x+y+1, −x+1, z−1; (ii) x−y+1, x, z−1/2; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) y−1, −x+y, z−1/2; (ix) x−y, x−1, z−1/2; (x) −x, −y, z−1/2; (xi) −x, −y, z+1/2; (xii) −y+1, x−y, z; (xiii) x−1, y−1, z; (xiv) −x+y, −x+1, z; (xv) −x, −y, z−3/2; (xvi) −x+1, −y+1, z+1/2; (xvii) y−1, −x+y, z+1/2; (xviii) x−y, x−1, z+1/2; (xix) −x, −y, z+3/2; (xx) −y+1, x−y, z+1; (xxi) −x+y, −x+1, z+1; (xxii) x−1, y−1, z+1; (xxiii) x−y, x, z−1/2; (xxiv) x, y, z+1; (xxv) x−y, x, z+1/2; (xxvi) y, −x+y+1, z+1/2; (xxvii) x−y+1, x, z+1/2.

(nd)

Crystal data

Ag0.84GeNd3S7	Dx = 5.245 Mg m^−3
Mr = 819.80	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 700 reflections
Hall symbol: P 6c	θ = 4.2–26.4°
a = 10.1930 (14) Å	µ = 20.49 mm^−1
c = 5.7693 (12) Å	T = 295 K
V = 519.11 (15) Å^3	Prism, dark red
Z = 2	0.11 × 0.09 × 0.08 mm
F(000) = 726

Data collection

KUMA KM-4 with area CCD detector diffractometer	713 independent reflections
Radiation source: fine-focus sealed tube	700 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.4°, θmin = 4.2°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.093, Tmax = 0.261	l = −7→7
5463 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0193P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max = 0.001
wR(F^2) = 0.035	Δρmax = 0.72 e Å^−3
S = 1.08	Δρmin = −0.75 e Å^−3
713 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0335 (7)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 320 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.027 (19)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Nd	0.87317 (3)	0.64140 (3)	0.24353 (16)	0.01001 (11)
Ag1	0.0000	0.0000	0.159 (2)	0.053 (4)	0.69 (2)
Ag2	0.0000	0.0000	0.971 (7)	0.029 (9)	0.15 (2)
Ge1	0.3333	0.6667	0.3272 (2)	0.0087 (2)
S1	0.3333	0.6667	0.9504 (4)	0.0110 (5)
S2	0.90545 (14)	0.73476 (15)	0.7252 (3)	0.0140 (3)
S3	0.58466 (16)	0.47936 (16)	0.9818 (3)	0.0103 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd	0.00997 (15)	0.00902 (15)	0.01111 (16)	0.00481 (11)	−0.00099 (18)	−0.00074 (16)
Ag1	0.0114 (6)	0.0114 (6)	0.136 (11)	0.0057 (3)	0.000	0.000
Ag2	0.013 (2)	0.013 (2)	0.06 (3)	0.0063 (12)	0.000	0.000
Ge1	0.0094 (3)	0.0094 (3)	0.0072 (5)	0.00472 (16)	0.000	0.000
S1	0.0135 (8)	0.0135 (8)	0.0061 (13)	0.0067 (4)	0.000	0.000
S2	0.0111 (6)	0.0188 (6)	0.0125 (7)	0.0078 (5)	−0.0005 (7)	−0.0023 (8)
S3	0.0119 (7)	0.0094 (6)	0.0102 (7)	0.0058 (6)	0.0010 (6)	0.0006 (6)

Geometric parameters (Å, º)

Nd—S3^i	2.8538 (14)	Ag2—S2^xvi	2.79 (2)
Nd—S2^ii	2.8792 (13)	Ag2—S2^xvii	2.79 (2)
Nd—S2^iii	2.8935 (13)	Ag2—S2^xviii	2.79 (2)
Nd—S2	2.9025 (19)	Ag2—Ag2^viii	2.8846 (6)
Nd—S3^iv	2.9664 (15)	Ag2—Ag2^xi	2.8846 (6)
Nd—S1^v	3.0174 (11)	Ag2—Nd^xviii	3.467 (15)
Nd—S3^ii	3.0316 (15)	Ag2—Nd^xvi	3.467 (15)
Nd—S2^iv	3.1051 (19)	Ge1—S1^iv	2.174 (3)
Nd—Ag1^vi	3.247 (2)	Ge1—S3^iii	2.2256 (16)
Nd—Ag2^v	3.467 (15)	Ge1—S3^xix	2.2256 (16)
Nd—Ag2^vii	3.576 (17)	Ge1—S3^v	2.2256 (16)
Ag1—Ag2^iv	1.09 (3)	S1—Ge1^xv	2.174 (3)
Ag1—Ag2^viii	1.80 (3)	S1—Nd^xx	3.0174 (11)
Ag1—S2^v	2.404 (2)	S1—Nd^xvi	3.0174 (11)
Ag1—S2^ix	2.404 (2)	S1—Nd^xxi	3.0174 (11)
Ag1—S2^x	2.404 (2)	S2—Ag1^xvi	2.404 (2)
Ag1—Ag1^viii	2.8846 (6)	S2—Ag2^vi	2.76 (2)
Ag1—Ag1^xi	2.8846 (6)	S2—Ag2^v	2.79 (2)
Ag1—Nd^xii	3.247 (2)	S2—Nd^xxi	2.8792 (13)
Ag1—Nd^xiii	3.247 (2)	S2—Nd^xxii	2.8935 (13)
Ag1—Nd^xiv	3.247 (2)	S2—Nd^xv	3.1051 (19)
Ag2—Ag1^xv	1.09 (3)	S3—Ge1^xvi	2.2256 (16)
Ag2—Ag1^xi	1.80 (3)	S3—Nd^xxiii	2.8538 (14)
Ag2—S2^xiii	2.76 (2)	S3—Nd^xv	2.9664 (15)
Ag2—S2^xiv	2.76 (2)	S3—Nd^xxi	3.0316 (15)
Ag2—S2^xii	2.76 (2)
S3^i—Nd—S2^ii	105.37 (4)	Ag1^xi—Ag2—S2^xiii	59.2 (7)
S3^i—Nd—S2^iii	140.80 (5)	Ag1^xv—Ag2—S2^xiv	120.8 (7)
S2^ii—Nd—S2^iii	90.81 (5)	Ag1^xi—Ag2—S2^xiv	59.2 (7)
S3^i—Nd—S2	136.85 (4)	S2^xiii—Ag2—S2^xiv	96.1 (9)
S2^ii—Nd—S2	80.49 (4)	Ag1^xv—Ag2—S2^xii	120.8 (7)
S2^iii—Nd—S2	80.26 (4)	Ag1^xi—Ag2—S2^xii	59.2 (7)
S3^i—Nd—S3^iv	74.70 (6)	S2^xiii—Ag2—S2^xii	96.1 (9)
S2^ii—Nd—S3^iv	142.13 (5)	S2^xiv—Ag2—S2^xii	96.1 (9)
S2^iii—Nd—S3^iv	70.99 (4)	Ag1^xv—Ag2—S2^xvi	58.2 (7)
S2—Nd—S3^iv	126.04 (4)	Ag1^xi—Ag2—S2^xvi	121.8 (7)
S3^i—Nd—S1^v	70.38 (4)	S2^xiii—Ag2—S2^xvi	179.0 (14)
S2^ii—Nd—S1^v	147.99 (4)	S2^xiv—Ag2—S2^xvi	84.52 (3)
S2^iii—Nd—S1^v	112.70 (3)	S2^xii—Ag2—S2^xvi	84.52 (3)
S2—Nd—S1^v	82.43 (5)	Ag1^xv—Ag2—S2^xvii	58.2 (7)
S3^iv—Nd—S1^v	68.92 (4)	Ag1^xi—Ag2—S2^xvii	121.8 (7)
S3^i—Nd—S3^ii	72.75 (3)	S2^xiii—Ag2—S2^xvii	84.52 (3)
S2^ii—Nd—S3^ii	68.73 (4)	S2^xiv—Ag2—S2^xvii	179.0 (14)
S2^iii—Nd—S3^ii	145.91 (5)	S2^xii—Ag2—S2^xvii	84.52 (3)
S2—Nd—S3^ii	69.95 (4)	S2^xvi—Ag2—S2^xvii	94.8 (9)
S3^iv—Nd—S3^ii	140.86 (4)	Ag1^xv—Ag2—S2^xviii	58.2 (7)
S1^v—Nd—S3^ii	80.04 (3)	Ag1^xi—Ag2—S2^xviii	121.8 (7)
S3^i—Nd—S2^iv	72.46 (4)	S2^xiii—Ag2—S2^xviii	84.52 (3)
S2^ii—Nd—S2^iv	77.15 (4)	S2^xiv—Ag2—S2^xviii	84.52 (3)
S2^iii—Nd—S2^iv	76.94 (4)	S2^xii—Ag2—S2^xviii	179.0 (14)
S2—Nd—S2^iv	147.60 (5)	S2^xvi—Ag2—S2^xviii	94.8 (9)
S3^iv—Nd—S2^iv	66.67 (4)	S2^xvii—Ag2—S2^xviii	94.8 (9)
S1^v—Nd—S2^iv	127.71 (5)	Ag1^xv—Ag2—Ag2^viii	180.00 (2)
S3^ii—Nd—S2^iv	121.46 (4)	Ag1^xi—Ag2—Ag2^viii	0.000 (1)
S3^i—Nd—Ag1^vi	132.9 (2)	S2^xiii—Ag2—Ag2^viii	59.2 (7)
S2^ii—Nd—Ag1^vi	45.72 (3)	S2^xiv—Ag2—Ag2^viii	59.2 (7)
S2^iii—Nd—Ag1^vi	45.64 (3)	S2^xii—Ag2—Ag2^viii	59.2 (7)
S2—Nd—Ag1^vi	81.9 (2)	S2^xvi—Ag2—Ag2^viii	121.8 (7)
S3^iv—Nd—Ag1^vi	106.03 (13)	S2^xvii—Ag2—Ag2^viii	121.8 (7)
S1^v—Nd—Ag1^vi	155.33 (14)	S2^xviii—Ag2—Ag2^viii	121.8 (7)
S3^ii—Nd—Ag1^vi	111.93 (10)	Ag1^xv—Ag2—Ag2^xi	0.000 (4)
S2^iv—Nd—Ag1^vi	65.7 (2)	Ag1^xi—Ag2—Ag2^xi	180.000 (15)
S3^i—Nd—Ag2^v	155.8 (3)	S2^xiii—Ag2—Ag2^xi	120.8 (7)
S2^ii—Nd—Ag2^v	50.6 (2)	S2^xiv—Ag2—Ag2^xi	120.8 (7)
S2^iii—Nd—Ag2^v	50.5 (2)	S2^xii—Ag2—Ag2^xi	120.8 (7)
S2—Nd—Ag2^v	51.0 (6)	S2^xvi—Ag2—Ag2^xi	58.2 (7)
S3^iv—Nd—Ag2^v	121.5 (2)	S2^xvii—Ag2—Ag2^xi	58.2 (7)
S1^v—Nd—Ag2^v	130.2 (5)	S2^xviii—Ag2—Ag2^xi	58.2 (7)
S3^ii—Nd—Ag2^v	96.6 (3)	Ag2^viii—Ag2—Ag2^xi	180.000 (13)
S2^iv—Nd—Ag2^v	96.6 (6)	Ag1^xv—Ag2—Nd^xviii	112.2 (6)
Ag1^vi—Nd—Ag2^v	30.8 (4)	Ag1^xi—Ag2—Nd^xviii	67.8 (6)
S3^i—Nd—Ag2^vii	117.2 (5)	S2^xiii—Ag2—Nd^xviii	53.6 (3)
S2^ii—Nd—Ag2^vii	49.8 (2)	S2^xiv—Ag2—Nd^xviii	53.9 (3)
S2^iii—Nd—Ag2^vii	49.8 (2)	S2^xii—Ag2—Nd^xviii	127.0 (13)
S2—Nd—Ag2^vii	99.4 (6)	S2^xvi—Ag2—Nd^xviii	126.48 (18)
S3^iv—Nd—Ag2^vii	95.5 (3)	S2^xvii—Ag2—Nd^xviii	126.18 (18)
S1^v—Nd—Ag2^vii	160.99 (5)	S2^xviii—Ag2—Nd^xviii	53.96 (9)
S3^ii—Nd—Ag2^vii	118.49 (18)	Ag2^viii—Ag2—Nd^xviii	67.8 (6)
S2^iv—Nd—Ag2^vii	48.2 (6)	Ag2^xi—Ag2—Nd^xviii	112.2 (6)
Ag1^vi—Nd—Ag2^vii	17.5 (3)	Ag1^xv—Ag2—Nd^xvi	112.2 (6)
Ag2^v—Nd—Ag2^vii	48.32 (4)	Ag1^xi—Ag2—Nd^xvi	67.8 (6)
Ag2^iv—Ag1—Ag2^viii	180.000 (4)	S2^xiii—Ag2—Nd^xvi	127.0 (13)
Ag2^iv—Ag1—S2^v	99.1 (3)	S2^xiv—Ag2—Nd^xvi	53.6 (3)
Ag2^viii—Ag1—S2^v	80.9 (3)	S2^xii—Ag2—Nd^xvi	53.9 (3)
Ag2^iv—Ag1—S2^ix	99.1 (3)	S2^xvi—Ag2—Nd^xvi	53.96 (9)
Ag2^viii—Ag1—S2^ix	80.9 (3)	S2^xvii—Ag2—Nd^xvi	126.48 (18)
S2^v—Ag1—S2^ix	117.52 (16)	S2^xviii—Ag2—Nd^xvi	126.18 (18)
Ag2^iv—Ag1—S2^x	99.1 (3)	Ag2^viii—Ag2—Nd^xvi	67.8 (6)
Ag2^viii—Ag1—S2^x	80.9 (3)	Ag2^xi—Ag2—Nd^xvi	112.2 (6)
S2^v—Ag1—S2^x	117.52 (16)	Nd^xviii—Ag2—Nd^xvi	106.6 (6)
S2^ix—Ag1—S2^x	117.52 (16)	S1^iv—Ge1—S3^iii	113.61 (4)
Ag2^iv—Ag1—Ag1^viii	0.000 (1)	S1^iv—Ge1—S3^xix	113.61 (4)
Ag2^viii—Ag1—Ag1^viii	180.000 (5)	S3^iii—Ge1—S3^xix	105.03 (5)
S2^v—Ag1—Ag1^viii	99.1 (3)	S1^iv—Ge1—S3^v	113.61 (4)
S2^ix—Ag1—Ag1^viii	99.1 (3)	S3^iii—Ge1—S3^v	105.03 (5)
S2^x—Ag1—Ag1^viii	99.1 (3)	S3^xix—Ge1—S3^v	105.03 (5)
Ag2^iv—Ag1—Ag1^xi	180.000 (1)	Ge1^xv—S1—Nd^xx	113.29 (4)
Ag2^viii—Ag1—Ag1^xi	0.000 (4)	Ge1^xv—S1—Nd^xvi	113.29 (4)
S2^v—Ag1—Ag1^xi	80.9 (3)	Nd^xx—S1—Nd^xvi	105.39 (5)
S2^ix—Ag1—Ag1^xi	80.9 (3)	Ge1^xv—S1—Nd^xxi	113.29 (4)
S2^x—Ag1—Ag1^xi	80.9 (3)	Nd^xx—S1—Nd^xxi	105.39 (5)
Ag1^viii—Ag1—Ag1^xi	180.000 (1)	Nd^xvi—S1—Nd^xxi	105.39 (5)
Ag2^iv—Ag1—Nd^xii	98.6 (2)	Ag2^vi—S2—Ag2^v	62.57 (3)
Ag2^viii—Ag1—Nd^xii	81.4 (2)	Ag1^xvi—S2—Nd^xxi	75.25 (5)
S2^v—Ag1—Nd^xii	59.03 (5)	Ag2^vi—S2—Nd^xxi	75.80 (9)
S2^ix—Ag1—Nd^xii	162.2 (5)	Ag2^v—S2—Nd^xxi	78.17 (13)
S2^x—Ag1—Nd^xii	59.39 (5)	Ag1^xvi—S2—Nd^xxii	74.97 (4)
Ag1^viii—Ag1—Nd^xii	98.6 (2)	Ag2^vi—S2—Nd^xxii	75.57 (9)
Ag1^xi—Ag1—Nd^xii	81.4 (2)	Ag2^v—S2—Nd^xxii	77.93 (13)
Ag2^iv—Ag1—Nd^xiii	98.6 (2)	Nd^xxi—S2—Nd^xxii	148.84 (5)
Ag2^viii—Ag1—Nd^xiii	81.4 (2)	Ag1^xvi—S2—Nd	97.6 (3)
S2^v—Ag1—Nd^xiii	162.2 (5)	Ag2^vi—S2—Nd	137.6 (7)
S2^ix—Ag1—Nd^xiii	59.39 (5)	Ag2^v—S2—Nd	75.0 (7)
S2^x—Ag1—Nd^xiii	59.03 (5)	Nd^xxi—S2—Nd	96.58 (5)
Ag1^viii—Ag1—Nd^xiii	98.6 (2)	Nd^xxii—S2—Nd	96.26 (5)
Ag1^xi—Ag1—Nd^xiii	81.4 (2)	Ag1^xvi—S2—Nd^xv	114.8 (3)
Nd^xii—Ag1—Nd^xiii	117.79 (11)	Ag2^vi—S2—Nd^xv	74.8 (7)
Ag2^iv—Ag1—Nd^xiv	98.6 (2)	Ag2^v—S2—Nd^xv	137.4 (7)
Ag2^viii—Ag1—Nd^xiv	81.4 (2)	Nd^xxi—S2—Nd^xv	92.23 (4)
S2^v—Ag1—Nd^xiv	59.39 (5)	Nd^xxii—S2—Nd^xv	91.96 (4)
S2^ix—Ag1—Nd^xiv	59.03 (5)	Nd—S2—Nd^xv	147.60 (5)
S2^x—Ag1—Nd^xiv	162.2 (5)	Ge1^xvi—S3—Nd^xxiii	91.59 (5)
Ag1^viii—Ag1—Nd^xiv	98.6 (2)	Ge1^xvi—S3—Nd^xv	88.68 (5)
Ag1^xi—Ag1—Nd^xiv	81.4 (2)	Nd^xxiii—S3—Nd^xv	111.12 (5)
Nd^xii—Ag1—Nd^xiv	117.79 (11)	Ge1^xvi—S3—Nd^xxi	120.99 (6)
Nd^xiii—Ag1—Nd^xiv	117.79 (11)	Nd^xxiii—S3—Nd^xxi	140.93 (6)
Ag1^xv—Ag2—Ag1^xi	180.000 (12)	Nd^xv—S3—Nd^xxi	92.03 (4)
Ag1^xv—Ag2—S2^xiii	120.8 (7)

Symmetry codes: (i) −x+y+1, −x+1, z−1; (ii) x−y+1, x, z−1/2; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) −x, −y, z−1/2; (ix) y−1, −x+y, z−1/2; (x) x−y, x−1, z−1/2; (xi) −x, −y, z+1/2; (xii) −y+1, x−y, z; (xiii) x−1, y−1, z; (xiv) −x+y, −x+1, z; (xv) x, y, z+1; (xvi) −x+1, −y+1, z+1/2; (xvii) x−y, x−1, z+1/2; (xviii) y−1, −x+y, z+1/2; (xix) x−y, x, z−1/2; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) −y+1, x−y, z+1.

(sm)

Crystal data

Ag0.74GeS7Sm3	Dx = 5.420 Mg m^−3
Mr = 827.34	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 601 reflections
Hall symbol: P 6c	θ = 4.2–25.3°
a = 10.0809 (14) Å	µ = 22.80 mm^−1
c = 5.7604 (12) Å	T = 295 K
V = 506.97 (15) Å^3	Prism, dark red
Z = 2	0.13 × 0.11 × 0.09 mm
F(000) = 729

Data collection

KUMA KM-4 with area CCD detector diffractometer	604 independent reflections
Radiation source: fine-focus sealed tube	601 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 25.3°, θmin = 4.2°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −11→12
Tmin = 0.029, Tmax = 0.242	l = −6→6
4935 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0181P)^2 + 0.5015P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.014	(Δ/σ)max = 0.001
wR(F^2) = 0.034	Δρmax = 0.70 e Å^−3
S = 1.17	Δρmin = −0.51 e Å^−3
604 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0097 (4)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 270 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.029 (18)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Sm	0.87145 (3)	0.64163 (2)	0.24346 (12)	0.00914 (12)
Ag1	0.0000	0.0000	0.137 (3)	0.075 (5)	0.548 (18)
Ag2	0.0000	0.0000	0.967 (3)	0.020 (4)	0.187 (18)
Ge1	0.3333	0.6667	0.32606 (16)	0.0069 (2)
S1	0.3333	0.6667	0.9482 (4)	0.0092 (5)
S2	0.90414 (13)	0.73662 (14)	0.7212 (2)	0.0140 (3)
S3	0.58278 (15)	0.47996 (14)	0.9828 (2)	0.0091 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm	0.00824 (15)	0.00721 (14)	0.01210 (17)	0.00397 (10)	−0.00139 (13)	−0.00070 (13)
Ag1	0.0095 (7)	0.0095 (7)	0.205 (15)	0.0048 (4)	0.000	0.000
Ag2	0.0091 (17)	0.0091 (17)	0.043 (11)	0.0046 (9)	0.000	0.000
Ge1	0.0076 (3)	0.0076 (3)	0.0055 (5)	0.00380 (14)	0.000	0.000
S1	0.0105 (7)	0.0105 (7)	0.0066 (12)	0.0053 (3)	0.000	0.000
S2	0.0098 (5)	0.0202 (6)	0.0129 (6)	0.0082 (5)	0.0005 (5)	−0.0028 (6)
S3	0.0113 (6)	0.0083 (6)	0.0093 (6)	0.0062 (5)	0.0012 (5)	0.0006 (5)

Geometric parameters (Å, º)

Sm—S3^i	2.8332 (13)	Ag2—S2^xvi	2.751 (9)
Sm—S2^ii	2.8336 (12)	Ag2—S2^xvii	2.751 (9)
Sm—S2^iii	2.8602 (12)	Ag2—S2^xviii	2.751 (9)
Sm—S2	2.8780 (17)	Ag2—Ag2^viii	2.8802 (6)
Sm—S3^iv	2.9389 (14)	Ag2—Ag2^xi	2.8802 (6)
Sm—S1^v	2.9825 (10)	Ag2—Sm^xviii	3.421 (6)
Sm—S3^ii	3.0127 (13)	Ag2—Sm^xvi	3.421 (6)
Sm—S2^iv	3.1243 (17)	Ge1—S1^iv	2.177 (2)
Sm—Ag1^vi	3.229 (3)	Ge1—S3^iii	2.2281 (14)
Sm—Ag2^v	3.421 (6)	Ge1—S3^xix	2.2281 (14)
Sm—Ag2^vii	3.548 (8)	Ge1—S3^v	2.2281 (14)
Ag1—Ag2^iv	0.981 (7)	S1—Ge1^xv	2.177 (2)
Ag1—Ag2^viii	1.899 (7)	S1—Sm^xx	2.9825 (10)
Ag1—S2^v	2.378 (4)	S1—Sm^xvi	2.9825 (10)
Ag1—S2^ix	2.378 (4)	S1—Sm^xxi	2.9825 (10)
Ag1—S2^x	2.378 (4)	S2—Ag1^xvi	2.378 (4)
Ag1—Ag1^viii	2.8802 (6)	S2—Ag2^vi	2.724 (9)
Ag1—Ag1^xi	2.8802 (6)	S2—Ag2^v	2.751 (9)
Ag1—Sm^xii	3.229 (3)	S2—Sm^xxi	2.8336 (12)
Ag1—Sm^xiii	3.229 (3)	S2—Sm^xxii	2.8602 (12)
Ag1—Sm^xiv	3.229 (3)	S2—Sm^xv	3.1243 (17)
Ag2—Ag1^xv	0.981 (7)	S3—Ge1^xvi	2.2281 (14)
Ag2—Ag1^xi	1.899 (7)	S3—Sm^xxiii	2.8332 (13)
Ag2—S2^xiii	2.724 (9)	S3—Sm^xv	2.9389 (14)
Ag2—S2^xiv	2.724 (9)	S3—Sm^xxi	3.0127 (13)
Ag2—S2^xii	2.724 (9)
S3^i—Sm—S2^ii	104.33 (4)	Ag1^xi—Ag2—S2^xiii	58.7 (3)
S3^i—Sm—S2^iii	141.02 (5)	Ag1^xv—Ag2—S2^xiv	121.3 (3)
S2^ii—Sm—S2^iii	90.15 (5)	Ag1^xi—Ag2—S2^xiv	58.7 (3)
S3^i—Sm—S2	137.02 (4)	S2^xiii—Ag2—S2^xiv	95.5 (4)
S2^ii—Sm—S2	80.83 (4)	Ag1^xv—Ag2—S2^xii	121.3 (3)
S2^iii—Sm—S2	80.38 (4)	Ag1^xi—Ag2—S2^xii	58.7 (3)
S3^i—Sm—S3^iv	75.34 (5)	S2^xiii—Ag2—S2^xii	95.5 (4)
S2^ii—Sm—S3^iv	141.56 (4)	S2^xiv—Ag2—S2^xii	95.5 (4)
S2^iii—Sm—S3^iv	71.24 (4)	Ag1^xv—Ag2—S2^xvi	57.8 (3)
S2—Sm—S3^iv	126.16 (4)	Ag1^xi—Ag2—S2^xvi	122.2 (3)
S3^i—Sm—S1^v	70.70 (4)	S2^xiii—Ag2—S2^xvi	179.1 (6)
S2^ii—Sm—S1^v	148.01 (4)	S2^xiv—Ag2—S2^xvi	85.13 (2)
S2^iii—Sm—S1^v	113.86 (3)	S2^xii—Ag2—S2^xvi	85.13 (2)
S2—Sm—S1^v	82.71 (5)	Ag1^xv—Ag2—S2^xvii	57.8 (3)
S3^iv—Sm—S1^v	69.31 (4)	Ag1^xi—Ag2—S2^xvii	122.2 (3)
S3^i—Sm—S3^ii	72.32 (3)	S2^xiii—Ag2—S2^xvii	85.13 (2)
S2^ii—Sm—S3^ii	69.33 (3)	S2^xiv—Ag2—S2^xvii	179.1 (6)
S2^iii—Sm—S3^ii	145.90 (4)	S2^xii—Ag2—S2^xvii	85.13 (2)
S2—Sm—S3^ii	69.94 (4)	S2^xvi—Ag2—S2^xvii	94.2 (4)
S3^iv—Sm—S3^ii	140.72 (3)	Ag1^xv—Ag2—S2^xviii	57.8 (3)
S1^v—Sm—S3^ii	79.31 (3)	Ag1^xi—Ag2—S2^xviii	122.2 (3)
S3^i—Sm—S2^iv	72.34 (4)	S2^xiii—Ag2—S2^xviii	85.13 (2)
S2^ii—Sm—S2^iv	76.69 (4)	S2^xiv—Ag2—S2^xviii	85.13 (2)
S2^iii—Sm—S2^iv	76.31 (4)	S2^xii—Ag2—S2^xviii	179.1 (6)
S2—Sm—S2^iv	147.33 (5)	S2^xvi—Ag2—S2^xviii	94.2 (4)
S3^iv—Sm—S2^iv	66.51 (4)	S2^xvii—Ag2—S2^xviii	94.2 (4)
S1^v—Sm—S2^iv	127.74 (5)	Ag1^xv—Ag2—Ag2^viii	180.000 (16)
S3^ii—Sm—S2^iv	121.84 (3)	Ag1^xi—Ag2—Ag2^viii	0.000 (1)
S3^i—Sm—Ag1^vi	130.3 (3)	S2^xiii—Ag2—Ag2^viii	58.7 (3)
S2^ii—Sm—Ag1^vi	45.60 (4)	S2^xiv—Ag2—Ag2^viii	58.7 (3)
S2^iii—Sm—Ag1^vi	45.47 (4)	S2^xii—Ag2—Ag2^viii	58.7 (3)
S2—Sm—Ag1^vi	83.9 (3)	S2^xvi—Ag2—Ag2^viii	122.2 (3)
S3^iv—Sm—Ag1^vi	104.81 (18)	S2^xvii—Ag2—Ag2^viii	122.2 (3)
S1^v—Sm—Ag1^vi	157.29 (18)	S2^xviii—Ag2—Ag2^viii	122.2 (3)
S3^ii—Sm—Ag1^vi	112.96 (14)	Ag1^xv—Ag2—Ag2^xi	0.000 (4)
S2^iv—Sm—Ag1^vi	63.4 (3)	Ag1^xi—Ag2—Ag2^xi	180.000 (8)
S3^i—Sm—Ag2^v	154.81 (13)	S2^xiii—Ag2—Ag2^xi	121.3 (3)
S2^ii—Sm—Ag2^v	50.57 (10)	S2^xiv—Ag2—Ag2^xi	121.3 (3)
S2^iii—Sm—Ag2^v	50.43 (10)	S2^xii—Ag2—Ag2^xi	121.3 (3)
S2—Sm—Ag2^v	50.9 (3)	S2^xvi—Ag2—Ag2^xi	57.8 (3)
S3^iv—Sm—Ag2^v	121.66 (11)	S2^xvii—Ag2—Ag2^xi	57.8 (3)
S1^v—Sm—Ag2^v	130.6 (2)	S2^xviii—Ag2—Ag2^xi	57.8 (3)
S3^ii—Sm—Ag2^v	96.56 (15)	Ag2^viii—Ag2—Ag2^xi	180.000 (5)
S2^iv—Sm—Ag2^v	96.4 (3)	Ag1^xv—Ag2—Sm^xviii	112.1 (3)
Ag1^vi—Sm—Ag2^v	33.03 (12)	Ag1^xi—Ag2—Sm^xviii	67.9 (3)
S3^i—Sm—Ag2^vii	116.2 (2)	S2^xiii—Ag2—Sm^xviii	53.47 (13)
S2^ii—Sm—Ag2^vii	49.52 (9)	S2^xiv—Ag2—Sm^xviii	54.05 (14)
S2^iii—Sm—Ag2^vii	49.42 (9)	S2^xii—Ag2—Sm^xviii	126.6 (6)
S2—Sm—Ag2^vii	99.7 (2)	S2^xvi—Ag2—Sm^xviii	126.61 (9)
S3^iv—Sm—Ag2^vii	95.24 (15)	S2^xvii—Ag2—Sm^xviii	126.04 (9)
S1^v—Sm—Ag2^vii	161.57 (3)	S2^xviii—Ag2—Sm^xviii	54.29 (4)
S3^ii—Sm—Ag2^vii	118.78 (8)	Ag2^viii—Ag2—Sm^xviii	67.9 (3)
S2^iv—Sm—Ag2^vii	47.7 (2)	Ag2^xi—Ag2—Sm^xviii	112.1 (3)
Ag1^vi—Sm—Ag2^vii	15.75 (13)	Ag1^xv—Ag2—Sm^xvi	112.1 (3)
Ag2^v—Sm—Ag2^vii	48.78 (2)	Ag1^xi—Ag2—Sm^xvi	67.9 (3)
Ag2^iv—Ag1—Ag2^viii	180.000 (2)	S2^xiii—Ag2—Sm^xvi	126.6 (6)
Ag2^iv—Ag1—S2^v	101.8 (4)	S2^xiv—Ag2—Sm^xvi	53.47 (13)
Ag2^viii—Ag1—S2^v	78.2 (4)	S2^xii—Ag2—Sm^xvi	54.05 (14)
Ag2^iv—Ag1—S2^ix	101.8 (4)	S2^xvi—Ag2—Sm^xvi	54.29 (4)
Ag2^viii—Ag1—S2^ix	78.2 (4)	S2^xvii—Ag2—Sm^xvi	126.61 (9)
S2^v—Ag1—S2^ix	116.0 (3)	S2^xviii—Ag2—Sm^xvi	126.04 (9)
Ag2^iv—Ag1—S2^x	101.8 (4)	Ag2^viii—Ag2—Sm^xvi	67.9 (3)
Ag2^viii—Ag1—S2^x	78.2 (4)	Ag2^xi—Ag2—Sm^xvi	112.1 (3)
S2^v—Ag1—S2^x	116.0 (3)	Sm^xviii—Ag2—Sm^xvi	106.7 (3)
S2^ix—Ag1—S2^x	116.0 (3)	S1^iv—Ge1—S3^iii	113.90 (4)
Ag2^iv—Ag1—Ag1^viii	0.000 (1)	S1^iv—Ge1—S3^xix	113.90 (4)
Ag2^viii—Ag1—Ag1^viii	180.000 (2)	S3^iii—Ge1—S3^xix	104.71 (5)
S2^v—Ag1—Ag1^viii	101.8 (4)	S1^iv—Ge1—S3^v	113.90 (4)
S2^ix—Ag1—Ag1^viii	101.8 (4)	S3^iii—Ge1—S3^v	104.71 (5)
S2^x—Ag1—Ag1^viii	101.8 (4)	S3^xix—Ge1—S3^v	104.71 (5)
Ag2^iv—Ag1—Ag1^xi	180.000 (1)	Ge1^xv—S1—Sm^xx	113.29 (4)
Ag2^viii—Ag1—Ag1^xi	0.000 (1)	Ge1^xv—S1—Sm^xvi	113.29 (4)
S2^v—Ag1—Ag1^xi	78.2 (4)	Sm^xx—S1—Sm^xvi	105.40 (5)
S2^ix—Ag1—Ag1^xi	78.2 (4)	Ge1^xv—S1—Sm^xxi	113.29 (4)
S2^x—Ag1—Ag1^xi	78.2 (4)	Sm^xx—S1—Sm^xxi	105.40 (5)
Ag1^viii—Ag1—Ag1^xi	180.000 (2)	Sm^xvi—S1—Sm^xxi	105.40 (5)
Ag2^iv—Ag1—Sm^xii	100.9 (3)	Ag2^vi—S2—Ag2^v	63.49 (3)
Ag2^viii—Ag1—Sm^xii	79.1 (3)	Ag1^xvi—S2—Sm^xxi	76.01 (6)
S2^v—Ag1—Sm^xii	58.38 (8)	Ag2^vi—S2—Sm^xxi	75.96 (5)
S2^ix—Ag1—Sm^xii	59.04 (8)	Ag2^v—S2—Sm^xxi	78.89 (7)
S2^x—Ag1—Sm^xii	157.3 (7)	Ag1^xvi—S2—Sm^xxii	75.49 (6)
Ag1^viii—Ag1—Sm^xii	100.9 (3)	Ag2^vi—S2—Sm^xxii	75.52 (5)
Ag1^xi—Ag1—Sm^xii	79.1 (3)	Ag2^v—S2—Sm^xxii	78.43 (7)
Ag2^iv—Ag1—Sm^xiii	100.9 (3)	Sm^xxi—S2—Sm^xxii	149.30 (5)
Ag2^viii—Ag1—Sm^xiii	79.1 (3)	Ag1^xvi—S2—Sm	95.3 (4)
S2^v—Ag1—Sm^xiii	157.3 (7)	Ag2^vi—S2—Sm	138.3 (3)
S2^ix—Ag1—Sm^xiii	58.38 (8)	Ag2^v—S2—Sm	74.8 (3)
S2^x—Ag1—Sm^xiii	59.04 (8)	Sm^xxi—S2—Sm	97.16 (4)
Ag1^viii—Ag1—Sm^xiii	100.9 (3)	Sm^xxii—S2—Sm	96.56 (4)
Ag1^xi—Ag1—Sm^xiii	79.1 (3)	Ag1^xvi—S2—Sm^xv	117.4 (4)
Sm^xii—Ag1—Sm^xiii	116.48 (19)	Ag2^vi—S2—Sm^xv	74.4 (3)
Ag2^iv—Ag1—Sm^xiv	100.9 (3)	Ag2^v—S2—Sm^xv	137.8 (3)
Ag2^viii—Ag1—Sm^xiv	79.1 (3)	Sm^xxi—S2—Sm^xv	91.80 (4)
S2^v—Ag1—Sm^xiv	59.04 (8)	Sm^xxii—S2—Sm^xv	91.29 (4)
S2^ix—Ag1—Sm^xiv	157.3 (7)	Sm—S2—Sm^xv	147.33 (5)
S2^x—Ag1—Sm^xiv	58.38 (8)	Ge1^xvi—S3—Sm^xxiii	91.34 (4)
Ag1^viii—Ag1—Sm^xiv	100.9 (3)	Ge1^xvi—S3—Sm^xv	88.62 (4)
Ag1^xi—Ag1—Sm^xiv	79.1 (3)	Sm^xxiii—S3—Sm^xv	110.57 (5)
Sm^xii—Ag1—Sm^xiv	116.48 (19)	Ge1^xvi—S3—Sm^xxi	120.21 (6)
Sm^xiii—Ag1—Sm^xiv	116.48 (19)	Sm^xxiii—S3—Sm^xxi	142.07 (5)
Ag1^xv—Ag2—Ag1^xi	180.000 (18)	Sm^xv—S3—Sm^xxi	92.04 (4)
Ag1^xv—Ag2—S2^xiii	121.3 (3)

Symmetry codes: (i) −x+y+1, −x+1, z−1; (ii) x−y+1, x, z−1/2; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) −x, −y, z−1/2; (ix) x−y, x−1, z−1/2; (x) y−1, −x+y, z−1/2; (xi) −x, −y, z+1/2; (xii) −y+1, x−y, z; (xiii) x−1, y−1, z; (xiv) −x+y, −x+1, z; (xv) x, y, z+1; (xvi) −x+1, −y+1, z+1/2; (xvii) x−y, x−1, z+1/2; (xviii) y−1, −x+y, z+1/2; (xix) x−y, x, z−1/2; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) −y+1, x−y, z+1.

(gd)

Crystal data

Ag0.63Gd3GeS7	Dx = 5.602 Mg m^−3
Mr = 836.18	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 657 reflections
Hall symbol: P 6c	θ = 4.3–26.2°
a = 9.9637 (14) Å	µ = 25.41 mm^−1
c = 5.7660 (12) Å	T = 295 K
V = 495.73 (14) Å^3	Prism, dark red
Z = 2	0.13 × 0.12 × 0.10 mm
F(000) = 731

Data collection

KUMA KM-4 with area CCD detector diffractometer	658 independent reflections
Radiation source: fine-focus sealed tube	657 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.2°, θmin = 4.3°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→9
Tmin = 0.024, Tmax = 0.192	l = −7→7
5095 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0143P)^2 + 0.2664P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.013	(Δ/σ)max = 0.001
wR(F^2) = 0.029	Δρmax = 0.58 e Å^−3
S = 1.12	Δρmin = −0.81 e Å^−3
658 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0047 (3)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 296 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (15)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Gd	0.86849 (2)	0.64152 (2)	0.24476 (11)	0.01184 (9)
Ag1	0.0000	0.0000	0.085 (4)	0.093 (5)	0.50 (2)
Ag2	0.0000	0.0000	0.9545 (16)	0.014 (4)	0.12 (2)
Ge1	0.3333	0.6667	0.32630 (13)	0.00836 (18)
S1	0.3333	0.6667	0.9488 (3)	0.0104 (4)
S2	0.90148 (13)	0.73723 (14)	0.7161 (2)	0.0172 (3)
S3	0.58053 (14)	0.47996 (13)	0.9842 (2)	0.0106 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd	0.00971 (12)	0.00902 (11)	0.01695 (12)	0.00480 (8)	−0.00176 (12)	−0.00048 (12)
Ag1	0.0102 (9)	0.0102 (9)	0.258 (16)	0.0051 (4)	0.000	0.000
Ag2	0.011 (3)	0.011 (3)	0.020 (12)	0.0055 (13)	0.000	0.000
Ge1	0.0092 (2)	0.0092 (2)	0.0068 (3)	0.00458 (12)	0.000	0.000
S1	0.0117 (6)	0.0117 (6)	0.0077 (9)	0.0058 (3)	0.000	0.000
S2	0.0114 (5)	0.0237 (6)	0.0182 (7)	0.0100 (5)	−0.0006 (5)	−0.0076 (6)
S3	0.0135 (6)	0.0104 (5)	0.0099 (4)	0.0073 (5)	0.0003 (5)	0.0003 (5)

Geometric parameters (Å, º)

Gd—S2^i	2.7906 (12)	Ag2—S2^xiii	2.672 (5)
Gd—S3^ii	2.8160 (12)	Ag2—S2^xiv	2.672 (5)
Gd—S2^iii	2.8309 (12)	Ag2—S2^viii	2.743 (5)
Gd—S2	2.8443 (14)	Ag2—S2^xvii	2.743 (5)
Gd—S3^iv	2.9090 (13)	Ag2—S2^xviii	2.743 (5)
Gd—S1^v	2.9466 (9)	Ag2—Ag2^ix	2.8830 (6)
Gd—S3^i	3.0045 (12)	Ag2—Ag2^xii	2.8830 (6)
Gd—S2^iv	3.1616 (15)	Ag2—Gd^xviii	3.355 (3)
Gd—Ag1^vi	3.263 (7)	Ag2—Gd^xvii	3.355 (3)
Gd—Ag2^v	3.355 (4)	Ge1—S1^iv	2.1765 (19)
Gd—Ag2^vii	3.549 (5)	Ge1—S3^iii	2.2256 (13)
Gd—Ag1^viii	3.693 (14)	Ge1—S3^xix	2.2256 (13)
Ag1—Ag2^iv	0.75 (2)	Ge1—S3^v	2.2256 (12)
Ag1—Ag2^ix	2.13 (2)	S1—Ge1^xvi	2.1765 (19)
Ag1—S2^v	2.413 (8)	S1—Gd^xx	2.9466 (9)
Ag1—S2^x	2.413 (8)	S1—Gd^viii	2.9466 (9)
Ag1—S2^xi	2.413 (8)	S1—Gd^xxi	2.9466 (9)
Ag1—Ag1^ix	2.8830 (6)	S2—Ag1^viii	2.413 (8)
Ag1—Ag1^xii	2.8830 (6)	S2—Ag2^vi	2.672 (5)
Ag1—Gd^xiii	3.263 (7)	S2—Ag2^v	2.743 (5)
Ag1—Gd^xiv	3.263 (7)	S2—Gd^xxi	2.7906 (11)
Ag1—Gd^xv	3.263 (7)	S2—Gd^xxii	2.8309 (12)
Ag1—Gd^x	3.693 (14)	S2—Gd^xvi	3.1616 (15)
Ag1—Gd^xi	3.693 (14)	S3—Ge1^viii	2.2256 (12)
Ag2—Ag1^xvi	0.75 (2)	S3—Gd^xxiii	2.8160 (12)
Ag2—Ag1^xii	2.13 (2)	S3—Gd^xvi	2.9090 (13)
Ag2—S2^xv	2.672 (5)	S3—Gd^xxi	3.0045 (12)
S2^i—Gd—S3^ii	102.59 (4)	Gd^xiii—Ag1—Gd^x	164.3 (8)
S2^i—Gd—S2^iii	89.80 (5)	Gd^xiv—Ag1—Gd^x	75.14 (11)
S3^ii—Gd—S2^iii	140.84 (4)	Gd^xv—Ag1—Gd^x	75.14 (11)
S2^i—Gd—S2	81.61 (4)	Ag2^iv—Ag1—Gd^xi	57.9 (3)
S3^ii—Gd—S2	137.18 (4)	Ag2^ix—Ag1—Gd^xi	122.1 (3)
S2^iii—Gd—S2	80.91 (3)	S2^v—Ag1—Gd^xi	124.2 (3)
S2^i—Gd—S3^iv	140.77 (4)	S2^x—Ag1—Gd^xi	125.1 (3)
S3^ii—Gd—S3^iv	75.80 (5)	S2^xi—Ag1—Gd^xi	50.4 (2)
S2^iii—Gd—S3^iv	71.53 (3)	Ag1^ix—Ag1—Gd^xi	57.9 (3)
S2—Gd—S3^iv	126.56 (3)	Ag1^xii—Ag1—Gd^xi	122.1 (3)
S2^i—Gd—S1^v	147.63 (3)	Gd^xiii—Ag1—Gd^xi	75.14 (11)
S3^ii—Gd—S1^v	71.34 (4)	Gd^xiv—Ag1—Gd^xi	164.3 (8)
S2^iii—Gd—S1^v	115.33 (3)	Gd^xv—Ag1—Gd^xi	75.14 (11)
S2—Gd—S1^v	82.65 (4)	Gd^x—Ag1—Gd^xi	94.4 (5)
S3^iv—Gd—S1^v	70.08 (4)	Ag1^xvi—Ag2—Ag1^xii	180.00 (3)
S2^i—Gd—S3^i	69.67 (3)	Ag1^xvi—Ag2—S2^xv	120.96 (18)
S3^ii—Gd—S3^i	71.86 (2)	Ag1^xii—Ag2—S2^xv	59.04 (17)
S2^iii—Gd—S3^i	146.14 (4)	Ag1^xvi—Ag2—S2^xiii	120.96 (17)
S2—Gd—S3^i	69.95 (3)	Ag1^xii—Ag2—S2^xiii	59.04 (17)
S3^iv—Gd—S3^i	140.47 (3)	S2^xv—Ag2—S2^xiii	95.9 (2)
S1^v—Gd—S3^i	78.40 (3)	Ag1^xvi—Ag2—S2^xiv	120.96 (18)
S2^i—Gd—S2^iv	76.15 (3)	Ag1^xii—Ag2—S2^xiv	59.04 (17)
S3^ii—Gd—S2^iv	71.75 (3)	S2^xv—Ag2—S2^xiv	95.9 (2)
S2^iii—Gd—S2^iv	75.61 (3)	S2^xiii—Ag2—S2^xiv	95.9 (2)
S2—Gd—S2^iv	147.45 (5)	Ag1^xvi—Ag2—S2^viii	56.64 (17)
S3^iv—Gd—S2^iv	66.04 (3)	Ag1^xii—Ag2—S2^viii	123.36 (17)
S1^v—Gd—S2^iv	127.82 (4)	S2^xv—Ag2—S2^viii	177.6 (3)
S3^i—Gd—S2^iv	121.97 (3)	S2^xiii—Ag2—S2^viii	85.69 (2)
S2^i—Gd—Ag1^vi	46.17 (9)	S2^xiv—Ag2—S2^viii	85.69 (2)
S3^ii—Gd—Ag1^vi	124.6 (4)	Ag1^xvi—Ag2—S2^xvii	56.64 (16)
S2^iii—Gd—Ag1^vi	45.98 (9)	Ag1^xii—Ag2—S2^xvii	123.36 (17)
S2—Gd—Ag1^vi	89.3 (4)	S2^xv—Ag2—S2^xvii	85.69 (2)
S3^iv—Gd—Ag1^vi	101.8 (3)	S2^xiii—Ag2—S2^xvii	85.69 (2)
S1^v—Gd—Ag1^vi	160.90 (19)	S2^xiv—Ag2—S2^xvii	177.6 (3)
S3^i—Gd—Ag1^vi	115.01 (18)	S2^viii—Ag2—S2^xvii	92.7 (2)
S2^iv—Gd—Ag1^vi	58.2 (4)	Ag1^xvi—Ag2—S2^xviii	56.64 (16)
S2^i—Gd—Ag2^v	50.52 (6)	Ag1^xii—Ag2—S2^xviii	123.36 (16)
S3^ii—Gd—Ag2^v	152.98 (8)	S2^xv—Ag2—S2^xviii	85.69 (2)
S2^iii—Gd—Ag2^v	50.30 (6)	S2^xiii—Ag2—S2^xviii	177.6 (3)
S2—Gd—Ag2^v	51.72 (15)	S2^xiv—Ag2—S2^xviii	85.69 (2)
S3^iv—Gd—Ag2^v	121.83 (7)	S2^viii—Ag2—S2^xviii	92.7 (2)
S1^v—Gd—Ag2^v	131.70 (15)	S2^xvii—Ag2—S2^xviii	92.7 (2)
S3^i—Gd—Ag2^v	96.85 (9)	Ag1^xvi—Ag2—Ag2^ix	180.00 (2)
S2^iv—Gd—Ag2^v	95.74 (15)	Ag1^xii—Ag2—Ag2^ix	0.000 (3)
Ag1^vi—Gd—Ag2^v	37.5 (3)	S2^xv—Ag2—Ag2^ix	59.04 (17)
S2^i—Gd—Ag2^vii	49.52 (5)	S2^xiii—Ag2—Ag2^ix	59.04 (17)
S3^ii—Gd—Ag2^vii	114.12 (13)	S2^xiv—Ag2—Ag2^ix	59.04 (17)
S2^iii—Gd—Ag2^vii	49.37 (5)	S2^viii—Ag2—Ag2^ix	123.36 (17)
S2—Gd—Ag2^vii	100.99 (14)	S2^xvii—Ag2—Ag2^ix	123.36 (17)
S3^iv—Gd—Ag2^vii	94.53 (9)	S2^xviii—Ag2—Ag2^ix	123.36 (16)
S1^v—Gd—Ag2^vii	162.42 (3)	Ag1^xvi—Ag2—Ag2^xii	0.000 (12)
S3^i—Gd—Ag2^vii	119.08 (5)	Ag1^xii—Ag2—Ag2^xii	180.000 (5)
S2^iv—Gd—Ag2^vii	46.48 (14)	S2^xv—Ag2—Ag2^xii	120.96 (18)
Ag1^vi—Gd—Ag2^vii	11.7 (3)	S2^xiii—Ag2—Ag2^xii	120.96 (17)
Ag2^v—Gd—Ag2^vii	49.26 (2)	S2^xiv—Ag2—Ag2^xii	120.96 (17)
S2^i—Gd—Ag1^viii	55.56 (18)	S2^viii—Ag2—Ag2^xii	56.64 (17)
S3^ii—Gd—Ag1^viii	156.62 (6)	S2^xvii—Ag2—Ag2^xii	56.64 (17)
S2^iii—Gd—Ag1^viii	55.37 (18)	S2^xviii—Ag2—Ag2^xii	56.64 (17)
S2—Gd—Ag1^viii	40.8 (3)	Ag2^ix—Ag2—Ag2^xii	180.000 (3)
S3^iv—Gd—Ag1^viii	125.75 (11)	Ag1^xvi—Ag2—Gd^xviii	111.13 (16)
S1^v—Gd—Ag1^viii	121.5 (3)	Ag1^xii—Ag2—Gd^xviii	68.87 (15)
S3^i—Gd—Ag1^viii	90.9 (2)	S2^xv—Ag2—Gd^xviii	53.72 (8)
S2^iv—Gd—Ag1^viii	106.7 (3)	S2^xiii—Ag2—Gd^xviii	127.9 (3)
Ag1^vi—Gd—Ag1^viii	48.49 (10)	S2^xiv—Ag2—Gd^xviii	54.62 (8)
Ag2^v—Gd—Ag1^viii	10.9 (2)	S2^viii—Ag2—Gd^xviii	126.43 (6)
Ag2^vii—Gd—Ag1^viii	60.2 (3)	S2^xvii—Ag2—Gd^xviii	125.56 (6)
Ag2^iv—Ag1—Ag2^ix	180.000 (1)	S2^xviii—Ag2—Gd^xviii	54.49 (3)
Ag2^iv—Ag1—S2^v	108.3 (6)	Ag2^ix—Ag2—Gd^xviii	68.87 (15)
Ag2^ix—Ag1—S2^v	71.7 (6)	Ag2^xii—Ag2—Gd^xviii	111.13 (15)
Ag2^iv—Ag1—S2^x	108.3 (6)	Ag1^xvi—Ag2—Gd^xvii	111.13 (15)
Ag2^ix—Ag1—S2^x	71.7 (6)	Ag1^xii—Ag2—Gd^xvii	68.87 (15)
S2^v—Ag1—S2^x	110.6 (6)	S2^xv—Ag2—Gd^xvii	54.62 (8)
Ag2^iv—Ag1—S2^xi	108.3 (6)	S2^xiii—Ag2—Gd^xvii	53.72 (8)
Ag2^ix—Ag1—S2^xi	71.7 (6)	S2^xiv—Ag2—Gd^xvii	127.9 (3)
S2^v—Ag1—S2^xi	110.6 (6)	S2^viii—Ag2—Gd^xvii	125.56 (6)
S2^x—Ag1—S2^xi	110.6 (6)	S2^xvii—Ag2—Gd^xvii	54.49 (3)
Ag2^iv—Ag1—Ag1^ix	0.000 (1)	S2^xviii—Ag2—Gd^xvii	126.43 (6)
Ag2^ix—Ag1—Ag1^ix	180.000 (1)	Ag2^ix—Ag2—Gd^xvii	68.87 (15)
S2^v—Ag1—Ag1^ix	108.3 (6)	Ag2^xii—Ag2—Gd^xvii	111.13 (15)
S2^x—Ag1—Ag1^ix	108.3 (6)	Gd^xviii—Ag2—Gd^xvii	107.77 (16)
S2^xi—Ag1—Ag1^ix	108.3 (6)	S1^iv—Ge1—S3^iii	114.14 (3)
Ag2^iv—Ag1—Ag1^xii	180.000 (2)	S1^iv—Ge1—S3^xix	114.14 (3)
Ag2^ix—Ag1—Ag1^xii	0.000 (1)	S3^iii—Ge1—S3^xix	104.42 (4)
S2^v—Ag1—Ag1^xii	71.7 (6)	S1^iv—Ge1—S3^v	114.14 (3)
S2^x—Ag1—Ag1^xii	71.7 (6)	S3^iii—Ge1—S3^v	104.42 (4)
S2^xi—Ag1—Ag1^xii	71.7 (6)	S3^xix—Ge1—S3^v	104.42 (4)
Ag1^ix—Ag1—Ag1^xii	180.000 (2)	Ge1^xvi—S1—Gd^xx	113.54 (3)
Ag2^iv—Ag1—Gd^xiii	106.4 (4)	Ge1^xvi—S1—Gd^viii	113.54 (3)
Ag2^ix—Ag1—Gd^xiii	73.6 (4)	Gd^xx—S1—Gd^viii	105.12 (4)
S2^v—Ag1—Gd^xiii	56.55 (17)	Ge1^xvi—S1—Gd^xxi	113.54 (3)
S2^x—Ag1—Gd^xiii	145.3 (10)	Gd^xx—S1—Gd^xxi	105.12 (4)
S2^xi—Ag1—Gd^xiii	57.53 (17)	Gd^viii—S1—Gd^xxi	105.12 (4)
Ag1^ix—Ag1—Gd^xiii	106.4 (4)	Ag1^viii—S2—Ag2^vi	49.2 (5)
Ag1^xii—Ag1—Gd^xiii	73.6 (4)	Ag2^vi—S2—Ag2^v	64.33 (3)
Ag2^iv—Ag1—Gd^xiv	106.4 (4)	Ag1^viii—S2—Gd^xxi	77.28 (9)
Ag2^ix—Ag1—Gd^xiv	73.6 (4)	Ag2^vi—S2—Gd^xxi	75.76 (3)
S2^v—Ag1—Gd^xiv	57.53 (17)	Ag2^v—S2—Gd^xxi	79.78 (5)
S2^x—Ag1—Gd^xiv	56.55 (17)	Ag1^viii—S2—Gd^xxii	76.49 (10)
S2^xi—Ag1—Gd^xiv	145.3 (10)	Ag2^vi—S2—Gd^xxii	75.08 (4)
Ag1^ix—Ag1—Gd^xiv	106.4 (4)	Ag2^v—S2—Gd^xxii	79.08 (5)
Ag1^xii—Ag1—Gd^xiv	73.6 (4)	Gd^xxi—S2—Gd^xxii	149.27 (5)
Gd^xiii—Ag1—Gd^xiv	112.3 (4)	Ag1^viii—S2—Gd	88.9 (6)
Ag2^iv—Ag1—Gd^xv	106.4 (4)	Ag2^vi—S2—Gd	138.11 (18)
Ag2^ix—Ag1—Gd^xv	73.6 (4)	Ag2^v—S2—Gd	73.78 (17)
S2^v—Ag1—Gd^xv	145.3 (10)	Gd^xxi—S2—Gd	98.07 (4)
S2^x—Ag1—Gd^xv	57.53 (17)	Gd^xxii—S2—Gd	97.14 (4)
S2^xi—Ag1—Gd^xv	56.55 (17)	Ag1^viii—S2—Gd^xvi	123.7 (6)
Ag1^ix—Ag1—Gd^xv	106.4 (4)	Ag2^vi—S2—Gd^xvi	74.42 (18)
Ag1^xii—Ag1—Gd^xv	73.6 (4)	Ag2^v—S2—Gd^xvi	138.74 (17)
Gd^xiii—Ag1—Gd^xv	112.3 (4)	Gd^xxi—S2—Gd^xvi	91.05 (3)
Gd^xiv—Ag1—Gd^xv	112.3 (4)	Gd^xxii—S2—Gd^xvi	90.31 (3)
Ag2^iv—Ag1—Gd^x	57.9 (3)	Gd—S2—Gd^xvi	147.45 (5)
Ag2^ix—Ag1—Gd^x	122.1 (3)	Ge1^viii—S3—Gd^xxiii	91.08 (4)
S2^v—Ag1—Gd^x	125.1 (3)	Ge1^viii—S3—Gd^xvi	88.69 (4)
S2^x—Ag1—Gd^x	50.4 (2)	Gd^xxiii—S3—Gd^xvi	109.62 (4)
S2^xi—Ag1—Gd^x	124.2 (3)	Ge1^viii—S3—Gd^xxi	119.54 (5)
Ag1^ix—Ag1—Gd^x	57.9 (3)	Gd^xxiii—S3—Gd^xxi	143.30 (4)
Ag1^xii—Ag1—Gd^x	122.1 (3)	Gd^xvi—S3—Gd^xxi	92.02 (3)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) −x+y+1, −x+1, z−1; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) x+1, y+1, z−1; (viii) −x+1, −y+1, z+1/2; (ix) −x, −y, z−1/2; (x) y−1, −x+y, z−1/2; (xi) x−y, x−1, z−1/2; (xii) −x, −y, z+1/2; (xiii) −y+1, x−y, z; (xiv) −x+y, −x+1, z; (xv) x−1, y−1, z; (xvi) x, y, z+1; (xvii) x−y, x−1, z+1/2; (xviii) y−1, −x+y, z+1/2; (xix) x−y, x, z−1/2; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) −y+1, x−y, z+1.

(tb)

Crystal data

Ag0.59GeS7Tb3	Dx = 5.679 Mg m^−3
Mr = 836.87	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 597 reflections
Hall symbol: P 6c	θ = 4.1–25.6°
a = 9.9003 (14) Å	µ = 27.01 mm^−1
c = 5.7654 (12) Å	T = 295 K
V = 489.39 (14) Å^3	Prism, dark red
Z = 2	0.12 × 0.11 × 0.08 mm
F(000) = 733

Data collection

KUMA KM-4 with area CCD detector diffractometer	602 independent reflections
Radiation source: fine-focus sealed tube	597 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 25.6°, θmin = 4.1°
ω–scan	h = −10→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.044, Tmax = 0.187	l = −7→6
4229 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 1.1981P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.017	(Δ/σ)max = 0.001
wR(F^2) = 0.038	Δρmax = 0.84 e Å^−3
S = 1.17	Δρmin = −1.39 e Å^−3
602 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
39 parameters	Extinction coefficient: 0.0055 (3)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 265 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Tb	0.86677 (3)	0.64133 (3)	0.25005 (13)	0.01415 (13)
Ag2	0.0000	0.0000	0.0324 (9)	0.0939 (17)	0.586 (6)
Ge1	0.3333	0.6667	0.33058 (18)	0.0103 (3)
S1	0.3333	0.6667	0.9534 (5)	0.0108 (6)
S2	0.90025 (18)	0.7379 (2)	0.7165 (3)	0.0192 (4)
S3	0.57908 (19)	0.47987 (18)	0.9894 (3)	0.0120 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb	0.01170 (17)	0.01089 (16)	0.0201 (2)	0.00580 (11)	−0.00178 (17)	−0.00055 (17)
Ag2	0.0111 (8)	0.0111 (8)	0.260 (5)	0.0055 (4)	0.000	0.000
Ge1	0.0112 (4)	0.0112 (4)	0.0084 (6)	0.00560 (18)	0.000	0.000
S1	0.0140 (9)	0.0140 (9)	0.0045 (15)	0.0070 (4)	0.000	0.000
S2	0.0128 (7)	0.0251 (8)	0.0216 (10)	0.0109 (6)	−0.0018 (7)	−0.0106 (8)
S3	0.0154 (8)	0.0123 (8)	0.0113 (7)	0.0091 (7)	−0.0004 (7)	−0.0013 (6)

Geometric parameters (Å, º)

Tb—S2^i	2.7693 (15)	Ag2—Tb^xvii	3.353 (2)
Tb—S3^ii	2.8051 (17)	Ag2—Tb^viii	3.509 (3)
Tb—S2^iii	2.8147 (16)	Ge1—S1^iv	2.175 (3)
Tb—S2	2.818 (2)	Ge1—S3^iii	2.2256 (17)
Tb—S3^iv	2.8937 (17)	Ge1—S3^xviii	2.2256 (17)
Tb—S1^v	2.9251 (12)	Ge1—S3^v	2.2256 (17)
Tb—S3^i	2.9996 (17)	S1—Ge1^xix	2.175 (3)
Tb—S2^iv	3.189 (2)	S1—Tb^xx	2.9251 (12)
Tb—Ag2^vi	3.353 (2)	S1—Tb^vii	2.9251 (12)
Tb—Ag2^vii	3.509 (3)	S1—Tb^xxi	2.9251 (12)
Ag2—S2^v	2.504 (3)	S2—Ag2^vii	2.504 (3)
Ag2—S2^viii	2.504 (3)	S2—Tb^xxi	2.7693 (15)
Ag2—S2^ix	2.504 (3)	S2—Tb^xxii	2.8147 (16)
Ag2—Ag2^x	2.8827 (6)	S2—Ag2^xxiii	2.909 (4)
Ag2—Ag2^xi	2.8827 (6)	S2—Tb^xix	3.189 (2)
Ag2—S2^xii	2.909 (4)	S3—Ge1^vii	2.2256 (17)
Ag2—S2^xiii	2.909 (4)	S3—Tb^xxiv	2.8051 (17)
Ag2—S2^xiv	2.909 (4)	S3—Tb^xix	2.8937 (17)
Ag2—Tb^xv	3.353 (2)	S3—Tb^xxi	2.9996 (17)
Ag2—Tb^xvi	3.353 (2)
S2^i—Tb—S3^ii	101.56 (5)	S2^xiii—Ag2—S2^xiv	84.96 (13)
S2^i—Tb—S2^iii	89.41 (7)	S2^v—Ag2—Tb^xv	54.11 (5)
S3^ii—Tb—S2^iii	140.59 (6)	S2^viii—Ag2—Tb^xv	132.9 (2)
S2^i—Tb—S2	82.06 (5)	S2^ix—Ag2—Tb^xv	55.18 (6)
S3^ii—Tb—S2	137.38 (5)	Ag2^x—Ag2—Tb^xv	68.02 (8)
S2^iii—Tb—S2	81.26 (5)	Ag2^xi—Ag2—Tb^xv	111.98 (8)
S2^i—Tb—S3^iv	140.15 (6)	S2^xii—Ag2—Tb^xv	127.04 (5)
S3^ii—Tb—S3^iv	76.11 (7)	S2^xiii—Ag2—Tb^xv	126.11 (5)
S2^iii—Tb—S3^iv	71.65 (4)	S2^xiv—Ag2—Tb^xv	60.74 (4)
S2—Tb—S3^iv	126.83 (5)	S2^v—Ag2—Tb^xvi	132.9 (2)
S2^i—Tb—S1^v	147.60 (5)	S2^viii—Ag2—Tb^xvi	55.18 (6)
S3^ii—Tb—S1^v	71.70 (5)	S2^ix—Ag2—Tb^xvi	54.11 (5)
S2^iii—Tb—S1^v	116.29 (4)	Ag2^x—Ag2—Tb^xvi	68.02 (8)
S2—Tb—S1^v	82.81 (6)	Ag2^xi—Ag2—Tb^xvi	111.98 (8)
S3^iv—Tb—S1^v	70.47 (5)	S2^xii—Ag2—Tb^xvi	60.74 (4)
S2^i—Tb—S3^i	70.02 (5)	S2^xiii—Ag2—Tb^xvi	127.04 (5)
S3^ii—Tb—S3^i	71.56 (3)	S2^xiv—Ag2—Tb^xvi	126.11 (5)
S2^iii—Tb—S3^i	146.36 (5)	Tb^xv—Ag2—Tb^xvi	106.85 (9)
S2—Tb—S3^i	70.04 (5)	S2^v—Ag2—Tb^xvii	55.18 (6)
S3^iv—Tb—S3^i	140.33 (4)	S2^viii—Ag2—Tb^xvii	54.11 (5)
S1^v—Tb—S3^i	77.92 (4)	S2^ix—Ag2—Tb^xvii	132.9 (2)
S2^i—Tb—S2^iv	75.63 (5)	Ag2^x—Ag2—Tb^xvii	68.02 (8)
S3^ii—Tb—S2^iv	71.44 (5)	Ag2^xi—Ag2—Tb^xvii	111.98 (8)
S2^iii—Tb—S2^iv	75.03 (5)	S2^xii—Ag2—Tb^xvii	126.11 (5)
S2—Tb—S2^iv	147.33 (6)	S2^xiii—Ag2—Tb^xvii	60.74 (4)
S3^iv—Tb—S2^iv	65.84 (5)	S2^xiv—Ag2—Tb^xvii	127.04 (5)
S1^v—Tb—S2^iv	127.87 (6)	Tb^xv—Ag2—Tb^xvii	106.85 (9)
S3^i—Tb—S2^iv	122.00 (4)	Tb^xvi—Ag2—Tb^xvii	106.85 (9)
S2^i—Tb—Ag2^vi	47.11 (4)	S2^v—Ag2—Tb^viii	127.23 (4)
S3^ii—Tb—Ag2^vi	119.12 (9)	S2^viii—Ag2—Tb^viii	52.73 (6)
S2^iii—Tb—Ag2^vi	46.92 (4)	S2^ix—Ag2—Tb^viii	126.20 (4)
S2—Tb—Ag2^vi	94.62 (9)	Ag2^x—Ag2—Tb^viii	117.63 (8)
S3^iv—Tb—Ag2^vi	98.51 (7)	Ag2^xi—Ag2—Tb^viii	62.37 (8)
S1^v—Tb—Ag2^vi	163.109 (17)	S2^xii—Ag2—Tb^viii	50.06 (5)
S3^i—Tb—Ag2^vi	116.99 (4)	S2^xiii—Ag2—Tb^viii	50.98 (5)
S2^iv—Tb—Ag2^vi	52.73 (9)	S2^xiv—Ag2—Tb^viii	113.61 (16)
S2^i—Tb—Ag2^vii	53.64 (5)	Tb^xv—Ag2—Tb^viii	174.35 (16)
S3^ii—Tb—Ag2^vii	154.83 (4)	Tb^xvi—Ag2—Tb^viii	76.283 (11)
S2^iii—Tb—Ag2^vii	53.40 (5)	Tb^xvii—Ag2—Tb^viii	76.283 (11)
S2—Tb—Ag2^vii	45.01 (8)	S1^iv—Ge1—S3^iii	114.29 (5)
S3^iv—Tb—Ag2^vii	124.61 (4)	S1^iv—Ge1—S3^xviii	114.29 (5)
S1^v—Tb—Ag2^vii	125.80 (9)	S3^iii—Ge1—S3^xviii	104.25 (6)
S3^i—Tb—Ag2^vii	93.19 (6)	S1^iv—Ge1—S3^v	114.29 (5)
S2^iv—Tb—Ag2^vii	102.34 (9)	S3^iii—Ge1—S3^v	104.25 (6)
Ag2^vi—Tb—Ag2^vii	49.618 (13)	S3^xviii—Ge1—S3^v	104.25 (6)
S2^v—Ag2—S2^viii	103.32 (14)	Ge1^xix—S1—Tb^xx	113.62 (5)
S2^v—Ag2—S2^ix	103.32 (14)	Ge1^xix—S1—Tb^vii	113.62 (5)
S2^viii—Ag2—S2^ix	103.32 (14)	Tb^xx—S1—Tb^vii	105.02 (6)
S2^v—Ag2—Ag2^x	64.91 (12)	Ge1^xix—S1—Tb^xxi	113.62 (5)
S2^viii—Ag2—Ag2^x	64.91 (12)	Tb^xx—S1—Tb^xxi	105.02 (6)
S2^ix—Ag2—Ag2^x	64.91 (12)	Tb^vii—S1—Tb^xxi	105.02 (6)
S2^v—Ag2—Ag2^xi	115.09 (12)	Ag2^vii—S2—Tb^xxi	78.77 (5)
S2^viii—Ag2—Ag2^xi	115.09 (12)	Ag2^vii—S2—Tb^xxii	77.91 (5)
S2^ix—Ag2—Ag2^xi	115.09 (12)	Tb^xxi—S2—Tb^xxii	149.29 (7)
Ag2^x—Ag2—Ag2^xi	180.0	Ag2^vii—S2—Tb	82.27 (12)
S2^v—Ag2—S2^xii	166.3 (2)	Tb^xxi—S2—Tb	98.72 (6)
S2^viii—Ag2—S2^xii	84.97 (4)	Tb^xxii—S2—Tb	97.65 (5)
S2^ix—Ag2—S2^xii	84.97 (4)	Ag2^vii—S2—Ag2^xxiii	63.85 (5)
Ag2^x—Ag2—S2^xii	128.76 (9)	Tb^xxi—S2—Ag2^xxiii	76.30 (4)
Ag2^xi—Ag2—S2^xii	51.24 (9)	Tb^xxii—S2—Ag2^xxiii	75.61 (4)
S2^v—Ag2—S2^xiii	84.97 (4)	Tb—S2—Ag2^xxiii	146.11 (10)
S2^viii—Ag2—S2^xiii	84.97 (4)	Ag2^vii—S2—Tb^xix	130.37 (13)
S2^ix—Ag2—S2^xiii	166.3 (2)	Tb^xxi—S2—Tb^xix	90.44 (5)
Ag2^x—Ag2—S2^xiii	128.76 (9)	Tb^xxii—S2—Tb^xix	89.63 (5)
Ag2^xi—Ag2—S2^xiii	51.24 (9)	Tb—S2—Tb^xix	147.33 (6)
S2^xii—Ag2—S2^xiii	84.96 (13)	Ag2^xxiii—S2—Tb^xix	66.53 (9)
S2^v—Ag2—S2^xiv	84.97 (4)	Ge1^vii—S3—Tb^xxiv	90.96 (5)
S2^viii—Ag2—S2^xiv	166.3 (2)	Ge1^vii—S3—Tb^xix	88.68 (5)
S2^ix—Ag2—S2^xiv	84.97 (4)	Tb^xxiv—S3—Tb^xix	109.07 (6)
Ag2^x—Ag2—S2^xiv	128.76 (9)	Ge1^vii—S3—Tb^xxi	119.16 (7)
Ag2^xi—Ag2—S2^xiv	51.24 (9)	Tb^xxiv—S3—Tb^xxi	144.01 (6)
S2^xii—Ag2—S2^xiv	84.96 (13)	Tb^xix—S3—Tb^xxi	91.99 (5)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) −x+y+1, −x+1, z−1; (iii) y, −x+y+1, z−1/2; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) −x+1, −y+1, z+1/2; (viii) y−1, −x+y, z−1/2; (ix) x−y, x−1, z−1/2; (x) −x, −y, z+1/2; (xi) −x, −y, z−1/2; (xii) x−1, y−1, z−1; (xiii) −x+y, −x+1, z−1; (xiv) −y+1, x−y, z−1; (xv) −y+1, x−y, z; (xvi) x−1, y−1, z; (xvii) −x+y, −x+1, z; (xviii) x−y, x, z−1/2; (xix) x, y, z+1; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) x+1, y+1, z+1; (xxiv) −y+1, x−y, z+1.

(dy)

Crystal data

Ag0.51Dy3GeS7	Dx = 5.795 Mg m^−3
Mr = 840.06	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 644 reflections
Hall symbol: P 6c	θ = 4.3–26.4°
a = 9.8003 (14) Å	µ = 28.56 mm^−1
c = 5.7879 (12) Å	T = 295 K
V = 481.43 (14) Å^3	Prism, dark red
Z = 2	0.12 × 0.10 × 0.09 mm
F(000) = 732

Data collection

KUMA KM-4 with area CCD detector diffractometer	655 independent reflections
Radiation source: fine-focus sealed tube	644 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.4°, θmin = 4.3°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→10
Tmin = 0.035, Tmax = 0.244	l = −7→7
5667 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0114P)^2 + 0.9002P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max = 0.001
wR(F^2) = 0.032	Δρmax = 0.99 e Å^−3
S = 1.12	Δρmin = −1.03 e Å^−3
655 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
39 parameters	Extinction coefficient: 0.0034 (2)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 293 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.005 (19)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Dy	0.86393 (3)	0.64111 (3)	0.24397 (11)	0.01554 (10)
Ag2	0.0000	0.0000	0.0017 (9)	0.0735 (13)	0.517 (5)
Ge1	0.3333	0.6667	0.32315 (16)	0.0100 (2)
S1	0.3333	0.6667	0.9457 (4)	0.0110 (5)
S2	0.89852 (18)	0.7401 (2)	0.7034 (2)	0.0197 (4)
S3	0.57703 (18)	0.47943 (18)	0.9824 (2)	0.0123 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Dy	0.01188 (14)	0.01160 (14)	0.02330 (15)	0.00598 (10)	−0.00218 (19)	−0.00039 (17)
Ag2	0.0108 (7)	0.0108 (7)	0.199 (3)	0.0054 (4)	0.000	0.000
Ge1	0.0113 (3)	0.0113 (3)	0.0076 (4)	0.00564 (17)	0.000	0.000
S1	0.0137 (8)	0.0137 (8)	0.0057 (11)	0.0069 (4)	0.000	0.000
S2	0.0119 (7)	0.0251 (8)	0.0232 (10)	0.0100 (6)	−0.0014 (6)	−0.0127 (7)
S3	0.0165 (8)	0.0122 (7)	0.0114 (6)	0.0096 (7)	−0.0002 (7)	−0.0008 (6)

Geometric parameters (Å, º)

Dy—S2^i	2.7330 (15)	Ag2—Dy^xvii	3.380 (2)
Dy—S2^ii	2.7879 (15)	Ag2—Dy^viii	3.418 (2)
Dy—S2	2.7922 (16)	Ge1—S1^iv	2.185 (2)
Dy—S3^iii	2.7946 (16)	Ge1—S3^ii	2.2202 (16)
Dy—S3^iv	2.8727 (16)	Ge1—S3^xviii	2.2202 (16)
Dy—S1^v	2.8926 (11)	Ge1—S3^v	2.2202 (16)
Dy—S3^i	2.9970 (16)	S1—Ge1^xix	2.185 (2)
Dy—S2^iv	3.2430 (17)	S1—Dy^xx	2.8926 (11)
Dy—Ag2^vi	3.380 (2)	S1—Dy^vii	2.8926 (11)
Dy—Ag2^vii	3.418 (2)	S1—Dy^xxi	2.8926 (11)
Ag2—S2^v	2.511 (3)	S2—Ag2^vii	2.511 (3)
Ag2—S2^viii	2.511 (3)	S2—Dy^xxi	2.7330 (15)
Ag2—S2^ix	2.511 (3)	S2—Dy^xxii	2.7879 (15)
Ag2—S2^x	2.816 (4)	S2—Ag2^xxiii	2.816 (4)
Ag2—S2^xi	2.816 (4)	S2—Dy^xix	3.2430 (17)
Ag2—S2^xii	2.816 (4)	S3—Ge1^vii	2.2202 (16)
Ag2—Ag2^xiii	2.8939 (6)	S3—Dy^xxiv	2.7946 (16)
Ag2—Ag2^xiv	2.8939 (6)	S3—Dy^xix	2.8727 (16)
Ag2—Dy^xv	3.380 (2)	S3—Dy^xxi	2.9970 (16)
Ag2—Dy^xvi	3.380 (2)
S2^i—Dy—S2^ii	88.48 (7)	Ag2^xiii—Ag2—Ag2^xiv	180.0
S2^i—Dy—S2	82.68 (5)	S2^v—Ag2—Dy^xv	52.81 (6)
S2^ii—Dy—S2	81.70 (4)	S2^viii—Ag2—Dy^xv	127.80 (19)
S2^i—Dy—S3^iii	100.10 (5)	S2^ix—Ag2—Dy^xv	54.08 (6)
S2^ii—Dy—S3^iii	140.01 (5)	S2^x—Ag2—Dy^xv	128.44 (5)
S2—Dy—S3^iii	137.91 (5)	S2^xi—Ag2—Dy^xv	127.28 (5)
S2^i—Dy—S3^iv	138.99 (5)	S2^xii—Ag2—Dy^xv	62.34 (4)
S2^ii—Dy—S3^iv	72.14 (4)	Ag2^xiii—Ag2—Dy^xv	114.51 (8)
S2—Dy—S3^iv	127.50 (4)	Ag2^xiv—Ag2—Dy^xv	65.49 (8)
S3^iii—Dy—S3^iv	76.22 (6)	S2^v—Ag2—Dy^xvi	127.80 (19)
S2^i—Dy—S1^v	147.56 (4)	S2^viii—Ag2—Dy^xvi	54.08 (6)
S2^ii—Dy—S1^v	117.99 (4)	S2^ix—Ag2—Dy^xvi	52.81 (6)
S2—Dy—S1^v	83.09 (6)	S2^x—Ag2—Dy^xvi	62.34 (4)
S3^iii—Dy—S1^v	72.32 (4)	S2^xi—Ag2—Dy^xvi	128.44 (5)
S3^iv—Dy—S1^v	71.21 (4)	S2^xii—Ag2—Dy^xvi	127.28 (5)
S2^i—Dy—S3^i	70.61 (5)	Ag2^xiii—Ag2—Dy^xvi	114.51 (8)
S2^ii—Dy—S3^i	146.52 (5)	Ag2^xiv—Ag2—Dy^xvi	65.49 (8)
S2—Dy—S3^i	70.21 (4)	Dy^xv—Ag2—Dy^xvi	104.00 (10)
S3^iii—Dy—S3^i	71.32 (3)	S2^v—Ag2—Dy^xvii	54.08 (6)
S3^iv—Dy—S3^i	140.07 (4)	S2^viii—Ag2—Dy^xvii	52.81 (6)
S1^v—Dy—S3^i	77.17 (3)	S2^ix—Ag2—Dy^xvii	127.80 (19)
S2^i—Dy—S2^iv	74.74 (4)	S2^x—Ag2—Dy^xvii	127.28 (5)
S2^ii—Dy—S2^iv	74.05 (4)	S2^xi—Ag2—Dy^xvii	62.34 (4)
S2—Dy—S2^iv	146.99 (6)	S2^xii—Ag2—Dy^xvii	128.44 (5)
S3^iii—Dy—S2^iv	70.87 (4)	Ag2^xiii—Ag2—Dy^xvii	114.51 (8)
S3^iv—Dy—S2^iv	65.40 (4)	Ag2^xiv—Ag2—Dy^xvii	65.49 (8)
S1^v—Dy—S2^iv	128.07 (5)	Dy^xv—Ag2—Dy^xvii	104.00 (10)
S3^i—Dy—S2^iv	122.04 (4)	Dy^xvi—Ag2—Dy^xvii	104.00 (10)
S2^i—Dy—Ag2^vi	47.06 (4)	S2^v—Ag2—Dy^viii	127.59 (3)
S2^ii—Dy—Ag2^vi	46.85 (4)	S2^viii—Ag2—Dy^viii	53.57 (4)
S2—Dy—Ag2^vi	96.74 (9)	S2^ix—Ag2—Dy^viii	126.32 (3)
S3^iii—Dy—Ag2^vi	115.94 (9)	S2^x—Ag2—Dy^viii	50.89 (6)
S3^iv—Dy—Ag2^vi	97.09 (6)	S2^xi—Ag2—Dy^viii	52.04 (6)
S1^v—Dy—Ag2^vi	164.310 (10)	S2^xii—Ag2—Dy^viii	116.29 (17)
S3^i—Dy—Ag2^vi	117.64 (4)	Ag2^xiii—Ag2—Dy^viii	64.12 (8)
S2^iv—Dy—Ag2^vi	50.26 (9)	Ag2^xiv—Ag2—Dy^viii	115.88 (8)
S2^i—Dy—Ag2^vii	53.07 (5)	Dy^xv—Ag2—Dy^viii	178.63 (17)
S2^ii—Dy—Ag2^vii	52.78 (5)	Dy^xvi—Ag2—Dy^viii	76.803 (7)
S2—Dy—Ag2^vii	46.36 (9)	Dy^xvii—Ag2—Dy^viii	76.803 (7)
S3^iii—Dy—Ag2^vii	153.01 (5)	S1^iv—Ge1—S3^ii	114.54 (4)
S3^iv—Dy—Ag2^vii	124.63 (4)	S1^iv—Ge1—S3^xviii	114.54 (4)
S1^v—Dy—Ag2^vii	127.61 (9)	S3^ii—Ge1—S3^xviii	103.96 (5)
S3^i—Dy—Ag2^vii	93.94 (6)	S1^iv—Ge1—S3^v	114.54 (4)
S2^iv—Dy—Ag2^vii	100.65 (9)	S3^ii—Ge1—S3^v	103.96 (5)
Ag2^vi—Dy—Ag2^vii	50.384 (12)	S3^xviii—Ge1—S3^v	103.96 (5)
S2^v—Ag2—S2^viii	100.14 (14)	Ge1^xix—S1—Dy^xx	113.80 (4)
S2^v—Ag2—S2^ix	100.14 (14)	Ge1^xix—S1—Dy^vii	113.80 (4)
S2^viii—Ag2—S2^ix	100.14 (14)	Dy^xx—S1—Dy^vii	104.82 (5)
S2^v—Ag2—S2^x	169.9 (2)	Ge1^xix—S1—Dy^xxi	113.80 (4)
S2^viii—Ag2—S2^x	86.29 (4)	Dy^xx—S1—Dy^xxi	104.82 (5)
S2^ix—Ag2—S2^x	86.29 (4)	Dy^vii—S1—Dy^xxi	104.82 (5)
S2^v—Ag2—S2^xi	86.29 (4)	Ag2^vii—S2—Dy^xxi	80.13 (5)
S2^viii—Ag2—S2^xi	86.29 (4)	Ag2^vii—S2—Dy^xxii	79.07 (5)
S2^ix—Ag2—S2^xi	169.9 (2)	Dy^xxi—S2—Dy^xxii	149.54 (7)
S2^x—Ag2—S2^xi	86.32 (13)	Ag2^vii—S2—Dy	80.07 (11)
S2^v—Ag2—S2^xii	86.29 (4)	Dy^xxi—S2—Dy	99.69 (5)
S2^viii—Ag2—S2^xii	169.9 (2)	Dy^xxii—S2—Dy	98.37 (5)
S2^ix—Ag2—S2^xii	86.29 (4)	Ag2^vii—S2—Ag2^xxiii	65.52 (5)
S2^x—Ag2—S2^xii	86.32 (13)	Dy^xxi—S2—Ag2^xxiii	76.04 (4)
S2^xi—Ag2—S2^xii	86.32 (13)	Dy^xxii—S2—Ag2^xxiii	75.18 (4)
S2^v—Ag2—Ag2^xiii	117.69 (11)	Dy—S2—Ag2^xxiii	145.58 (10)
S2^viii—Ag2—Ag2^xiii	117.69 (11)	Ag2^vii—S2—Dy^xix	132.91 (12)
S2^ix—Ag2—Ag2^xiii	117.69 (11)	Dy^xxi—S2—Dy^xix	89.51 (4)
S2^x—Ag2—Ag2^xiii	52.17 (9)	Dy^xxii—S2—Dy^xix	88.56 (4)
S2^xi—Ag2—Ag2^xiii	52.17 (9)	Dy—S2—Dy^xix	146.99 (6)
S2^xii—Ag2—Ag2^xiii	52.17 (9)	Ag2^xxiii—S2—Dy^xix	67.39 (9)
S2^v—Ag2—Ag2^xiv	62.31 (11)	Ge1^vii—S3—Dy^xxiv	90.91 (5)
S2^viii—Ag2—Ag2^xiv	62.31 (11)	Ge1^vii—S3—Dy^xix	88.90 (5)
S2^ix—Ag2—Ag2^xiv	62.31 (11)	Dy^xxiv—S3—Dy^xix	107.96 (5)
S2^x—Ag2—Ag2^xiv	127.83 (9)	Ge1^vii—S3—Dy^xxi	118.61 (6)
S2^xi—Ag2—Ag2^xiv	127.83 (9)	Dy^xxiv—S3—Dy^xxi	145.01 (6)
S2^xii—Ag2—Ag2^xiv	127.83 (9)	Dy^xix—S3—Dy^xxi	91.99 (4)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) y, −x+y+1, z−1/2; (iii) −x+y+1, −x+1, z−1; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) −x+1, −y+1, z+1/2; (viii) y−1, −x+y, z−1/2; (ix) x−y, x−1, z−1/2; (x) x−1, y−1, z−1; (xi) −x+y, −x+1, z−1; (xii) −y+1, x−y, z−1; (xiii) −x, −y, z−1/2; (xiv) −x, −y, z+1/2; (xv) −y+1, x−y, z; (xvi) x−1, y−1, z; (xvii) −x+y, −x+1, z; (xviii) x−y, x, z−1/2; (xix) x, y, z+1; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) x+1, y+1, z+1; (xxiv) −y+1, x−y, z+1.

(ho)

Crystal data

Ag0.50GeHo3S7	Dx = 5.895 Mg m^−3
Mr = 845.73	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 630 reflections
Hall symbol: P 6c	θ = 4.3–26.7°
a = 9.7401 (14) Å	µ = 30.22 mm^−1
c = 5.7994 (12) Å	T = 295 K
V = 476.48 (14) Å^3	Prism, dark red
Z = 2	0.09 × 0.07 × 0.03 mm
F(000) = 737

Data collection

KUMA KM-4 with area CCD detector diffractometer	649 independent reflections
Radiation source: fine-focus sealed tube	630 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.7°, θmin = 4.3°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.061, Tmax = 0.304	l = −7→6
5792 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.004P)^2 + 2.2568P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.017	(Δ/σ)max = 0.001
wR(F^2) = 0.033	Δρmax = 0.79 e Å^−3
S = 1.19	Δρmin = −2.26 e Å^−3
649 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
38 parameters	Extinction coefficient: 0.0054 (2)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Ho	0.86127 (3)	0.64077 (3)	0.24376 (13)	0.01686 (11)
Ag2	0.0000	0.0000	0.9801 (12)	0.0699 (11)	0.50
Ge1	0.3333	0.6667	0.32172 (19)	0.0101 (3)
S1	0.3333	0.6667	0.9456 (5)	0.0104 (6)
S2	0.8968 (2)	0.7410 (2)	0.6976 (3)	0.0204 (5)
S3	0.5748 (2)	0.4782 (2)	0.9815 (3)	0.0130 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ho	0.01145 (15)	0.01179 (15)	0.02747 (19)	0.00591 (12)	−0.0023 (2)	0.0000 (2)
Ag2	0.0155 (6)	0.0155 (6)	0.179 (3)	0.0078 (3)	0.000	0.000
Ge1	0.0112 (4)	0.0112 (4)	0.0079 (6)	0.00562 (19)	0.000	0.000
S1	0.0127 (9)	0.0127 (9)	0.0058 (15)	0.0064 (5)	0.000	0.000
S2	0.0112 (8)	0.0234 (9)	0.0278 (15)	0.0095 (7)	−0.0009 (7)	−0.0124 (8)
S3	0.0169 (9)	0.0133 (8)	0.0126 (8)	0.0104 (7)	−0.0006 (8)	−0.0005 (8)

Geometric parameters (Å, º)

Ho—S2^i	2.7141 (17)	Ag2—Ho^viii	3.349 (3)
Ho—S2	2.768 (2)	Ag2—Ho^xv	3.417 (3)
Ho—S2^ii	2.7731 (17)	Ge1—S1^iv	2.181 (3)
Ho—S3^iii	2.7845 (19)	Ge1—S3^ii	2.2169 (18)
Ho—S3^iv	2.8617 (19)	Ge1—S3^xvi	2.2169 (18)
Ho—S1^v	2.8730 (14)	Ge1—S3^v	2.2169 (18)
Ho—S3^i	3.0063 (18)	S1—Ge1^xvii	2.181 (3)
Ho—Ag2^v	3.349 (3)	S1—Ho^xviii	2.8730 (13)
Ho—Ag2^vi	3.417 (3)	S1—Ho^vii	2.8730 (13)
Ag2—S2^vii	2.535 (4)	S1—Ho^xix	2.8730 (13)
Ag2—S2^viii	2.535 (4)	S2—Ag2^v	2.535 (4)
Ag2—S2^ix	2.535 (4)	S2—Ho^xix	2.7141 (17)
Ag2—S2^x	2.743 (5)	S2—Ag2^xx	2.743 (5)
Ag2—S2^xi	2.743 (5)	S2—Ho^xxi	2.7731 (17)
Ag2—S2^xii	2.743 (5)	S3—Ge1^vii	2.2169 (18)
Ag2—Ag2^xiii	2.8997 (6)	S3—Ho^xv	2.7845 (19)
Ag2—Ag2^xiv	2.8997 (6)	S3—Ho^xvii	2.8617 (19)
Ag2—Ho^ix	3.349 (3)	S3—Ho^xix	3.0063 (18)
Ag2—Ho^vii	3.349 (3)
S2^i—Ho—S2	83.19 (6)	S2^viii—Ag2—Ho^ix	126.14 (4)
S2^i—Ho—S2^ii	87.93 (8)	S2^ix—Ag2—Ho^ix	53.99 (5)
S2—Ho—S2^ii	82.11 (5)	S2^x—Ag2—Ho^ix	51.75 (7)
S2^i—Ho—S3^iii	98.76 (6)	S2^xi—Ag2—Ho^ix	53.03 (7)
S2—Ho—S3^iii	138.23 (6)	S2^xii—Ag2—Ho^ix	119.2 (2)
S2^ii—Ho—S3^iii	139.49 (6)	Ag2^xiii—Ag2—Ho^ix	114.15 (12)
S2^i—Ho—S3^iv	138.26 (6)	Ag2^xiv—Ag2—Ho^ix	65.85 (11)
S2—Ho—S3^iv	128.02 (5)	S2^vii—Ag2—Ho^vii	53.99 (5)
S2^ii—Ho—S3^iv	72.58 (5)	S2^viii—Ag2—Ho^vii	127.50 (4)
S3^iii—Ho—S3^iv	76.30 (7)	S2^ix—Ag2—Ho^vii	126.14 (4)
S2^i—Ho—S1^v	147.28 (5)	S2^x—Ag2—Ho^vii	119.2 (2)
S2—Ho—S1^v	83.18 (7)	S2^xi—Ag2—Ho^vii	51.75 (7)
S2^ii—Ho—S1^v	119.33 (4)	S2^xii—Ag2—Ho^vii	53.03 (7)
S3^iii—Ho—S1^v	72.90 (5)	Ag2^xiii—Ag2—Ho^vii	114.15 (11)
S3^iv—Ho—S1^v	71.78 (6)	Ag2^xiv—Ag2—Ho^vii	65.85 (12)
S2^i—Ho—S3^i	70.93 (5)	Ho^ix—Ag2—Ho^vii	104.41 (13)
S2—Ho—S3^i	70.44 (5)	S2^vii—Ag2—Ho^viii	126.14 (4)
S2^ii—Ho—S3^i	146.77 (5)	S2^viii—Ag2—Ho^viii	53.99 (5)
S3^iii—Ho—S3^i	70.95 (3)	S2^ix—Ag2—Ho^viii	127.50 (4)
S3^iv—Ho—S3^i	139.65 (5)	S2^x—Ag2—Ho^viii	53.03 (7)
S1^v—Ho—S3^i	76.49 (4)	S2^xi—Ag2—Ho^viii	119.2 (2)
S2^i—Ho—Ag2^v	52.52 (7)	S2^xii—Ag2—Ho^viii	51.75 (7)
S2—Ho—Ag2^v	47.81 (12)	Ag2^xiii—Ag2—Ho^viii	114.15 (11)
S2^ii—Ho—Ag2^v	52.20 (7)	Ag2^xiv—Ag2—Ho^viii	65.85 (12)
S3^iii—Ho—Ag2^v	151.24 (7)	Ho^ix—Ag2—Ho^viii	104.41 (13)
S3^iv—Ho—Ag2^v	124.60 (6)	Ho^vii—Ag2—Ho^viii	104.41 (13)
S1^v—Ho—Ag2^v	129.30 (13)	S2^vii—Ag2—Ho^xv	51.70 (7)
S3^i—Ho—Ag2^v	94.77 (8)	S2^viii—Ag2—Ho^xv	53.05 (8)
S2^i—Ho—Ag2^vi	47.15 (5)	S2^ix—Ag2—Ho^xv	123.6 (3)
S2—Ho—Ag2^vi	98.54 (12)	S2^x—Ag2—Ho^xv	129.38 (5)
S2^ii—Ho—Ag2^vi	46.94 (5)	S2^xi—Ag2—Ho^xv	128.11 (5)
S3^iii—Ho—Ag2^vi	113.31 (11)	S2^xii—Ag2—Ho^xv	63.27 (5)
S3^iv—Ho—Ag2^vi	96.06 (8)	Ag2^xiii—Ag2—Ho^xv	63.42 (11)
S1^v—Ho—Ag2^vi	165.13 (2)	Ag2^xiv—Ag2—Ho^xv	116.58 (11)
S3^i—Ho—Ag2^vi	118.08 (5)	Ho^ix—Ag2—Ho^xv	177.6 (2)
Ag2^v—Ho—Ag2^vi	50.735 (13)	Ho^vii—Ag2—Ho^xv	77.003 (9)
S2^vii—Ag2—S2^viii	97.40 (19)	Ho^viii—Ag2—Ho^xv	77.003 (9)
S2^vii—Ag2—S2^ix	97.40 (19)	S1^iv—Ge1—S3^ii	114.70 (6)
S2^viii—Ag2—S2^ix	97.40 (19)	S1^iv—Ge1—S3^xvi	114.70 (6)
S2^vii—Ag2—S2^x	173.1 (3)	S3^ii—Ge1—S3^xvi	103.77 (6)
S2^viii—Ag2—S2^x	87.10 (4)	S1^iv—Ge1—S3^v	114.70 (6)
S2^ix—Ag2—S2^x	87.10 (4)	S3^ii—Ge1—S3^v	103.77 (6)
S2^vii—Ag2—S2^xi	87.10 (4)	S3^xvi—Ge1—S3^v	103.77 (6)
S2^viii—Ag2—S2^xi	173.1 (3)	Ge1^xvii—S1—Ho^xviii	114.05 (6)
S2^ix—Ag2—S2^xi	87.10 (4)	Ge1^xvii—S1—Ho^vii	114.05 (6)
S2^x—Ag2—S2^xi	87.98 (18)	Ho^xviii—S1—Ho^vii	104.53 (7)
S2^vii—Ag2—S2^xii	87.10 (4)	Ge1^xvii—S1—Ho^xix	114.05 (6)
S2^viii—Ag2—S2^xii	87.10 (4)	Ho^xviii—S1—Ho^xix	104.53 (7)
S2^ix—Ag2—S2^xii	173.1 (3)	Ho^vii—S1—Ho^xix	104.53 (7)
S2^x—Ag2—S2^xii	87.98 (18)	Ag2^v—S2—Ho^xix	81.16 (6)
S2^xi—Ag2—S2^xii	87.98 (18)	Ag2^v—S2—Ag2^xx	66.52 (5)
S2^vii—Ag2—Ag2^xiii	60.17 (15)	Ho^xix—S2—Ag2^xx	75.73 (5)
S2^viii—Ag2—Ag2^xiii	60.17 (15)	Ag2^v—S2—Ho	78.20 (15)
S2^ix—Ag2—Ag2^xiii	60.17 (15)	Ho^xix—S2—Ho	100.43 (6)
S2^x—Ag2—Ag2^xiii	126.68 (13)	Ag2^xx—S2—Ho	144.70 (14)
S2^xi—Ag2—Ag2^xiii	126.68 (13)	Ag2^v—S2—Ho^xxi	80.01 (6)
S2^xii—Ag2—Ag2^xiii	126.68 (13)	Ho^xix—S2—Ho^xxi	149.46 (8)
S2^vii—Ag2—Ag2^xiv	119.83 (15)	Ag2^xx—S2—Ho^xxi	74.78 (5)
S2^viii—Ag2—Ag2^xiv	119.83 (15)	Ho—S2—Ho^xxi	98.98 (6)
S2^ix—Ag2—Ag2^xiv	119.83 (15)	Ge1^vii—S3—Ho^xv	90.96 (6)
S2^x—Ag2—Ag2^xiv	53.32 (13)	Ge1^vii—S3—Ho^xvii	88.96 (6)
S2^xi—Ag2—Ag2^xiv	53.32 (13)	Ho^xv—S3—Ho^xvii	107.19 (7)
S2^xii—Ag2—Ag2^xiv	53.32 (13)	Ge1^vii—S3—Ho^xix	118.19 (8)
Ag2^xiii—Ag2—Ag2^xiv	180.000 (3)	Ho^xv—S3—Ho^xix	145.83 (7)
S2^vii—Ag2—Ho^ix	127.50 (4)	Ho^xvii—S3—Ho^xix	91.74 (5)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) y, −x+y+1, z−1/2; (iii) −x+y+1, −x+1, z−1; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z−1; (vii) −x+1, −y+1, z+1/2; (viii) x−y, x−1, z+1/2; (ix) y−1, −x+y, z+1/2; (x) x−1, y−1, z; (xi) −x+y, −x+1, z; (xii) −y+1, x−y, z; (xiii) −x, −y, z+1/2; (xiv) −x, −y, z−1/2; (xv) −y+1, x−y, z+1; (xvi) x−y, x, z−1/2; (xvii) x, y, z+1; (xviii) x−y, x, z+1/2; (xix) y, −x+y+1, z+1/2; (xx) x+1, y+1, z; (xxi) x−y+1, x, z+1/2.

(er)

Crystal data

Ag0.50Er3GeS7	Dx = 5.970 Mg m^−3
Mr = 852.72	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 628 reflections
Hall symbol: P 6c	θ = 4.2–26.4°
a = 9.6921 (14) Å	µ = 31.87 mm^−1
c = 5.8308 (12) Å	T = 295 K
V = 474.35 (14) Å^3	Prism, dark red
Z = 2	0.13 × 0.10 × 0.08 mm
F(000) = 743

Data collection

KUMA KM-4 with area CCD detector diffractometer	633 independent reflections
Radiation source: fine-focus sealed tube	628 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.4°, θmin = 4.2°
ω–scan	h = −12→12
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→11
Tmin = 0.038, Tmax = 0.131	l = −7→7
4994 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0131P)^2 + 7.731P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.022	(Δ/σ)max = 0.001
wR(F^2) = 0.053	Δρmax = 0.86 e Å^−3
S = 1.15	Δρmin = −2.84 e Å^−3
633 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
38 parameters	Extinction coefficient: 0.0081 (5)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 280 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Er	0.85842 (5)	0.64061 (5)	0.24518 (19)	0.02066 (18)
Ag2	0.0000	0.0000	0.9635 (19)	0.076 (2)	0.50
Ge1	0.3333	0.6667	0.3216 (3)	0.0119 (4)
S1	0.3333	0.6667	0.9460 (7)	0.0134 (9)
S2	0.8949 (3)	0.7418 (3)	0.6936 (5)	0.0238 (7)
S3	0.5725 (3)	0.4776 (3)	0.9825 (4)	0.0154 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Er	0.0144 (2)	0.0150 (2)	0.0327 (3)	0.00742 (17)	−0.0022 (3)	0.0004 (3)
Ag2	0.0231 (9)	0.0231 (9)	0.181 (7)	0.0115 (5)	0.000	0.000
Ge1	0.0140 (6)	0.0140 (6)	0.0077 (8)	0.0070 (3)	0.000	0.000
S1	0.0159 (13)	0.0159 (13)	0.008 (2)	0.0079 (6)	0.000	0.000
S2	0.0136 (11)	0.0252 (13)	0.0340 (19)	0.0107 (10)	−0.0022 (10)	−0.0143 (11)
S3	0.0202 (12)	0.0155 (12)	0.0148 (12)	0.0122 (10)	−0.0006 (11)	−0.0001 (10)

Geometric parameters (Å, º)

Er—S2^i	2.699 (3)	Ag2—Er^viii	3.295 (4)
Er—S2	2.753 (3)	Ag2—Er^xv	3.454 (5)
Er—S2^ii	2.761 (3)	Ge1—S1^iv	2.190 (4)
Er—S3^iii	2.784 (3)	Ge1—S3^ii	2.223 (3)
Er—S3^iv	2.853 (3)	Ge1—S3^xvi	2.223 (3)
Er—S1^v	2.8566 (19)	Ge1—S3^v	2.223 (3)
Er—S3^i	3.020 (3)	S1—Ge1^xvii	2.190 (4)
Er—Ag2^v	3.295 (4)	S1—Er^xviii	2.8566 (19)
Er—Ag2^vi	3.454 (6)	S1—Er^vii	2.8566 (19)
Ag2—S2^vii	2.560 (7)	S1—Er^xix	2.8566 (19)
Ag2—S2^viii	2.560 (7)	S2—Ag2^v	2.560 (7)
Ag2—S2^ix	2.560 (7)	S2—Ag2^xx	2.688 (7)
Ag2—S2^x	2.688 (7)	S2—Er^xix	2.699 (2)
Ag2—S2^xi	2.688 (7)	S2—Er^xxi	2.761 (3)
Ag2—S2^xii	2.688 (7)	S3—Ge1^vii	2.223 (3)
Ag2—Ag2^xiii	2.9154 (6)	S3—Er^xv	2.784 (3)
Ag2—Ag2^xiv	2.9154 (6)	S3—Er^xvii	2.853 (3)
Ag2—Er^ix	3.295 (4)	S3—Er^xix	3.020 (3)
Ag2—Er^vii	3.295 (4)
S2^i—Er—S2	83.78 (8)	S2^viii—Ag2—Er^ix	125.81 (7)
S2^i—Er—S2^ii	87.49 (12)	S2^ix—Ag2—Er^ix	54.35 (7)
S2—Er—S2^ii	82.62 (8)	S2^x—Ag2—Er^ix	52.43 (11)
S2^i—Er—S3^iii	97.24 (8)	S2^xi—Ag2—Er^ix	53.82 (11)
S2—Er—S3^iii	138.35 (8)	S2^xii—Ag2—Er^ix	121.4 (4)
S2^ii—Er—S3^iii	138.98 (9)	Ag2^xiii—Ag2—Er^ix	67.27 (18)
S2^i—Er—S3^iv	137.50 (9)	Ag2^xiv—Ag2—Er^ix	112.73 (18)
S2—Er—S3^iv	128.56 (8)	S2^vii—Ag2—Er^vii	54.35 (7)
S2^ii—Er—S3^iv	72.95 (7)	S2^viii—Ag2—Er^vii	127.26 (8)
S3^iii—Er—S3^iv	76.52 (10)	S2^ix—Ag2—Er^vii	125.81 (7)
S2^i—Er—S1^v	146.88 (8)	S2^x—Ag2—Er^vii	121.4 (4)
S2—Er—S1^v	83.26 (10)	S2^xi—Ag2—Er^vii	52.43 (11)
S2^ii—Er—S1^v	120.73 (7)	S2^xii—Ag2—Er^vii	53.82 (11)
S3^iii—Er—S1^v	73.40 (8)	Ag2^xiii—Ag2—Er^vii	67.27 (18)
S3^iv—Er—S1^v	72.38 (8)	Ag2^xiv—Ag2—Er^vii	112.73 (18)
S2^i—Er—S3^i	71.23 (8)	Er^ix—Ag2—Er^vii	106.0 (2)
S2—Er—S3^i	70.50 (7)	S2^vii—Ag2—Er^viii	125.81 (7)
S2^ii—Er—S3^i	146.97 (8)	S2^viii—Ag2—Er^viii	54.35 (7)
S3^iii—Er—S3^i	70.57 (4)	S2^ix—Ag2—Er^viii	127.26 (7)
S3^iv—Er—S3^i	139.30 (7)	S2^x—Ag2—Er^viii	53.82 (11)
S1^v—Er—S3^i	75.73 (6)	S2^xi—Ag2—Er^viii	121.4 (4)
S2^i—Er—Ag2^v	52.15 (11)	S2^xii—Ag2—Er^viii	52.43 (11)
S2—Er—Ag2^v	49.08 (19)	Ag2^xiii—Ag2—Er^viii	67.27 (18)
S2^ii—Er—Ag2^v	51.80 (10)	Ag2^xiv—Ag2—Er^viii	112.73 (18)
S3^iii—Er—Ag2^v	149.39 (11)	Er^ix—Ag2—Er^viii	106.0 (2)
S3^iv—Er—Ag2^v	124.65 (10)	Er^vii—Ag2—Er^viii	106.0 (2)
S1^v—Er—Ag2^v	130.8 (2)	S2^vii—Ag2—Er^xv	50.69 (11)
S3^i—Er—Ag2^v	95.37 (12)	S2^viii—Ag2—Er^xv	52.12 (12)
S2^i—Er—Ag2^vi	47.22 (8)	S2^ix—Ag2—Er^xv	120.0 (4)
S2—Er—Ag2^vi	100.19 (17)	S2^x—Ag2—Er^xv	130.10 (7)
S2^ii—Er—Ag2^vi	47.02 (8)	S2^xi—Ag2—Er^xv	128.73 (6)
S3^iii—Er—Ag2^vi	110.90 (16)	S2^xii—Ag2—Er^xv	64.22 (7)
S3^iv—Er—Ag2^vi	95.13 (13)	Ag2^xiii—Ag2—Er^xv	118.39 (17)
S1^v—Er—Ag2^vi	165.81 (5)	Ag2^xiv—Ag2—Er^xv	61.61 (17)
S3^i—Er—Ag2^vi	118.43 (7)	Er^ix—Ag2—Er^xv	174.3 (3)
Ag2^v—Er—Ag2^vi	51.12 (2)	Er^vii—Ag2—Er^xv	77.17 (2)
S2^vii—Ag2—S2^viii	95.0 (3)	Er^viii—Ag2—Er^xv	77.17 (2)
S2^vii—Ag2—S2^ix	95.0 (3)	S1^iv—Ge1—S3^ii	114.96 (8)
S2^viii—Ag2—S2^ix	95.0 (3)	S1^iv—Ge1—S3^xvi	114.96 (8)
S2^vii—Ag2—S2^x	175.8 (4)	S3^ii—Ge1—S3^xvi	103.46 (9)
S2^viii—Ag2—S2^x	87.80 (5)	S1^iv—Ge1—S3^v	114.96 (8)
S2^ix—Ag2—S2^x	87.80 (5)	S3^ii—Ge1—S3^v	103.46 (9)
S2^vii—Ag2—S2^xi	87.80 (5)	S3^xvi—Ge1—S3^v	103.46 (9)
S2^viii—Ag2—S2^xi	175.8 (4)	Ge1^xvii—S1—Er^xviii	114.20 (8)
S2^ix—Ag2—S2^xi	87.80 (5)	Ge1^xvii—S1—Er^vii	114.20 (8)
S2^x—Ag2—S2^xi	89.2 (3)	Er^xviii—S1—Er^vii	104.35 (9)
S2^vii—Ag2—S2^xii	87.80 (5)	Ge1^xvii—S1—Er^xix	114.20 (8)
S2^viii—Ag2—S2^xii	87.80 (5)	Er^xviii—S1—Er^xix	104.35 (9)
S2^ix—Ag2—S2^xii	175.8 (4)	Er^vii—S1—Er^xix	104.35 (9)
S2^x—Ag2—S2^xii	89.2 (3)	Ag2^v—S2—Ag2^xx	67.44 (7)
S2^xi—Ag2—S2^xii	89.2 (3)	Ag2^v—S2—Er^xix	82.09 (10)
S2^vii—Ag2—Ag2^xiii	121.6 (2)	Ag2^xx—S2—Er^xix	75.42 (7)
S2^viii—Ag2—Ag2^xiii	121.6 (2)	Ag2^v—S2—Er	76.6 (2)
S2^ix—Ag2—Ag2^xiii	121.6 (2)	Ag2^xx—S2—Er	144.0 (2)
S2^x—Ag2—Ag2^xiii	54.2 (2)	Er^xix—S2—Er	101.16 (9)
S2^xi—Ag2—Ag2^xiii	54.2 (2)	Ag2^v—S2—Er^xxi	80.87 (10)
S2^xii—Ag2—Ag2^xiii	54.2 (2)	Ag2^xx—S2—Er^xxi	74.39 (7)
S2^vii—Ag2—Ag2^xiv	58.4 (2)	Er^xix—S2—Er^xxi	149.19 (11)
S2^viii—Ag2—Ag2^xiv	58.4 (2)	Er—S2—Er^xxi	99.59 (8)
S2^ix—Ag2—Ag2^xiv	58.4 (2)	Ge1^vii—S3—Er^xv	90.90 (8)
S2^x—Ag2—Ag2^xiv	125.8 (2)	Ge1^vii—S3—Er^xvii	89.11 (8)
S2^xi—Ag2—Ag2^xiv	125.8 (2)	Er^xv—S3—Er^xvii	106.35 (9)
S2^xii—Ag2—Ag2^xiv	125.8 (2)	Ge1^vii—S3—Er^xix	117.62 (11)
Ag2^xiii—Ag2—Ag2^xiv	180.000 (4)	Er^xv—S3—Er^xix	146.82 (9)
S2^vii—Ag2—Er^ix	127.26 (7)	Er^xvii—S3—Er^xix	91.58 (7)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) y, −x+y+1, z−1/2; (iii) −x+y+1, −x+1, z−1; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z−1; (vii) −x+1, −y+1, z+1/2; (viii) x−y, x−1, z+1/2; (ix) y−1, −x+y, z+1/2; (x) x−1, y−1, z; (xi) −x+y, −x+1, z; (xii) −y+1, x−y, z; (xiii) −x, −y, z−1/2; (xiv) −x, −y, z+1/2; (xv) −y+1, x−y, z+1; (xvi) x−y, x, z−1/2; (xvii) x, y, z+1; (xviii) x−y, x, z+1/2; (xix) y, −x+y+1, z+1/2; (xx) x+1, y+1, z; (xxi) x−y+1, x, z+1/2.

(y)

Crystal data

Ag0.50GeS7Y3	Dx = 4.240 Mg m^−3
Mr = 617.67	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63	Cell parameters from 641 reflections
Hall symbol: P 6c	θ = 4.2–26.3°
a = 9.8090 (14) Å	µ = 23.31 mm^−1
c = 5.8059 (12) Å	T = 295 K
V = 483.78 (14) Å^3	Prism, dark red
Z = 2	0.09 × 0.06 × 0.05 mm
F(000) = 569

Data collection

KUMA KM-4 with area CCD detector diffractometer	657 independent reflections
Radiation source: fine-focus sealed tube	641 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm^-1	θmax = 26.3°, θmin = 4.2°
ω–scan	h = −12→11
Absorption correction: numerical CrysAlis (Oxford Diffraction, 2007)	k = −12→12
Tmin = 0.107, Tmax = 0.210	l = −7→7
5168 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0228P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.021	(Δ/σ)max < 0.001
wR(F^2) = 0.044	Δρmax = 0.60 e Å^−3
S = 1.12	Δρmin = −1.38 e Å^−3
657 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
38 parameters	Extinction coefficient: 0.0058 (9)
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 294 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.036 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
Y	0.86329 (5)	0.64088 (5)	0.24445 (13)	0.01737 (15)
Ag2	0.0000	0.0000	0.0009 (7)	0.0814 (10)	0.50
Ge1	0.3333	0.6667	0.32329 (13)	0.0112 (2)
S1	0.3333	0.6667	0.9465 (4)	0.0115 (5)
S2	0.89780 (14)	0.73969 (16)	0.7021 (2)	0.0207 (3)
S3	0.57643 (15)	0.47892 (15)	0.9833 (2)	0.0136 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Y	0.0132 (2)	0.0128 (2)	0.0263 (3)	0.00662 (18)	−0.0023 (2)	−0.0006 (2)
Ag2	0.0172 (5)	0.0172 (5)	0.210 (3)	0.0086 (2)	0.000	0.000
Ge1	0.0124 (3)	0.0124 (3)	0.0088 (4)	0.00618 (15)	0.000	0.000
S1	0.0139 (7)	0.0139 (7)	0.0065 (11)	0.0070 (3)	0.000	0.000
S2	0.0126 (6)	0.0267 (7)	0.0243 (8)	0.0108 (5)	−0.0017 (5)	−0.0117 (6)
S3	0.0174 (6)	0.0137 (6)	0.0123 (6)	0.0097 (5)	−0.0010 (6)	−0.0003 (5)

Geometric parameters (Å, º)

Y—S2^i	2.7361 (14)	Ag2—Y^xvii	3.3885 (19)
Y—S2	2.7906 (16)	Ag2—Y^ix	3.4207 (19)
Y—S2^ii	2.7944 (13)	Ge1—S1^iv	2.188 (2)
Y—S3^iii	2.7946 (14)	Ge1—S3^ii	2.2249 (14)
Y—S3^iv	2.8758 (14)	Ge1—S3^xviii	2.2249 (14)
Y—S1^v	2.8944 (11)	Ge1—S3^v	2.2249 (13)
Y—S3^i	3.0089 (14)	S1—Ge1^xix	2.188 (2)
Y—S2^iv	3.2618 (17)	S1—Y^xx	2.8944 (11)
Y—Ag2^vi	3.3885 (19)	S1—Y^vii	2.8944 (11)
Y—Ag2^vii	3.421 (2)	S1—Y^xxi	2.8944 (11)
Ag2—S2^v	2.516 (2)	S2—Ag2^vii	2.516 (2)
Ag2—S2^viii	2.516 (2)	S2—Y^xxi	2.7361 (13)
Ag2—S2^ix	2.516 (2)	S2—Y^xxii	2.7944 (13)
Ag2—S2^x	2.824 (3)	S2—Ag2^xxiii	2.824 (3)
Ag2—S2^xi	2.824 (3)	S2—Y^xix	3.2618 (17)
Ag2—S2^xii	2.824 (3)	S3—Ge1^vii	2.2249 (13)
Ag2—Ag2^xiii	2.9029 (6)	S3—Y^xxiv	2.7946 (14)
Ag2—Ag2^xiv	2.9029 (6)	S3—Y^xix	2.8758 (14)
Ag2—Y^xv	3.3885 (19)	S3—Y^xxi	3.0089 (14)
Ag2—Y^xvi	3.3885 (19)
S2^i—Y—S2	82.92 (4)	Ag2^xiii—Ag2—Ag2^xiv	180.0
S2^i—Y—S2^ii	88.50 (6)	S2^v—Ag2—Y^xv	52.73 (4)
S2—Y—S2^ii	81.88 (4)	S2^viii—Ag2—Y^xv	54.08 (5)
S2^i—Y—S3^iii	99.71 (4)	S2^ix—Ag2—Y^xv	127.67 (15)
S2—Y—S3^iii	137.94 (4)	S2^x—Ag2—Y^xv	128.55 (4)
S2^ii—Y—S3^iii	139.84 (5)	S2^xi—Ag2—Y^xv	127.33 (4)
S2^i—Y—S3^iv	138.86 (5)	S2^xii—Ag2—Y^xv	62.57 (3)
S2—Y—S3^iv	127.53 (4)	Ag2^xiii—Ag2—Y^xv	65.34 (7)
S2^ii—Y—S3^iv	72.15 (4)	Ag2^xiv—Ag2—Y^xv	114.66 (7)
S3^iii—Y—S3^iv	76.26 (5)	S2^v—Ag2—Y^xvi	127.67 (15)
S2^i—Y—S1^v	147.46 (4)	S2^viii—Ag2—Y^xvi	52.73 (4)
S2—Y—S1^v	83.00 (5)	S2^ix—Ag2—Y^xvi	54.08 (5)
S2^ii—Y—S1^v	118.23 (3)	S2^x—Ag2—Y^xvi	62.57 (3)
S3^iii—Y—S1^v	72.48 (4)	S2^xi—Ag2—Y^xvi	128.55 (4)
S3^iv—Y—S1^v	71.33 (4)	S2^xii—Ag2—Y^xvi	127.33 (4)
S2^i—Y—S3^i	70.64 (4)	Ag2^xiii—Ag2—Y^xvi	65.34 (7)
S2—Y—S3^i	70.20 (4)	Ag2^xiv—Ag2—Y^xvi	114.66 (7)
S2^ii—Y—S3^i	146.62 (4)	Y^xv—Ag2—Y^xvi	103.82 (8)
S3^iii—Y—S3^i	71.28 (3)	S2^v—Ag2—Y^xvii	54.08 (5)
S3^iv—Y—S3^i	139.99 (4)	S2^viii—Ag2—Y^xvii	127.67 (15)
S1^v—Y—S3^i	77.00 (3)	S2^ix—Ag2—Y^xvii	52.73 (4)
S2^i—Y—S2^iv	74.62 (4)	S2^x—Ag2—Y^xvii	127.33 (4)
S2—Y—S2^iv	147.08 (5)	S2^xi—Ag2—Y^xvii	62.57 (3)
S2^ii—Y—S2^iv	73.90 (4)	S2^xii—Ag2—Y^xvii	128.55 (4)
S3^iii—Y—S2^iv	70.70 (4)	Ag2^xiii—Ag2—Y^xvii	65.34 (7)
S3^iv—Y—S2^iv	65.34 (4)	Ag2^xiv—Ag2—Y^xvii	114.66 (7)
S1^v—Y—S2^iv	128.09 (5)	Y^xv—Ag2—Y^xvii	103.82 (8)
S3^i—Y—S2^iv	122.05 (4)	Y^xvi—Ag2—Y^xvii	103.82 (8)
S2^i—Y—Ag2^vi	47.03 (4)	S2^v—Ag2—Y^ix	127.60 (3)
S2—Y—Ag2^vi	96.89 (7)	S2^viii—Ag2—Y^ix	126.26 (3)
S2^ii—Y—Ag2^vi	46.81 (4)	S2^ix—Ag2—Y^ix	53.48 (4)
S3^iii—Y—Ag2^vi	115.64 (7)	S2^x—Ag2—Y^ix	50.88 (5)
S3^iv—Y—Ag2^vi	97.10 (6)	S2^xi—Ag2—Y^ix	52.10 (4)
S1^v—Y—Ag2^vi	164.509 (17)	S2^xii—Ag2—Y^ix	116.28 (13)
S3^i—Y—Ag2^vi	117.64 (4)	Ag2^xiii—Ag2—Y^ix	115.81 (7)
S2^iv—Y—Ag2^vi	50.21 (7)	Ag2^xiv—Ag2—Y^ix	64.19 (7)
S2^i—Y—Ag2^vii	53.20 (4)	Y^xv—Ag2—Y^ix	178.85 (13)
S2—Y—Ag2^vii	46.43 (7)	Y^xvi—Ag2—Y^ix	76.853 (8)
S2^ii—Y—Ag2^vii	52.89 (4)	Y^xvii—Ag2—Y^ix	76.853 (8)
S3^iii—Y—Ag2^vii	152.76 (4)	S1^iv—Ge1—S3^ii	114.68 (4)
S3^iv—Y—Ag2^vii	124.74 (4)	S1^iv—Ge1—S3^xviii	114.68 (4)
S1^v—Y—Ag2^vii	127.64 (8)	S3^ii—Ge1—S3^xviii	103.79 (4)
S3^i—Y—Ag2^vii	93.92 (5)	S1^iv—Ge1—S3^v	114.68 (4)
S2^iv—Y—Ag2^vii	100.67 (7)	S3^ii—Ge1—S3^v	103.79 (4)
Ag2^vi—Y—Ag2^vii	50.467 (13)	S3^xviii—Ge1—S3^v	103.79 (4)
S2^v—Ag2—S2^viii	100.17 (11)	Ge1^xix—S1—Y^xx	113.90 (4)
S2^v—Ag2—S2^ix	100.17 (11)	Ge1^xix—S1—Y^vii	113.90 (4)
S2^viii—Ag2—S2^ix	100.17 (11)	Y^xx—S1—Y^vii	104.70 (5)
S2^v—Ag2—S2^x	169.76 (16)	Ge1^xix—S1—Y^xxi	113.90 (4)
S2^viii—Ag2—S2^x	86.32 (3)	Y^xx—S1—Y^xxi	104.70 (5)
S2^ix—Ag2—S2^x	86.32 (3)	Y^vii—S1—Y^xxi	104.70 (5)
S2^v—Ag2—S2^xi	86.32 (3)	Ag2^vii—S2—Y^xxi	80.24 (4)
S2^viii—Ag2—S2^xi	169.76 (16)	Ag2^vii—S2—Y	80.09 (9)
S2^ix—Ag2—S2^xi	86.32 (3)	Y^xxi—S2—Y	99.94 (4)
S2^x—Ag2—S2^xi	86.21 (11)	Ag2^vii—S2—Y^xxii	79.11 (4)
S2^v—Ag2—S2^xii	86.32 (3)	Y^xxi—S2—Y^xxii	149.35 (6)
S2^viii—Ag2—S2^xii	86.32 (3)	Y—S2—Y^xxii	98.53 (4)
S2^ix—Ag2—S2^xii	169.76 (16)	Ag2^vii—S2—Ag2^xxiii	65.57 (4)
S2^x—Ag2—S2^xii	86.21 (11)	Y^xxi—S2—Ag2^xxiii	75.92 (3)
S2^xi—Ag2—S2^xii	86.21 (11)	Y—S2—Ag2^xxiii	145.65 (9)
S2^v—Ag2—Ag2^xiii	62.33 (9)	Y^xxii—S2—Ag2^xxiii	75.01 (3)
S2^viii—Ag2—Ag2^xiii	62.33 (9)	Ag2^vii—S2—Y^xix	132.79 (10)
S2^ix—Ag2—Ag2^xiii	62.33 (9)	Y^xxi—S2—Y^xix	89.31 (4)
S2^x—Ag2—Ag2^xiii	127.90 (7)	Y—S2—Y^xix	147.08 (5)
S2^xi—Ag2—Ag2^xiii	127.90 (7)	Y^xxii—S2—Y^xix	88.31 (4)
S2^xii—Ag2—Ag2^xiii	127.90 (7)	Ag2^xxiii—S2—Y^xix	67.22 (7)
S2^v—Ag2—Ag2^xiv	117.67 (9)	Ge1^vii—S3—Y^xxiv	91.02 (5)
S2^viii—Ag2—Ag2^xiv	117.67 (9)	Ge1^vii—S3—Y^xix	88.93 (4)
S2^ix—Ag2—Ag2^xiv	117.67 (9)	Y^xxiv—S3—Y^xix	107.85 (5)
S2^x—Ag2—Ag2^xiv	52.10 (7)	Ge1^vii—S3—Y^xxi	118.37 (5)
S2^xi—Ag2—Ag2^xiv	52.10 (7)	Y^xxiv—S3—Y^xxi	145.19 (5)
S2^xii—Ag2—Ag2^xiv	52.10 (7)	Y^xix—S3—Y^xxi	91.94 (4)

Symmetry codes: (i) x−y+1, x, z−1/2; (ii) y, −x+y+1, z−1/2; (iii) −x+y+1, −x+1, z−1; (iv) x, y, z−1; (v) −x+1, −y+1, z−1/2; (vi) x+1, y+1, z; (vii) −x+1, −y+1, z+1/2; (viii) x−y, x−1, z−1/2; (ix) y−1, −x+y, z−1/2; (x) x−1, y−1, z−1; (xi) −x+y, −x+1, z−1; (xii) −y+1, x−y, z−1; (xiii) −x, −y, z+1/2; (xiv) −x, −y, z−1/2; (xv) −y+1, x−y, z; (xvi) x−1, y−1, z; (xvii) −x+y, −x+1, z; (xviii) x−y, x, z−1/2; (xix) x, y, z+1; (xx) x−y, x, z+1/2; (xxi) y, −x+y+1, z+1/2; (xxii) x−y+1, x, z+1/2; (xxiii) x+1, y+1, z+1; (xxiv) −y+1, x−y, z+1.