Phase transition at high pressure in Cu₂CO₃(OH)₂ related to the reduction of the Jahn-Teller effect

Hydroxycarbonates with the general formula Me₂(CO₃)(OH)₂ are widely used materials in industrial processes and are widespread in nature. The Cu term, malachite, Cu₂CO₃(OH)₂, is monoclinic, P2₁/a. Substitution of Cu²⁺ with other bivalent cations such as Mg, Zn, Fe, Cu or Ni is possible and leads to a different structure type, rosasite, P2₁/a or P2₁/b11 in the same cell setting as malachite. Rosasite structure is topologically similar to malachite, but the symmetry elements are oriented differently with respect to structural units. The stability of the malachite-like structure (MS) compared with the rosasite-like structure (RS) has been suggested to be related to the Jahn-Teller effect in CuO₆ coordination polyhedra. For this reason the hypothesis of the phase transition of malachite, Cu₂CO₃(OH)₂, to a rosasite structure at high pressure, as a result of the reduced Jahn-Teller effect, has been tested and confirmed by powder and single-crystal diffraction structural studies: above 6 GPa the malachite structure is no longer stable and transforms to a RS structure. RS Cu₂CO₃(OH)₂ is 3% more dense than malachite and the bulk modulus is remarkably higher, 80 (2) GPa compared with 48 (4) GPa. The longer apical Cu-O bonds in the distorted Me1 octahedral site are progressively shortened with increasing pressure, revealing a decrease in the Jahn-Teller effect at high pressure. The transition has a first-order character, is reversible with a significant hysteresis, and there is no evidence of any intermediate phase between the two structures. We then have further evidence that in the Me₂(CO₃)(OH)₂ compounds, the two main structural types, MS and RS, are closely related. The former structure is stabilized only when Cu is the prevalent cation in the octahedral sites, and it can transform directly to the RS as a function of thermodynamic changes.

Computing details

For all compounds, data collection: unknown; cell refinement: unknown; data reduction: unknown; program(s) used to solve structure: unknown; molecular graphics: unknown.

Figures

(malachite_p0)

Crystal data

CCu2O5	V = 363.11 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.007 Mg m^−3
a = 9.473 Å	X-ray radiation, λ = 0.414 Å
b = 11.977 Å	µ = 2.59 mm^−1
c = 3.2377 Å	T = 293 K
β = 98.71°	× × mm

Data collection

724 measured reflections	h = −11→11
455 independent reflections	k = −8→8
308 reflections with I > 3σ(I)	l = −4→4
θmax = 15.3°, θmin = 2.5°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.087	3 restraints
wR(F^2) = 0.131	0 constraints
S = 5.69	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
455 reflections	(Δ/σ)max = 0.001

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

	x	y	z	Uiso*/Ueq
Cu1	0.4995 (5)	0.2884 (9)	0.8936 (12)	0.0113 (15)*
Cu2	0.2324 (4)	0.3929 (9)	0.3891 (10)	0.0086 (15)*
O1	0.132 (2)	0.137 (5)	0.343 (7)	0.024 (7)*
O2	0.342 (2)	0.235 (3)	0.459 (7)	0.016 (7)*
O3	0.335 (2)	0.059 (3)	0.633 (6)	0.012 (6)*
O4	0.083 (2)	0.347 (5)	0.918 (6)	0.009 (6)*
O5	0.3779 (17)	0.409 (4)	0.860 (4)	0.000 (5)*
C	0.268 (2)	0.145 (3)	0.461 (10)	0.010 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.49 (3)	Cu2—O5	1.904 (15)
Cu1—O1^ii	1.98 (3)	O1—O2	2.30 (4)
Cu1—O2	1.99 (2)	O1—O3	2.22 (4)
Cu1—O2^iii	2.61 (3)	O1—O5^vi	2.72 (3)
Cu1—O4^i	1.80 (5)	O1—C	1.29 (3)
Cu1—O5	1.84 (4)	O2—O3	2.19 (5)
Cu2—O2	2.15 (4)	O2—O4^i	2.71 (4)
Cu2—O3^iv	2.09 (4)	O2—O5	2.45 (5)
Cu2—O4^v	1.99 (2)	O2—C	1.29 (5)
Cu2—O4	2.44 (2)	O3—O4^i	2.64 (4)
Cu2—O5^v	2.364 (17)	O3—C	1.29 (5)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) x−1/2, −y+1/2, z−1.

(malachite_p1)

Crystal data

CCu2O5	V = 355.68 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.090 Mg m^−3
a = 9.3887 Å	X-ray radiation, λ = 0.414 Å
b = 11.968 Å	µ = 2.59 mm^−1
c = 3.196 Å	T = 293 K
β = 97.93°	× × mm

Data collection

711 measured reflections	h = −11→11
423 independent reflections	k = −8→8
316 reflections with I > 3σ(I)	l = −4→4
θmax = 15.4°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.075	3 restraints
wR(F^2) = 0.094	0 constraints
S = 4.61	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
423 reflections	(Δ/σ)max = 0.001

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

	x	y	z	Uiso*/Ueq
Cu1	0.4999 (3)	0.2880 (6)	0.8875 (8)	0.0107 (11)*
Cu2	0.2327 (3)	0.3936 (6)	0.3851 (7)	0.0098 (11)*
O1	0.1323 (13)	0.136 (3)	0.337 (4)	0.011 (4)*
O2	0.3398 (16)	0.235 (2)	0.447 (5)	0.015 (4)*
O3	0.3388 (14)	0.058 (2)	0.635 (4)	0.006 (4)*
O4	0.0940 (15)	0.346 (3)	0.906 (4)	0.012 (4)*
O5	0.3802 (13)	0.418 (3)	0.858 (3)	0.002 (4)*
C	0.2690 (13)	0.143 (2)	0.460 (6)	0.001 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.46 (2)	O1—O2	2.27 (3)
Cu1—O1^ii	1.99 (2)	O1—O3	2.24 (2)
Cu1—O2	2.015 (16)	O1—O5^vi	2.68 (5)
Cu1—O2^iii	2.571 (17)	O1—O5^vii	2.71 (2)
Cu1—O4^i	1.83 (4)	O1—C	1.292 (17)
Cu1—O5	1.91 (3)	O2—O3	2.20 (3)
Cu2—O2	2.15 (2)	O2—O4^i	2.80 (3)
Cu2—O3^iv	2.08 (2)	O2—O5	2.56 (4)
Cu2—O4^v	1.953 (18)	O2—C	1.29 (3)
Cu2—O4	2.322 (18)	O3—O4^i	2.69 (3)
Cu2—O5^v	2.341 (13)	O3—C	1.29 (3)
Cu2—O5	1.927 (12)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.

(malachite_p2)

Crystal data

CCu2O5	V = 349.85 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.158 Mg m^−3
a = 9.3174 Å	X-ray radiation, λ = 0.414 Å
b = 11.9774 Å	µ = 2.59 mm^−1
c = 3.1597 Å	T = 293 K
β = 97.1782°	× × mm

Data collection

704 measured reflections	h = −11→11
704 independent reflections	k = −8→8
454 reflections with I > 3σ(I)	l = −4→4
θmax = 15.2°, θmin = 2.5°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.064	3 restraints
wR(F^2) = 0.077	0 constraints
S = 3.32	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
704 reflections	(Δ/σ)max = 0.001

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

	x	y	z	Uiso*/Ueq
Cu1	0.5008 (2)	0.2885 (4)	0.8810 (6)	0.0139 (7)*
Cu2	0.2328 (2)	0.3935 (4)	0.3804 (5)	0.0127 (7)*
O1	0.1310 (10)	0.135 (2)	0.334 (3)	0.022 (3)*
O2	0.3367 (10)	0.2340 (13)	0.437 (3)	0.009 (3)*
O3	0.3369 (10)	0.0551 (13)	0.627 (3)	0.011 (3)*
O4	0.0910 (10)	0.352 (2)	0.905 (3)	0.015 (3)*
O5	0.3820 (9)	0.4194 (19)	0.849 (2)	0.011 (3)*
C	0.2682 (10)	0.1408 (13)	0.457 (5)	0.016 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.411 (13)	Cu2—O5	1.925 (9)
Cu1—O1^ii	1.980 (14)	O1—O2	2.240 (19)
Cu1—O2	2.049 (10)	O1—O3	2.240 (17)
Cu1—O2^iii	2.552 (10)	O1—O5^vi	2.65 (3)
Cu1—O4^i	1.88 (2)	O1—O5^vii	2.697 (14)
Cu1—O5	1.91 (2)	O1—C	1.291 (13)
Cu2—O2	2.139 (15)	O2—O3	2.22 (2)
Cu2—O3^iv	2.041 (16)	O2—O5	2.58 (2)
Cu2—O4^v	1.936 (11)	O2—C	1.29 (2)
Cu2—O4	2.299 (11)	O3—O4^i	2.661 (17)
Cu2—O5^v	2.331 (9)	O3—C	1.29 (2)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.

(malachite_p3)

Crystal data

CCu2O5	V = 343.50 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.235 Mg m^−3
a = 9.2363 Å	X-ray radiation, λ = 0.414 Å
b = 11.9873 Å	µ = 2.59 mm^−1
c = 3.1205 Å	T = 293 K
β = 96.1667°	× × mm

Data collection

676 measured reflections	h = −11→11
546 independent reflections	k = −8→8
371 reflections with I > 3σ(I)	l = −4→3
θmax = 15.3°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.066	3 restraints
wR(F^2) = 0.080	0 constraints
S = 3.77	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
546 reflections	(Δ/σ)max = 0.002

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

	x	y	z	Uiso*/Ueq
Cu1	0.5022 (2)	0.2891 (5)	0.8744 (9)	0.0149 (10)*
Cu2	0.2330 (2)	0.3934 (4)	0.3753 (7)	0.0131 (9)*
O1	0.1336 (11)	0.138 (2)	0.325 (4)	0.019 (4)*
O2	0.3399 (12)	0.2334 (15)	0.430 (4)	0.018 (4)*
O3	0.3400 (12)	0.0558 (16)	0.631 (4)	0.012 (4)*
O4	0.0943 (11)	0.348 (2)	0.891 (4)	0.010 (4)*
O5	0.3817 (11)	0.418 (2)	0.845 (4)	0.013 (4)*
C	0.2709 (12)	0.1405 (16)	0.455 (6)	0.007 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.375 (16)	O1—O2	2.22 (2)
Cu1—O1^ii	1.964 (16)	O1—O3	2.261 (19)
Cu1—O2	2.042 (13)	O1—O5^vi	2.69 (4)
Cu1—O2^iii	2.501 (14)	O1—O5^vii	2.710 (17)
Cu1—O4^i	1.85 (2)	O1—C	1.290 (15)
Cu1—O5	1.90 (2)	O2—O3	2.22 (3)
Cu2—O2	2.156 (18)	O2—O4^i	2.796 (18)
Cu2—O3^iv	2.060 (19)	O2—O5	2.57 (3)
Cu2—O4^v	1.951 (13)	O2—C	1.29 (2)
Cu2—O4	2.229 (14)	O3—O4^i	2.665 (19)
Cu2—O5^v	2.280 (12)	O3—C	1.29 (2)
Cu2—O5	1.920 (11)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.

(malachite_p4)

Crystal data

CCu2O5	V = 339.33 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.287 Mg m^−3
a = 9.1834 Å	X-ray radiation, λ = 0.414 Å
b = 12.0234 Å	µ = 2.59 mm^−1
c = 3.0886 Å	T = 293 K
β = 95.7294°	× × mm

Data collection

605 measured reflections	h = −11→11
605 independent reflections	k = −8→8
436 reflections with I > 3σ(I)	l = −4→3
θmax = 15.5°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.074	3 restraints
wR(F^2) = 0.091	0 constraints
S = 4.36	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
605 reflections	(Δ/σ)max = 0.001

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

	x	y	z	Uiso*/Ueq
Cu1	0.5033 (3)	0.2887 (5)	0.8718 (8)	0.0134 (9)*
Cu2	0.2328 (3)	0.3942 (5)	0.3701 (7)	0.0138 (9)*
O1	0.1336 (14)	0.137 (3)	0.321 (5)	0.028 (5)*
O2	0.3403 (13)	0.2323 (18)	0.426 (4)	0.016 (4)*
O3	0.3397 (13)	0.0545 (18)	0.623 (4)	0.014 (4)*
O4	0.0934 (14)	0.347 (3)	0.880 (5)	0.020 (4)*
O5	0.3779 (12)	0.416 (2)	0.846 (4)	0.012 (4)*
C	0.2717 (14)	0.1392 (18)	0.445 (6)	0.017 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.350 (18)	O1—O2	2.21 (3)
Cu1—O1^ii	1.953 (19)	O1—O3	2.26 (2)
Cu1—O2	2.046 (14)	O1—O5^vi	2.71 (4)
Cu1—O2^iii	2.478 (14)	O1—O5^vii	2.720 (19)
Cu1—O4^i	1.83 (3)	O1—C	1.289 (18)
Cu1—O5	1.92 (3)	O2—O3	2.22 (3)
Cu2—O2	2.18 (2)	O2—O4^i	2.76 (2)
Cu2—O3^iv	2.04 (2)	O2—O5	2.57 (3)
Cu2—O4^v	1.965 (15)	O2—C	1.29 (3)
Cu2—O4	2.201 (16)	O3—O4^i	2.66 (2)
Cu2—O5^v	2.214 (12)	O3—C	1.29 (3)
Cu2—O5	1.901 (11)	O4—O5	2.75 (2)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.

(malachite_p5)

Crystal data

CCu2O5	V = 334.58 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.348 Mg m^−3
a = 9.1142 Å	X-ray radiation, λ = 0.414 Å
b = 12.0534 Å	µ = 2.59 mm^−1
c = 3.0574 Å	T = 293 K
β = 95.0321°	× × mm

Data collection

643 measured reflections	h = −10→11
612 independent reflections	k = −8→8
442 reflections with I > 3σ(I)	l = −3→3
θmax = 15.3°, θmin = 2.6°

Refinement

Refinement on F	34 parameters
R[F^2 > 2σ(F^2)] = 0.080	3 restraints
wR(F^2) = 0.094	0 constraints
S = 4.60	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
612 reflections	(Δ/σ)max = 0.002

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

	x	y	z	Uiso*/Ueq
Cu1	0.5042 (2)	0.2894 (5)	0.8647 (9)	0.0138 (9)*
Cu2	0.2337 (3)	0.3939 (5)	0.3669 (7)	0.0127 (9)*
O1	0.1355 (11)	0.137 (2)	0.311 (4)	0.008 (4)*
O2	0.3451 (13)	0.2327 (17)	0.420 (5)	0.019 (4)*
O3	0.3432 (11)	0.0586 (17)	0.627 (4)	0.002 (3)*
O4	0.0923 (12)	0.349 (2)	0.876 (4)	0.009 (4)*
O5	0.3800 (12)	0.415 (3)	0.847 (4)	0.015 (4)*
C	0.2744 (12)	0.1404 (17)	0.431 (6)	0.006 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.330 (15)	O1—O3	2.257 (19)
Cu1—O1^ii	1.947 (16)	O1—O5^vi	2.72 (4)
Cu1—O2	2.017 (14)	O1—O5^vii	2.693 (17)
Cu1—O2^iii	2.425 (15)	O1—C	1.288 (15)
Cu1—O4^i	1.85 (3)	O2—O3	2.19 (3)
Cu1—O5	1.89 (3)	O2—O4^i	2.73 (2)
Cu2—O2	2.191 (19)	O2—O5	2.56 (3)
Cu2—O3^iv	2.11 (2)	O2—C	1.29 (3)
Cu2—O4^v	1.967 (14)	O3—O4^i	2.58 (2)
Cu2—O4	2.174 (14)	O3—C	1.29 (2)
Cu2—O5^v	2.177 (13)	O3—C^iii	2.77 (2)
Cu2—O5	1.912 (12)	O4—O5	2.750 (19)
O1—O2	2.23 (2)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.

(malachite_p6)

Crystal data

CCu2O5	V = 328.37 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.430 Mg m^−3
a = 12.699 Å	X-ray radiation, λ = 0.414 Å
b = 9.039 Å	µ = 2.89 mm^−1
c = 2.9943 Å	T = 293 K
β = 107.18°	× × mm

Data collection

664 measured reflections	h = −8→9
664 independent reflections	k = −11→11
448 reflections with I > 3σ(I)	l = −3→3
θmax = 15.4°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.125	3 restraints
wR(F^2) = 0.171	0 constraints
S = 7.70	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
664 reflections	(Δ/σ)max = 0.002

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

	x	y	z	Uiso*/Ueq
Cu1	0.2064 (9)	0.0102 (5)	0.439 (2)	0.0127 (17)*
Cu2	0.3909 (9)	0.2361 (5)	0.1810 (18)	0.0136 (17)*
C	0.140 (3)	0.283 (2)	0.717 (11)	0.008 (10)*
O1	0.129 (4)	0.143 (2)	0.772 (11)	0.017 (8)*
O2	0.231 (3)	0.353 (2)	0.887 (9)	0.003 (7)*
O3	0.059 (3)	0.342 (2)	0.406 (8)	0.000 (7)*
O4	0.360 (5)	0.103 (2)	0.656 (10)	0.008 (7)*
O5	0.430 (4)	0.385 (2)	−0.254 (10)	0.016 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—Cu1^i	2.994 (10)	Cu2—Cu2^ii	2.994 (9)
Cu1—Cu1^ii	2.994 (10)	Cu2—C^i	3.10 (4)
Cu1—Cu2	3.365 (13)	Cu2—C^vi	3.10 (3)
Cu1—Cu2^ii	3.393 (9)	Cu2—O2^i	2.22 (3)
Cu1—Cu2^iii	3.124 (7)	Cu2—O3^vi	2.16 (4)
Cu1—Cu2^iv	3.128 (10)	Cu2—O4^i	1.93 (3)
Cu1—C^i	3.22 (3)	Cu2—O4	1.99 (4)
Cu1—C	2.81 (3)	Cu2—O5	2.03 (4)
Cu1—C^iv	2.96 (3)	Cu2—O5^ii	2.10 (3)
Cu1—O1^i	2.29 (3)	C—O1	1.29 (3)
Cu1—O1	2.00 (4)	C—O2	1.29 (4)
Cu1—O2^iv	2.01 (3)	C—O3	1.29 (4)
Cu1—O2^v	2.40 (2)	O1—O2	2.27 (4)
Cu1—O4	2.04 (5)	O1—O3	2.16 (3)
Cu1—O5^iii	2.01 (5)	O2—O3	2.24 (4)
Cu2—Cu2^i	2.994 (9)

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x+1/2, y−1/2, −z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+2; (vi) x+1/2, −y+1/2, z.

(rosasite_p7)

Crystal data

CCu2O5	V = 325.49 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.470 Mg m^−3
a = 12.6665 Å	X-ray radiation, λ = 0.414 Å
b = 9.0153 Å	µ = 2.89 mm^−1
c = 2.9827 Å	T = 293 K
β = 107.13°	× × mm

Data collection

654 measured reflections	h = −8→9
622 independent reflections	k = −10→10
420 reflections with I > 3σ(I)	l = −3→3
θmax = 15.4°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.092	3 restraints
wR(F^2) = 0.101	0 constraints
S = 4.41	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
622 reflections	(Δ/σ)max = 0.002

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

	x	y	z	Uiso*/Ueq
Cu1	0.2106 (5)	0.0108 (3)	0.4453 (12)	0.0134 (10)*
Cu2	0.3929 (5)	0.2371 (2)	0.1862 (10)	0.0101 (10)*
C	0.1364 (18)	0.2861 (12)	0.756 (7)	0.017 (7)*
O1	0.131 (2)	0.1443 (11)	0.789 (6)	0.009 (4)*
O2	0.2293 (18)	0.3552 (13)	0.884 (5)	0.013 (4)*
O3	0.065 (2)	0.3475 (13)	0.407 (5)	0.017 (5)*
O4	0.355 (2)	0.1049 (11)	0.639 (5)	−0.001 (4)*
O5	0.428 (2)	0.3833 (12)	−0.266 (6)	0.011 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—Cu1^i	2.983 (6)	Cu2—Cu2^ii	2.983 (5)
Cu1—Cu1^ii	2.983 (6)	Cu2—O2^i	2.27 (2)
Cu1—Cu2^iii	3.147 (4)	Cu2—O3^vi	2.22 (2)
Cu1—Cu2^iv	3.141 (6)	Cu2—O4^i	1.964 (12)
Cu1—O1^i	2.266 (15)	Cu2—O4	1.965 (19)
Cu1—O1	2.03 (2)	Cu2—O5	2.027 (19)
Cu1—O2^iv	1.988 (18)	Cu2—O5^ii	2.045 (14)
Cu1—O2^v	2.378 (14)	C—O1	1.286 (15)
Cu1—O4	1.94 (3)	C—O2	1.29 (3)
Cu1—O5^iii	2.03 (2)	C—O3	1.29 (2)
Cu2—Cu2^i	2.983 (5)

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x+1/2, y−1/2, −z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+2; (vi) x+1/2, −y+1/2, z.

(rosasite_p8)

Crystal data

CCu2O5	V = 322.33 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.513 Mg m^−3
a = 12.6235 Å	X-ray radiation, λ = 0.414 Å
b = 8.9926 Å	µ = 2.89 mm^−1
c = 2.9704 Å	T = 293 K
β = 107.0757°	× × mm

Data collection

594 measured reflections	h = −8→9
594 independent reflections	k = −11→11
464 reflections with I > 3σ(I)	l = −3→3
θmax = 15.5°, θmin = 2.6°

Refinement

Refinement on F	45 parameters
R[F^2 > 2σ(F^2)] = 0.068	3 restraints
wR(F^2) = 0.081	0 constraints
S = 4.55	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
594 reflections	(Δ/σ)max = 0.002

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

	x	y	z	Uiso*/Ueq
Cu1	0.2091 (4)	0.0118 (2)	0.4407 (10)	0.022 (3)
Cu2	0.3933 (4)	0.2381 (2)	0.1886 (9)	0.022 (2)
C	0.1416 (15)	0.2832 (11)	0.699 (6)	0.029 (6)*
O1	0.131 (2)	0.1436 (10)	0.768 (5)	0.014 (3)*
O2	0.2316 (15)	0.3546 (11)	0.892 (4)	0.012 (4)*
O3	0.0589 (16)	0.3500 (11)	0.414 (4)	0.012 (3)*
O4	0.352 (3)	0.1060 (12)	0.642 (5)	0.022 (4)*
O5	0.428 (2)	0.3858 (12)	−0.266 (5)	0.019 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.030 (7)	0.0050 (14)	0.0353 (17)	−0.0008 (14)	0.014 (3)	−0.0008 (10)
Cu2	0.036 (6)	0.0037 (13)	0.0299 (17)	−0.0019 (14)	0.013 (3)	−0.0011 (12)

Bond lengths (Å)

Cu1—Cu1^i	2.970 (5)	Cu2—Cu2^ii	2.970 (4)
Cu1—Cu1^ii	2.970 (5)	Cu2—O2^i	2.232 (16)
Cu1—Cu2^iii	3.131 (3)	Cu2—O3^vi	2.150 (19)
Cu1—Cu2^iv	3.127 (5)	Cu2—O4^i	1.955 (13)
Cu1—O1^i	2.282 (13)	Cu2—O4	1.98 (2)
Cu1—O1	1.97 (2)	Cu2—O5	2.032 (17)
Cu1—O2^iv	1.992 (15)	Cu2—O5^ii	2.040 (13)
Cu1—O2^v	2.369 (11)	C—O1	1.285 (15)
Cu1—O4	1.92 (3)	C—O2	1.28 (2)
Cu1—O5^iii	2.01 (2)	C—O3	1.28 (2)
Cu2—Cu2^i	2.970 (4)

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x+1/2, y−1/2, −z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+2; (vi) x+1/2, −y+1/2, z.

(rosasite_p9)

Crystal data

CCu2O5	V = 318.91 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.562 Mg m^−3
a = 12.582 Å	X-ray radiation, λ = 0.414 Å
b = 8.965 Å	µ = 2.89 mm^−1
c = 2.9572 Å	T = 293 K
β = 107.05°	× × mm

Data collection

630 measured reflections	h = −8→9
630 independent reflections	k = −10→10
445 reflections with I > 3σ(I)	l = −3→3
θmax = 15.2°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.099	3 restraints
wR(F^2) = 0.130	0 constraints
S = 6.16	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
630 reflections	(Δ/σ)max = 0.001

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

	x	y	z	Uiso*/Ueq
Cu1	0.2080 (6)	0.0129 (4)	0.4362 (15)	0.0125 (13)*
Cu2	0.3926 (7)	0.2391 (4)	0.1893 (14)	0.0131 (13)*
C	0.139 (2)	0.2869 (16)	0.712 (9)	0.012 (8)*
O1	0.129 (3)	0.1460 (15)	0.761 (8)	0.010 (5)*
O2	0.231 (2)	0.3571 (16)	0.902 (7)	0.004 (5)*
O3	0.057 (2)	0.3495 (18)	0.409 (6)	0.010 (5)*
O4	0.358 (4)	0.1057 (16)	0.665 (7)	0.006 (5)*
O5	0.429 (3)	0.3875 (18)	−0.261 (8)	0.017 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—Cu1^i	2.957 (7)	Cu2—Cu2^i	2.957 (7)
Cu1—Cu1^ii	2.957 (7)	Cu2—Cu2^ii	2.957 (7)
Cu1—Cu2	3.321 (10)	Cu2—O2^i	2.23 (2)
Cu1—Cu2^iii	3.111 (5)	Cu2—O3^vi	2.13 (3)
Cu1—Cu2^iv	3.111 (7)	Cu2—O4^i	1.905 (19)
Cu1—O1^i	2.29 (2)	Cu2—O4	1.99 (3)
Cu1—O1	1.98 (3)	Cu2—O5	2.03 (3)
Cu1—O2^iv	2.00 (2)	Cu2—O5^ii	2.05 (2)
Cu1—O2^v	2.344 (18)	C—O1	1.28 (2)
Cu1—O4	1.99 (4)	C—O2	1.28 (3)
Cu1—O5^iii	2.00 (3)	C—O3	1.28 (3)

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x+1/2, y−1/2, −z; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+2; (vi) x+1/2, −y+1/2, z.

(rosasite_p10)

Crystal data

CCu2O5	V = 343.12 Å^3
Mr = 219.1	Z = 4
Monoclinic, P21/a	F(000) = 416
Hall symbol: -P 2yab	Dx = 4.24 Mg m^−3
a = 9.2295 Å	X-ray radiation, λ = 0.414 Å
b = 12.0064 Å	µ = 2.59 mm^−1
c = 3.1155 Å	T = 293 K
β = 96.3516°	× × mm

Data collection

671 measured reflections	h = −11→11
671 independent reflections	k = −8→8
491 reflections with I > 3σ(I)	l = −4→3
θmax = 15.6°, θmin = 2.6°

Refinement

Refinement on F	35 parameters
R[F^2 > 2σ(F^2)] = 0.068	3 restraints
wR(F^2) = 0.088	0 constraints
S = 4.20	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
671 reflections	(Δ/σ)max = 0.013

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

	x	y	z	Uiso*/Ueq
Cu1	0.5021 (2)	0.2891 (5)	0.8752 (7)	0.0157 (8)*
Cu2	0.2330 (2)	0.3942 (4)	0.3752 (6)	0.0137 (8)*
O1	0.1330 (10)	0.133 (2)	0.331 (3)	0.008 (3)*
O2	0.3424 (11)	0.2332 (15)	0.430 (4)	0.016 (4)*
O3	0.3399 (11)	0.0573 (16)	0.632 (4)	0.010 (3)*
O4	0.0942 (11)	0.351 (2)	0.898 (4)	0.010 (3)*
O5	0.3795 (10)	0.420 (2)	0.855 (3)	0.007 (3)*
C	0.2709 (10)	0.1415 (16)	0.451 (5)	0.010 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Bond lengths (Å)

Cu1—O1^i	2.376 (14)	O1—O2	2.27 (2)
Cu1—O1^ii	1.991 (15)	O1—O3	2.228 (18)
Cu1—O2	2.024 (12)	O1—O5^vi	2.63 (4)
Cu1—O2^iii	2.484 (12)	O1—O5^vii	2.705 (15)
Cu1—O4^i	1.89 (3)	O1—C	1.290 (13)
Cu1—O5	1.93 (2)	O2—O3	2.20 (3)
Cu2—O2	2.179 (18)	O2—O4^i	2.794 (18)
Cu2—O3^iv	2.070 (19)	O2—O5	2.60 (3)
Cu2—O4^v	1.923 (12)	O2—C	1.29 (2)
Cu2—O4	2.240 (13)	O3—O4^i	2.640 (19)
Cu2—O5^v	2.244 (10)	O3—C	1.29 (2)
Cu2—O5	1.925 (10)	O4—O5	2.775 (17)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z+1; (iii) x, y, z+1; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z−1; (vi) −x+1/2, y−1/2, −z+1; (vii) x−1/2, −y+1/2, z−1.