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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.
Supporting information
CCDC references: 2113764; 2113763
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 |
Mr = 655.9 | Dx = 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 | Rint = 0.023 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | h = −16→16 |
Tmin = 0.664, Tmax = 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 | Δρmax = 1.08 e Å−3 |
207 parameters | Δρmin = −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 | Uiso*/Ueq | 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—O1iv | 2.281 (3) | C8—H1c8 | 0.98 |
Ca2—O3v | 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—O4iv | 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—O1iv | 2.278 (3) | C9a—H2c9a | 0.97 |
Ca2—O3v | 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—O4iv | 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—O1iv | 180 | C7—C8—C9 | 124.8 (12) |
O1—Ca2—O3v | 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—O4iv | 99.21 (11) | H1c8—C8—C9a | 67.89 |
O1iv—Ca2—O3v | 82.26 (10) | H2c8—C8—C9 | 109.47 |
O1iv—Ca2—O3i | 97.74 (10) | H1c8a—C8—C9a | 109.47 |
O1iv—Ca2—O4 | 99.21 (11) | H2c8a—C8—C9a | 109.47 |
O1iv—Ca2—O4iv | 80.79 (11) | C9—C8—C9a | 99.0 (18) |
O3v—Ca2—O3i | 180 | C8—C9—H1c9 | 109.47 |
O3v—Ca2—O4 | 98.47 (11) | C8—C9—H2c9 | 109.47 |
O3v—Ca2—O4iv | 81.53 (11) | C8—C9—H3c9 | 109.47 |
O3i—Ca2—O4 | 81.53 (11) | H1c9—C9—H2c9 | 109.47 |
O3i—Ca2—O4iv | 98.47 (11) | H1c9—C9—H3c9 | 109.47 |
O4—Ca2—O4iv | 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 |
Mr = 655.9 | Dx = 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 | Rint = 0.0 |
φ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | h = −16→16 |
Tmin = 0.809, Tmax = 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 | Δρmax = 1.29 e Å−3 |
6471 reflections | Δρmin = −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 | Uiso*/Ueq | 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—Ca1iv | 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—Ca1iv | 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) topT1 (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 topCompound | 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 topPhase (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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