Terephthalate salts of dipositive cations

Kaduk, J.A.

doi:10.1107/S0108768102009102

Terephthalate salts of dipositive cations

The crystal structures of M(C₈H₄O₄)(H₂O)₂, M = Mg, Mn, Fe and Co, have been determined by applying Monte Carlo simulated annealing techniques to synchrotron powder diffraction data and refined by the Rietveld method using both synchrotron and laboratory powder data. These isostructural compounds crystallize in the monoclinic space group C2/c, with 18.2734 (9) ≤ a ≤ 18.7213 (13), 6.5186 (13) ≤ b ≤ 6.5960 (4), 7.2968 ≤ c ≤ 7.4034 (6) Å, 98.653 (2) ≤ β ≤ 99.675 (1)° and Z = 4. The structure consists of alternating layers (perpendicular to a) of terephthalate anions and octahedrally coordinated metal cations. The octahedra are isolated; each carboxylate bridges two metal cations. The equatorial metal coordination consists of four terephthalate O atoms and there are two axial water molecules. Both water-molecule H atoms participate in normal-strength hydrogen bonds to carboxylate O atoms. Quantum chemical calculations (using CASTEP) were used to determine the H-atom positions and analyze the hydrogen bonding and the metal coordination. Both the atomic charges and the M—O bond-overlap populations indicate that, despite the fact that these compounds are isostructural, the metal–terephthalate bonding is different. The bonding in the Mg complex is essentially ionic, while the M—O bonds in the Mn, Fe and Co complexes have significant covalent character. Comparison of a new Rietveld refinement of the structure of copper(II) terephthalate trihydrate with the reported single-crystal structure provides an opportunity to assess the accuracy and precision that can be expected from structures of aromatic carboxylates determined using X-ray powder data. The average difference between the bond distances in the two structures is 0.03 Å and the average difference in bond angles is only 1.1°.

Keywords: terephthalate salts; hydrogen bonding; Monte Carlo simulated annealing techniques; synchrotron powder diffraction data; Rietveld method.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768102009102/bk0107sup1.cif Contains datablocks BK0107, Co, Mg1, Fe, Cu, Mn, Mg3, Mg2
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Cosup2.rtv Contains datablock CO
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Cosup3.hkl Contains datablock Co
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg1sup4.rtv Contains datablock Mg1
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg1sup5.hkl Contains datablock Mg1
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg2sup6.rtv Contains datablock Mg2
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg2sup7.hkl Contains datablock Mg2
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg3sup8.rtv Contains datablock Mg3
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mg3sup9.hkl Contains datablock Mg3
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Fesup10.rtv Contains datablock Fe
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Fesup11.hkl Contains datablock Fe
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Cusup12.rtv Contains datablock Cu
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Cusup13.hkl Contains datablock Cu
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mnsup14.rtv Contains datablock Mn
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102009102/bk0107Mnsup15.hkl Contains datablock Mn

CCDC references: 195794; 195795; 195796; 195797; 195798

Computing details top

For all compounds, program(s) used to refine structure: GSAS.

Figures top

(Co) top

Crystal data top

?	β = 98.653 (2)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.2731 (8) Å	K^G₁, K^G₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5417 (3) Å	?, ? × ? × ? mm
c = 7.2966 (3) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 99.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.042	4148 data points
R_wp = 0.056	31 parameters
R_exp = 0.038	7 restraints
χ² = 2.132	(Δ/σ)_max = 0.04

Crystal data top

?	β = 98.653 (2)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.2731 (8) Å	K^G₁, K^G₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5417 (3) Å	?, ? × ? × ? mm
c = 7.2966 (3) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 99.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.042	4148 data points
R_wp = 0.056	31 parameters
R_exp = 0.038	7 restraints
χ² = 2.132

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.0693 (3)	−0.001 (2)	0.1115 (13)	0.017 (4)*	0.5
C2	0.0400 (7)	0.1820 (12)	0.0321 (14)	0.017 (4)*	0.5
C3	−0.0293 (7)	0.1825 (12)	−0.0794 (13)	0.017 (4)*	0.5
C4	−0.0693 (3)	0.001 (2)	−0.1115 (13)	0.017 (4)*	0.5
C5	−0.0400 (7)	−0.1820 (12)	−0.0321 (14)	0.017 (4)*	0.5
C6	0.0293 (7)	−0.1825 (12)	0.0794 (13)	0.017 (4)*	0.5
H2	0.0676 (12)	0.307 (2)	0.054 (2)	0.029*	0.5
H3	−0.0495 (12)	0.308 (2)	−0.134 (2)	0.029*	0.5
H5	−0.0676 (12)	−0.307 (2)	−0.054 (2)	0.029*	0.5
H6	0.0495 (12)	−0.308 (2)	0.134 (2)	0.029*	0.5
C11	0.1478 (8)	0.001 (3)	0.211 (3)	0.014 (3)*
O12	0.1863 (6)	0.1544 (16)	0.2044 (18)	0.014 (3)*
O13	0.1802 (6)	−0.1687 (16)	0.2638 (18)	0.014 (3)*
Co14	0.25	0.25	0.0	0.026 (2)*
O15	0.1952 (6)	0.5340 (14)	−0.0140 (14)	0.018 (5)*
H16	0.18709	0.54683	0.1097	0.016*
H17	0.24861	0.5982	−0.0057	0.016*

(Mg1) top

Crystal data top

?	β = 99.6767 (11)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.5048 (3) Å	? radiation, λ = 1.149986 Å
b = 6.53513 (10) Å	?, ? × ? × ? mm
c = 7.31801 (10) Å

Data collection top

2θ_min = 7.005°, 2θ_max = 54.99°, 2θ_step = 0.005°

Refinement top

R_p = 0.144	9598 data points
R_wp = 0.190	69 parameters
R_exp = 0.068	7 restraints
χ² = 12.320	(Δ/σ)_max = 1.23

Crystal data top

?	β = 99.6767 (11)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.5048 (3) Å	? radiation, λ = 1.149986 Å
b = 6.53513 (10) Å	?, ? × ? × ? mm
c = 7.31801 (10) Å

Data collection top

2θ_min = 7.005°, 2θ_max = 54.99°, 2θ_step = 0.005°

Refinement top

R_p = 0.144	9598 data points
R_wp = 0.190	69 parameters
R_exp = 0.068	7 restraints
χ² = 12.320	(Δ/σ)_max = 1.23

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.07140 (7)	0.0041 (9)	0.0997 (4)	0.0137 (13)*	0.5
C2	0.0362 (3)	0.1868 (4)	0.0382 (5)	0.0137 (13)*	0.5
C3	−0.0352 (3)	0.1827 (5)	−0.0614 (5)	0.0137 (13)*	0.5
C4	−0.07140 (7)	−0.0041 (9)	−0.0997 (4)	0.0137 (13)*	0.5
C5	−0.0362 (3)	−0.1868 (4)	−0.0382 (5)	0.0137 (13)*	0.5
C6	0.0352 (3)	−0.1827 (5)	0.0614 (5)	0.0137 (13)*	0.5
H7	0.0611 (5)	0.3157 (7)	0.0646 (9)	0.018*	0.5
H8	−0.0595 (5)	0.3087 (8)	−0.1038 (9)	0.018*	0.5
H9	−0.0611 (5)	−0.3157 (7)	−0.0646 (9)	0.018*	0.5
H10	0.0595 (5)	−0.3087 (8)	0.1038 (9)	0.018*	0.5
C11	0.1487 (2)	0.0083 (7)	0.1986 (8)	0.0152 (10)*
O12	0.1869 (2)	0.1629 (6)	0.1973 (5)	0.0152 (10)*
O13	0.1714 (2)	−0.1568 (5)	0.2754 (5)	0.0152 (10)*
Mg14	0.25	0.25	0.0	0.0339 (13)*
O15	0.19849 (17)	0.5365 (4)	−0.0230 (5)	0.0138 (14)*
H16	0.18709	0.54683	0.10907	0.019*
H17	0.24861	0.5982	−0.0057	0.019*

(Fe) top

Crystal data top

?	β = 99.563 (9)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.695 (4) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5186 (13) Å	?, ? × ? × ? mm
c = 7.3015 (16) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 69.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.120	2648 data points
R_wp = 0.149	38 parameters
R_exp = 0.089	7 restraints
χ² = 2.993	(Δ/σ)_max = 0.06

Crystal data top

?	β = 99.563 (9)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.695 (4) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5186 (13) Å	?, ? × ? × ? mm
c = 7.3015 (16) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 69.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.120	2648 data points
R_wp = 0.149	38 parameters
R_exp = 0.089	7 restraints
χ² = 2.993

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.0690 (3)	0.0014 (10)	0.1088 (16)	0.0136*	0.5
C2	0.0376 (4)	0.1849 (5)	0.0360 (15)	0.0136*	0.5
C3	−0.0314 (4)	0.1835 (5)	−0.0728 (14)	0.0136*	0.5
C4	−0.0690 (3)	−0.0014 (10)	−0.1088 (16)	0.0136*	0.5
C5	−0.0376 (4)	−0.1849 (5)	−0.0360 (15)	0.0136*	0.5
C6	0.0314 (4)	−0.1835 (5)	0.0728 (14)	0.0136*	0.5
H7	0.0635 (7)	0.3124 (9)	0.061 (3)	0.04*	0.5
H8	−0.0530 (7)	0.3100 (9)	−0.123 (2)	0.04*	0.5
H9	−0.0635 (7)	−0.3124 (9)	−0.061 (3)	0.04*	0.5
H10	0.0530 (7)	−0.3100 (9)	0.123 (2)	0.04*	0.5
C11	0.1470 (4)	0.0021 (14)	0.204 (3)	0.0155*
O12	0.1810 (4)	0.1691 (17)	0.1844 (12)	0.0155*
O13	0.1731 (6)	−0.1705 (15)	0.2685 (16)	0.0155*
Fe14	0.25	0.25	0.0	0.006 (3)*
O15	0.1947 (9)	0.5256 (16)	−0.018 (3)	0.0138*
H16	0.18709	0.54683	0.10907	0.04*
H17	0.24861	0.5982	−0.0057	0.04*

(Cu) top

Crystal data top

?	c = 6.2999 (3) Å
M_r = ?	V = ? Å³
Orthorhombic, Pbcn	Z = ?
a = 6.8740 (3) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 22.9815 (6) Å	?, ? × ? × ? mm

Data collection top

2θ_min = 18.043°, 2θ_max = 120.003°, 2θ_step = 0.02°

Refinement top

R_p = 0.030	5099 data points
R_wp = 0.039	40 parameters
R_exp = 0.020	9 restraints
χ² = 3.920	(Δ/σ)_max = 0.06

Crystal data top

?	c = 6.2999 (3) Å
M_r = ?	V = ? Å³
Orthorhombic, Pbcn	Z = ?
a = 6.8740 (3) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 22.9815 (6) Å	?, ? × ? × ? mm

Data collection top

2θ_min = 18.043°, 2θ_max = 120.003°, 2θ_step = 0.02°

Refinement top

R_p = 0.030	5099 data points
R_wp = 0.039	40 parameters
R_exp = 0.020	9 restraints
χ² = 3.920

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5	0.6701 (2)	0.25	0.048 (3)*
C2	0.4422 (11)	0.7005 (2)	0.0685 (4)	0.048 (3)*	0.5
C3	0.4422 (11)	0.7614 (2)	0.0685 (4)	0.048 (3)*	0.5
C4	0.5	0.7918 (2)	0.25	0.048 (3)*
C5	0.5578 (11)	0.7614 (2)	0.4315 (4)	0.048 (3)*	0.5
C6	0.5578 (11)	0.7005 (2)	0.4315 (4)	0.048 (3)*	0.5
H7	0.4023 (19)	0.6796 (2)	−0.0567 (7)	0.05*	0.5
H8	0.4023 (19)	0.7823 (2)	−0.0567 (7)	0.05*	0.5
H9	0.5977 (19)	0.7823 (2)	0.5567 (7)	0.05*	0.5
H10	0.4023 (19)	0.6796 (2)	−0.0567 (7)	0.05*	0.5
C11	0.5	0.6066 (4)	0.25	0.005 (2)*
O12	0.5276 (16)	0.58049 (18)	0.4277 (9)	0.005 (2)*
C13	0.5	0.8591 (4)	0.25	0.005 (2)*
O14	0.4035 (14)	0.8838 (2)	0.1023 (13)	0.005 (2)*
Cu15	0.5	0.5	0.5	0.0206 (12)*
O16	0.7210 (14)	0.4824 (3)	0.3255 (16)	0.025 (5)*
H17	0.781	0.505	0.267	0.05*
H18	0.772	0.45	0.332	0.05*
O19	0.5	0.9353 (3)	0.75	0.016 (4)*
H20	0.513	0.926	0.642	0.05*

(Mn) top

Crystal data top

?	β = 99.287 (3)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.7213 (13) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5960 (4) Å	?, ? × ? × ? mm
c = 7.4035 (6) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 99.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.106	4148 data points
R_wp = 0.133	48 parameters
R_exp = 0.077	7 restraints
χ² = 3.098	(Δ/σ)_max = 0.04

Crystal data top

?	β = 99.287 (3)°
M_r = ?	V = ? Å³
Monoclinic, C2/c	Z = ?
a = 18.7213 (13) Å	K=07₁, K=07₂ radiation, λ = 1.540629, 1.544451 Å
b = 6.5960 (4) Å	?, ? × ? × ? mm
c = 7.4035 (6) Å

Data collection top

2θ_min = 17.025°, 2θ_max = 99.965°, 2θ_step = 0.02°

Refinement top

R_p = 0.106	4148 data points
R_wp = 0.133	48 parameters
R_exp = 0.077	7 restraints
χ² = 3.098

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.06975 (17)	0.0001 (7)	0.1016 (9)	0.012 (5)*	0.5
C2	0.0371 (3)	0.1829 (4)	0.0381 (8)	0.012 (5)*	0.5
C3	−0.0326 (3)	0.1827 (3)	−0.0635 (10)	0.012 (5)*	0.5
C4	−0.06975 (17)	−0.0001 (7)	−0.1016 (9)	0.012 (5)*	0.5
C5	−0.0371 (3)	−0.1829 (4)	−0.0381 (8)	0.012 (5)*	0.5
C6	0.0326 (3)	−0.1827 (3)	0.0635 (10)	0.012 (5)*	0.5
H2	0.0627 (4)	0.3090 (6)	0.0644 (14)	0.017*	0.5
H3	−0.0551 (5)	0.3087 (6)	−0.1073 (17)	0.017*	0.5
H5	−0.0627 (4)	−0.3090 (6)	−0.0644 (14)	0.017*	0.5
H6	0.0551 (5)	−0.3087 (6)	0.1073 (17)	0.017*	0.5
C7	0.1463 (3)	−0.0009 (9)	0.2055 (15)	0.019 (5)*
O1	0.1817 (2)	0.1615 (10)	0.2019 (7)	0.019 (5)*
O2	0.1709 (3)	−0.1721 (9)	0.2589 (8)	0.019 (5)*
Mn	0.25	0.25	0.0	0.037 (5)*
O3	0.1949 (3)	0.5448 (6)	−0.0204 (15)	0.017 (5)*
H16	0.18709	0.54683	0.10907	0.022*
H17	0.24861	0.5982	−0.0057	0.022*

Experimental details

	(Co)	(Mg1)	(Fe)	(Cu)
Crystal data
Chemical formula	?	?	?	?
M_r	?	?	?	?
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c	Monoclinic, C2/c	Orthorhombic, Pbcn
Temperature (K)	?	?	?	?
a, b, c (Å)	18.2731 (8), 6.5417 (3), 7.2966 (3)	18.5048 (3), 6.53513 (10), 7.31801 (10)	18.695 (4), 6.5186 (13), 7.3015 (16)	6.8740 (3), 22.9815 (6), 6.2999 (3)
α, β, γ (°)	90, 98.653 (2), 90	90, 99.6767 (11), 90	90, 99.563 (9), 90	90, 90, 90
V (Å³)	?	?	?	?
Z	?	?	?	?
Radiation type	K^G₁, K^G₂, λ = 1.540629, 1.544451 Å	?, λ = 1.149986 Å	K=07₁, K=07₂, λ = 1.540629, 1.544451 Å	K=07₁, K=07₂, λ = 1.540629, 1.544451 Å
Specimen shape, size (mm)	?, ? × ? × ?	?, ? × ? × ?	?, ? × ? × ?	?, ? × ? × ?

Data collection
Diffractometer	?	?	?	?
Specimen mounting	?	?	?	?
Data collection mode	?	?	?	?
Scan method	?	?	?	?
2θ values (°)	2θ_min = 17.025 2θ_max = 99.965 2θ_step = 0.02	2θ_min = 7.005 2θ_max = 54.99 2θ_step = 0.005	2θ_min = 17.025 2θ_max = 69.965 2θ_step = 0.02	2θ_min = 18.043 2θ_max = 120.003 2θ_step = 0.02

Refinement
R factors and goodness of fit	R_p = 0.042, R_wp = 0.056, R_exp = 0.038, χ² = 2.132	R_p = 0.144, R_wp = 0.190, R_exp = 0.068, χ² = 12.320	R_p = 0.120, R_wp = 0.149, R_exp = 0.089, χ² = 2.993	R_p = 0.030, R_wp = 0.039, R_exp = 0.020, χ² = 3.920
No. of data points	4148	9598	2648	5099
No. of parameters	31	69	38	40
No. of restraints	7	7	7	9
(Δ/σ)_max	0.04	1.23	0.06	0.06

	(Mn)
Crystal data
Chemical formula	?
M_r	?
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	?
a, b, c (Å)	18.7213 (13), 6.5960 (4), 7.4035 (6)
α, β, γ (°)	90, 99.287 (3), 90
V (Å³)	?
Z	?
Radiation type	K=07₁, K=07₂, λ = 1.540629, 1.544451 Å
Specimen shape, size (mm)	?, ? × ? × ?

Data collection
Diffractometer	?
Specimen mounting	?
Data collection mode	?
Scan method	?
2θ values (°)	2θ_min = 17.025 2θ_max = 99.965 2θ_step = 0.02

Refinement
R factors and goodness of fit	R_p = 0.106, R_wp = 0.133, R_exp = 0.077, χ² = 3.098
No. of data points	4148
No. of parameters	48
No. of restraints	7
(Δ/σ)_max	0.04

Computer programs: GSAS.

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