Metal–organic framework assembled from erbium and a tetra­podal polyphospho­nic acid organic linker

A three-dimensional metal–organic framework (MOF), poly[[μ₆-5′-pentahydrogen [1,1′-biphen­yl]-3,3′,5,5′-tetrayltetrakis(­phospho­nato)]erbium(III)] 2.5-hydrate], formulated as [Er(C₁₂H₁₁O₁₂P₄)]·2.5H₂O or [Er(H₅btp)]·2.5H₂O (I) and isotypical with a Y³⁺-based MOF reported previously by our research group [Firmino et al. (2017b). Inorg. Chem. 56, 1193–1208], was constructed based solely on Er³⁺ and on the polyphospho­nic organic linker [1,1′-biphen­yl]-3,3′,5,5′-tetra­kis­(phospho­nic acid) (H₈btp). The present work describes our efforts to introduce lanthanide cations into the flexible network, demonstrating that, on the one hand, the compound can be obtained using three distinct experimental methods, i.e. hydro­(solvo)thermal (Hy), microwave-assisted (MW) and one-pot (Op), and, on the other hand, that crystallite size can be approximately fine-tuned according to the method employed. MOF I contains hexa­coordinated Er³⁺ cations which are distributed in a zigzag inorganic chain running parallel to the [100] direction of the unit cell. The chains are, in turn, bridged by the anionic organic linker to form a three-dimensional 6,6-connected binodal network. This connectivity leads to the existence of one-dimensional channels (also running parallel to the [100] direction) filled with disordered and partially occupied water mol­ecules of crystalization which are engaged in O—H...O hydrogen-bonding inter­actions with the [Er(H₅btp)] framework. Additional weak π–π inter­actions [inter­centroid distance = 3.957 (7) Å] exist between aromatic rings, which help to maintain the structural integrity of the network.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Poly[[µ₆-pentahydrogen [1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(phosphonato)]erbium(III)] 2.5-hydrate]

Crystal data

[Er(C12H11O12P4)]·2.5H2O	F(000) = 1328
Mr = 1366.77	Dx = 2.224 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1557 (11) Å	Cell parameters from 9994 reflections
b = 23.753 (3) Å	θ = 2.6–25.4°
c = 10.3790 (13) Å	µ = 4.50 mm^−1
β = 115.261 (4)°	T = 150 K
V = 2041.3 (4) Å^3	Block, colourless
Z = 2	0.04 × 0.02 × 0.01 mm

Data collection

Bruker D8 QUEST diffractometer	3726 independent reflections
Radiation source: Sealed tube	2799 reflections with I > 2σ(I)
Multi-layer X-ray mirror monochromator	Rint = 0.116
Detector resolution: 10.4167 pixels mm^-1	θmax = 25.3°, θmin = 3.6°
ω/φ scans	h = −11→10
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −28→28
	l = −12→12
37649 measured reflections

Refinement

Refinement on F^2	78 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + 38.9895P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max < 0.001
3726 reflections	Δρmax = 1.81 e Å^−3
286 parameters	Δρmin = −1.69 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Er1	0.27760 (6)	0.04946 (2)	1.04347 (6)	0.01629 (16)
P1	0.3811 (4)	0.17420 (12)	0.9026 (4)	0.0175 (7)
P2	0.8544 (4)	0.06748 (12)	0.8092 (4)	0.0167 (7)
P3	0.6971 (3)	0.45502 (13)	0.7233 (3)	0.0180 (7)
P4	1.2091 (4)	0.33477 (14)	0.7346 (5)	0.0314 (10)
O1	0.3695 (9)	0.1160 (3)	0.9503 (9)	0.0186 (19)
O2	0.3873 (12)	0.2208 (4)	1.0061 (12)	0.045 (3)
H2	0.3211	0.2136	1.0402	0.068*
O3	0.2340 (10)	0.1835 (4)	0.7581 (11)	0.035 (2)
H3	0.2438	0.2144	0.7233	0.053*
O4	0.7740 (10)	0.0190 (3)	0.8426 (9)	0.0198 (19)
O5	1.0329 (10)	0.0707 (3)	0.8943 (10)	0.030 (2)
O6	0.8288 (11)	0.0663 (4)	0.6507 (9)	0.030 (2)
H6	0.7319	0.0585	0.5979	0.044*
O7	0.5307 (9)	0.4486 (3)	0.7153 (8)	0.0207 (18)
O8	0.8084 (11)	0.4822 (4)	0.8666 (9)	0.031 (2)
H8	0.8205	0.5165	0.8540	0.047*
O9	0.7021 (10)	0.4865 (3)	0.6034 (9)	0.024 (2)
O10	1.2402 (10)	0.3913 (3)	0.6898 (9)	0.025 (2)
O11	1.2029 (15)	0.2869 (4)	0.6343 (15)	0.071 (4)
O12	1.3410 (11)	0.3235 (5)	0.8888 (14)	0.071 (4)
H12	1.3157	0.2949	0.9223	0.107*
C1	0.5587 (13)	0.1795 (5)	0.8717 (12)	0.015 (2)
C2	0.6163 (14)	0.2305 (5)	0.8479 (13)	0.019 (2)
H2A	0.5645	0.2644	0.8542	0.022*
C3	0.7484 (14)	0.2334 (4)	0.8149 (13)	0.017 (2)
C4	0.8146 (14)	0.1826 (5)	0.8010 (13)	0.019 (2)
H4	0.9008	0.1830	0.7729	0.023*
C5	0.7608 (13)	0.1316 (4)	0.8262 (13)	0.016 (2)
C6	0.6307 (13)	0.1306 (5)	0.8601 (13)	0.017 (2)
H6A	0.5907	0.0955	0.8756	0.021*
C7	0.8102 (14)	0.2875 (5)	0.7856 (13)	0.018 (2)
C8	0.7300 (14)	0.3382 (5)	0.7679 (13)	0.018 (2)
H8A	0.6307	0.3393	0.7763	0.022*
C9	0.7908 (14)	0.3874 (5)	0.7383 (14)	0.020 (2)
C10	0.9345 (14)	0.3861 (5)	0.7234 (14)	0.023 (2)
H10	0.9740	0.4196	0.6994	0.028*
C11	1.0206 (15)	0.3364 (5)	0.7433 (14)	0.024 (2)
C12	0.9572 (15)	0.2881 (5)	0.7747 (14)	0.023 (2)
H12A	1.0161	0.2540	0.7893	0.027*
O1W	0.538 (2)	0.4262 (9)	0.976 (2)	0.039 (2)*	0.5
O2W	0.525 (2)	0.4604 (9)	0.971 (2)	0.039 (2)*	0.5
O3W	0.094 (2)	0.4158 (6)	0.0882 (18)	0.039 (2)*	0.7
O4W	0.093 (5)	0.3959 (14)	0.108 (4)	0.039 (2)*	0.3
O5W	0.352 (4)	0.3820 (13)	0.028 (3)	0.039 (2)*	0.3
O6W	0.256 (5)	0.443 (2)	−0.017 (5)	0.039 (2)*	0.2

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Er1	0.0169 (3)	0.0068 (2)	0.0322 (3)	−0.0015 (3)	0.0172 (2)	−0.0030 (3)
P1	0.0166 (16)	0.0151 (15)	0.026 (2)	−0.0002 (12)	0.0141 (15)	0.0016 (14)
P2	0.0142 (15)	0.0110 (14)	0.0276 (19)	0.0011 (12)	0.0114 (15)	0.0027 (13)
P3	0.0196 (15)	0.0101 (14)	0.0292 (18)	0.0032 (13)	0.0152 (14)	0.0077 (15)
P4	0.032 (2)	0.0145 (16)	0.066 (3)	0.0013 (15)	0.038 (2)	0.0070 (18)
O1	0.022 (5)	0.014 (4)	0.024 (5)	0.000 (3)	0.014 (4)	0.006 (4)
O2	0.054 (7)	0.027 (5)	0.085 (8)	−0.022 (5)	0.059 (6)	−0.021 (5)
O3	0.024 (5)	0.026 (5)	0.050 (7)	0.002 (4)	0.009 (5)	0.022 (5)
O4	0.024 (5)	0.012 (4)	0.030 (5)	−0.001 (4)	0.019 (4)	0.002 (4)
O5	0.017 (5)	0.022 (4)	0.049 (6)	0.003 (4)	0.011 (5)	0.004 (4)
O6	0.043 (5)	0.023 (5)	0.030 (5)	0.002 (4)	0.023 (5)	0.003 (4)
O7	0.027 (4)	0.012 (4)	0.032 (5)	−0.002 (4)	0.022 (4)	−0.007 (4)
O8	0.029 (5)	0.028 (5)	0.028 (6)	−0.006 (4)	0.003 (4)	0.001 (4)
O9	0.022 (5)	0.017 (4)	0.036 (6)	0.007 (4)	0.015 (4)	0.007 (4)
O10	0.034 (5)	0.018 (4)	0.035 (6)	0.005 (4)	0.026 (5)	0.006 (4)
O11	0.108 (10)	0.013 (5)	0.164 (13)	−0.009 (6)	0.127 (10)	−0.013 (6)
O12	0.027 (6)	0.072 (8)	0.124 (11)	0.032 (5)	0.041 (7)	0.085 (8)
C1	0.016 (5)	0.014 (5)	0.020 (5)	0.000 (4)	0.012 (4)	0.004 (4)
C2	0.020 (5)	0.012 (5)	0.026 (5)	0.006 (4)	0.012 (4)	0.004 (4)
C3	0.019 (4)	0.011 (4)	0.026 (5)	0.004 (4)	0.016 (4)	0.003 (4)
C4	0.016 (5)	0.016 (5)	0.033 (6)	0.002 (4)	0.017 (4)	0.007 (5)
C5	0.016 (5)	0.007 (4)	0.026 (5)	0.003 (4)	0.009 (4)	0.008 (4)
C6	0.018 (5)	0.010 (4)	0.022 (5)	−0.001 (4)	0.007 (4)	0.004 (4)
C7	0.022 (4)	0.009 (4)	0.027 (5)	−0.004 (4)	0.016 (4)	−0.001 (4)
C8	0.019 (5)	0.015 (5)	0.029 (5)	0.001 (4)	0.018 (4)	0.003 (4)
C9	0.021 (5)	0.014 (5)	0.033 (6)	0.006 (4)	0.018 (5)	0.012 (5)
C10	0.025 (5)	0.014 (5)	0.042 (6)	0.005 (4)	0.025 (5)	0.015 (5)
C11	0.027 (5)	0.015 (5)	0.043 (6)	0.003 (4)	0.027 (5)	0.011 (5)
C12	0.030 (5)	0.014 (5)	0.036 (6)	0.004 (4)	0.025 (5)	0.002 (5)

Geometric parameters (Å, º)

Er1—O1	2.199 (7)	O7—Er1^vii	2.242 (8)
Er1—O4^i	2.179 (8)	O8—H8	0.8400
Er1—O5^ii	2.171 (8)	O9—Er1^viii	2.200 (8)
Er1—O7^iii	2.242 (8)	O10—Er1^ix	2.202 (8)
Er1—O9^iv	2.200 (8)	O12—H12	0.8400
Er1—O10^v	2.202 (8)	C1—C6	1.367 (15)
P1—O1	1.487 (8)	C1—C2	1.385 (15)
P1—O2	1.526 (9)	C2—C3	1.392 (15)
P1—O3	1.546 (10)	C2—H2A	0.9500
P1—C1	1.791 (11)	C3—C4	1.385 (15)
P2—O4	1.484 (8)	C3—C7	1.488 (15)
P2—O5	1.491 (9)	C4—C5	1.374 (15)
P2—O6	1.560 (9)	C4—H4	0.9500
P2—C5	1.793 (11)	C5—C6	1.379 (15)
P3—O9	1.468 (9)	C6—H6A	0.9500
P3—O7	1.498 (7)	C7—C8	1.380 (15)
P3—O8	1.541 (9)	C7—C12	1.398 (15)
P3—C9	1.796 (11)	C8—C9	1.385 (15)
P4—O10	1.487 (8)	C8—H8A	0.9500
P4—O11	1.527 (11)	C9—C10	1.389 (15)
P4—O12	1.562 (12)	C10—C11	1.384 (15)
P4—C11	1.767 (11)	C10—H10	0.9500
O2—H2	0.8400	C11—C12	1.385 (15)
O3—H3	0.8400	C12—H12A	0.9500
O4—Er1^i	2.179 (8)	O1W—O2W	0.82 (2)
O5—Er1^vi	2.171 (8)	O3W—O4W	0.52 (4)
O6—H6	0.8400	O5W—O6W	1.66 (5)
O1—Er1—O9^iv	91.3 (3)	P2—O5—Er1^vi	161.2 (5)
O1—Er1—O7^iii	82.8 (3)	P2—O6—H6	109.5
O1—Er1—O10^v	92.6 (3)	P3—O7—Er1^vii	136.3 (5)
O4^i—Er1—O1	171.1 (3)	P3—O8—H8	109.5
O4^i—Er1—O7^iii	88.5 (3)	P3—O9—Er1^viii	167.3 (6)
O4^i—Er1—O9^iv	88.3 (3)	P4—O10—Er1^ix	154.1 (6)
O4^i—Er1—O10^v	88.3 (3)	P4—O12—H12	109.5
O5^ii—Er1—O1	89.5 (3)	C6—C1—C2	119.6 (10)
O5^ii—Er1—O4^i	99.4 (3)	C6—C1—P1	117.7 (8)
O5^ii—Er1—O7^iii	164.7 (3)	C2—C1—P1	122.5 (8)
O5^ii—Er1—O9^iv	91.8 (3)	C1—C2—C3	121.6 (10)
O5^ii—Er1—O10^v	85.8 (3)	C1—C2—H2A	119.2
O9^iv—Er1—O7^iii	101.6 (3)	C3—C2—H2A	119.2
O9^iv—Er1—O10^v	175.4 (3)	C4—C3—C2	116.6 (10)
O10^v—Er1—O7^iii	81.4 (3)	C4—C3—C7	120.7 (9)
O1—P1—O2	115.2 (5)	C2—C3—C7	122.5 (10)
O1—P1—O3	107.4 (5)	C5—C4—C3	122.6 (10)
O2—P1—O3	109.5 (6)	C5—C4—H4	118.7
O1—P1—C1	109.0 (5)	C3—C4—H4	118.7
O2—P1—C1	108.1 (5)	C4—C5—C6	118.9 (10)
O3—P1—C1	107.4 (5)	C4—C5—P2	120.3 (8)
O4—P2—O5	115.4 (5)	C6—C5—P2	120.8 (8)
O4—P2—O6	111.5 (5)	C1—C6—C5	120.6 (10)
O5—P2—O6	105.0 (5)	C1—C6—H6A	119.7
O4—P2—C5	109.3 (5)	C5—C6—H6A	119.7
O5—P2—C5	110.3 (5)	C8—C7—C12	117.2 (10)
O6—P2—C5	104.8 (5)	C8—C7—C3	123.6 (10)
O9—P3—O7	113.8 (5)	C12—C7—C3	119.2 (10)
O9—P3—O8	111.0 (5)	C7—C8—C9	121.6 (10)
O7—P3—O8	109.5 (5)	C7—C8—H8A	119.2
O9—P3—C9	110.0 (5)	C9—C8—H8A	119.2
O7—P3—C9	110.5 (5)	C8—C9—C10	119.6 (10)
O8—P3—C9	101.3 (6)	C8—C9—P3	123.5 (8)
O10—P4—O11	114.6 (6)	C10—C9—P3	116.8 (8)
O10—P4—O12	107.9 (6)	C11—C10—C9	120.6 (10)
O11—P4—O12	111.0 (7)	C11—C10—H10	119.7
O10—P4—C11	108.5 (5)	C9—C10—H10	119.7
O11—P4—C11	107.4 (6)	C10—C11—C12	118.1 (10)
O12—P4—C11	107.2 (6)	C10—C11—P4	121.2 (8)
P1—O1—Er1	155.5 (5)	C12—C11—P4	120.6 (9)
P1—O2—H2	109.5	C11—C12—C7	122.8 (11)
P1—O3—H3	109.5	C11—C12—H12A	118.6
P2—O4—Er1^i	161.8 (6)	C7—C12—H12A	118.6
O2—P1—O1—Er1	44.2 (14)	O4—P2—C5—C6	−2.3 (12)
O3—P1—O1—Er1	−78.1 (13)	O5—P2—C5—C6	−130.1 (10)
C1—P1—O1—Er1	165.9 (12)	O6—P2—C5—C6	117.3 (10)
O5—P2—O4—Er1^i	26.4 (17)	C2—C1—C6—C5	0.6 (18)
O6—P2—O4—Er1^i	146.0 (15)	P1—C1—C6—C5	175.3 (9)
C5—P2—O4—Er1^i	−98.6 (16)	C4—C5—C6—C1	−1.4 (19)
O4—P2—O5—Er1^vi	5 (2)	P2—C5—C6—C1	−179.4 (9)
O6—P2—O5—Er1^vi	−118.4 (18)	C4—C3—C7—C8	165.8 (13)
C5—P2—O5—Er1^vi	129.2 (18)	C2—C3—C7—C8	−9.8 (19)
O9—P3—O7—Er1^vii	22.9 (9)	C4—C3—C7—C12	−14.0 (18)
O8—P3—O7—Er1^vii	147.8 (6)	C2—C3—C7—C12	170.4 (12)
C9—P3—O7—Er1^vii	−101.4 (8)	C12—C7—C8—C9	1.0 (19)
O7—P3—O9—Er1^viii	96 (2)	C3—C7—C8—C9	−178.8 (12)
O8—P3—O9—Er1^viii	−28 (3)	C7—C8—C9—C10	1 (2)
C9—P3—O9—Er1^viii	−139 (2)	C7—C8—C9—P3	−176.7 (10)
O11—P4—O10—Er1^ix	4.4 (15)	O9—P3—C9—C8	−138.8 (11)
O12—P4—O10—Er1^ix	128.6 (13)	O7—P3—C9—C8	−12.3 (13)
C11—P4—O10—Er1^ix	−115.5 (13)	O8—P3—C9—C8	103.7 (12)
O1—P1—C1—C6	15.7 (11)	O9—P3—C9—C10	43.3 (12)
O2—P1—C1—C6	141.6 (10)	O7—P3—C9—C10	169.8 (10)
O3—P1—C1—C6	−100.3 (10)	O8—P3—C9—C10	−74.1 (11)
O1—P1—C1—C2	−169.7 (10)	C8—C9—C10—C11	−2 (2)
O2—P1—C1—C2	−43.8 (12)	P3—C9—C10—C11	175.5 (11)
O3—P1—C1—C2	74.3 (11)	C9—C10—C11—C12	2 (2)
C6—C1—C2—C3	−1.3 (19)	C9—C10—C11—P4	−176.4 (11)
P1—C1—C2—C3	−175.7 (10)	O10—P4—C11—C10	−5.7 (14)
C1—C2—C3—C4	2.8 (19)	O11—P4—C11—C10	−130.1 (12)
C1—C2—C3—C7	178.6 (11)	O12—P4—C11—C10	110.5 (12)
C2—C3—C4—C5	−3.7 (19)	O10—P4—C11—C12	176.2 (11)
C7—C3—C4—C5	−179.7 (12)	O11—P4—C11—C12	51.9 (13)
C3—C4—C5—C6	3.1 (19)	O12—P4—C11—C12	−67.5 (13)
C3—C4—C5—P2	−178.9 (10)	C10—C11—C12—C7	1 (2)
O4—P2—C5—C4	179.8 (10)	P4—C11—C12—C7	178.6 (11)
O5—P2—C5—C4	51.9 (12)	C8—C7—C12—C11	−1.9 (19)
O6—P2—C5—C4	−60.7 (11)	C3—C7—C12—C11	177.9 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O11^v	0.84	1.74	2.564 (12)	166
O3—H3···O11^ii	0.84	1.91	2.728 (13)	164
O6—H6···O1W^vii	0.84	1.73	2.51 (2)	155
O6—H6···O2W^vii	0.84	1.85	2.68 (2)	175
O8—H8···O3W^x	0.84	1.78	2.556 (17)	153
O8—H8···O4W^x	0.84	2.20	3.01 (3)	162
O12—H12···O2^vi	0.84	1.95	2.679 (14)	145

Symmetry codes: (ii) x−1, y, z; (v) x−1, −y+1/2, z+1/2; (vi) x+1, y, z; (vii) x, −y+1/2, z−1/2; (x) −x+1, −y+1, −z+1.