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Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110 °C under hydro­thermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetra­aqua­zinc(II)]-μ-5-carb­oxy­benzene-1,3-di­car­boxyl­ato-[tetra­aqua­calcium(II)]-μ-5-carb­oxy­benzene-1,3-di­carboxyl­ato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetra­aqua­cobalt(II)]-μ-5-carb­oxy­benzene-1,3-di­carboxyl­ato-[tetra­aqua­calcium(II)]-μ-5-carb­oxy­benzene-1,3-di­carboxyl­ato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2− ligand to create a one-dimensional (1D) zigzag chain. Poly[[deca­aqua­bis­(μ3-benzene-1,3,5-tri­carboxyl­ato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a tem­per­a­ture of 140 °C. It forms crystals in the ortho­rhom­bic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer com­posed of [Zn(TMA)] chains that are inter­connected by CaII ions. The presence of aromatic carb­oxy­lic acid ligands and water mol­ecules, which can form numerous hydrogen bonds and π–π inter­actions, increases the stability of the three-dimensional (3D) supra­molecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420 °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low mol­ecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone mol­ecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229624003528/jx3081sup1.cif
Contains datablocks 1, 2, 3, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229624003528/jx30811sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229624003528/jx30812sup3.hkl
Contains datablock 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229624003528/jx30813sup4.hkl
Contains datablock 3

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229624003528/jx3081sup5.pdf
Supplementary material

CCDC references: 2299479; 2299478; 2299477

Computing details top

catena-Poly[[tetraaquazinc(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato] (1) top
Crystal data top
[CaZn(C6H4O6)2(H2O)8]F(000) = 1368
Mr = 665.82Dx = 1.886 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.848 (2) ÅCell parameters from 9954 reflections
b = 20.106 (2) Åθ = 3.1–28.2°
c = 6.5975 (8) ŵ = 1.37 mm1
β = 97.997 (4)°T = 296 K
V = 2344.6 (5) Å3Block, light colourless
Z = 40.4 × 0.4 × 0.2 mm
Data collection top
Bruker D8 QUEST CMOS PHOTON II
diffractometer
2927 independent reflections
Radiation source: sealed x-ray tube, Mo2515 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 7.39 pixels mm-1θmax = 28.4°, θmin = 3.1°
φ and ω scansh = 2323
Absorption correction: multi-scan
(SADABS; Bruker, 2021)
k = 2626
Tmin = 0.670, Tmax = 0.746l = 88
33766 measured reflections
Refinement top
Refinement on F2Primary atom site location: inferred from neighbouring sites
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0666P)2 + 7.9545P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2927 reflectionsΔρmax = 1.82 e Å3
207 parametersΔρmin = 0.66 e Å3
17 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.2500000.2500000.0000000.02274 (15)
Ca10.0000000.12347 (4)0.2500000.0267 (2)
O10.26118 (11)0.14947 (10)0.0196 (3)0.0277 (5)
O20.38491 (13)0.13984 (11)0.0214 (4)0.0385 (6)
O30.09102 (13)0.04009 (12)0.1144 (4)0.0397 (6)
O40.13318 (12)0.14232 (10)0.0626 (4)0.0306 (5)
O50.41958 (12)0.17737 (11)0.0329 (4)0.0376 (6)
O60.48724 (13)0.08593 (12)0.0044 (5)0.0478 (7)
H60.5222 (12)0.1125 (14)0.022 (18)0.20 (5)*
O70.35518 (13)0.27055 (12)0.2084 (4)0.0328 (5)
H7A0.355 (2)0.2979 (17)0.311 (4)0.049*
H7B0.380 (2)0.2392 (13)0.278 (5)0.049*
O80.19164 (13)0.24842 (10)0.2530 (4)0.0299 (5)
H8A0.179 (2)0.2116 (12)0.301 (6)0.045*
H8B0.1523 (17)0.2724 (17)0.251 (6)0.045*
O90.05389 (16)0.09054 (14)0.0538 (5)0.0476 (6)
H9A0.0641340.0524890.0940030.14 (3)*
H9B0.0720040.1218690.1176030.7 (2)*
O100.02472 (16)0.22086 (14)0.0502 (5)0.0497 (7)
H10A0.002 (3)0.2600 (13)0.051 (8)0.075*
H10B0.059 (2)0.2266 (18)0.029 (7)0.075*
C10.32004 (15)0.11523 (13)0.0183 (4)0.0212 (5)
C20.30924 (15)0.04058 (12)0.0121 (4)0.0193 (5)
C30.23620 (15)0.01466 (13)0.0152 (4)0.0209 (5)
H30.1950710.0434970.0280150.025*
C40.22367 (15)0.05379 (13)0.0237 (4)0.0198 (5)
C50.28557 (15)0.09729 (13)0.0044 (4)0.0205 (5)
H50.2779510.1430600.0068640.025*
C60.35852 (15)0.07142 (12)0.0186 (4)0.0202 (5)
C70.37041 (15)0.00283 (13)0.0277 (4)0.0223 (5)
H70.4194560.0139240.0442920.027*
C80.14446 (15)0.07985 (14)0.0669 (4)0.0236 (5)
C90.42460 (15)0.11709 (14)0.0210 (5)0.0238 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0226 (2)0.0145 (2)0.0321 (3)0.00139 (15)0.00695 (18)0.00118 (16)
Ca10.0137 (3)0.0310 (4)0.0342 (4)0.0000.0004 (3)0.000
O10.0235 (10)0.0152 (9)0.0456 (12)0.0039 (7)0.0085 (9)0.0022 (8)
O20.0234 (10)0.0165 (10)0.0764 (18)0.0004 (8)0.0095 (11)0.0011 (10)
O30.0216 (10)0.0280 (11)0.0666 (17)0.0035 (9)0.0043 (10)0.0032 (11)
O40.0234 (10)0.0208 (10)0.0475 (13)0.0042 (8)0.0040 (9)0.0041 (9)
O50.0247 (10)0.0156 (10)0.0718 (17)0.0030 (8)0.0040 (11)0.0022 (10)
O60.0230 (11)0.0194 (11)0.104 (2)0.0014 (9)0.0193 (13)0.0030 (12)
O70.0292 (11)0.0281 (11)0.0390 (12)0.0041 (9)0.0018 (9)0.0014 (9)
O80.0300 (11)0.0241 (11)0.0384 (12)0.0040 (8)0.0143 (9)0.0039 (8)
O90.0494 (16)0.0383 (14)0.0563 (16)0.0072 (12)0.0120 (13)0.0036 (12)
O100.0445 (15)0.0367 (14)0.0719 (19)0.0077 (12)0.0220 (13)0.0119 (13)
C10.0225 (12)0.0139 (11)0.0270 (13)0.0018 (9)0.0029 (10)0.0019 (9)
C20.0216 (12)0.0124 (11)0.0239 (12)0.0007 (9)0.0031 (9)0.0004 (9)
C30.0214 (12)0.0169 (12)0.0241 (12)0.0028 (9)0.0024 (10)0.0001 (9)
C40.0185 (11)0.0179 (12)0.0229 (12)0.0017 (9)0.0020 (9)0.0003 (9)
C50.0208 (12)0.0147 (11)0.0261 (12)0.0001 (9)0.0037 (10)0.0009 (9)
C60.0193 (12)0.0138 (11)0.0277 (13)0.0014 (9)0.0038 (10)0.0010 (9)
C70.0199 (12)0.0156 (12)0.0316 (13)0.0003 (9)0.0043 (10)0.0002 (10)
C80.0181 (12)0.0240 (13)0.0284 (13)0.0008 (10)0.0020 (10)0.0039 (10)
C90.0196 (12)0.0179 (12)0.0334 (14)0.0002 (10)0.0020 (10)0.0005 (10)
Geometric parameters (Å, º) top
Zn1—O12.033 (2)O7—H7A0.872 (18)
Zn1—O1i2.033 (2)O7—H7B0.865 (18)
Zn1—O72.206 (2)O8—H8A0.848 (18)
Zn1—O7i2.206 (2)O8—H8B0.851 (18)
Zn1—O8i2.087 (2)O9—H9A0.8383
Zn1—O82.087 (2)O9—H9B0.8465
Ca1—O3ii2.418 (2)O10—H10A0.886 (18)
Ca1—O32.418 (2)O10—H10B0.870 (18)
Ca1—O42.551 (2)C1—C21.513 (3)
Ca1—O4ii2.551 (2)C2—C31.392 (4)
Ca1—O92.432 (3)C2—C71.390 (4)
Ca1—O9ii2.432 (3)C3—H30.9300
Ca1—O102.435 (3)C3—C41.394 (4)
Ca1—O10ii2.435 (3)C4—C51.401 (4)
O1—C11.257 (3)C4—C81.497 (4)
O2—C11.257 (3)C5—H50.9300
O3—C81.250 (4)C5—C61.391 (4)
O4—C81.273 (4)C6—C71.395 (4)
O5—C91.219 (4)C6—C91.493 (4)
O6—H60.82 (2)C7—H70.9300
O6—C91.300 (4)
O1—Zn1—O1i180.0C1—O1—Zn1128.22 (18)
O1—Zn1—O7i85.46 (9)C8—O3—Ca195.70 (18)
O1i—Zn1—O7i94.54 (9)C8—O4—Ca188.97 (17)
O1—Zn1—O794.54 (9)C9—O6—H6108.8 (16)
O1i—Zn1—O785.46 (9)Zn1—O7—H7A121 (2)
O1—Zn1—O8i90.60 (8)Zn1—O7—H7B121 (2)
O1—Zn1—O889.40 (8)H7A—O7—H7B96 (3)
O1i—Zn1—O8i89.40 (8)Zn1—O8—H8A120 (2)
O1i—Zn1—O890.60 (8)Zn1—O8—H8B119 (2)
O7—Zn1—O7i180.0H8A—O8—H8B104 (3)
O8i—Zn1—O7i88.88 (9)Ca1—O9—H9A129.7
O8i—Zn1—O791.11 (9)Ca1—O9—H9B115.4
O8—Zn1—O788.89 (9)H9A—O9—H9B114.0
O8—Zn1—O7i91.11 (9)Ca1—O10—H10A126 (2)
O8i—Zn1—O8180.0Ca1—O10—H10B129 (2)
O3ii—Ca1—O392.20 (11)H10A—O10—H10B104 (4)
O3—Ca1—O4ii144.62 (8)O1—C1—C2116.1 (2)
O3ii—Ca1—O4ii52.46 (7)O2—C1—O1123.6 (2)
O3—Ca1—O452.46 (7)O2—C1—C2120.3 (2)
O3ii—Ca1—O4144.62 (8)C3—C2—C1119.2 (2)
O3ii—Ca1—O978.10 (10)C7—C2—C1121.7 (2)
O3—Ca1—O980.14 (10)C7—C2—C3119.1 (2)
O3ii—Ca1—O9ii80.14 (10)C2—C3—H3119.4
O3—Ca1—O9ii78.09 (10)C2—C3—C4121.1 (2)
O3ii—Ca1—O10ii121.36 (10)C4—C3—H3119.4
O3—Ca1—O10121.36 (10)C3—C4—C5119.5 (2)
O3—Ca1—O10ii126.51 (9)C3—C4—C8119.7 (2)
O3ii—Ca1—O10126.51 (9)C5—C4—C8120.7 (2)
O4ii—Ca1—O4162.91 (10)C4—C5—H5120.3
O9—Ca1—O4ii89.49 (9)C6—C5—C4119.4 (2)
O9—Ca1—O495.15 (9)C6—C5—H5120.3
O9ii—Ca1—O489.49 (9)C5—C6—C7120.6 (2)
O9ii—Ca1—O4ii95.15 (9)C5—C6—C9119.8 (2)
O9—Ca1—O9ii148.40 (15)C7—C6—C9119.5 (2)
O9ii—Ca1—O10141.92 (10)C2—C7—C6120.3 (2)
O9—Ca1—O1069.56 (10)C2—C7—H7119.9
O9—Ca1—O10ii141.92 (10)C6—C7—H7119.9
O9ii—Ca1—O10ii69.56 (10)O3—C8—O4121.3 (3)
O10ii—Ca1—O485.19 (9)O3—C8—C4119.4 (3)
O10—Ca1—O4ii85.19 (9)O4—C8—C4119.3 (2)
O10—Ca1—O481.08 (9)O5—C9—O6123.8 (3)
O10ii—Ca1—O4ii81.08 (9)O5—C9—C6123.2 (3)
O10—Ca1—O10ii72.92 (15)O6—C9—C6113.0 (2)
Zn1—O1—C1—O26.3 (4)C3—C4—C5—C61.4 (4)
Zn1—O1—C1—C2173.57 (17)C3—C4—C8—O36.8 (4)
Ca1—O3—C8—O413.4 (3)C3—C4—C8—O4175.9 (3)
Ca1—O3—C8—C4163.8 (2)C4—C5—C6—C71.6 (4)
Ca1—O4—C8—O312.6 (3)C4—C5—C6—C9174.7 (2)
Ca1—O4—C8—C4164.6 (2)C5—C4—C8—O3169.1 (3)
O1—C1—C2—C37.2 (4)C5—C4—C8—O48.1 (4)
O1—C1—C2—C7174.4 (3)C5—C6—C7—C20.6 (4)
O2—C1—C2—C3172.6 (3)C5—C6—C9—O510.7 (4)
O2—C1—C2—C75.7 (4)C5—C6—C9—O6167.7 (3)
C1—C2—C3—C4179.4 (2)C7—C2—C3—C41.1 (4)
C1—C2—C7—C6179.1 (2)C7—C6—C9—O5172.9 (3)
C2—C3—C4—C50.0 (4)C7—C6—C9—O68.7 (4)
C2—C3—C4—C8176.0 (2)C8—C4—C5—C6174.6 (2)
C3—C2—C7—C60.8 (4)C9—C6—C7—C2175.8 (3)
Symmetry codes: (i) x1/2, y1/2, z; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6···O2iii0.82 (2)1.81 (4)2.553 (3)151 (6)
O7—H7A···O4iv0.87 (2)2.04 (2)2.905 (3)174 (3)
O7—H7B···O5v0.87 (2)2.13 (2)2.955 (3)159 (4)
O8—H8A···O4v0.85 (2)1.90 (2)2.734 (3)166 (3)
O8—H8B···O2i0.85 (2)2.54 (3)3.083 (3)122 (3)
O8—H8B···O5iv0.85 (2)2.28 (3)2.990 (3)141 (3)
O9—H9A···O3vi0.84 (2)1.93 (2)2.752 (4)166 (1)
O10—H10A···O5vii0.89 (2)1.93 (3)2.768 (3)158 (5)
O10—H10B···O7viii0.87 (2)2.06 (2)2.925 (4)173 (3)
Symmetry codes: (i) x1/2, y1/2, z; (iii) x1, y, z; (iv) x1/2, y1/2, z1/2; (v) x, y, z1/2; (vi) x, y, z; (vii) x1/2, y+1/2, z; (viii) x+1/2, y+1/2, z.
catena-Poly[[tetraaquacobalt(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato] (2) top
Crystal data top
[CaCo(C6H4O6)2(H2O)8]F(000) = 1356
Mr = 659.38Dx = 1.878 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.875 (5) ÅCell parameters from 1029 reflections
b = 20.192 (4) Åθ = 3.1–25.2°
c = 6.5339 (16) ŵ = 1.06 mm1
β = 98.557 (9)°T = 296 K
V = 2332.0 (9) Å3Block, light pink
Z = 40.14 × 0.12 × 0.08 mm
Data collection top
Bruker D8 QUEST CMOS PHOTON II
diffractometer
2391 independent reflections
Radiation source: sealed x-ray tube, Mo1996 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 7.39 pixels mm-1θmax = 26.4°, θmin = 3.1°
ω and φ scansh = 2222
Absorption correction: multi-scan
(SADABS; Bruker, 2021)
k = 2525
Tmin = 0.689, Tmax = 0.745l = 78
15563 measured reflections
Refinement top
Refinement on F2Primary atom site location: inferred from neighbouring sites
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068 w = 1/[σ2(Fo2) + (0.0313P)2 + 2.5603P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2391 reflectionsΔρmax = 0.33 e Å3
207 parametersΔρmin = 0.28 e Å3
17 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.2500000.2500000.0000000.01469 (11)
Ca10.0000000.12635 (3)0.2500000.01778 (14)
O10.26153 (7)0.14844 (6)0.0159 (2)0.0206 (3)
O20.38504 (8)0.13906 (7)0.0181 (3)0.0313 (4)
O30.09133 (8)0.04081 (7)0.1066 (3)0.0310 (4)
O40.13376 (8)0.14265 (6)0.0630 (2)0.0215 (3)
O50.42037 (8)0.17700 (7)0.0281 (3)0.0297 (4)
O60.48777 (9)0.08571 (7)0.0039 (3)0.0407 (5)
H60.5234 (11)0.1125 (10)0.002 (6)0.087 (13)*
O70.35291 (8)0.26895 (7)0.2116 (2)0.0227 (3)
H7A0.3494 (13)0.2972 (10)0.300 (3)0.034*
H7B0.3705 (12)0.2350 (9)0.276 (3)0.034*
O80.19074 (8)0.24851 (7)0.2501 (2)0.0229 (3)
H8A0.1800 (13)0.2130 (9)0.301 (3)0.034*
H8B0.1526 (11)0.2726 (11)0.246 (4)0.034*
O90.05539 (10)0.08955 (8)0.0523 (3)0.0356 (4)
H9A0.0656340.0515010.0925190.073 (11)*
H9B0.0735040.1208810.1161190.29 (4)*
O100.02452 (9)0.22094 (8)0.0473 (3)0.0334 (4)
H10A0.0001 (14)0.2577 (9)0.046 (4)0.050*
H10B0.0613 (13)0.2272 (12)0.016 (4)0.050*
C10.32040 (11)0.11426 (9)0.0148 (3)0.0160 (4)
C20.30970 (11)0.03988 (9)0.0098 (3)0.0147 (4)
C30.23698 (11)0.01371 (9)0.0155 (3)0.0157 (4)
H30.1957390.0422610.0273250.019*
C40.22463 (11)0.05446 (9)0.0235 (3)0.0142 (4)
C50.28623 (11)0.09733 (9)0.0050 (3)0.0145 (4)
H50.2786780.1429060.0068900.017*
C60.35936 (11)0.07153 (9)0.0162 (3)0.0152 (4)
C70.37086 (11)0.00333 (9)0.0247 (3)0.0167 (4)
H70.4198270.0134620.0405460.020*
C80.14511 (11)0.08041 (9)0.0646 (3)0.0174 (4)
C90.42526 (11)0.11676 (9)0.0183 (3)0.0185 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0140 (2)0.00937 (18)0.0211 (2)0.00099 (13)0.00395 (15)0.00086 (14)
Ca10.0118 (3)0.0136 (3)0.0271 (3)0.0000.0001 (2)0.000
O10.0165 (7)0.0100 (6)0.0362 (9)0.0026 (5)0.0069 (6)0.0012 (6)
O20.0152 (8)0.0116 (7)0.0677 (12)0.0012 (6)0.0083 (7)0.0022 (7)
O30.0159 (8)0.0177 (7)0.0563 (11)0.0013 (6)0.0044 (7)0.0065 (7)
O40.0172 (7)0.0128 (7)0.0343 (8)0.0026 (5)0.0029 (6)0.0010 (6)
O50.0199 (8)0.0102 (7)0.0587 (11)0.0022 (6)0.0046 (7)0.0010 (7)
O60.0166 (8)0.0150 (7)0.0939 (15)0.0013 (6)0.0188 (9)0.0009 (8)
O70.0234 (8)0.0177 (7)0.0257 (8)0.0022 (6)0.0005 (6)0.0007 (6)
O80.0234 (8)0.0177 (7)0.0301 (8)0.0034 (6)0.0119 (6)0.0039 (6)
O90.0410 (10)0.0236 (9)0.0443 (10)0.0073 (7)0.0130 (8)0.0057 (8)
O100.0291 (9)0.0220 (8)0.0530 (11)0.0070 (7)0.0190 (8)0.0120 (8)
C10.0186 (10)0.0117 (9)0.0178 (10)0.0007 (7)0.0029 (8)0.0005 (7)
C20.0173 (10)0.0112 (9)0.0158 (10)0.0001 (7)0.0034 (8)0.0005 (7)
C30.0164 (10)0.0141 (9)0.0165 (10)0.0029 (7)0.0017 (8)0.0003 (7)
C40.0149 (9)0.0131 (9)0.0146 (9)0.0010 (7)0.0019 (7)0.0007 (7)
C50.0169 (10)0.0094 (8)0.0175 (10)0.0016 (7)0.0030 (8)0.0001 (7)
C60.0138 (10)0.0127 (9)0.0191 (10)0.0015 (7)0.0028 (8)0.0007 (7)
C70.0146 (10)0.0131 (9)0.0221 (10)0.0019 (7)0.0025 (8)0.0004 (8)
C80.0169 (10)0.0155 (9)0.0199 (10)0.0005 (8)0.0023 (8)0.0028 (8)
C90.0157 (10)0.0137 (10)0.0256 (11)0.0008 (7)0.0012 (8)0.0010 (8)
Geometric parameters (Å, º) top
Co1—O12.0620 (13)O7—H7A0.819 (15)
Co1—O1i2.0621 (13)O7—H7B0.839 (15)
Co1—O72.1645 (15)O8—H8A0.824 (15)
Co1—O7i2.1646 (15)O8—H8B0.835 (15)
Co1—O8i2.0760 (15)O9—H9A0.8410
Co1—O82.0760 (15)O9—H9B0.8481
Ca1—O3ii2.4641 (15)O10—H10A0.861 (15)
Ca1—O32.4641 (15)O10—H10B0.835 (16)
Ca1—O42.5393 (15)C1—C21.514 (3)
Ca1—O4ii2.5393 (15)C2—C31.390 (3)
Ca1—O9ii2.4526 (17)C2—C71.391 (3)
Ca1—O92.4526 (17)C3—H30.9300
Ca1—O102.4013 (16)C3—C41.394 (3)
Ca1—O10ii2.4013 (16)C4—C51.392 (3)
O1—C11.259 (2)C4—C81.501 (3)
O2—C11.257 (2)C5—H50.9300
O3—C81.249 (2)C5—C61.395 (3)
O4—C81.273 (2)C6—C71.392 (3)
O5—C91.222 (2)C6—C91.489 (3)
O6—H60.841 (18)C7—H70.9300
O6—C91.297 (2)
O1—Co1—O1i180.0C1—O1—Co1128.47 (12)
O1i—Co1—O785.73 (5)C8—O3—Ca194.55 (12)
O1—Co1—O7i85.73 (5)C8—O4—Ca190.45 (11)
O1—Co1—O794.27 (5)C9—O6—H6111.1 (13)
O1i—Co1—O7i94.27 (5)Co1—O7—H7A115.2 (16)
O1—Co1—O8i89.72 (5)Co1—O7—H7B113.2 (15)
O1—Co1—O890.27 (5)H7A—O7—H7B106 (2)
O1i—Co1—O8i90.28 (5)Co1—O8—H8A120.2 (15)
O1i—Co1—O889.73 (5)Co1—O8—H8B118.4 (15)
O7—Co1—O7i180.0H8A—O8—H8B106 (2)
O8—Co1—O789.10 (6)Ca1—O9—H9A131.4
O8i—Co1—O790.90 (6)Ca1—O9—H9B113.5
O8—Co1—O7i90.90 (6)H9A—O9—H9B114.3
O8i—Co1—O7i89.10 (6)Ca1—O10—H10A123.9 (15)
O8i—Co1—O8180.0Ca1—O10—H10B127.9 (16)
O3—Ca1—O3ii90.98 (7)H10A—O10—H10B107 (2)
O3ii—Ca1—O4ii52.03 (5)O1—C1—C2116.17 (17)
O3—Ca1—O452.03 (5)O2—C1—O1123.26 (17)
O3—Ca1—O4ii142.83 (5)O2—C1—C2120.57 (17)
O3ii—Ca1—O4142.83 (5)C3—C2—C1119.52 (17)
O4ii—Ca1—O4165.11 (6)C3—C2—C7118.76 (17)
O9—Ca1—O3ii76.69 (6)C7—C2—C1121.70 (17)
O9ii—Ca1—O3ii78.78 (6)C2—C3—H3119.3
O9ii—Ca1—O376.69 (6)C2—C3—C4121.34 (17)
O9—Ca1—O378.78 (6)C4—C3—H3119.3
O9ii—Ca1—O4ii96.66 (5)C3—C4—C8119.47 (17)
O9ii—Ca1—O487.86 (6)C5—C4—C3119.48 (17)
O9—Ca1—O496.66 (5)C5—C4—C8120.95 (17)
O9—Ca1—O4ii87.86 (6)C4—C5—H5120.2
O9ii—Ca1—O9144.73 (8)C4—C5—C6119.61 (17)
O10—Ca1—O3ii127.04 (5)C6—C5—H5120.2
O10ii—Ca1—O3ii120.85 (6)C5—C6—C9120.02 (16)
O10—Ca1—O3120.85 (6)C7—C6—C5120.26 (17)
O10ii—Ca1—O3127.04 (5)C7—C6—C9119.63 (17)
O10—Ca1—O4ii85.77 (5)C2—C7—C6120.52 (18)
O10—Ca1—O482.40 (5)C2—C7—H7119.7
O10ii—Ca1—O485.77 (5)C6—C7—H7119.7
O10ii—Ca1—O4ii82.40 (5)O3—C8—O4121.02 (18)
O10ii—Ca1—O9144.47 (6)O3—C8—C4119.55 (17)
O10—Ca1—O9ii144.47 (6)O4—C8—C4119.39 (17)
O10ii—Ca1—O9ii70.62 (6)O5—C9—O6123.65 (18)
O10—Ca1—O970.62 (6)O5—C9—C6123.26 (18)
O10ii—Ca1—O1074.63 (9)O6—C9—C6113.07 (16)
Co1—O1—C1—O25.3 (3)C3—C4—C5—C61.5 (3)
Co1—O1—C1—C2174.87 (12)C3—C4—C8—O35.4 (3)
Ca1—O3—C8—O414.5 (2)C3—C4—C8—O4177.01 (18)
Ca1—O3—C8—C4163.08 (15)C4—C5—C6—C71.8 (3)
Ca1—O4—C8—O314.0 (2)C4—C5—C6—C9174.90 (17)
Ca1—O4—C8—C4163.57 (16)C5—C4—C8—O3170.90 (19)
O1—C1—C2—C36.8 (3)C5—C4—C8—O46.7 (3)
O1—C1—C2—C7174.80 (18)C5—C6—C7—C20.8 (3)
O2—C1—C2—C3173.34 (19)C5—C6—C9—O59.4 (3)
O2—C1—C2—C75.1 (3)C5—C6—C9—O6169.1 (2)
C1—C2—C3—C4179.23 (17)C7—C2—C3—C40.8 (3)
C1—C2—C7—C6178.93 (17)C7—C6—C9—O5173.9 (2)
C2—C3—C4—C50.2 (3)C7—C6—C9—O67.6 (3)
C2—C3—C4—C8176.09 (18)C8—C4—C5—C6174.76 (17)
C3—C2—C7—C60.5 (3)C9—C6—C7—C2175.93 (18)
Symmetry codes: (i) x1/2, y1/2, z; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6···O2iii0.84 (2)1.74 (2)2.539 (2)158 (2)
O7—H7A···O4iv0.82 (2)2.09 (2)2.890 (2)165 (2)
O7—H7B···O5v0.84 (2)2.11 (2)2.904 (2)158 (2)
O8—H8A···O4v0.82 (2)1.93 (2)2.732 (2)165 (2)
O8—H8B···O2i0.84 (2)2.50 (2)3.058 (2)125 (2)
O8—H8B···O5iv0.84 (2)2.34 (2)3.027 (2)140 (2)
O9—H9A···O3vi0.84 (2)1.93 (2)2.745 (2)165 (1)
O10—H10A···O5vii0.86 (2)1.93 (2)2.768 (2)163 (3)
O10—H10B···O7viii0.84 (2)2.14 (2)2.968 (2)171 (3)
Symmetry codes: (i) x1/2, y1/2, z; (iii) x1, y, z; (iv) x1/2, y1/2, z1/2; (v) x, y, z1/2; (vi) x, y, z; (vii) x1/2, y+1/2, z; (viii) x+1/2, y+1/2, z.
Poly[[decaaquabis(µ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate] (3) top
Crystal data top
[CaZn2(C6H3O6)2(H2O)10]·2H2ODx = 1.932 Mg m3
Mr = 801.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, CcceCell parameters from 1824 reflections
a = 6.9927 (9) Åθ = 3.3–27.1°
b = 18.934 (2) ŵ = 2.04 mm1
c = 20.808 (2) ÅT = 296 K
V = 2755.0 (6) Å3Block, light colourless
Z = 40.4 × 0.2 × 0.2 mm
F(000) = 1640
Data collection top
Bruker D8 QUEST CMOS PHOTON II
diffractometer
1730 independent reflections
Radiation source: sealed x-ray tube1184 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
Detector resolution: 7.39 pixels mm-1θmax = 28.3°, θmin = 2.9°
φ and ω scansh = 98
Absorption correction: multi-scan
(SADABS; Bruker, 2021)
k = 2524
Tmin = 0.640, Tmax = 0.746l = 2727
12352 measured reflections
Refinement top
Refinement on F2Primary atom site location: inferred from neighbouring sites
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0412P)2 + 7.6311P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1730 reflectionsΔρmax = 0.72 e Å3
134 parametersΔρmin = 0.48 e Å3
15 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.2500000.5000000.63791 (3)0.03042 (19)
Ca10.0000000.2500000.2500000.0306 (3)
O10.1624 (4)0.42831 (13)0.57094 (13)0.0408 (7)
O20.0367 (4)0.38210 (14)0.65775 (12)0.0390 (7)
O30.0178 (5)0.19294 (13)0.35990 (11)0.0386 (7)
O40.5142 (5)0.44813 (14)0.64670 (15)0.0450 (7)
H4A0.577 (5)0.461 (2)0.6138 (16)0.068*
H4B0.491 (6)0.4052 (11)0.640 (2)0.068*
O50.2500000.5000000.7385 (2)0.0506 (11)
H5A0.261 (18)0.5417 (17)0.753 (3)0.076*0.5
H5B0.351 (10)0.481 (6)0.753 (3)0.076*0.5
O60.2492 (5)0.3353 (2)0.25836 (15)0.0640 (10)
H6A0.327 (6)0.342 (3)0.2270 (16)0.096*
H6B0.324 (6)0.338 (3)0.2905 (16)0.096*
O70.226 (5)0.493 (2)0.4497 (3)0.055 (5)0.5
H7A0.200 (19)0.521 (4)0.481 (4)0.082*0.5
H7B0.228 (19)0.453 (3)0.468 (4)0.082*0.5
C10.0790 (5)0.37818 (17)0.59974 (17)0.0274 (8)
C20.0350 (5)0.31241 (16)0.56248 (15)0.0221 (7)
C30.0339 (5)0.31200 (16)0.49550 (15)0.0237 (7)
H30.0560380.3536800.4730650.028*
C40.0000000.2500000.4621 (2)0.0207 (9)
C50.0000000.2500000.5956 (2)0.0247 (10)
H50.0000010.2499990.6402580.030*
C60.0000000.2500000.3896 (2)0.0237 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0465 (4)0.0193 (3)0.0255 (3)0.0017 (3)0.0000.000
Ca10.0312 (8)0.0416 (8)0.0189 (6)0.0000.0000.000
O10.0603 (19)0.0231 (12)0.0389 (15)0.0133 (13)0.0042 (14)0.0038 (11)
O20.062 (2)0.0312 (13)0.0241 (12)0.0019 (13)0.0007 (13)0.0075 (10)
O30.069 (2)0.0255 (12)0.0211 (12)0.0053 (13)0.0018 (13)0.0042 (10)
O40.0502 (19)0.0266 (13)0.0583 (18)0.0004 (13)0.0048 (16)0.0022 (13)
O50.076 (4)0.045 (2)0.031 (2)0.003 (2)0.0000.000
O60.053 (2)0.108 (3)0.0309 (15)0.036 (2)0.0006 (15)0.0057 (18)
O70.060 (16)0.065 (13)0.040 (3)0.016 (8)0.004 (5)0.006 (5)
C10.031 (2)0.0197 (15)0.0313 (18)0.0004 (14)0.0059 (15)0.0017 (13)
C20.0258 (18)0.0182 (14)0.0222 (16)0.0002 (13)0.0011 (13)0.0014 (12)
C30.030 (2)0.0196 (14)0.0214 (15)0.0002 (14)0.0001 (14)0.0022 (12)
C40.023 (2)0.018 (2)0.022 (2)0.0015 (17)0.0000.000
C50.031 (3)0.021 (2)0.022 (2)0.003 (2)0.0000.000
C60.028 (3)0.024 (2)0.020 (2)0.000 (2)0.0000.000
Geometric parameters (Å, º) top
Zn1—O12.039 (3)O5—H5A0.85 (2)
Zn1—O1i2.039 (3)O5—H5Ai0.85 (2)
Zn1—O42.100 (3)O5—H5Bi0.85 (2)
Zn1—O4i2.100 (3)O5—H5B0.85 (2)
Zn1—O52.093 (4)O6—H6A0.862 (19)
Ca1—O32.532 (2)O6—H6B0.850 (19)
Ca1—O3ii2.532 (2)O7—H7Ai0.87 (8)
Ca1—O3iii2.532 (2)O7—H7A0.85 (2)
Ca1—O3iv2.532 (2)O7—H7B0.85 (2)
Ca1—O6iv2.383 (3)O7—H7Bi1.13 (8)
Ca1—O6ii2.383 (3)C1—C21.499 (4)
Ca1—O6iii2.383 (3)C2—C31.394 (4)
Ca1—O62.383 (3)C2—C51.389 (4)
O1—C11.265 (4)C3—H30.9300
O2—C11.245 (4)C3—C41.384 (4)
O3—C61.251 (3)C4—C61.509 (6)
O3—C6iii1.251 (3)C4—C6iii1.509 (6)
O4—H4A0.850 (19)C5—H50.9300
O4—H4B0.840 (19)C6—C6iii0.000 (9)
O1—Zn1—O1i93.81 (15)H4A—O4—H4B104 (4)
O1i—Zn1—O4i90.72 (12)Zn1—O5—H5A111 (4)
O1—Zn1—O490.72 (12)Zn1—O5—H5Ai111 (4)
O1—Zn1—O4i96.12 (12)Zn1—O5—H5B111 (4)
O1i—Zn1—O496.12 (12)Zn1—O5—H5Bi111 (4)
O1—Zn1—O5133.10 (7)H5A—O5—H5Ai137 (9)
O1i—Zn1—O5133.10 (7)H5A—O5—H5Bi63 (7)
O4i—Zn1—O4170.00 (17)H5A—O5—H5B101 (4)
O5—Zn1—O485.00 (8)H5Ai—O5—H5Bi101 (4)
O5—Zn1—O4i85.00 (8)H5B—O5—H5Ai63 (7)
O3—Ca1—O3ii129.49 (11)H5B—O5—H5Bi138 (9)
O3ii—Ca1—O3iii174.38 (15)Ca1—O6—H6A121 (3)
O3—Ca1—O3iii50.87 (11)Ca1—O6—H6B123 (3)
O3—Ca1—O3iv174.38 (15)H6A—O6—H6B101 (4)
O3iii—Ca1—O3iv129.49 (11)H7A—O7—H7Ai76 (10)
O3ii—Ca1—O3iv50.87 (11)H7Ai—O7—H7Bi82 (6)
O6—Ca1—O3ii113.03 (10)H7A—O7—H7B103 (5)
O6iii—Ca1—O3iv113.03 (10)H7A—O7—H7Bi42 (10)
O6ii—Ca1—O3113.03 (10)H7B—O7—H7Ai52 (10)
O6iv—Ca1—O374.98 (10)H7B—O7—H7Bi131 (10)
O6iv—Ca1—O3iv100.80 (10)O1—C1—C2118.2 (3)
O6iii—Ca1—O3iii100.80 (10)O2—C1—O1121.6 (3)
O6iii—Ca1—O371.37 (10)O2—C1—C2120.1 (3)
O6ii—Ca1—O3iii74.98 (10)C3—C2—C1121.5 (3)
O6ii—Ca1—O3iv71.37 (10)C5—C2—C1119.1 (3)
O6iv—Ca1—O3iii113.03 (10)C5—C2—C3119.3 (3)
O6—Ca1—O3iv74.98 (10)C2—C3—H3119.8
O6—Ca1—O3iii71.37 (10)C4—C3—C2120.5 (3)
O6—Ca1—O3100.81 (10)C4—C3—H3119.8
O6iii—Ca1—O3ii74.98 (10)C3iii—C4—C3119.8 (4)
O6iv—Ca1—O3ii71.37 (10)C3—C4—C6120.1 (2)
O6ii—Ca1—O3ii100.80 (10)C3iii—C4—C6iii120.1 (2)
O6ii—Ca1—O6iv171.62 (15)C3iii—C4—C6120.1 (2)
O6iii—Ca1—O6iv94.6 (2)C3—C4—C6iii120.1 (2)
O6iv—Ca1—O686.0 (2)C6—C4—C6iii0.0
O6iii—Ca1—O6171.62 (15)C2—C5—C2iii120.6 (4)
O6ii—Ca1—O694.6 (2)C2—C5—H5119.7
O6iii—Ca1—O6ii86.0 (2)C2iii—C5—H5119.7
C1—O1—Zn1108.3 (2)O3iii—C6—O3120.7 (4)
C6—O3—Ca194.2 (2)O3—C6—C4119.6 (2)
C6iii—O3—Ca194.2 (2)O3iii—C6—C4119.6 (2)
C6iii—O3—C60.0 (3)C6iii—C6—O30 (10)
Zn1—O4—H4A105 (3)C6iii—C6—O3iii0 (10)
Zn1—O4—H4B106 (3)C6iii—C6—C40 (10)
Zn1—O1—C1—O210.3 (4)C2—C3—C4—C6iii179.7 (2)
Zn1—O1—C1—C2168.4 (3)C3—C2—C5—C2iii0.3 (2)
Ca1—O3—C6—O3iii0.000 (1)C3—C4—C6—O3162.0 (2)
Ca1—O3—C6—C4180.000 (1)C3iii—C4—C6—O318.0 (2)
Ca1—O3—C6—C6iii0.00 (13)C3—C4—C6—O3iii18.0 (2)
O1—C1—C2—C318.0 (5)C3iii—C4—C6—O3iii162.0 (2)
O1—C1—C2—C5160.1 (3)C3iii—C4—C6—C6iii0.0 (5)
O2—C1—C2—C3163.3 (3)C3—C4—C6—C6iii0 (100)
O2—C1—C2—C518.6 (5)C5—C2—C3—C40.6 (5)
C1—C2—C3—C4177.5 (3)C6iii—O3—C6—O3iii0 (100)
C1—C2—C5—C2iii177.9 (4)C6iii—O3—C6—C40 (100)
C2—C3—C4—C3iii0.3 (2)C6iii—C4—C6—O3iii0 (100)
C2—C3—C4—C6179.7 (2)C6iii—C4—C6—O30 (100)
Symmetry codes: (i) x+1/2, y+1, z; (ii) x, y, z+1/2; (iii) x, y+1/2, z; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O7v0.85 (2)1.79 (3)2.636 (17)174 (5)
O4—H4A···O7vi0.85 (2)2.09 (3)2.926 (19)165 (5)
O4—H4B···O3vii0.84 (2)1.86 (2)2.684 (4)167 (4)
O5—H5A···O6viii0.85 (2)2.33 (3)3.145 (4)160 (6)
O5—H5B···O4ix0.85 (2)2.37 (4)3.065 (5)139 (6)
O6—H6A···O2x0.86 (2)1.88 (2)2.722 (4)164 (6)
O6—H6B···O2v0.85 (2)2.02 (2)2.806 (4)153 (4)
O7—H7A···O1i0.85 (2)2.32 (9)3.030 (17)141 (12)
O7—H7B···O10.85 (2)2.25 (9)2.841 (15)127 (9)
Symmetry codes: (i) x+1/2, y+1, z; (v) x+1/2, y, z+1; (vi) x+1, y+1, z+1; (vii) x+1/2, y+1/2, z+1; (viii) x, y+1, z+1/2; (ix) x+1, y, z+3/2; (x) x+1/2, y, z1/2.
 

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