High-pressure study of a 3d–4f heterometallic CuEu–organic skeleton

Yang, K.; Yang, Y.; Yao, Z.; Cheng, S.; Cui, X.; Wang, X.; Han, Y.; Yi, F.; Mo, G.

doi:10.1107/S205322962400010X

High-pressure study of a 3d–4f heterometallic CuEu–organic skeleton

K. Yang, Y. Yang, Z. Yao, S. Cheng, X. Cui, X. Wang, Y. Han, F. Yi and G. Mo

We prepared a 3d–4f heterobimetallic CuEu–organic framework NBU-8 with a density of 1921 kg m⁻³ belonging to the family of dense packing materials (dense metal–organic frameworks or MOFs). This MOF material was prepared from 4-(pyrimidin-5-yl)benzoic acid (HPBA) with a bifunctional ligand site as a tripodal ligand and Cu²⁺ and Eu³⁺ as the metal centres; the molecular formula is Cu₃Eu₂(PBA)₆(NO₃)₆·H₂O. This material is a very promising dimethylformamide (DMF) molecular chemical sensor. Systematic high-pressure studies of NBU-8 were carried out by powder X-ray diffraction, high-pressure X-ray diffraction and molecular dynamics simulation. The high-pressure experiment shows that the (006) diffraction peak of the crystal structure moves toward a low angle with increasing pressure, accompanied by the phenomenon that the d-spacing increases, and as the pressure increases, the (10 $\overline{2}$ ) diffraction peak moves to a higher angle, the amplitude of the d-spacing is significantly reduced and finally merges with the (006) diffraction peak into one peak. The amplitude of the d-spacing is significantly reduced, indicating that NBU-8 compresses and deforms along the a-axis direction when subjected to uniform pressure. This is caused by tilting of the ligands to become more vertical along the c direction, leading to its expansion. This allows greater contraction along the a direction. We also carried out a Rietveld structure refinement and a Birch–Murnaghan solid-state equation fitting for the high-pressure experimental results. We calculated the bulk modulus of the material to be 45.68 GPa, which is consistent with the calculated results. The framework is among the most rigid MOFs reported to date, exceeding that of Cu–BTC. Molecular dynamics simulations estimated that the mechanical energy absorbed by the system when pressurized to 5.128 GPa was 249.261 kcal mol⁻¹. The present work will provide fresh ideas for the study of mechanical energy in other materials.

Keywords: metal–organic framework; MOF; high pressure; X-ray diffraction; Rietveld refinement; bulk modulus; DMF sensor; molecular dynamics.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205322962400010X/oc3022sup1.cif Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S205322962400010X/oc3022sup2.pdf Additional figures

CCDC reference: 1561729

Computing details top

(I) top

Crystal data top

C₆₆H₄₄Cu₃Eu₂N₁₈O₃₁	D_x = 1.921 Mg m⁻³
M_r = 2079.73	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 4858 reflections
a = 14.0021 (3) Å	θ = 2.9–26.1°
c = 63.523 (3) Å	µ = 2.70 mm⁻¹
V = 10785.7 (5) Å³	T = 296 K
Z = 6	Brick, blue
F(000) = 6162	0.25 × 0.23 × 0.20 mm

Data collection top

CCD area detector diffractometer	2373 independent reflections
Radiation source: fine-focus sealed tube	2002 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
phi and ω scans	θ_max = 26.1°, θ_min = 1.9°
Absorption correction: multi-scan Sheldrick, G. M.. SADABS	h = −17→14
T_min = 0.659, T_max = 0.745	k = −17→17
21300 measured reflections	l = −78→65

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0569P)² + 20.0828P] where P = (F_o² + 2F_c²)/3
2373 reflections	(Δ/σ)_max < 0.001
180 parameters	Δρ_max = 2.15 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Eu1	1.0000	0.0000	0.075327 (4)	0.02052 (13)
Cu1	1.0000	0.37628 (4)	0.2500	0.02130 (17)
N1	0.9450 (2)	0.2460 (2)	0.22993 (4)	0.0241 (6)
N2	0.8518 (3)	0.0527 (3)	0.22484 (5)	0.0469 (10)
N3	0.8745 (3)	−0.2084 (3)	0.05255 (6)	0.0338 (8)
C1	1.0971 (3)	0.2270 (3)	0.11008 (5)	0.0216 (7)
C2	1.0514 (3)	0.2191 (3)	0.13157 (5)	0.0221 (7)
C3	0.9584 (3)	0.1229 (3)	0.13794 (5)	0.0286 (8)
H3A	0.9197	0.0670	0.1282	0.034*
C4	0.9224 (3)	0.1088 (3)	0.15859 (6)	0.0294 (8)
H4A	0.8604	0.0432	0.1626	0.035*
C5	0.9774 (3)	0.1907 (3)	0.17335 (5)	0.0229 (7)
C6	1.0691 (3)	0.2882 (3)	0.16693 (6)	0.0348 (9)
H6A	1.1062	0.3448	0.1766	0.042*
C7	1.1062 (3)	0.3027 (3)	0.14626 (5)	0.0306 (8)
H7A	1.1678	0.3686	0.1422	0.037*
C8	0.9432 (3)	0.1740 (3)	0.19581 (5)	0.0248 (7)
C9	0.8809 (4)	0.0704 (3)	0.20466 (6)	0.0412 (11)
H9A	0.8579	0.0094	0.1960	0.049*
C10	0.8846 (4)	0.1413 (3)	0.23663 (6)	0.0357 (10)
H10A	0.8642	0.1304	0.2507	0.043*
C11	0.9723 (3)	0.2605 (3)	0.20960 (5)	0.0245 (7)
H11A	1.0127	0.3321	0.2045	0.029*
O1	1.0467 (2)	0.1468 (2)	0.09779 (4)	0.0377 (7)
O2	1.1875 (2)	0.3124 (2)	0.10583 (4)	0.0259 (5)
O3	0.9371 (2)	−0.1995 (2)	0.06795 (4)	0.0350 (6)
O4	0.8741 (2)	−0.1208 (2)	0.04757 (4)	0.0383 (7)
O5	0.8196 (3)	−0.2949 (3)	0.04348 (6)	0.0617 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.02541 (15)	0.02541 (15)	0.01072 (18)	0.01271 (8)	0.000	0.000
Cu1	0.0318 (3)	0.0254 (2)	0.0088 (3)	0.01592 (17)	−0.0010 (2)	−0.00049 (11)
N1	0.0315 (16)	0.0256 (15)	0.0143 (13)	0.0136 (13)	0.0033 (12)	0.0008 (11)
N2	0.073 (3)	0.0261 (18)	0.0212 (16)	0.0094 (19)	0.0104 (17)	0.0038 (14)
N3	0.0319 (17)	0.033 (2)	0.0339 (19)	0.0141 (16)	0.0010 (15)	−0.0067 (15)
C1	0.0302 (19)	0.0273 (19)	0.0127 (16)	0.0185 (16)	0.0000 (14)	−0.0006 (14)
C2	0.0290 (18)	0.0288 (18)	0.0134 (15)	0.0181 (16)	0.0001 (13)	−0.0012 (13)
C3	0.031 (2)	0.031 (2)	0.0163 (17)	0.0094 (16)	−0.0001 (14)	−0.0081 (15)
C4	0.0299 (19)	0.0263 (18)	0.0197 (18)	0.0048 (16)	0.0045 (15)	−0.0020 (14)
C5	0.0323 (19)	0.0267 (18)	0.0124 (16)	0.0168 (15)	0.0043 (13)	−0.0014 (13)
C6	0.048 (2)	0.0265 (19)	0.0164 (17)	0.0088 (18)	0.0051 (16)	−0.0063 (15)
C7	0.041 (2)	0.0232 (19)	0.0169 (17)	0.0077 (17)	0.0060 (15)	−0.0027 (14)
C8	0.0332 (19)	0.0274 (19)	0.0143 (16)	0.0155 (16)	0.0045 (14)	0.0022 (13)
C9	0.066 (3)	0.024 (2)	0.0220 (19)	0.014 (2)	0.004 (2)	−0.0040 (16)
C10	0.049 (2)	0.028 (2)	0.0202 (19)	0.0114 (19)	0.0094 (17)	0.0039 (15)
C11	0.0295 (19)	0.0256 (18)	0.0158 (16)	0.0118 (16)	0.0035 (14)	0.0015 (14)
O1	0.0471 (17)	0.0382 (17)	0.0201 (14)	0.0155 (14)	0.0028 (12)	−0.0103 (12)
O2	0.0280 (13)	0.0335 (14)	0.0146 (12)	0.0141 (12)	0.0031 (10)	−0.0006 (10)
O3	0.0389 (16)	0.0338 (15)	0.0338 (15)	0.0194 (13)	−0.0063 (13)	−0.0001 (12)
O4	0.0457 (17)	0.0376 (16)	0.0345 (15)	0.0230 (14)	−0.0144 (13)	−0.0074 (12)
O5	0.059 (2)	0.041 (2)	0.077 (3)	0.0188 (18)	−0.026 (2)	−0.0295 (18)

Geometric parameters (Å, º) top

Eu1—O1ⁱ	2.312 (3)	N3—O4	1.270 (4)
Eu1—O1ⁱⁱ	2.312 (3)	N3—O3	1.277 (4)
Eu1—O1	2.312 (3)	C1—O1	1.256 (4)
Eu1—O4ⁱ	2.469 (3)	C1—O2	1.261 (5)
Eu1—O4ⁱⁱ	2.469 (3)	C1—C2	1.488 (5)
Eu1—O4	2.469 (3)	C2—C3	1.386 (5)
Eu1—O3	2.518 (3)	C2—C7	1.390 (5)
Eu1—O3ⁱⁱ	2.518 (3)	C3—C4	1.384 (5)
Eu1—O3ⁱ	2.518 (3)	C3—H3A	0.9300
Eu1—N3ⁱ	2.927 (3)	C4—C5	1.380 (5)
Eu1—N3	2.927 (3)	C4—H4A	0.9300
Eu1—N3ⁱⁱ	2.927 (3)	C5—C6	1.388 (5)
Cu1—O2ⁱⁱⁱ	1.945 (2)	C5—C8	1.486 (4)
Cu1—O2^iv	1.945 (2)	C6—C7	1.389 (5)
Cu1—N1	2.035 (3)	C6—H6A	0.9300
Cu1—N1^v	2.035 (3)	C7—H7A	0.9300
Cu1—O3^vi	2.580 (3)	C8—C11	1.380 (5)
Cu1—O3^vii	2.580 (3)	C8—C9	1.384 (5)
N1—C11	1.334 (4)	C9—H9A	0.9300
N1—C10	1.343 (5)	C10—H10A	0.9300
N2—C10	1.319 (5)	C11—H11A	0.9300
N2—C9	1.330 (5)	O2—Cu1^viii	1.945 (2)
N3—O5	1.208 (4)

O1ⁱ—Eu1—O1ⁱⁱ	85.90 (11)	N3ⁱ—Eu1—N3ⁱⁱ	97.68 (9)
O1ⁱ—Eu1—O1	85.90 (11)	N3—Eu1—N3ⁱⁱ	97.68 (9)
O1ⁱⁱ—Eu1—O1	85.90 (11)	O2ⁱⁱⁱ—Cu1—O2^iv	96.56 (15)
O1ⁱ—Eu1—O4ⁱ	146.86 (10)	O2ⁱⁱⁱ—Cu1—N1	166.84 (11)
O1ⁱⁱ—Eu1—O4ⁱ	124.99 (9)	O2^iv—Cu1—N1	88.14 (11)
O1—Eu1—O4ⁱ	84.92 (10)	O2ⁱⁱⁱ—Cu1—N1^v	88.14 (11)
O1ⁱ—Eu1—O4ⁱⁱ	84.92 (10)	O2^iv—Cu1—N1^v	166.84 (11)
O1ⁱⁱ—Eu1—O4ⁱⁱ	146.86 (10)	N1—Cu1—N1^v	89.98 (16)
O1—Eu1—O4ⁱⁱ	124.99 (9)	O2ⁱⁱⁱ—Cu1—O3^vi	100.65 (10)
O4ⁱ—Eu1—O4ⁱⁱ	74.64 (11)	O2^iv—Cu1—O3^vi	82.50 (10)
O1ⁱ—Eu1—O4	125.00 (9)	N1—Cu1—O3^vi	92.13 (10)
O1ⁱⁱ—Eu1—O4	84.92 (11)	N1^v—Cu1—O3^vi	84.56 (10)
O1—Eu1—O4	146.86 (10)	O2ⁱⁱⁱ—Cu1—O3^vii	82.50 (10)
O4ⁱ—Eu1—O4	74.64 (11)	O2^iv—Cu1—O3^vii	100.65 (10)
O4ⁱⁱ—Eu1—O4	74.64 (11)	N1—Cu1—O3^vii	84.56 (10)
O1ⁱ—Eu1—O3	74.13 (9)	N1^v—Cu1—O3^vii	92.13 (10)
O1ⁱⁱ—Eu1—O3	74.35 (10)	O3^vi—Cu1—O3^vii	175.33 (13)
O1—Eu1—O3	152.61 (10)	C11—N1—C10	116.7 (3)
O4ⁱ—Eu1—O3	121.91 (10)	C11—N1—Cu1	121.3 (2)
O4ⁱⁱ—Eu1—O3	72.51 (9)	C10—N1—Cu1	122.0 (2)
O4—Eu1—O3	51.18 (9)	C10—N2—C9	116.2 (3)
O1ⁱ—Eu1—O3ⁱⁱ	74.35 (10)	O5—N3—O4	122.8 (4)
O1ⁱⁱ—Eu1—O3ⁱⁱ	152.62 (10)	O5—N3—O3	121.6 (4)
O1—Eu1—O3ⁱⁱ	74.13 (9)	O4—N3—O3	115.6 (3)
O4ⁱ—Eu1—O3ⁱⁱ	72.51 (9)	O5—N3—Eu1	177.8 (3)
O4ⁱⁱ—Eu1—O3ⁱⁱ	51.18 (9)	O4—N3—Eu1	56.68 (17)
O4—Eu1—O3ⁱⁱ	121.90 (10)	O3—N3—Eu1	58.92 (18)
O3—Eu1—O3ⁱⁱ	116.62 (4)	O1—C1—O2	124.3 (3)
O1ⁱ—Eu1—O3ⁱ	152.62 (10)	O1—C1—C2	118.4 (3)
O1ⁱⁱ—Eu1—O3ⁱ	74.13 (9)	O2—C1—C2	117.2 (3)
O1—Eu1—O3ⁱ	74.35 (10)	C3—C2—C7	118.5 (3)
O4ⁱ—Eu1—O3ⁱ	51.18 (9)	C3—C2—C1	120.0 (3)
O4ⁱⁱ—Eu1—O3ⁱ	121.91 (10)	C7—C2—C1	121.2 (3)
O4—Eu1—O3ⁱ	72.51 (9)	C4—C3—C2	120.9 (3)
O3—Eu1—O3ⁱ	116.62 (4)	C4—C3—H3A	119.5
O3ⁱⁱ—Eu1—O3ⁱ	116.61 (4)	C2—C3—H3A	119.5
O1ⁱ—Eu1—N3ⁱ	162.42 (10)	C5—C4—C3	120.9 (3)
O1ⁱⁱ—Eu1—N3ⁱ	99.78 (10)	C5—C4—H4A	119.6
O1—Eu1—N3ⁱ	78.00 (11)	C3—C4—H4A	119.6
O4ⁱ—Eu1—N3ⁱ	25.45 (9)	C4—C5—C6	118.4 (3)
O4ⁱⁱ—Eu1—N3ⁱ	98.49 (10)	C4—C5—C8	121.3 (3)
O4—Eu1—N3ⁱ	72.33 (9)	C6—C5—C8	120.2 (3)
O3—Eu1—N3ⁱ	123.38 (9)	C5—C6—C7	121.0 (3)
O3ⁱⁱ—Eu1—N3ⁱ	94.27 (10)	C5—C6—H6A	119.5
O3ⁱ—Eu1—N3ⁱ	25.74 (9)	C7—C6—H6A	119.5
O1ⁱ—Eu1—N3	99.78 (10)	C6—C7—C2	120.2 (3)
O1ⁱⁱ—Eu1—N3	78.00 (11)	C6—C7—H7A	119.9
O1—Eu1—N3	162.42 (10)	C2—C7—H7A	119.9
O4ⁱ—Eu1—N3	98.49 (10)	C11—C8—C9	114.6 (3)
O4ⁱⁱ—Eu1—N3	72.33 (9)	C11—C8—C5	122.7 (3)
O4—Eu1—N3	25.45 (9)	C9—C8—C5	122.6 (3)
O3—Eu1—N3	25.74 (9)	N2—C9—C8	124.1 (4)
O3ⁱⁱ—Eu1—N3	123.38 (9)	N2—C9—H9A	118.0
O3ⁱ—Eu1—N3	94.27 (10)	C8—C9—H9A	118.0
N3ⁱ—Eu1—N3	97.68 (9)	N2—C10—N1	125.4 (4)
O1ⁱ—Eu1—N3ⁱⁱ	77.99 (11)	N2—C10—H10A	117.3
O1ⁱⁱ—Eu1—N3ⁱⁱ	162.42 (10)	N1—C10—H10A	117.3
O1—Eu1—N3ⁱⁱ	99.78 (10)	N1—C11—C8	123.0 (3)
O4ⁱ—Eu1—N3ⁱⁱ	72.33 (9)	N1—C11—H11A	118.5
O4ⁱⁱ—Eu1—N3ⁱⁱ	25.45 (9)	C8—C11—H11A	118.5
O4—Eu1—N3ⁱⁱ	98.49 (10)	C1—O1—Eu1	164.0 (3)
O3—Eu1—N3ⁱⁱ	94.28 (10)	C1—O2—Cu1^viii	128.1 (2)
O3ⁱⁱ—Eu1—N3ⁱⁱ	25.74 (9)	N3—O3—Eu1	95.3 (2)
O3ⁱ—Eu1—N3ⁱⁱ	123.38 (9)	N3—O4—Eu1	97.9 (2)

Symmetry codes: (i) −x+y+2, −x+1, z; (ii) −y+1, x−y−1, z; (iii) −y+4/3, −x+5/3, z+1/6; (iv) y+2/3, −x+y+4/3, −z+1/3; (v) −x+2, −x+y+1, −z+1/2; (vi) −x+y+7/3, y+2/3, z+1/6; (vii) x−y−1/3, x−2/3, −z+1/3; (viii) x−y+2/3, x−2/3, −z+1/3.

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