Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806040980/bi2073sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806040980/bi2073Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (b-S) = 0.003 Å
- Disorder in main residue
- R factor = 0.024
- wR factor = 0.045
- Data-to-parameter ratio = 19.3
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level C PLAT220_ALERT_2_C Large Non-Solvent S Ueq(max)/Ueq(min) ... 2.98 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S14 PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 16.27 Deg. SB10 -S20 -SB10 1.555 1.555 4.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 16.27 Deg. SB10 -S20 -SB10 4.555 1.555 1.555
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the description and relation of the crystal structure of marrucciite to other mineral species and related compounds, see Orlandi et al. (2007).
Black needle fragments of the mineral marrucciite were found embedded in a quartz-siderite vein in the Gelnica ore district. They were separated from quartz by means of hydrofluoric acid. Of many fibrous crystals that were examined, only a few were suitable for X-ray single-crystal structure determination.
For the disordered sites Pb8/Sb8 and Pb9/Sb9, atoms on the same site were constrained to have identical atomic coordinates and anisotropic displacement parameters, and the site occupancy factores at each site were constrained to sum to unity. No other constraints were apllied. The highest residual peak in the final difference Fourier map was 0.7 Å from Sb1 and the deepest hole 0.44 Å from Sb1.
The structure model proposed by Orlandi et al. (2007) is, in basic outline, confirmed; only minor deviations were found. The most striking difference is the absence of 2b superstructure diffraction spots, which were observed in the marrucciite from Bucca della Vena. Consequently, no split positions with half-occupancy occur in the structure model proposed in the present paper. Moreover, we present anisotropic displacement parameters for all atoms of the marrucciite structure.
Fig. 1 depicts the projection of the crystal structure of the title compound along b. The asymmetric unit contains two HgII positions, seven pure PbII positions, eight pure SbIII positions, two mixed PbII/SbIII positions [refined to Pb0.612 (5)Sb0.388 (5) and Pb0.388 (6)Sb0.612 (6)] and 23 S positions. One of the main characteristics of the structure of this compound is the ordering of Sb atoms to form so-called lone electron pair micelles (Fig. 1, left part) where the stereochemically active lone pairs of electrons on Sb are accommodated.
For the description and relation of the crystal structure of marrucciite to other mineral species and related compounds, see Orlandi et al. (2007).
Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2004); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: Jana2000 (Petricek et al., 2000); molecular graphics: DIAMOND 3 (Brandenburg and Putz, 2005); software used to prepare material for publication: Jana2000.
Fig. 1. A projection along b of the crystal structure of marrucciite, monoclinic Hg3Pb16Sb18S48. Grey areas (left side of figure) highlight lone electron pair micelles. |
Hg3Pb16S46Sb18 | F(000) = 6412 |
Mr = 7583.1 | Dx = 6.055 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2y | Cell parameters from 9276 reflections |
a = 48.124 (11) Å | θ = 2.5–26.5° |
b = 4.1083 (2) Å | µ = 44.67 mm−1 |
c = 23.990 (5) Å | T = 292 K |
β = 118.76 (2)° | Prism, black |
V = 4158.2 (15) Å3 | 0.04 × 0.02 × 0.00230 mm |
Z = 2 |
Oxford Diffraction XCalibur CCD diffractometer | 4942 independent reflections |
Radiation source: X-ray tube | 3000 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.6°, θmin = 2.5° |
Rotation method data acquisition using ω scans | h = −59→60 |
Absorption correction: analytical Clark & Reid (1995) | k = −5→5 |
Tmin = 0.198, Tmax = 0.805 | l = −30→30 |
26009 measured reflections |
Refinement on F2 | 256 parameters |
R[F2 > 2σ(F2)] = 0.024 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.045 | (Δ/σ)max = 0.031 |
S = 0.85 | Δρmax = 1.20 e Å−3 |
4942 reflections | Δρmin = −1.09 e Å−3 |
Hg3Pb16S46Sb18 | V = 4158.2 (15) Å3 |
Mr = 7583.1 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 48.124 (11) Å | µ = 44.67 mm−1 |
b = 4.1083 (2) Å | T = 292 K |
c = 23.990 (5) Å | 0.04 × 0.02 × 0.00230 mm |
β = 118.76 (2)° |
Oxford Diffraction XCalibur CCD diffractometer | 4942 independent reflections |
Absorption correction: analytical Clark & Reid (1995) | 3000 reflections with I > 3σ(I) |
Tmin = 0.198, Tmax = 0.805 | Rint = 0.052 |
26009 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 256 parameters |
wR(F2) = 0.045 | Δρmax = 1.20 e Å−3 |
S = 0.85 | Δρmin = −1.09 e Å−3 |
4942 reflections |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors are based on F, with F set to zero for negative F2. The threshold expression of F2 > n*σ(F2) is used only for calculating R-factors etc. and is not relevant to the choice of reflections for refinement. The program used for refinement, Jana2000, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger then the ones from the SHELX program. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Sb1 | 0.42917 (2) | 0 | 0.01409 (5) | 0.0410 (5) | |
Sb2 | 0.29529 (2) | 0 | 0.04272 (5) | 0.0326 (4) | |
S1 | 0.04720 (8) | 0 | 0.04514 (15) | 0.0315 (15) | |
S2 | 0.34675 (8) | 0 | 0.04430 (13) | 0.0183 (14) | |
Pb1 | 0.160743 (13) | 0 | 0.05141 (2) | 0.0257 (2) | |
S3 | 0.22457 (8) | 0 | 0.04890 (17) | 0.0483 (19) | |
S4 | 0.90931 (7) | 0 | 0.05559 (14) | 0.0235 (14) | |
Sb3 | 0.52171 (2) | 0 | 0.08609 (5) | 0.0467 (5) | |
S5 | 0.61989 (7) | 0 | 0.08618 (14) | 0.0190 (13) | |
S6 | 0.81662 (9) | 0 | 0.13629 (17) | 0.053 (2) | |
S7 | −0.00105 (8) | 0 | 0.13619 (15) | 0.0269 (14) | |
Sb4 | 0.74970 (2) | 0 | 0.15156 (4) | 0.0228 (4) | |
Pb2 | 0.880439 (12) | 0 | 0.14750 (2) | 0.0219 (2) | |
S8 | 0.69971 (7) | 0 | 0.15478 (14) | 0.0193 (13) | |
Pb3 | 0.110919 (12) | 0 | 0.16376 (2) | 0.0242 (2) | |
Sb9 | 0.464070 (18) | 0 | 0.18486 (4) | 0.0415 (4) | 0.612 (6) |
Pb9 | 0.46407 | 0 | 0.184862 | 0.0415 (4) | 0.388 (6) |
S9 | 0.57042 (7) | 0 | 0.18714 (14) | 0.0190 (13) | |
S10 | 0.27134 (8) | 0 | 0.23034 (15) | 0.0310 (15) | |
Sb5 | 0.33940 (2) | 0 | 0.24093 (4) | 0.0229 (4) | |
S11 | 0.39219 (7) | 0 | 0.24290 (14) | 0.0187 (13) | |
S12 | 0.95232 (8) | 0 | 0.24303 (14) | 0.0253 (15) | |
Pb8 | 0.052297 (17) | 0 | 0.25068 (3) | 0.0319 (4) | 0.612 (5) |
Sb8 | 0.052297 | 0 | 0.250683 | 0.0319 (4) | 0.388 (5) |
S13 | 0.66387 (7) | 0 | 0.24881 (13) | 0.0178 (13) | |
Pb4 | 0.215046 (13) | 0 | 0.26212 (2) | 0.0271 (2) | |
S14 | 0.52026 (8) | 0 | 0.27747 (14) | 0.0235 (14) | |
S15 | 0.85629 (10) | 0 | 0.32046 (17) | 0.052 (2) | |
S16 | 0.12719 (9) | 0 | 0.33026 (16) | 0.0437 (18) | |
S17 | 0.76523 (7) | 0 | 0.34565 (13) | 0.0194 (13) | |
Pb5 | 0.931045 (13) | 0 | 0.34166 (2) | 0.0258 (2) | |
Sb6 | 0.67121 (2) | 0 | 0.35664 (4) | 0.0245 (4) | |
Pb6 | 0.313833 (12) | 0 | 0.37726 (2) | 0.0259 (2) | |
Pb7 | 0.026006 (13) | 0 | 0.38264 (2) | 0.0255 (2) | |
S18 | 0.48083 (7) | 0 | 0.38906 (13) | 0.0182 (13) | |
S19 | 0.21658 (8) | 0 | 0.39248 (16) | 0.0443 (18) | |
S20 | 0.57670 (8) | 0 | 0.41998 (14) | 0.0233 (14) | |
Hg1 | 0.129886 (14) | 0 | 0.43129 (3) | 0.0323 (3) | |
Sb7 | 0.76574 (2) | 0 | 0.44928 (4) | 0.0293 (5) | |
S21 | 0.86164 (7) | 0 | 0.46313 (13) | 0.0178 (13) | |
S22 | 0.94500 (7) | 0 | 0.47995 (14) | 0.0188 (13) | |
S23 | 0.30691 (8) | 0 | 0.48875 (15) | 0.0297 (15) | |
Hg2 | 0.5 | 0 | 0.5 | 0.0271 (3) | |
Sb10 | 0.59584 (3) | 0.0842 (3) | 0.53354 (5) | 0.0196 (6) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sb1 | 0.0181 (5) | 0.0697 (8) | 0.0277 (5) | 0 | 0.0050 (4) | 0 |
Sb2 | 0.0193 (5) | 0.0187 (5) | 0.0557 (6) | 0 | 0.0149 (5) | 0 |
S1 | 0.0209 (19) | 0.055 (3) | 0.0199 (17) | 0 | 0.0105 (15) | 0 |
S2 | 0.0292 (19) | 0.0127 (17) | 0.0171 (16) | 0 | 0.0145 (14) | 0 |
Pb1 | 0.0381 (3) | 0.0180 (3) | 0.0249 (3) | 0 | 0.0185 (3) | 0 |
S3 | 0.017 (2) | 0.098 (4) | 0.026 (2) | 0 | 0.0077 (16) | 0 |
S4 | 0.0183 (18) | 0.034 (2) | 0.0193 (16) | 0 | 0.0097 (14) | 0 |
Sb3 | 0.0328 (6) | 0.0650 (8) | 0.0242 (5) | 0 | −0.0009 (5) | 0 |
S5 | 0.0168 (17) | 0.0203 (18) | 0.0176 (16) | 0 | 0.0063 (13) | 0 |
S6 | 0.018 (2) | 0.113 (4) | 0.032 (2) | 0 | 0.0153 (17) | 0 |
S7 | 0.0181 (18) | 0.040 (2) | 0.0193 (17) | 0 | 0.0068 (14) | 0 |
Sb4 | 0.0172 (5) | 0.0269 (5) | 0.0241 (5) | 0 | 0.0098 (4) | 0 |
Pb2 | 0.0259 (3) | 0.0175 (3) | 0.0232 (3) | 0 | 0.0127 (2) | 0 |
S8 | 0.0218 (18) | 0.0180 (18) | 0.0168 (16) | 0 | 0.0082 (14) | 0 |
Pb3 | 0.0262 (3) | 0.0226 (3) | 0.0280 (3) | 0 | 0.0165 (2) | 0 |
Sb9 | 0.0259 (5) | 0.0376 (6) | 0.0552 (6) | 0 | 0.0149 (4) | 0 |
Pb9 | 0.0259 (5) | 0.0376 (6) | 0.0552 (6) | 0 | 0.0149 (4) | 0 |
S9 | 0.0142 (17) | 0.0216 (19) | 0.0180 (16) | 0 | 0.0053 (13) | 0 |
S10 | 0.0231 (19) | 0.050 (3) | 0.0181 (17) | 0 | 0.0085 (15) | 0 |
Sb5 | 0.0252 (5) | 0.0250 (5) | 0.0225 (5) | 0 | 0.0146 (4) | 0 |
S11 | 0.0184 (17) | 0.0153 (18) | 0.0189 (16) | 0 | 0.0062 (14) | 0 |
S12 | 0.028 (2) | 0.034 (2) | 0.0205 (17) | 0 | 0.0165 (15) | 0 |
Pb8 | 0.0472 (5) | 0.0259 (4) | 0.0341 (4) | 0 | 0.0287 (4) | 0 |
Sb8 | 0.0472 (5) | 0.0259 (4) | 0.0341 (4) | 0 | 0.0287 (4) | 0 |
S13 | 0.0179 (17) | 0.0193 (18) | 0.0142 (15) | 0 | 0.0062 (13) | 0 |
Pb4 | 0.0285 (3) | 0.0205 (3) | 0.0245 (3) | 0 | 0.0065 (2) | 0 |
S14 | 0.0219 (19) | 0.031 (2) | 0.0168 (16) | 0 | 0.0088 (14) | 0 |
S15 | 0.041 (3) | 0.090 (4) | 0.027 (2) | 0 | 0.0183 (19) | 0 |
S16 | 0.028 (2) | 0.086 (3) | 0.0161 (17) | 0 | 0.0094 (16) | 0 |
S17 | 0.0217 (18) | 0.0160 (18) | 0.0154 (16) | 0 | 0.0048 (14) | 0 |
Pb5 | 0.0339 (3) | 0.0169 (3) | 0.0244 (3) | 0 | 0.0123 (2) | 0 |
Sb6 | 0.0391 (6) | 0.0181 (5) | 0.0153 (4) | 0 | 0.0123 (4) | 0 |
Pb6 | 0.0244 (3) | 0.0251 (3) | 0.0266 (3) | 0 | 0.0109 (2) | 0 |
Pb7 | 0.0322 (3) | 0.0251 (3) | 0.0234 (3) | 0 | 0.0168 (2) | 0 |
S18 | 0.0179 (17) | 0.0174 (18) | 0.0181 (16) | 0 | 0.0077 (14) | 0 |
S19 | 0.019 (2) | 0.090 (4) | 0.0230 (19) | 0 | 0.0097 (16) | 0 |
S20 | 0.0218 (19) | 0.024 (2) | 0.0158 (16) | 0 | 0.0025 (14) | 0 |
Hg1 | 0.0443 (4) | 0.0367 (4) | 0.0230 (3) | 0 | 0.0219 (3) | 0 |
Sb7 | 0.0457 (6) | 0.0193 (5) | 0.0383 (5) | 0 | 0.0326 (5) | 0 |
S21 | 0.0189 (17) | 0.0179 (18) | 0.0141 (15) | 0 | 0.0059 (13) | 0 |
S22 | 0.0169 (17) | 0.0227 (19) | 0.0176 (16) | 0 | 0.0090 (14) | 0 |
S23 | 0.0227 (19) | 0.045 (2) | 0.0176 (17) | 0 | 0.0063 (15) | 0 |
Hg2 | 0.0288 (4) | 0.0328 (5) | 0.0176 (4) | 0 | 0.0096 (3) | 0 |
Sb10 | 0.0213 (6) | 0.0203 (12) | 0.0162 (5) | 0.0021 (5) | 0.0082 (4) | 0.0009 (5) |
Hg1—S21i | 2.364 (3) | Sb3—S7iv | 2.851 (3) |
Hg1—S16 | 2.364 (4) | Sb3—S7v | 2.851 (3) |
Hg2—S18 | 2.360 (3) | Sb3—S9 | 2.430 (3) |
Pb1ii—S2 | 2.971 (3) | Sb4vi—S3 | 2.980 (3) |
Pb1iii—S2 | 2.971 (3) | Sb4vii—S3 | 2.980 (3) |
Pb2—S6 | 2.951 (5) | Sb4—S8 | 2.444 (4) |
Pb2—S11iv | 2.921 (2) | Sb4—S10iv | 2.6424 (19) |
Pb2—S11v | 2.921 (2) | Sb4—S10v | 2.6424 (19) |
Pb3iv—S5 | 2.940 (3) | Sb5—S11 | 2.519 (4) |
Pb3v—S5 | 2.940 (3) | Sb5—S15vi | 2.651 (2) |
Pb5—S12 | 2.996 (4) | Sb5—S15vii | 2.651 (2) |
Pb5—S18iv | 2.938 (2) | Sb6—S13 | 2.437 (4) |
Pb5—S18v | 2.938 (2) | Sb6vi—S16 | 2.796 (3) |
Pb6iv—S17 | 2.926 (2) | S16—Sb6vii | 2.796 (3) |
Pb6v—S17 | 2.926 (2) | Sb6—S19iv | 2.814 (3) |
Pb6—S23 | 2.850 (4) | Sb6—S19v | 2.814 (3) |
Pb7—S20vi | 2.979 (3) | Sb7—S17 | 2.474 (4) |
Pb7—S20vii | 2.979 (3) | Sb7vi—S19 | 2.928 (2) |
Pb7—S22i | 2.896 (3) | Sb7vii—S19 | 2.928 (2) |
Pb8—S7 | 2.711 (3) | Sb7—S23iv | 2.690 (2) |
Pb8iv—S9 | 2.930 (3) | Sb7—S23v | 2.690 (2) |
Pb8v—S9 | 2.930 (3) | Sb8iv—S9 | 2.930 (3) |
Pb8—S14vi | 2.822 (3) | Sb8v—S9 | 2.930 (3) |
Pb8—S14vii | 2.822 (3) | Sb8—S14vi | 2.822 (3) |
Pb9—S12vi | 2.692 (3) | Sb8—S14vii | 2.822 (3) |
Pb9—S12vii | 2.692 (3) | Sb8—S7 | 2.711 (3) |
Pb9—S14 | 2.543 (3) | Sb9—S12vi | 2.692 (3) |
Sb1—S4vi | 2.653 (3) | Sb9—S12vii | 2.692 (3) |
Sb1—S4vii | 2.653 (3) | Sb9—S14 | 2.543 (3) |
Sb1—S5viii | 2.428 (3) | Sb10ix—S21 | 2.637 (3) |
Sb2—S2 | 2.459 (4) | Sb10x—S21 | 2.637 (3) |
Sb2—S3iii | 2.818 (3) | Sb10ix—S22 | 2.505 (3) |
Sb2—S3ii | 2.818 (3) | Sb10x—S22 | 2.505 (3) |
Sb2—S6vi | 2.845 (3) | Sb10—S20 | 2.445 (3) |
Sb2—S6vii | 2.845 (3) | Sb10xi—S20 | 2.445 (3) |
Sb3vi—S1 | 2.802 (3) | Sb10—Sb10xi | 0.6919 (15) |
Sb3vii—S1 | 2.802 (3) | ||
S4vi—Sb1—S4vii | 101.46 (11) | S9vi—Pb8—S14vi | 86.57 (9) |
S4vi—Sb1—S5viii | 91.01 (9) | S9vi—Pb8—S14vii | 163.93 (7) |
S4vii—Sb1—S4vi | 101.46 (11) | S9vii—Pb8—S9vi | 89.03 (8) |
S4vii—Sb1—S5viii | 91.01 (9) | S9vii—Pb8—S14vi | 163.93 (7) |
S2—Sb2—S3iii | 88.47 (11) | S9vii—Pb8—S14vii | 86.57 (9) |
S2—Sb2—S3ii | 88.47 (11) | S14vi—Pb8—S14vii | 93.43 (9) |
S2—Sb2—S6vi | 90.53 (11) | S14vii—Pb8—S14vi | 93.43 (9) |
S2—Sb2—S6vii | 90.53 (11) | S7—Sb8—S9vi | 81.18 (8) |
S3iii—Sb2—S3ii | 93.58 (8) | S7—Sb8—S9vii | 81.18 (8) |
S3iii—Sb2—S6vi | 86.98 (8) | S7—Sb8—S14vi | 82.88 (8) |
S3iii—Sb2—S6vii | 178.84 (11) | S7—Sb8—S14vii | 82.88 (8) |
S3ii—Sb2—S3iii | 93.58 (8) | S9vi—Sb8—S9vii | 89.03 (8) |
S3ii—Sb2—S6vi | 178.84 (11) | S9vi—Sb8—S14vi | 86.57 (9) |
S3ii—Sb2—S6vii | 86.98 (8) | S9vi—Sb8—S14vii | 163.93 (7) |
S6vi—Sb2—S6vii | 92.44 (8) | S9vii—Sb8—S9vi | 89.03 (8) |
S6vii—Sb2—S6vi | 92.44 (8) | S9vii—Sb8—S14vi | 163.93 (7) |
Sb3vi—S1—Sb3vii | 94.31 (14) | S9vii—Sb8—S14vii | 86.57 (9) |
Sb3vii—S1—Sb3vi | 94.31 (14) | S14vi—Sb8—S14vii | 93.43 (9) |
Sb2—S2—Pb1iii | 103.96 (8) | S14vii—Sb8—S14vi | 93.43 (9) |
Sb2—S2—Pb1ii | 103.96 (8) | Sb9—S14—Pb8iv | 105.60 (8) |
Pb1iii—S2—Pb1ii | 87.49 (9) | Sb9—S14—Pb8v | 105.60 (8) |
Pb1ii—S2—Pb1iii | 87.49 (9) | Sb9—S14—Sb8iv | 105.60 (8) |
S2iii—Pb1—S2ii | 87.49 (7) | Sb9—S14—Sb8v | 105.60 (8) |
S2ii—Pb1—S2iii | 87.49 (7) | Pb9—S14—Pb8iv | 105.60 (8) |
Sb2iii—S3—Sb2ii | 93.58 (11) | Pb9—S14—Pb8v | 105.60 (8) |
Sb2iii—S3—Sb4vi | 89.578 (19) | Pb9—S14—Sb8iv | 105.60 (8) |
Sb2iii—S3—Sb4vii | 175.88 (10) | Pb9—S14—Sb8v | 105.60 (8) |
Sb2ii—S3—Sb2iii | 93.58 (11) | Pb8iv—S14—Pb8v | 93.43 (13) |
Sb2ii—S3—Sb4vi | 175.88 (10) | Pb8iv—S14—Sb8v | 93.43 (13) |
Sb2ii—S3—Sb4vii | 89.578 (19) | Pb8v—S14—Pb8iv | 93.43 (13) |
Sb4vi—S3—Sb4vii | 87.15 (9) | Pb8v—S14—Sb8iv | 93.43 (13) |
Sb4vii—S3—Sb4vi | 87.15 (9) | Sb8iv—S14—Sb8v | 93.43 (12) |
Sb1iv—S4—Sb1v | 101.46 (15) | Sb8v—S14—Sb8iv | 93.43 (12) |
Sb1v—S4—Sb1iv | 101.46 (15) | Sb5iv—S15—Sb5v | 101.58 (13) |
S1iv—Sb3—S1v | 94.31 (10) | Sb5v—S15—Sb5iv | 101.58 (13) |
S1iv—Sb3—S7iv | 86.64 (9) | Sb6vi—S16—Sb6vii | 94.55 (12) |
S1iv—Sb3—S7v | 176.19 (8) | Sb6vi—S16—Hg1 | 96.08 (8) |
S1iv—Sb3—S9 | 88.55 (9) | Sb6vii—S16—Sb6vi | 94.55 (12) |
S1v—Sb3—S1iv | 94.31 (10) | Sb6vii—S16—Hg1 | 96.08 (8) |
S1v—Sb3—S7iv | 176.19 (8) | Pb6iv—S17—Pb6v | 89.19 (9) |
S1v—Sb3—S7v | 86.64 (9) | Pb6iv—S17—Sb7 | 96.85 (7) |
S1v—Sb3—S9 | 88.55 (9) | Pb6v—S17—Pb6iv | 89.19 (9) |
S7iv—Sb3—S7v | 92.18 (10) | Pb6v—S17—Sb7 | 96.85 (7) |
S7iv—Sb3—S9 | 87.78 (9) | S12—Pb5—S18iv | 77.34 (8) |
S7v—Sb3—S7iv | 92.18 (10) | S12—Pb5—S18v | 77.34 (8) |
S7v—Sb3—S9 | 87.78 (9) | S18iv—Pb5—S18v | 88.73 (6) |
Sb1viii—S5—Pb3iv | 104.96 (10) | S18v—Pb5—S18iv | 88.73 (6) |
Sb1viii—S5—Pb3v | 104.96 (10) | S13—Sb6—S16iv | 93.02 (10) |
Pb3iv—S5—Pb3v | 88.64 (11) | S13—Sb6—S16v | 93.02 (10) |
Pb3v—S5—Pb3iv | 88.64 (11) | S13—Sb6—S19iv | 91.10 (10) |
Sb2iv—S6—Sb2v | 92.44 (11) | S13—Sb6—S19v | 91.10 (10) |
Sb2iv—S6—Pb2 | 92.10 (13) | S16iv—Sb6—S16v | 94.55 (9) |
Sb2v—S6—Sb2iv | 92.44 (11) | S16iv—Sb6—S19iv | 85.69 (8) |
Sb2v—S6—Pb2 | 92.10 (13) | S16iv—Sb6—S19v | 175.85 (12) |
Sb3vi—S7—Sb3vii | 92.18 (13) | S16v—Sb6—S16iv | 94.55 (9) |
Sb3vi—S7—Pb8 | 93.36 (9) | S16v—Sb6—S19iv | 175.85 (12) |
Sb3vi—S7—Sb8 | 93.36 (9) | S16v—Sb6—S19v | 85.69 (8) |
Sb3vii—S7—Sb3vi | 92.18 (13) | S19iv—Sb6—S19v | 93.76 (8) |
Sb3vii—S7—Pb8 | 93.36 (9) | S19v—Sb6—S19iv | 93.76 (8) |
Sb3vii—S7—Sb8 | 93.36 (9) | S17vi—Pb6—S17vii | 89.19 (7) |
S3iv—Sb4—S3v | 87.15 (7) | S17vi—Pb6—S23 | 78.66 (8) |
S3iv—Sb4—S8 | 90.69 (10) | S17vii—Pb6—S17vi | 89.19 (7) |
S3iv—Sb4—S10iv | 85.35 (7) | S17vii—Pb6—S23 | 78.66 (8) |
S3iv—Sb4—S10v | 172.09 (10) | S20vi—Pb7—S20vii | 87.20 (7) |
S3v—Sb4—S3iv | 87.15 (7) | S20vi—Pb7—S22i | 77.37 (8) |
S3v—Sb4—S8 | 90.69 (10) | S20vii—Pb7—S20vi | 87.20 (7) |
S3v—Sb4—S10iv | 172.09 (10) | S20vii—Pb7—S22i | 77.37 (8) |
S3v—Sb4—S10v | 85.35 (7) | Pb5vi—S18—Pb5vii | 88.73 (8) |
S8—Sb4—S10iv | 91.87 (11) | Pb5vi—S18—Hg2 | 103.89 (11) |
S8—Sb4—S10v | 91.87 (11) | Pb5vii—S18—Pb5vi | 88.73 (8) |
S10iv—Sb4—S10v | 102.04 (8) | Pb5vii—S18—Hg2 | 103.89 (11) |
S10v—Sb4—S10iv | 102.04 (8) | Sb6vi—S19—Sb6vii | 93.76 (11) |
S6—Pb2—S11iv | 82.66 (9) | Sb6vi—S19—Sb7vi | 87.97 (2) |
S6—Pb2—S11v | 82.66 (9) | Sb6vi—S19—Sb7vii | 171.40 (16) |
S11iv—Pb2—S11v | 89.38 (7) | Sb6vii—S19—Sb6vi | 93.76 (11) |
S11v—Pb2—S11iv | 89.38 (7) | Sb6vii—S19—Sb7vi | 171.40 (16) |
S5vi—Pb3—S5vii | 88.64 (8) | Sb6vii—S19—Sb7vii | 87.97 (2) |
S5vii—Pb3—S5vi | 88.64 (8) | Sb7vi—S19—Sb7vii | 89.11 (9) |
S12vi—Sb9—S12vii | 99.48 (10) | Sb7vii—S19—Sb7vi | 89.11 (9) |
S12vi—Sb9—S14 | 86.98 (9) | Pb7iv—S20—Pb7v | 87.20 (9) |
S12vii—Sb9—S12vi | 99.48 (10) | Pb7iv—S20—Sb10 | 104.34 (13) |
S12vii—Sb9—S14 | 86.98 (9) | Pb7iv—S20—Sb10xi | 93.01 (10) |
S12vi—Pb9—S12vii | 99.48 (10) | Pb7v—S20—Pb7iv | 87.20 (9) |
S12vi—Pb9—S14 | 86.98 (8) | Pb7v—S20—Sb10 | 93.01 (10) |
S12vii—Pb9—S12vi | 99.48 (10) | Pb7v—S20—Sb10xi | 104.34 (13) |
S12vii—Pb9—S14 | 86.98 (8) | Sb10—S20—Sb10xi | 16.27 (4) |
Sb3—S9—Pb8iv | 97.66 (9) | Sb10xi—S20—Sb10 | 16.27 (4) |
Sb3—S9—Pb8v | 97.66 (9) | S16—Hg1—S21i | 174.07 (12) |
Sb3—S9—Sb8iv | 97.66 (9) | S17—Sb7—S19iv | 85.25 (10) |
Sb3—S9—Sb8v | 97.66 (9) | S17—Sb7—S19v | 85.25 (10) |
Pb8iv—S9—Pb8v | 89.03 (11) | S17—Sb7—S23iv | 90.20 (10) |
Pb8iv—S9—Sb8v | 89.03 (11) | S17—Sb7—S23v | 90.20 (10) |
Pb8v—S9—Pb8iv | 89.03 (11) | S19iv—Sb7—S19v | 89.11 (7) |
Pb8v—S9—Sb8iv | 89.03 (11) | S19iv—Sb7—S23iv | 85.50 (7) |
Sb8iv—S9—Sb8v | 89.03 (11) | S19iv—Sb7—S23v | 173.21 (8) |
Sb8v—S9—Sb8iv | 89.03 (11) | S19v—Sb7—S19iv | 89.11 (7) |
Sb4vi—S10—Sb4vii | 102.04 (10) | S19v—Sb7—S23iv | 173.21 (8) |
Sb4vii—S10—Sb4vi | 102.04 (10) | S19v—Sb7—S23v | 85.50 (7) |
S11—Sb5—S15vi | 91.67 (12) | S23iv—Sb7—S23v | 99.57 (8) |
S11—Sb5—S15vii | 91.67 (12) | S23v—Sb7—S23iv | 99.57 (8) |
S15vi—Sb5—S15vii | 101.58 (9) | Hg1i—S21—Sb10ix | 103.66 (8) |
S15vii—Sb5—S15vi | 101.58 (9) | Hg1i—S21—Sb10x | 103.66 (8) |
Pb2vi—S11—Pb2vii | 89.38 (9) | Sb10ix—S21—Sb10x | 80.75 (11) |
Pb2vi—S11—Sb5 | 99.90 (7) | Sb10x—S21—Sb10ix | 80.75 (11) |
Pb2vii—S11—Pb2vi | 89.38 (9) | Pb7i—S22—Sb10ix | 93.75 (11) |
Pb2vii—S11—Sb5 | 99.90 (7) | Pb7i—S22—Sb10x | 93.75 (11) |
Sb9iv—S12—Sb9v | 99.48 (14) | Sb10ix—S22—Sb10x | 85.99 (12) |
Sb9iv—S12—Pb9v | 99.48 (14) | Sb10x—S22—Sb10ix | 85.99 (12) |
Sb9iv—S12—Pb5 | 130.26 (7) | Pb6—S23—Sb7vi | 93.92 (8) |
Sb9v—S12—Sb9iv | 99.48 (14) | Pb6—S23—Sb7vii | 93.92 (8) |
Sb9v—S12—Pb9iv | 99.48 (14) | Sb7vi—S23—Sb7vii | 99.57 (11) |
Sb9v—S12—Pb5 | 130.26 (7) | Sb7vii—S23—Sb7vi | 99.57 (11) |
Pb9iv—S12—Pb9v | 99.48 (14) | S18—Hg2—S18i | 180 |
Pb9iv—S12—Pb5 | 130.26 (7) | S18i—Hg2—S18 | 180 |
Pb9v—S12—Pb9iv | 99.48 (14) | S20—Sb10—S21ix | 89.78 (10) |
Pb9v—S12—Pb5 | 130.26 (7) | S20—Sb10—S22ix | 95.80 (10) |
S7—Pb8—S9vi | 81.18 (8) | S20—Sb10—Sb10xi | 81.87 (13) |
S7—Pb8—S9vii | 81.18 (8) | S21ix—Sb10—S22ix | 96.39 (8) |
S7—Pb8—S14vi | 82.88 (8) | S21ix—Sb10—Sb10xi | 130.38 (18) |
S7—Pb8—S14vii | 82.88 (8) | S22ix—Sb10—Sb10xi | 133.00 (17) |
S9vi—Pb8—S9vii | 89.03 (8) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, −y+1/2, −z; (iii) −x+1/2, −y−1/2, −z; (iv) x+1/2, y−1/2, z; (v) x+1/2, y+1/2, z; (vi) x−1/2, y−1/2, z; (vii) x−1/2, y+1/2, z; (viii) −x+1, −y, −z; (ix) −x+3/2, −y+1/2, −z+1; (x) −x+3/2, y−1/2, −z+1; (xi) x, −y, z. |
Experimental details
Crystal data | |
Chemical formula | Hg3Pb16S46Sb18 |
Mr | 7583.1 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 292 |
a, b, c (Å) | 48.124 (11), 4.1083 (2), 23.990 (5) |
β (°) | 118.76 (2) |
V (Å3) | 4158.2 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 44.67 |
Crystal size (mm) | 0.04 × 0.02 × 0.00230 |
Data collection | |
Diffractometer | Oxford Diffraction XCalibur CCD |
Absorption correction | Analytical Clark & Reid (1995) |
Tmin, Tmax | 0.198, 0.805 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 26009, 4942, 3000 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.045, 0.85 |
No. of reflections | 4942 |
No. of parameters | 256 |
No. of restraints | ? |
Δρmax, Δρmin (e Å−3) | 1.20, −1.09 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2004), CrysAlis RED, SIR2002 (Burla et al., 2003), Jana2000 (Petricek et al., 2000), DIAMOND 3 (Brandenburg and Putz, 2005), Jana2000.
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The structure model proposed by Orlandi et al. (2007) is, in basic outline, confirmed; only minor deviations were found. The most striking difference is the absence of 2b superstructure diffraction spots, which were observed in the marrucciite from Bucca della Vena. Consequently, no split positions with half-occupancy occur in the structure model proposed in the present paper. Moreover, we present anisotropic displacement parameters for all atoms of the marrucciite structure.
Fig. 1 depicts the projection of the crystal structure of the title compound along b. The asymmetric unit contains two HgII positions, seven pure PbII positions, eight pure SbIII positions, two mixed PbII/SbIII positions [refined to Pb0.612 (5)Sb0.388 (5) and Pb0.388 (6)Sb0.612 (6)] and 23 S positions. One of the main characteristics of the structure of this compound is the ordering of Sb atoms to form so-called lone electron pair micelles (Fig. 1, left part) where the stereochemically active lone pairs of electrons on Sb are accommodated.