Low-temperature phases of dicalcium barium hexa­kis­(propano­ate)

Fábry, J.; Dušek, M.

doi:10.1107/S205322962101024X

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Low-temperature phases of dicalcium barium hexakis(propanoate)

J. Fábry and M. Dušek

The structure determinations of phases (II) and (III) of barium dicalcium hexakis(propanoate) {or poly[hexa-μ₄-propanoato-bariumdicalcium], [BaCa₂(C₃H₅O₂)₆]_n} are reported at 240 and 130 K, respectively [phase (I) was determined previously by Stadnicka & Glazer (1980). Acta Cryst. B36, 2977–2985; our structure determination of phase (I) at room temperature is included in the supporting information]. In the high-temperature phase, the Ba²⁺ cation is surrounded by six carboxylate groups in bidentate bridging modes. In the low-temperature phases, five carboxylate groups act in bidentate bridging modes and one acts in a monodentate bridging mode around Ba²⁺. The Ca²⁺ cations are surrounded by six carboxylate O atoms in a trigonal antiprism in all the structures. The Ba²⁺ and Ca²⁺ cations are underbonded and significantly overbonded, respectively, in all the phases. The bonding of the Ba²⁺ cation increases slightly at the cost of the bonding of Ca²⁺ cations during cooling to the low-temperature phases. The phase transitions during cooling are accompanied by ordering of the ethyl chains. In room-temperature phase (I), all six ethyl chains are positionally disordered over two positions in the crossed mode, with additional splitting of the ethyl α- and β-C atoms. In phase (II), on the other hand, there are three disordered ethyl chains, one with positionally disordered ethyl α- and β-C atoms, and the other two with positionally disordered ethyl β-C atoms only, and in the lowest-temperature phase (III) there are four ordered ethyl chains and two disordered ethyl chains with positionally disordered ethyl β-C atoms only.

Keywords: barium dicalcium propanoate; positional disorder; first-order phase transition; second-order phase transition; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205322962101024X/jx3066sup1.cif Contains datablocks global, I, II
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962101024X/jx3066Isup2.hkl Contains datablock I
	Smiles format file https://doi.org/10.1107/S205322962101024X/jx3066Isup4.smi Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962101024X/jx3066Isup6.cml Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962101024X/jx3066IIsup3.hkl Contains datablock II
	Smiles format file https://doi.org/10.1107/S205322962101024X/jx3066IIsup5.smi Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962101024X/jx3066IIsup7.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S205322962101024X/jx3066sup8.pdf Experimantal data for redetermined phase (I)
	Crystallographic Information File (CIF) https://doi.org/10.1107/S205322962101024X/jx3066sup9.cif CIF for phase (I)

CCDC references: 2113764; 2113763

Computing details top

For both structures, data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: DIAMOND (Brandenburg, 2015); software used to prepare material for publication: JANA2006 (Petříček et al., 2014).

Poly[hexa-µ-propanoato-bariumdicalcium] (I) top

Crystal data top

[BaCa₂(C₃H₅O₂)₆]	F(000) = 1320
M_r = 655.9	D_x = 1.503 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 9689 reflections
a = 12.4158 (6) Å	θ = 2.6–26.7°
b = 12.7108 (9) Å	µ = 1.77 mm⁻¹
c = 18.3698 (7) Å	T = 240 K
V = 2899.0 (3) Å³	Plate, colourless
Z = 4	0.13 × 0.10 × 0.05 mm

Data collection top

Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS diffractometer	3460 independent reflections
Radiation source: X-ray tube	2926 reflections with I > 3σ(I)
Quazar Mo multilayer optic monochromator	R_int = 0.023
φ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −16→16
T_min = 0.664, T_max = 0.746	k = −16→16
6398 measured reflections	l = −23→23

Refinement top

Refinement on F²	102 constraints
R[F > 3σ(F)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F) = 0.077	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0004I²)
S = 2.22	(Δ/σ)_max = 0.049
3460 reflections	Δρ_max = 1.08 e Å⁻³
207 parameters	Δρ_min = −0.79 e Å⁻³
10 restraints

Special details top

Refinement. There have been excluded 12 diffractions for which |Iobs-Icalc|>10σ(Iobs): 4 2 0, 3 2 1, 1 2 2, 3 0 3, 3 4 3, 6 1 5, 2 3 6, 4 3 7, 7 2 9, 4 5 9, 5 5 10, 7 2 11

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.533672 (17)	0.25	0.123030 (11)	0.02751 (8)
Ca1	0.31052 (7)	0.25	0.28042 (5)	0.0375 (3)
Ca2	0.5	0.5	0	0.0471 (3)
O1	0.4313 (3)	0.3345 (2)	−0.01255 (16)	0.0830 (12)
C1	0.4171 (5)	0.25	−0.0452 (3)	0.069 (2)
C2	0.3745 (11)	0.2795 (7)	−0.1194 (5)	0.121 (6)	0.5
H1c2	0.297726	0.296484	−0.11569	0.1453*	0.5
H2c2	0.412654	0.341892	−0.137187	0.1453*	0.5
C3	0.389 (2)	0.1951 (10)	−0.1694 (6)	0.230 (12)	0.5
H1c3	0.363976	0.216487	−0.217185	0.3455*	0.5
H2c3	0.464742	0.176921	−0.171936	0.3455*	0.5
H3c3	0.348041	0.134543	−0.153119	0.3455*	0.5
O2	0.7395 (2)	0.1337 (2)	0.13653 (13)	0.0634 (9)
O3	0.64893 (19)	0.0917 (2)	0.03938 (15)	0.0681 (10)
C4	0.7310 (3)	0.0838 (3)	0.0795 (2)	0.0593 (13)
C5	0.8211 (4)	0.0158 (4)	0.0524 (3)	0.115 (2)
H1c5	0.791251	−0.047602	0.029706	0.1378*
H2c5	0.855226	0.049406	0.010322	0.1378*
C6	0.9029 (5)	−0.0139 (5)	0.1047 (4)	0.132 (3)
H1c6	0.920365	0.046156	0.135043	0.1978*
H2c6	0.876131	−0.070733	0.134901	0.1978*
H3c6	0.967012	−0.036975	0.079073	0.1978*
O4	0.4472 (3)	0.4712 (3)	0.11727 (14)	0.0787 (12)
O5	0.3690 (2)	0.36883 (19)	0.19529 (13)	0.0624 (9)
C7	0.3748 (3)	0.4543 (3)	0.1624 (2)	0.0618 (14)
C8	0.2973 (7)	0.5417 (6)	0.1799 (4)	0.146 (4)
H1c8	0.335783	0.598619	0.20473	0.1757*	0.476 (15)
H2c8	0.288546	0.586967	0.137143	0.1757*	0.476 (15)
H1c8a	0.22952	0.51167	0.197691	0.1757*	0.524 (15)
H2c8a	0.294908	0.552317	0.232713	0.1757*	0.524 (15)
O6	0.6325 (3)	0.25	0.26112 (16)	0.0614 (13)
O7	0.4824 (3)	0.25	0.3235 (2)	0.0779 (17)
C9	0.1944 (13)	0.5259 (19)	0.2140 (15)	0.218 (13)	0.476 (15)
H1c9	0.147868	0.585176	0.203409	0.3273*	0.476 (15)
H2c9	0.161964	0.461849	0.195495	0.3273*	0.476 (15)
H3c9	0.204062	0.519914	0.266287	0.3273*	0.476 (15)
C9a	0.276 (3)	0.6394 (16)	0.1437 (14)	0.252 (13)	0.524 (15)
H1c9a	0.203185	0.662038	0.154667	0.3775*	0.524 (15)
H2c9a	0.326667	0.692208	0.160506	0.3775*	0.524 (15)
H3c9a	0.283806	0.630066	0.091605	0.3775*	0.524 (15)
C10	0.5812 (4)	0.25	0.3197 (3)	0.0539 (18)
C11	0.6422 (6)	0.25	0.3900 (3)	0.118 (4)
H1c11	0.694758	0.192475	0.389795	0.1421*	0.5
H2c11	0.694758	0.307525	0.389795	0.1421*	0.5
C12	0.5850 (7)	0.25	0.4578 (3)	0.114 (4)
H1c12	0.6361 (10)	0.25	0.4978 (3)	0.1703*
H2c12	0.5401 (7)	0.31234 (14)	0.4608 (4)	0.1703*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.02535 (13)	0.03127 (14)	0.02593 (14)	0	−0.00143 (10)	0
Ca1	0.0299 (4)	0.0477 (5)	0.0350 (4)	0	0.0109 (4)	0
Ca2	0.0480 (5)	0.0470 (6)	0.0463 (5)	0.0006 (4)	−0.0056 (4)	0.0262 (5)
O1	0.107 (2)	0.0530 (17)	0.089 (2)	−0.0170 (17)	−0.0285 (19)	0.0165 (16)
C1	0.071 (4)	0.086 (5)	0.049 (3)	0	−0.016 (3)	0
C2	0.226 (15)	0.075 (11)	0.062 (5)	−0.012 (8)	−0.067 (7)	0.004 (5)
C3	0.48 (3)	0.133 (13)	0.082 (9)	−0.029 (17)	−0.103 (15)	−0.021 (8)
O2	0.0530 (15)	0.0708 (17)	0.0665 (15)	0.0096 (13)	−0.0145 (12)	−0.0317 (14)
O3	0.0458 (13)	0.0784 (18)	0.0802 (17)	0.0016 (13)	−0.0084 (13)	−0.0390 (15)
C4	0.0392 (19)	0.061 (2)	0.078 (3)	0.0050 (17)	−0.0018 (19)	−0.031 (2)
C5	0.070 (3)	0.142 (5)	0.132 (4)	0.050 (3)	−0.017 (3)	−0.068 (4)
C6	0.080 (4)	0.138 (6)	0.177 (6)	0.049 (4)	−0.031 (4)	−0.058 (5)
O4	0.107 (2)	0.069 (2)	0.0596 (17)	0.0080 (18)	0.0293 (16)	0.0264 (14)
O5	0.0695 (16)	0.0506 (15)	0.0673 (15)	0.0120 (13)	0.0316 (13)	0.0184 (12)
C7	0.072 (3)	0.055 (2)	0.059 (2)	0.023 (2)	0.009 (2)	0.008 (2)
C8	0.163 (7)	0.116 (5)	0.160 (7)	0.093 (5)	0.051 (6)	0.004 (5)
O6	0.0417 (18)	0.110 (3)	0.0330 (17)	0	−0.0004 (15)	0
O7	0.041 (2)	0.111 (4)	0.082 (3)	0	−0.001 (2)	0
C9	0.129 (12)	0.124 (13)	0.40 (3)	0.062 (10)	0.003 (16)	−0.023 (16)
C9a	0.34 (3)	0.211 (18)	0.208 (17)	0.17 (2)	0.080 (17)	0.046 (13)
C10	0.032 (2)	0.089 (4)	0.040 (3)	0	−0.001 (2)	0
C11	0.070 (4)	0.247 (11)	0.038 (3)	0	−0.004 (3)	0
C12	0.147 (7)	0.142 (7)	0.051 (4)	0	−0.002 (4)	0

Geometric parameters (Å, º) top

Ba1—O1	2.996 (3)	C2—H2c2	0.98
Ba1—O1ⁱ	2.996 (3)	C2—C3	1.423 (15)
Ba1—O2	2.963 (3)	C2—C3ⁱ	0.990 (15)
Ba1—O2ⁱ	2.963 (3)	C3—C3ⁱ	1.394 (17)
Ba1—O3	2.908 (3)	C3—H1c3	0.97
Ba1—O3ⁱ	2.908 (3)	C3—H2c3	0.97
Ba1—O4	3.011 (3)	C3—H3c3	0.97
Ba1—O4ⁱ	3.011 (3)	O2—C4	1.230 (5)
Ba1—O5	2.868 (3)	O3—C4	1.262 (4)
Ba1—O5ⁱ	2.868 (3)	C4—C5	1.498 (6)
Ba1—O6	2.818 (3)	C5—H1c5	0.98
Ba1—O7	3.736 (4)	C5—H2c5	0.98
Ca1—O2ⁱⁱ	2.300 (3)	C5—C6	1.447 (8)
Ca1—O2ⁱⁱⁱ	2.300 (3)	C6—H1c6	0.97
Ca1—O5	2.292 (3)	C6—H2c6	0.97
Ca1—O5ⁱ	2.292 (3)	C6—H3c6	0.97
Ca1—O6ⁱⁱ	2.338 (3)	O4—C7	1.241 (5)
Ca1—O7	2.276 (4)	O5—C7	1.245 (5)
Ca2—O1	2.281 (3)	C7—C8	1.504 (9)
Ca2—O1^iv	2.281 (3)	C8—H1c8	0.98
Ca2—O3^v	2.302 (2)	C8—H2c8	0.98
Ca2—O3ⁱ	2.302 (2)	C8—H1c8a	0.98
Ca2—O4	2.281 (3)	C8—H2c8a	0.98
Ca2—O4^iv	2.281 (3)	C8—C9	1.44 (2)
Ca1—O2ⁱⁱ	2.299 (3)	C8—C9a	1.43 (2)
Ca1—O2ⁱⁱⁱ	2.299 (3)	O6—C10	1.250 (6)
Ca1—O5	2.295 (3)	O7—C10	1.228 (6)
Ca1—O5ⁱ	2.295 (3)	C9—H1c9	0.97
Ca1—O6ⁱⁱ	2.336 (3)	C9—H2c9	0.97
Ca1—O7	2.275 (4)	C9—H3c9	0.97
Ca2—O1	2.278 (3)	C9a—H1c9a	0.97
Ca2—O1^iv	2.278 (3)	C9a—H2c9a	0.97
Ca2—O3^v	2.301 (3)	C9a—H3c9a	0.97
Ca2—O3ⁱ	2.301 (3)	C10—C11	1.498 (7)
Ca2—O4	2.284 (3)	C11—H1c11	0.98
Ca2—O4^iv	2.284 (3)	C11—H1c11ⁱ	0.98
O1—C1	1.244 (4)	C11—C12	1.434 (8)
C1—C2	1.508 (11)	C12—H1c12	0.970 (12)
C1—C2ⁱ	1.508 (11)	C12—H2c12	0.970 (7)
C2—C2ⁱ	0.750 (12)	C12—H2c12ⁱ	0.970 (7)
C2—H1c2	0.98

O1—Ba1—O1ⁱ	42.04 (8)	H1c5—C5—H2c5	100.72
O1—Ba1—O2	127.92 (8)	H1c5—C5—C6	109.47
O1—Ba1—O2ⁱ	104.87 (8)	H2c5—C5—C6	109.47
O1—Ba1—O3	91.01 (8)	C5—C6—H1c6	109.47
O1—Ba1—O3ⁱ	61.40 (8)	C5—C6—H2c6	109.47
O1—Ba1—O4	58.98 (7)	C5—C6—H3c6	109.47
O1—Ba1—O4ⁱ	98.88 (8)	H1c6—C6—H2c6	109.47
O1—Ba1—O5	83.88 (8)	H1c6—C6—H3c6	109.47
O1—Ba1—O5ⁱ	105.74 (8)	H2c6—C6—H3c6	109.47
O1—Ba1—O6	158.95 (5)	O4—C7—O5	121.1 (4)
O1—Ba1—O7	138.34 (7)	O4—C7—C8	118.6 (4)
O1ⁱ—Ba1—O2	104.87 (8)	O5—C7—C8	120.2 (4)
O1ⁱ—Ba1—O2ⁱ	127.92 (8)	C7—C8—H1c8	109.47
O1ⁱ—Ba1—O3	61.40 (8)	C7—C8—H2c8	109.47
O1ⁱ—Ba1—O3ⁱ	91.01 (8)	C7—C8—H1c8a	109.47
O1ⁱ—Ba1—O4	98.88 (8)	C7—C8—H2c8a	109.47
O1ⁱ—Ba1—O4ⁱ	58.98 (7)	C7—C8—C9	124.0 (11)
O1ⁱ—Ba1—O5	105.74 (8)	C7—C8—C9a	131.2 (12)
O1ⁱ—Ba1—O5ⁱ	83.88 (8)	H1c8—C8—H2c8	89.6
O1ⁱ—Ba1—O6	158.95 (5)	H1c8—C8—C9	109.47
O1ⁱ—Ba1—O7	138.34 (7)	H2c8—C8—C9	109.47
O2—Ba1—O2ⁱ	59.86 (7)	H1c8a—C8—C9a	109.47
O2—Ba1—O3	43.50 (7)	H2c8a—C8—C9a	109.47
O2—Ba1—O3ⁱ	88.00 (7)	C8—C9—H1c9	109.47
O2—Ba1—O4	140.92 (8)	C8—C9—H2c9	109.47
O2—Ba1—O4ⁱ	81.06 (8)	C8—C9—H3c9	109.47
O2—Ba1—O5	147.04 (7)	H1c9—C9—H2c9	109.47
O2—Ba1—O5ⁱ	108.26 (7)	H1c9—C9—H3c9	109.47
O2—Ba1—O6	63.19 (7)	H2c9—C9—H3c9	109.47
O2—Ba1—O7	93.69 (7)	C8—C9a—H1c9a	109.47
O2ⁱ—Ba1—O3	88.00 (7)	C8—C9a—H2c9a	109.47
O2ⁱ—Ba1—O3ⁱ	43.50 (7)	C8—C9a—H3c9a	109.47
O2ⁱ—Ba1—O4	81.06 (8)	O6—C10—O7	123.9 (5)
O2ⁱ—Ba1—O4ⁱ	140.92 (8)	O6—C10—C11	118.9 (4)
O2ⁱ—Ba1—O5	108.26 (7)	O7—C10—C11	117.1 (5)
O2ⁱ—Ba1—O5ⁱ	147.04 (7)	C10—C11—H1c11	109.47
O2ⁱ—Ba1—O6	63.19 (7)	C10—C11—H1c11ⁱ	109.47
O2ⁱ—Ba1—O7	93.69 (7)	C10—C11—C12	119.9 (6)
O3—Ba1—O3ⁱ	87.56 (7)	H1c11—C11—C12	109.47
O3—Ba1—O4	143.40 (7)	H1c11ⁱ—C11—C12	109.47
O3—Ba1—O4ⁱ	60.72 (8)	C11—C12—H1c12	109.5 (10)
O3—Ba1—O5	163.71 (7)	C11—C12—H2c12	109.5 (6)
O3—Ba1—O5ⁱ	103.35 (7)	C11—C12—H2c12ⁱ	109.5 (6)
O3—Ba1—O6	105.15 (7)	H1c12—C12—H2c12	109.5 (7)
O3—Ba1—O7	127.19 (6)	H1c12—C12—H2c12ⁱ	109.5 (7)
O3ⁱ—Ba1—O4	60.72 (8)	H2c12—C12—H2c12ⁱ	109.5 (10)
O3ⁱ—Ba1—O4ⁱ	143.40 (7)	O1—C1—O1ⁱ	119.3 (5)
O3ⁱ—Ba1—O5	103.35 (7)	O1—C1—C2	105.9 (4)
O3ⁱ—Ba1—O5ⁱ	163.71 (7)	C1—C2—H1c2	109.47
O3ⁱ—Ba1—O6	105.15 (7)	C1—C2—H2c2	109.47
O3ⁱ—Ba1—O7	127.19 (6)	C1—C2—C3	110.6 (9)
O4—Ba1—O4ⁱ	138.02 (9)	H1c2—C2—H2c2	108.33
O4—Ba1—O5	43.14 (8)	H1c2—C2—C3	109.47
O4—Ba1—O5ⁱ	104.71 (8)	H2c2—C2—C3	109.47
O4—Ba1—O6	100.77 (6)	C2—C3—H2c3	109.47
O4—Ba1—O7	88.51 (5)	C2—C3—H3c3	109.47
O4ⁱ—Ba1—O5	104.71 (8)	H1c3—C3—H2c3	109.47
O4ⁱ—Ba1—O5ⁱ	43.14 (8)	H1c3—C3—H3c3	109.47
O4ⁱ—Ba1—O6	100.77 (6)	H2c3—C3—H3c3	109.47
O4ⁱ—Ba1—O7	88.51 (5)	O2—C4—O3	121.8 (4)
O5—Ba1—O5ⁱ	63.57 (7)	O2—C4—C5	121.1 (4)
O5—Ba1—O6	83.90 (7)	O3—C4—C5	117.0 (4)
O5—Ba1—O7	54.72 (6)	C4—C5—H1c5	109.47
O5ⁱ—Ba1—O6	83.90 (7)	C4—C5—H2c5	109.47
O5ⁱ—Ba1—O7	54.72 (6)	C4—C5—C6	116.9 (5)
O6—Ba1—O7	35.62 (8)	H1c5—C5—H2c5	100.81
O2ⁱⁱ—Ca1—O2ⁱⁱⁱ	79.99 (9)	H1c5—C5—C6	109.47
O2ⁱⁱ—Ca1—O5	98.65 (9)	H2c5—C5—C6	109.47
O2ⁱⁱ—Ca1—O5ⁱ	175.94 (10)	C5—C6—H1c6	109.47
O2ⁱⁱ—Ca1—O6ⁱⁱ	81.61 (9)	C5—C6—H2c6	109.47
O2ⁱⁱ—Ca1—O7	97.41 (11)	C5—C6—H3c6	109.47
O2ⁱⁱⁱ—Ca1—O5	175.94 (10)	H1c6—C6—H2c6	109.47
O2ⁱⁱⁱ—Ca1—O5ⁱ	98.65 (9)	H1c6—C6—H3c6	109.47
O2ⁱⁱⁱ—Ca1—O6ⁱⁱ	81.61 (9)	H2c6—C6—H3c6	109.47
O2ⁱⁱⁱ—Ca1—O7	97.41 (11)	O4—C7—O5	121.1 (4)
O5—Ca1—O5ⁱ	82.44 (9)	O4—C7—C8	117.9 (5)
O5—Ca1—O6ⁱⁱ	94.41 (9)	O5—C7—C8	120.9 (4)
O5—Ca1—O7	86.55 (11)	C7—C8—H1c8	109.47
O5ⁱ—Ca1—O6ⁱⁱ	94.41 (9)	C7—C8—H2c8	109.47
O5ⁱ—Ca1—O7	86.55 (11)	C7—C8—H1c8a	109.47
O6ⁱⁱ—Ca1—O7	178.72 (14)	C7—C8—H2c8a	109.47
O1—Ca2—O1^iv	180	C7—C8—C9	124.8 (12)
O1—Ca2—O3^v	97.74 (10)	C7—C8—C9a	131.4 (14)
O1—Ca2—O3ⁱ	82.26 (10)	H1c8—C8—H2c8	88.05
O1—Ca2—O4	80.79 (11)	H1c8—C8—C9	109.47
O1—Ca2—O4^iv	99.21 (11)	H1c8—C8—C9a	67.89
O1^iv—Ca2—O3^v	82.26 (10)	H2c8—C8—C9	109.47
O1^iv—Ca2—O3ⁱ	97.74 (10)	H1c8a—C8—C9a	109.47
O1^iv—Ca2—O4	99.21 (11)	H2c8a—C8—C9a	109.47
O1^iv—Ca2—O4^iv	80.79 (11)	C9—C8—C9a	99.0 (18)
O3^v—Ca2—O3ⁱ	180	C8—C9—H1c9	109.47
O3^v—Ca2—O4	98.47 (11)	C8—C9—H2c9	109.47
O3^v—Ca2—O4^iv	81.53 (11)	C8—C9—H3c9	109.47
O3ⁱ—Ca2—O4	81.53 (11)	H1c9—C9—H2c9	109.47
O3ⁱ—Ca2—O4^iv	98.47 (11)	H1c9—C9—H3c9	109.47
O4—Ca2—O4^iv	180	H2c9—C9—H3c9	109.47
O1—C1—O1ⁱ	119.6 (5)	C8—C9a—H1c9a	109.47
O1—C1—C2	105.7 (4)	C8—C9a—H2c9a	109.47
C1—C2—H1c2	109.47	C8—C9a—H3c9a	109.47
C1—C2—H2c2	109.47	H1c9a—C9a—H2c9a	109.47
C1—C2—C3	110.6 (9)	H1c9a—C9a—H3c9a	109.47
H1c2—C2—H2c2	108.34	H2c9a—C9a—H3c9a	109.47
H1c2—C2—C3	109.47	O6—C10—O7	123.9 (5)
H2c2—C2—C3	109.47	O6—C10—C11	118.8 (5)
C2—C3—H1c3	109.47	O7—C10—C11	117.3 (5)
C2—C3—H2c3	109.47	C10—C11—H1c11	109.47
C2—C3—H3c3	109.47	C10—C11—H1c11ⁱ	109.47
H1c3—C3—H2c3	109.47	C10—C11—C12	120.1 (6)
H1c3—C3—H3c3	109.47	H1c11—C11—H1c11ⁱ	96.21
H1c3ⁱ—C3—H2c3	111.16	H1c11—C11—C12	109.47
H1c3ⁱ—C3—H3c3	133.26	H1c11ⁱ—C11—C12	109.47
H2c3—C3—H3c3	109.47	C11—C12—H1c12	109.5 (10)
O2—C4—O3	121.7 (3)	C11—C12—H2c12	109.5 (6)
O2—C4—C5	121.1 (3)	C11—C12—H2c12ⁱ	109.5 (6)
O3—C4—C5	117.1 (4)	H1c12—C12—H2c12	109.5 (7)
C4—C5—H1c5	109.47	H1c12—C12—H2c12ⁱ	109.5 (7)
C4—C5—H2c5	109.47	H2c12—C12—H2c12ⁱ	109.5 (10)
C4—C5—C6	117.0 (5)

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

Poly[hexakis-µ-propanoato-bariumdicalcium] (II) top

Crystal data top

[Ca₂Ba(C₃H₅O₂)₆]	F(000) = 1320
M_r = 655.9	D_x = 1.547 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9817 reflections
a = 12.3585 (6) Å	θ = 2.6–27.5°
b = 12.6000 (6) Å	µ = 1.82 mm⁻¹
c = 18.0846 (8) Å	T = 130 K
V = 2816.1 (2) Å³	Plate, colourless
Z = 4	0.13 × 0.10 × 0.05 mm

Data collection top

Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS diffractometer	6471 independent reflections
Radiation source: X-ray tube	6056 reflections with I > 3σ(I)
Quazar Mo multilayer optic monochromator	R_int = 0.0
φ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2017)	h = −16→16
T_min = 0.809, T_max = 0.923	k = −16→16
6473 measured reflections	l = −23→23

Refinement top

Refinement on F²	H-atom parameters constrained
R[F > 3σ(F)] = 0.028	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0004I²)
wR(F) = 0.061	(Δ/σ)_max = 0.045
S = 1.65	Δρ_max = 1.29 e Å⁻³
6471 reflections	Δρ_min = −0.60 e Å⁻³
278 parameters	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
4 restraints	Extinction coefficient: 3800 (600)
222 constraints	Absolute structure: 2848 of Friedel pairs used in the refinement
Primary atom site location: dual	Absolute structure parameter: 0.238 (12)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.533911 (13)	0.236431 (13)	0.372682 (9)	0.01261 (5)
Ca1	0.30970 (5)	0.25375 (6)	0.53125 (3)	0.01620 (18)
Ca2	0.50172 (6)	0.47626 (5)	0.23834 (3)	0.01769 (18)
O1	0.4161 (2)	0.14073 (19)	0.25201 (13)	0.0237 (8)
O1a	0.4212 (2)	0.31284 (19)	0.23286 (13)	0.0270 (8)
C1	0.4026 (3)	0.2197 (3)	0.21097 (18)	0.0208 (10)
C2	0.3590 (3)	0.2019 (3)	0.1339 (2)	0.0380 (13)
H1c2	0.396176	0.140435	0.111153	0.0456*
H2c2	0.283777	0.17522	0.136968	0.0456*
C3	0.3632 (6)	0.2928 (5)	0.0830 (3)	0.074 (2)
H1c3	0.330861	0.27282	0.035518	0.1103*
H2c3	0.322854	0.352426	0.104254	0.1103*
H3c3	0.438716	0.313848	0.075283	0.1103*
O2	0.73666 (19)	0.35472 (19)	0.37877 (15)	0.0260 (8)
O3	0.6513 (2)	0.3792 (2)	0.27327 (14)	0.0243 (8)
C4	0.7317 (3)	0.3949 (3)	0.3157 (2)	0.0214 (7)
C5	0.8232 (3)	0.4618 (3)	0.2877 (2)	0.0394 (10)
H1c5	0.793809	0.524821	0.261907	0.0473*
H2c5	0.861042	0.423817	0.24736	0.0473*
C6	0.9044 (4)	0.4968 (4)	0.3450 (3)	0.0470 (11)
H1c6	0.960392	0.540241	0.321387	0.0705*
H2c6	0.867725	0.538662	0.383189	0.0705*
H3c6	0.937915	0.434273	0.367689	0.0705*
O2a	0.7404 (2)	0.1203 (2)	0.38947 (14)	0.0263 (8)
O3a	0.6493 (2)	0.0752 (2)	0.28936 (13)	0.0238 (8)
C4a	0.7319 (3)	0.0699 (3)	0.3303 (2)	0.0214 (7)
C5a	0.8244 (3)	0.0016 (3)	0.3038 (2)	0.0394 (10)
H1c5a	0.860151	0.036345	0.261176	0.0473*
H2c5a	0.795418	−0.064771	0.282149	0.0473*
C6a	0.9081 (3)	−0.0252 (4)	0.3617 (3)	0.0470 (11)
H1c6a	0.962884	−0.072173	0.340307	0.0705*
H2c6a	0.942654	0.040245	0.379101	0.0705*
H3c6a	0.872899	−0.060893	0.403453	0.0705*
O5	0.3716 (2)	0.36435 (19)	0.44014 (14)	0.0257 (8)
O4	0.4639 (2)	0.46270 (18)	0.36264 (12)	0.0237 (7)
C7	0.3859 (3)	0.4498 (3)	0.40617 (19)	0.0218 (7)
C8	0.3071 (4)	0.5391 (4)	0.4185 (3)	0.0523 (12)
H1c8	0.337961	0.590022	0.454474	0.0627*	0.380 (9)
H2c8	0.317211	0.593694	0.379785	0.0627*	0.380 (9)
H1c8d	0.2367	0.520767	0.395777	0.0627*	0.620 (9)
H2c8d	0.276759	0.533896	0.469049	0.0627*	0.620 (9)
C9	0.1986 (8)	0.5262 (10)	0.4323 (8)	0.053 (2)	0.380 (9)
H1c9	0.16089	0.593544	0.423946	0.08*	0.380 (9)
H2c9	0.169151	0.471928	0.399062	0.08*	0.380 (9)
H3c9	0.188219	0.503811	0.483723	0.08*	0.380 (9)
C9a	0.3321 (9)	0.6443 (6)	0.4030 (6)	0.083 (4)	0.620 (9)
H1c9a	0.279683	0.690859	0.427505	0.124*	0.6201
H2c9a	0.405024	0.660311	0.421099	0.124*	0.6201
H3c9a	0.329161	0.655846	0.349451	0.124*	0.6201
O5a	0.3651 (2)	0.12375 (19)	0.45065 (14)	0.0252 (8)
O4a	0.5415 (2)	0.51162 (18)	0.11629 (12)	0.0277 (7)
C7a	0.3785 (3)	0.0334 (3)	0.42329 (19)	0.0218 (7)
C8a	0.2991 (4)	−0.0545 (4)	0.4373 (3)	0.0523 (12)
H1c8a	0.296183	−0.101885	0.393663	0.0627*	0.792 (9)
H2c8a	0.329888	−0.104958	0.473612	0.0627*	0.792 (9)
H1c8e	0.274578	−0.051649	0.489389	0.0627*	0.208 (9)
H2c8e	0.226145	−0.031982	0.420945	0.0627*	0.208 (9)
C9b	0.1897 (5)	−0.0262 (5)	0.4594 (4)	0.053 (2)	0.792 (9)
C9c	0.317 (2)	−0.1612 (12)	0.4167 (17)	0.083 (4)	0.208 (9)
O6	0.63144 (17)	0.2464 (2)	0.51182 (11)	0.0246 (7)
O7	0.48091 (17)	0.2564 (2)	0.57792 (13)	0.0308 (8)
C10	0.5809 (2)	0.2513 (3)	0.57297 (16)	0.0209 (10)
C11	0.6479 (3)	0.2521 (4)	0.64312 (17)	0.0376 (13)
H1c11	0.693372	0.187464	0.644978	0.0452*
H2c11	0.702364	0.309498	0.6403	0.0452*
C12	0.5855 (3)	0.2621 (4)	0.71359 (18)	0.0399 (13)
H1c12	0.635844	0.265553	0.755362	0.0599*
H2c12	0.541644	0.326844	0.712196	0.0599*
H3c12	0.538002	0.200305	0.719396	0.0599*
H1c9b	0.190182	−0.00098	0.510619	0.08*	0.792 (9)
H2c9b	0.162386	0.030052	0.426938	0.08*	0.792 (9)
H3c9b	0.142745	−0.088654	0.455406	0.08*	0.792 (9)
H1c9c	0.364503	−0.163636	0.373564	0.124*	0.2083
H2c9c	0.349993	−0.199537	0.457865	0.124*	0.2083
H3c9c	0.247137	−0.194343	0.404227	0.124*	0.2083

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.01195 (9)	0.01327 (9)	0.01261 (8)	−0.00011 (7)	−0.00061 (7)	−0.00062 (7)
Ca1	0.0128 (3)	0.0204 (4)	0.0154 (3)	0.0000 (3)	0.0037 (2)	−0.0010 (3)
Ca2	0.0197 (3)	0.0153 (3)	0.0181 (3)	−0.0012 (3)	−0.0032 (3)	0.0069 (3)
O1	0.0277 (13)	0.0188 (13)	0.0245 (13)	0.0048 (10)	−0.0072 (11)	0.0002 (10)
O1a	0.0350 (15)	0.0189 (13)	0.0270 (13)	−0.0044 (11)	−0.0046 (12)	0.0038 (11)
C1	0.0149 (16)	0.024 (2)	0.0230 (16)	0.0014 (14)	0.0003 (13)	−0.0022 (15)
C2	0.053 (3)	0.033 (2)	0.028 (2)	−0.0026 (18)	−0.008 (2)	0.0010 (18)
C3	0.126 (6)	0.059 (4)	0.035 (3)	−0.011 (4)	−0.024 (3)	0.005 (2)
O2	0.0201 (13)	0.0320 (14)	0.0259 (13)	−0.0047 (10)	−0.0082 (13)	0.0120 (12)
O3	0.0194 (13)	0.0276 (14)	0.0258 (13)	0.0008 (11)	−0.0024 (11)	0.0067 (11)
C4	0.0178 (11)	0.0197 (13)	0.0268 (13)	0.0030 (10)	0.0010 (10)	0.0083 (11)
C5	0.0286 (13)	0.0487 (19)	0.0409 (17)	−0.0116 (14)	−0.0013 (13)	0.0205 (15)
C6	0.0299 (15)	0.0494 (19)	0.062 (2)	−0.0168 (14)	−0.0106 (15)	0.0211 (17)
O2a	0.0196 (13)	0.0299 (15)	0.0294 (15)	0.0019 (10)	−0.0042 (12)	−0.0135 (11)
O3a	0.0189 (13)	0.0254 (14)	0.0271 (13)	0.0001 (11)	−0.0027 (11)	−0.0086 (11)
C4a	0.0178 (11)	0.0197 (13)	0.0268 (13)	−0.0030 (10)	0.0010 (10)	−0.0083 (11)
C5a	0.0286 (13)	0.0487 (19)	0.0409 (17)	0.0116 (14)	−0.0013 (13)	−0.0205 (15)
C6a	0.0299 (15)	0.0494 (19)	0.062 (2)	0.0168 (14)	−0.0106 (15)	−0.0211 (17)
O5	0.0282 (15)	0.0222 (14)	0.0267 (13)	0.0020 (11)	0.0107 (12)	0.0037 (11)
O4	0.0299 (13)	0.0232 (12)	0.0179 (11)	−0.0029 (12)	0.0038 (12)	0.0049 (9)
C7	0.0257 (12)	0.0192 (13)	0.0207 (12)	0.0024 (10)	−0.0031 (11)	−0.0008 (10)
C8	0.057 (2)	0.038 (2)	0.062 (2)	0.0214 (17)	0.0103 (18)	−0.0038 (17)
C9	0.041 (3)	0.050 (4)	0.069 (4)	0.020 (3)	0.013 (3)	−0.002 (3)
C9a	0.124 (9)	0.026 (4)	0.098 (8)	0.035 (5)	0.053 (7)	0.018 (4)
O5a	0.0281 (15)	0.0202 (13)	0.0274 (14)	−0.0012 (11)	0.0093 (12)	−0.0061 (11)
O4a	0.0376 (14)	0.0265 (13)	0.0189 (12)	−0.0103 (12)	0.0028 (13)	0.0035 (10)
C7a	0.0257 (12)	0.0192 (13)	0.0207 (12)	−0.0024 (10)	−0.0031 (11)	0.0008 (10)
C8a	0.057 (2)	0.038 (2)	0.062 (2)	−0.0214 (17)	0.0103 (18)	0.0038 (17)
C9b	0.041 (3)	0.050 (4)	0.069 (4)	−0.020 (3)	0.013 (3)	0.002 (3)
C9c	0.124 (9)	0.026 (4)	0.098 (8)	−0.035 (5)	0.053 (7)	−0.018 (4)
O6	0.0190 (11)	0.0394 (16)	0.0156 (10)	−0.0017 (13)	−0.0003 (9)	−0.0024 (12)
O7	0.0147 (11)	0.0480 (17)	0.0298 (12)	0.0011 (13)	0.0009 (10)	−0.0001 (13)
C10	0.0164 (15)	0.027 (2)	0.0192 (15)	−0.0017 (16)	0.0025 (12)	−0.0021 (17)
C11	0.0273 (18)	0.067 (3)	0.0182 (16)	−0.002 (2)	−0.0018 (14)	0.000 (2)
C12	0.046 (2)	0.055 (3)	0.0189 (16)	−0.001 (3)	−0.0005 (16)	−0.006 (2)

Geometric parameters (Å, º) top

Ba1—O1	2.887 (2)	C8a—C9c	1.411 (18)
Ba1—O1a	3.043 (3)	O6—C10	1.271 (4)
Ba1—O2	2.918 (2)	O7—C10	1.241 (4)
Ba1—O3	2.928 (3)	C10—C11	1.514 (4)
Ba1—O2a	2.957 (2)	C11—C12	1.495 (5)
Ba1—O3a	2.904 (2)	C2—H1c2	0.99
Ba1—O5	2.848 (3)	C2—H2c2	0.99
Ba1—O4	2.985 (2)	C3—H1c3	0.98
Ba1—O5a	2.891 (3)	C3—H2c3	0.98
Ba1—O4aⁱ	2.989 (2)	C3—H3c3	0.98
Ba1—O6	2.793 (2)	C5—H1c5	0.99
Ba1—O7	3.777 (2)	C5—H2c5	0.99
Ca1—O2ⁱⁱ	2.309 (3)	C6—H1c6	0.98
Ca1—O2aⁱⁱ	2.304 (3)	C6—H2c6	0.98
Ca1—O5	2.290 (3)	C6—H3c6	0.98
Ca1—O5a	2.297 (3)	C5a—H1c5a	0.99
Ca1—O6	3.993 (2)	C5a—H2c5a	0.99
Ca1—O6ⁱⁱ	2.337 (2)	C6a—H1c6a	0.98
Ca1—O7	2.278 (2)	C6a—H2c6a	0.98
Ca2—O1ⁱⁱⁱ	2.314 (2)	C6a—H3c6a	0.98
Ca2—O1a	2.289 (3)	C8—H1c8	0.99
Ca2—O3	2.305 (3)	C8—H2c8	0.99
Ca2—O3aⁱⁱⁱ	2.300 (3)	C8—H1c8d	0.99
Ca2—O4	2.302 (2)	C8—H2c8d	0.99
Ca2—O4a	2.305 (2)	C9—H1c9	0.98
O1—C1	1.253 (4)	C9—H2c9	0.98
O1a—C1	1.259 (4)	C9—H3c9	0.98
C1—C2	1.512 (5)	C9a—H1c9a	0.98
C2—C3	1.470 (7)	C9a—H2c9a	0.98
O2—C4	1.250 (5)	C9a—H3c9a	0.98
O3—C4	1.270 (4)	C8a—H1c8a	0.99
C4—C5	1.499 (6)	C8a—H2c8a	0.99
C5—C6	1.509 (6)	C8a—H1c8e	0.99
O2a—C4a	1.248 (4)	C8a—H2c8e	0.99
O3a—C4a	1.263 (4)	C9b—H1c9b	0.98
C4a—C5a	1.510 (6)	C9b—H2c9b	0.98
C5a—C6a	1.511 (6)	C9b—H3c9b	0.98
O5—C7	1.252 (4)	C9c—H1c9c	0.98
O4—C7	1.255 (4)	C9c—H2c9c	0.98
C7—C8	1.504 (6)	C9c—H3c9c	0.98
C8—C9	1.374 (12)	C11—H1c11	0.99
C8—C9a	1.390 (9)	C11—H2c11	0.99
O5a—C7a	1.253 (4)	C12—H1c12	0.98
O4a—C7aⁱⁱⁱ	1.251 (5)	C12—H2c12	0.98
C7a—C8a	1.502 (6)	C12—H3c12	0.98
C8a—C9b	1.454 (8)

O1—Ba1—O1a	43.39 (7)	O1ⁱⁱⁱ—Ca2—O1a	178.13 (9)
O1—Ba1—O2	132.45 (7)	O1ⁱⁱⁱ—Ca2—O3	95.89 (9)
O1—Ba1—O3	92.43 (7)	O1ⁱⁱⁱ—Ca2—O3aⁱⁱⁱ	83.53 (9)
O1—Ba1—O2a	107.82 (7)	O1ⁱⁱⁱ—Ca2—O4	94.69 (8)
O1—Ba1—O3a	64.10 (7)	O1ⁱⁱⁱ—Ca2—O4a	78.79 (8)
O1—Ba1—O5	101.82 (7)	O1a—Ca2—O3	83.30 (9)
O1—Ba1—O4	101.94 (6)	O1a—Ca2—O3aⁱⁱⁱ	97.19 (9)
O1—Ba1—O5a	78.43 (7)	O1a—Ca2—O4	83.53 (9)
O1—Ba1—O4aⁱ	59.83 (6)	O1a—Ca2—O4a	103.01 (9)
O1—Ba1—O6	156.54 (8)	O3—Ca2—O3aⁱⁱⁱ	176.67 (9)
O1—Ba1—O7	133.08 (6)	O3—Ca2—O4	81.70 (9)
O1a—Ba1—O2	105.25 (7)	O3—Ca2—O4a	101.19 (9)
O1a—Ba1—O3	61.47 (7)	O3aⁱⁱⁱ—Ca2—O4	95.07 (9)
O1a—Ba1—O2a	129.56 (7)	O3aⁱⁱⁱ—Ca2—O4a	81.93 (9)
O1a—Ba1—O3a	90.86 (7)	O4—Ca2—O4a	173.06 (9)
O1a—Ba1—O5	81.62 (7)	Ba1—O1—Ca2ⁱ	95.49 (8)
O1a—Ba1—O4	60.96 (6)	Ba1—O1a—Ca2	92.83 (8)
O1a—Ba1—O5a	103.31 (7)	Ba1—O3—Ca2	95.55 (8)
O1a—Ba1—O4aⁱ	102.27 (7)	Ba1—O2a—Ca1^iv	92.52 (8)
O1a—Ba1—O6	158.74 (8)	Ba1—O3a—Ca2ⁱ	95.38 (8)
O1a—Ba1—O7	135.72 (6)	Ba1—O5—Ca1	101.48 (9)
O2—Ba1—O3	44.25 (7)	Ba1—O4—Ca2	94.10 (7)
O2—Ba1—O2a	60.52 (7)	Ba1—O5a—Ca1	100.04 (9)
O2—Ba1—O3a	87.44 (7)	Ba1ⁱⁱⁱ—O4a—Ca2	93.03 (8)
O2—Ba1—O5	107.44 (7)	Ba1—O6—Ca1	69.55 (4)
O2—Ba1—O4	76.30 (7)	Ba1—O6—Ca1^iv	96.11 (7)
O2—Ba1—O5a	148.47 (7)	Ba1—O7—Ca1	78.23 (6)
O2—Ba1—O4aⁱ	138.54 (7)	O1—C1—O1a	122.0 (3)
O2—Ba1—O6	64.68 (7)	O1—C1—C2	118.4 (3)
O2—Ba1—O7	94.46 (6)	O1a—C1—C2	119.5 (3)
O3—Ba1—O2a	86.52 (7)	C1—C2—C3	116.7 (4)
O3—Ba1—O3a	82.40 (7)	O2—C4—O3	121.8 (3)
O3—Ba1—O5	105.34 (7)	O2—C4—C5	119.9 (3)
O3—Ba1—O4	61.28 (7)	O3—C4—C5	118.3 (3)
O3—Ba1—O5a	163.51 (7)	C4—C5—C6	115.8 (4)
O3—Ba1—O4aⁱ	141.05 (7)	O2a—C4a—O3a	122.9 (3)
O3—Ba1—O6	108.17 (7)	O2a—C4a—C5a	120.0 (3)
O3—Ba1—O7	130.42 (6)	O3a—C4a—C5a	117.1 (3)
O2a—Ba1—O3a	44.21 (7)	C4a—C5a—C6a	115.1 (4)
O2a—Ba1—O5	147.56 (7)	O5—C7—O4	121.8 (3)
O2a—Ba1—O4	136.80 (7)	O5—C7—C8	118.6 (4)
O2a—Ba1—O5a	109.25 (7)	O4—C7—C8	119.6 (3)
O2a—Ba1—O4aⁱ	78.05 (7)	C7—C8—C9	124.8 (7)
O2a—Ba1—O6	63.73 (7)	C7—C8—C9a	122.7 (6)
O2a—Ba1—O7	94.69 (6)	C9—C8—C9a	111.5 (8)
O3a—Ba1—O5	164.62 (7)	O5a—C7a—O4aⁱ	122.0 (3)
O3a—Ba1—O4	141.17 (6)	O5a—C7a—C8a	121.1 (4)
O3a—Ba1—O5a	105.30 (7)	O4aⁱ—C7a—C8a	116.9 (3)
O3a—Ba1—O4aⁱ	61.61 (7)	C7a—C8a—C9b	118.3 (4)
O3a—Ba1—O6	106.68 (7)	C7a—C8a—C9c	123.9 (13)
O3a—Ba1—O7	129.91 (6)	C9b—C8a—C9c	116.6 (13)
O5—Ba1—O4	44.06 (7)	O6—C10—O7	123.7 (3)
O5—Ba1—O5a	63.93 (7)	O6—C10—C11	117.4 (3)
O5—Ba1—O4aⁱ	106.75 (7)	O7—C10—C11	118.9 (3)
O5—Ba1—O6	83.84 (7)	C10—C11—C12	115.7 (3)
O5—Ba1—O7	54.50 (6)	H1c2—C2—H2c2	101.16
O4—Ba1—O5a	106.84 (7)	H1c3—C3—H2c3	109.47
O4—Ba1—O4aⁱ	144.99 (7)	H1c3—C3—H3c3	109.47
O4—Ba1—O6	97.87 (7)	H2c3—C3—H3c3	109.47
O4—Ba1—O7	86.90 (6)	H1c5—C5—H2c5	102.34
O5a—Ba1—O4aⁱ	43.70 (7)	H1c6—C6—H2c6	109.47
O5a—Ba1—O6	83.92 (7)	H1c6—C6—H3c6	109.47
O5a—Ba1—O7	55.13 (6)	H2c6—C6—H3c6	109.47
O4aⁱ—Ba1—O6	96.72 (7)	H1c5a—C5a—H2c5a	103.18
O4aⁱ—Ba1—O7	86.76 (6)	H1c6a—C6a—H2c6a	109.47
O6—Ba1—O7	35.57 (5)	H1c6a—C6a—H3c6a	109.47
O2ⁱⁱ—Ca1—O2aⁱⁱ	79.85 (9)	H2c6a—C6a—H3c6a	109.47
O2ⁱⁱ—Ca1—O5	176.49 (9)	H1c8—C8—H2c8	88.02
O2ⁱⁱ—Ca1—O5a	98.14 (9)	H1c8d—C8—H2c8d	91.99
O2ⁱⁱ—Ca1—O6	115.95 (7)	H1c9—C9—H2c9	109.47
O2ⁱⁱ—Ca1—O6ⁱⁱ	82.29 (9)	H1c9—C9—H3c9	109.47
O2ⁱⁱ—Ca1—O7	96.35 (9)	H2c9—C9—H3c9	109.47
O2aⁱⁱ—Ca1—O5	98.79 (9)	H1c9a—C9a—H2c9a	109.47
O2aⁱⁱ—Ca1—O5a	175.48 (9)	H1c9a—C9a—H3c9a	109.47
O2aⁱⁱ—Ca1—O6	116.18 (7)	H2c9a—C9a—H3c9a	109.47
O2aⁱⁱ—Ca1—O6ⁱⁱ	81.79 (9)	H1c8a—C8a—H2c8a	98.96
O2aⁱⁱ—Ca1—O7	96.02 (9)	H1c9b—C9b—H2c9b	109.47
O5—Ca1—O5a	82.98 (9)	H1c9b—C9b—H3c9b	109.47
O5—Ca1—O6	67.56 (8)	H2c9b—C9b—H3c9b	109.47
O5—Ca1—O6ⁱⁱ	94.32 (9)	H1c9c—C9c—H2c9c	109.47
O5—Ca1—O7	87.00 (9)	H1c9c—C9c—H3c9c	109.47
O5a—Ca1—O6	68.34 (8)	H2c9c—C9c—H3c9c	109.47
O5a—Ca1—O6ⁱⁱ	93.94 (9)	H1c11—C11—H2c11	102.48
O5a—Ca1—O7	88.21 (9)	H1c12—C12—H2c12	109.47
O6—Ca1—O6ⁱⁱ	155.44 (6)	H1c12—C12—H3c12	109.47
O6—Ca1—O7	26.88 (6)	H2c12—C12—H3c12	109.47
O6ⁱⁱ—Ca1—O7	177.59 (8)

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

Important references regarding the phase transitions in the title structure of barium dicalcium hexakis(propanoate) top

T1 (K) [phase transition (I)→(II)]	T2 (K) [phase transition (II)→(III)]	Method	Reference	Comment
~266		DTA	[1]
268.48/264.05 – cooling		Calorimetry	[2]	Two-step phase transition, measured heat capacity
269.92/266.85 – heating		Calorimetry		Two-step phase transition, measured heat capacity
~268.5 – cooling ~270.0 – heating		Dilatometry		Two-step phase transition, measured heat capacity ΔV (I-II) [cm³]/mol = -9.0 (read from Fig. 8 of [2])
272	204	DTA	[3]	λ-type phase transition at 204 K
~267.15	~203.15	Dielectric measurements at different pressures	[4]	Pressure induced phases (IV)–(VII); no double hump in the phase transition at about 267 K in difference to [1] and [2]
264.65 (probably cooling) Hysteresis 2.5 K	204 (cooling and heating)	References to [2] and [3] Dilatometry Ultrasound velocity measurements	[5]	Δl/l \approx 1.2% in [100] of the cubic phase for the phase transition (I) (II), a kink observed in a thermal expansion plot in [110] which may be related to the two-step phase transition reported by [2] and [8]. For [110] (cubic phase direction) an anomaly corresponding to the second order phase transition at 204 K is observed.
267	203	Dielectric measurements	[6]	Suggestion that the ferrolectric high-pressure phases (IV) and (V) correspond to the respective phases (II) and (III) in lead dicalcium hexakis(propanoate) or in dicalcium strontium hexakis(propanoate)
Not given	Not given	Dielectric measurements at high pressure	[7]	Suggestion that the ferrolectric high-pressure phase (VI) corresponds to the respective phase (III) in lead dicalcium hexakis(propanoate) or in strontium dicalcium hexakis(propanoate)
~267	~204		[8]	Drastic first order transition (I)–(II), the crystals crack
267	198		[9]	Suggestion that the phase (II) is assumed to be orthorhombic
267.15 at 0.015 T		EPR of Mn²⁺
265.15 at 0.017 T
267 (cooling) (1st order)	207 (cooling) (2nd order)	EPR of Mn²⁺	[10]	Mn²⁺ substitute Ca²⁺; the authors suggest that low-temperature phases (II) and (III) are tetragonal.
266.9	204	Dielectric measurements	[11]	Deuterated phases
275	204.5
266.9 [reference to 2]	204 [reference to 4]	Dielectric measurements	[12]	Phase II (266.9–204 K) is possibly orthorhombic. Deuterated phase transition takes place at ~ 280 K.

Refewrences: [1] Seki et al. (1951); [2] Seki et al. (1955); [3] Nakamura et al. (1968); [4] Gesi & Ozawa (1975a); [5] Kameyama et al. (1975); [6] Sawada et al. (1979); [7] Ishibashi et al. (1979); [8] Stadnicka & Glazer (1980); [9] Bhat et al. (1981); [10] Misra & Jerzak (1989); [11] Gesi (1992); [12] Gesi (1993).

The bond valence sums of the substituting cations in selected structure determinations of Ca₂Ba(propanoate)₆, Ca₂Sr(propanoate)₆ and Ca₂Pb(propanoate)₆ top

Compound	Phase	Reference	Bond valence sum of Ca1	Bond valence sum of Ca2	Bond valence sum of Me²⁺
Ca₂Ba(propanoate)₆	(I) Fd	This work	2.61	-	1.79
	(II) Pnma (240 K)	This work	2.443 (8)	2.527 (8)	1.965 (5)
	(III) P2₁2₁2₁ (130 K)	This work	2.431 (7)	2.423 (7)	2.044 (4)

Ca₂Sr(propanoate)₆	(I) P4₃2₁2 (room temperature)	Glazer et al. (1981)	2.37	-	1.74
Ca₂Sr(propanoate)₆	(II) P4₃ (243.15 K)	Stadnicka et al. (1982)	2.39	2.28	1.73

Ca₂Pb(propanoate)₆	(I) P4₃2₁2 (343.15 K)	Kasatani (1990)	2.42	-	1.59
Ca₂Pb(propanoate)₆	(II) P4₃ (190 K)	Kasatani (1990)	2.46	2.57	1.72

Short nonbonding C—C distances up to 3.82 Å top

Phase (II)		Phase (III)
Interaction/symmetry code	Distance (Å)	Interaction/symmetry code	Distance (Å)
C2—C2 (x, -y+1/2, z)	0.756 (13)
C2—C3 (x, -y+1/2, z)	1.013 (16)
C3—C3 (x, -y+1/2, z)	1.463 (19)
C9a—C9a (x, -y+3/2, z)	2.80 (3)	C9—C9a (x, y, z)	2.284 (15)
		C9a—C9c (x, y+1, z)	2.471 (17)
		C9b—C9c (x, y, z)	2.44 (2)
C3—C9 (-x+1/2, y-1/2, z-1/2)	3.11 (3)	C3—C9 (-x+1/2, -y+1, z-1/2)	3.634 (15)
		C8—C9c (x, y+1, z)	3.778 (16)
		C9—C11 (x-1/2, -y+1/2, -z+1)	3.814 (14)

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Low-temperature phases of dicalcium barium hexa­kis­(propano­ate)

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Low-temperature phases of dicalcium barium hexakis(propanoate)