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The structure of meneghinite (CuPb13Sb7S24), from the Bottino mine in the Apuan Alps (Italy), has been solved and refined as an incommensurate structure in four-dimensional superspace. The structure is orthorhombic, superspace group Pnma(0β0)00s, cell parameters a = 24.0549 (3), b = 4.1291 (6), c = 11.3361 (16) Å, modulation vector q = 0.5433 (4)b*. The structure was refined from 6604 reflections to a final R = 0.0479. The model includes modulation of both atomic positions and displacement parameters, as well as occupational waves. The driving forces stabilizing the modulated structure of meneghinite are linked to the occupation modulation of Cu and some of the Pb atoms. As a consequence of the Cu/[] and Pb/Sb modulations, three- to sevenfold coordinations of the M cations (Pb/Sb) occur in different parts of the structure. The almost bimodal distribution of the occupation of Cu/[] and Pb/Sb at M5 conforms with the coupled substitution Sb3+ + [] → Pb2+ + Cu+, thus corroborating the hypothesis deduced previously for the incorporation of copper in the meneghinite structure. The very small departure (∼0.54 versus 0.50) from the commensurate value of the modulation raises the question of whether other sulfosalts considered superstructures have been properly described, and, in this light, if incommensurate modulation in sulfosalts could be much more common than thought.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520617002657/xk5035sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520617002657/xk5035Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520617002657/xk5035sup3.pdf
Supporting tables

B-IncStrDB reference: 13202EGzpbI

CCDC reference: 1533002

Computing details top

(I) top
Crystal data top
Cu0.966Pb13.196S24Sb6.804V = 1126.0 (2) Å3
Mr = 4393.3Z = 1
Orthorhombic, Pnma(0β0)00sF(000) = 1839
q = 0.543300b*Dx = 6.479 Mg m3
a = 24.0549 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 4.1291 (6) ŵ = 54.69 mm1
c = 11.3361 (16) ÅT = 297 K
† Symmetry operations: (1) x1, x2, x3, x4; (2) −x1+1/2, −x2, x3+1/2, −x4+1/2; (3) −x1, x2+1/2, −x3, x4+1/2; (4) x1+1/2, −x2+1/2, −x3+1/2, −x4; (5) −x1, −x2, −x3, −x4; (6) x1+1/2, x2, −x3+1/2, x4+1/2; (7) x1, −x2+1/2, x3, −x4+1/2; (8) −x1+1/2, x2+1/2, x3+1/2, x4.

Data collection top
Oxford Diffraction CCD
diffractometer
6604 independent reflections
Radiation source: X-ray tube4696 reflections with I > 3σ(I)
Graphite monochromator
Refinement top
Refinement on F2216 parameters
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.11578 constraints
S = 1.97Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
6604 reflections(Δ/σ)max = 0.807
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.247 (2)0.250.209 (5)0.0388 (11)0.239 (4)
Pb10.125229 (14)0.250.15769 (3)0.02675 (11)
Pb20.064759 (19)0.750.46575 (4)0.02537 (16)0.4800 (17)
Sb20.064759 (19)0.750.46575 (4)0.02537 (16)0.5199 (17)
Pb30.025121 (19)0.250.15251 (4)0.02636 (16)0.5246 (18)
Sb30.025121 (19)0.250.15251 (4)0.02636 (16)0.4754 (18)
Pb40.215255 (15)0.250.48311 (4)0.03405 (13)
Pb50.15041 (2)0.750.21855 (5)0.02817 (16)0.2841
Sb50.15041 (2)0.750.21855 (5)0.02817 (16)0.7159
S10.15229 (8)0.750.33925 (19)0.0214 (6)
S20.06368 (9)0.250.02736 (18)0.0214 (6)
S30.23688 (9)0.750.3373 (2)0.0244 (6)
S40.02045 (9)0.750.28375 (19)0.0240 (6)
S50.10735 (9)0.250.5944 (2)0.0263 (6)
S60.18416 (9)0.250.0896 (2)0.0353 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0318 (17)0.0351 (18)0.050 (2)00.0051 (14)0
Pb10.02884 (19)0.02372 (18)0.0277 (2)00.00114 (13)0
Pb20.0275 (3)0.0243 (3)0.0244 (3)00.00051 (18)0
Sb20.0275 (3)0.0243 (3)0.0244 (3)00.00051 (18)0
Pb30.0291 (3)0.0243 (3)0.0257 (3)00.00392 (18)0
Sb30.0291 (3)0.0243 (3)0.0257 (3)00.00392 (18)0
Pb40.02498 (19)0.0333 (2)0.0439 (3)00.00206 (15)0
Pb50.0236 (3)0.0335 (3)0.0275 (3)00.0003 (2)0
Sb50.0236 (3)0.0335 (3)0.0275 (3)00.0003 (2)0
S10.0222 (10)0.0230 (10)0.0189 (10)00.0000 (8)0
S20.0240 (10)0.0214 (10)0.0188 (10)00.0008 (8)0
S30.0255 (10)0.0248 (10)0.0229 (11)00.0033 (8)0
S40.0252 (10)0.0260 (10)0.0207 (11)00.0007 (8)0
S50.0273 (10)0.0279 (11)0.0237 (11)00.0002 (8)0
S60.0259 (11)0.0552 (15)0.0247 (12)00.0001 (9)0
Bond lengths (Å) top
AverageMinimumMaximum
Cu1—Pb4i3.22 (9)3.14 (14)3.32 (14)
Cu1—Pb4ii3.35 (8)3.10 (11)3.46 (11)
Cu1—Pb4iii3.35 (8)3.10 (11)3.46 (11)
Cu1—Pb5iv3.29 (8)3.16 (10)3.34 (10)
Cu1—Pb53.29 (8)3.15 (10)3.34 (10)
Cu1—S1iii2.41 (8)2.39 (13)2.45 (13)
Cu1—S3iv2.36 (8)2.29 (9)2.52 (9)
Cu1—S32.37 (8)2.29 (9)2.52 (9)
Cu1—S62.42 (9)2.29 (13)2.48 (13)
Pb1—S1iv2.988 (3)2.949 (4)3.042 (4)
Pb1—S12.988 (3)2.949 (4)3.042 (4)
Pb1—S2v2.939 (3)2.859 (4)2.987 (4)
Pb1—S2vi2.939 (3)2.859 (4)2.987 (4)
Pb1—S4v2.901 (4)2.891 (6)2.907 (6)
Pb2—Pb2vii3.7609 (11)3.7302 (13)3.9507 (13)
Pb2—Pb2viii3.7626 (11)3.7302 (13)3.9506 (13)
Pb2—Sb2000
Pb2—S12.587 (3)2.445 (6)2.673 (6)
Pb2—S4v3.044 (4)2.890 (5)3.342 (5)
Pb2—S4vi3.045 (4)2.890 (5)3.337 (5)
Pb2—S52.802 (4)2.496 (4)2.983 (4)
Pb2—S5ix2.803 (4)2.490 (4)2.983 (4)
Sb2—S12.529 (3)2.411 (6)2.660 (6)
Sb2—S52.684 (4)2.427 (4)2.982 (4)
Sb2—S5ix2.686 (4)2.427 (4)2.983 (4)
Pb3—Sb3000
Pb3—Pb5iv3.6940 (11)3.6708 (13)3.7470 (13)
Pb3—Pb53.6944 (11)3.6708 (13)3.7480 (13)
Pb3—S22.597 (3)2.462 (6)2.680 (6)
Pb3—S2v3.010 (3)2.936 (4)3.199 (4)
Pb3—S2vi3.010 (3)2.936 (4)3.200 (4)
Pb3—S4iv2.838 (4)2.517 (4)3.013 (4)
Pb3—S42.838 (4)2.520 (4)3.013 (4)
Sb3—S22.544 (3)2.438 (6)2.665 (6)
Sb3—S4iv2.717 (4)2.452 (4)2.993 (4)
Sb3—S42.717 (4)2.452 (4)2.994 (4)
Pb4—S1iv3.037 (3)2.890 (4)3.137 (4)
Pb4—S13.037 (3)2.890 (4)3.136 (4)
Pb4—S3x2.948 (4)2.830 (4)3.076 (4)
Pb4—S3xi2.947 (4)2.830 (4)3.076 (4)
Pb4—S52.893 (4)2.843 (6)2.953 (6)
Pb5—Sb5000
Pb5—S32.519 (4)2.429 (6)2.596 (6)
Pb5—S5i3.047 (4)2.894 (5)3.284 (5)
Pb5—S5xii3.045 (4)2.894 (5)3.280 (5)
Pb5—S62.781 (4)2.532 (5)2.996 (5)
Pb5—S6ix2.780 (4)2.529 (5)2.996 (5)
Sb5—S32.481 (4)2.419 (6)2.596 (6)
Sb5—S62.658 (4)2.411 (5)2.996 (5)
Sb5—S6ix2.658 (4)2.411 (5)2.996 (5)
Symmetry codes: (i) x1, x2, x31, x4; (ii) x1+1/2, x2, x31/2, x4+1/2; (iii) x1+1/2, x2+1, x31/2, x4+1/2; (iv) x1, x21, x3, x4; (v) x1, x21/2, x3, x4+1/2; (vi) x1, x2+1/2, x3, x4+1/2; (vii) x1, x21/2, x3+1, x4+1/2; (viii) x1, x2+1/2, x3+1, x4+1/2; (ix) x1, x2+1, x3, x4; (x) x1, x21, x3+1, x4; (xi) x1, x2, x3+1, x4; (xii) x1, x2+1, x31, x4.
 

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