Poly[bis­(1,3-dimethyl­imidazolidin-2-one)(μ2-2,5-dioxidoterephthalato)zirconium(IV)]

Maercz, M.; Wragg, D.S.; Dietzel, P.D.C.; Fjellvåg, H.

doi:10.1107/S1600536813003449

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page m152

doi:10.1107/S1600536813003449

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Poly[bis(1,3-dimethylimidazolidin-2-one)(μ₂-2,5-dioxidoterephthalato)zirconium(IV)]

Matthias Maercz,^a ^* David Stephen Wragg,^b Pascal Daniel Croumbie Dietzel ^c and Helmer Fjellvåg ^a

^aCentre for Materials Science and Nanotechnology, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, ^bCentre for Materials Science and Nanotechnology &, inGAP National Centre of Research-based Innovation, Department of Chemistry, University of Oslo, PO Box 1126, 0315 Oslo, Norway, and ^cDepartment of Chemistry, University of Bergen, PO Box 7803, 5020 Bergen, Norway
^*Correspondence e-mail: matthias.maercz@smn.uio.no

(Received 7 January 2013; accepted 4 February 2013; online 16 February 2013)

In the title coordination polymer, [Zr(C₈H₂O₆)(C₅H₁₀N₂O)₂]_n, the Zr^IV atom (site symmetry 2) is coordinated by two O,O′-bidentate 2,5-dioxidoterephthalate (DHTP⁴⁻) ligands and two O-bonded 1,3-dimethyl-2-imidazolidinone (DMI) ligands (the latter in a cis orientation) in a distorted ZrO₆ octahedral geometry. The deprotonated hydroxy and carboxy O atoms of the DHTP⁴⁻ ligand chelate the Zr^IV ion via a six-membered ring; the dihedral angle between the carboxylate group and the aromatic ring is 14.46 (11)°. The DHTP⁴⁻ ligand is completed by crystallographic inversion symmetry and coordinates to two Zr^IV atoms, thereby forming polymeric zigzag chains propagating in [001].

Related literature

For examples of DHTP-containing MOFs, see: Dietzel et al. (2005 , 2006 ). For examples of zirconium MOFs, see: Chavan et al. (2012 ).

Experimental

Crystal data

[Zr(C₈H₂O₆)(C₅H₁₀N₂O)₂]
M_r = 513.62
Monoclinic, C 2/c
a = 17.550 (3) Å
b = 8.0828 (12) Å
c = 15.425 (2) Å
β = 100.558 (2)°
V = 2151.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.946, T_max = 0.956
5721 measured reflections
2448 independent reflections
1958 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.03
2448 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Zr1—O1	2.058 (2)
Zr1—O2	2.0215 (17)
Zr1—O3	2.108 (2)

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813003449/hb7025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003449/hb7025Isup2.hkl

checkCIF report

Comment top

The title compound was synthesized as a part of a larger project in which the possibility to form new zirconium containing metal organic frameworks (MOFs) using the linker 2,5-dihydroxyterephthalic acid (DHTP) was investigated. Zirconium containing MOFs (Chavan et al., 2012) using terephthalic acid have shown extraordinary thermal stability whereas DHTP containing MOFs (Dietzel et al., 2005, 2006) have shown remarkable sorption properties.

Related literature top

For examples of DHTP-containing MOFs, see: Dietzel et al. (2005, 2006). For examples of zirconium MOFs, see: Chavan et al. (2012).

Experimental top

Zirconium(IV) acetylacetonate (0.098 g, 0.2 mmol) and 2,5-dihydroxyterephthalic acid (0.079 g, 0.4 mmol) were dissolved in in 5 ml 1,3-dimethyl-2-imidazolidinone (DMI) in a Teflon liner of 23 ml volume. The teflon liner was put into a steel autoclave, the steel autoclave was closed and shaken for homogeneity. The mixture was reacted for 3 d at 160°C. Reaction yielded a yellow crystalline substance with larger colorless block shaped crystals. The product was collected by filtration, washed with DMI and dried over night at room temperature in ambient atmosphere.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of the title compound with 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. Hydrogen atoms are omitted for clarity.

Poly[bis(1,3-dimethylimidazolidin-2-one)(µ₂-2,5-dioxidoterephthalato)zirconium(IV)] top

Crystal data top

[Zr(C₈H₂O₆)(C₅H₁₀N₂O)₂]	F(000) = 1048
M_r = 513.62	D_x = 1.586 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.550 (3) Å	Cell parameters from 1603 reflections
b = 8.0828 (12) Å	θ = 2.4–25.4°
c = 15.425 (2) Å	µ = 0.56 mm⁻¹
β = 100.558 (2)°	T = 293 K
V = 2151.0 (6) Å³	Block, colourless
Z = 4	0.10 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD diffractometer	2448 independent reflections
Radiation source: sealed tube	1958 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 27.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −22→22
T_min = 0.946, T_max = 0.956	k = −10→7
5721 measured reflections	l = −19→19

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0465P)² + 1.4169P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Zr(C₈H₂O₆)(C₅H₁₀N₂O)₂]	V = 2151.0 (6) Å³
M_r = 513.62	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.550 (3) Å	µ = 0.56 mm⁻¹
b = 8.0828 (12) Å	T = 293 K
c = 15.425 (2) Å	0.10 × 0.10 × 0.08 mm
β = 100.558 (2)°

Data collection top

Bruker SMART CCD diffractometer	2448 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1958 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.956	R_int = 0.022
5721 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.36 e Å⁻³
2448 reflections	Δρ_min = −0.34 e Å⁻³
141 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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
C1	0.10405 (16)	0.0141 (4)	0.37387 (19)	0.0479 (7)
C2	0.04841 (14)	0.0098 (3)	0.43769 (16)	0.0383 (6)
C3	−0.01428 (14)	0.1202 (3)	0.43241 (16)	0.0376 (6)
C4	0.06111 (15)	−0.1071 (3)	0.50427 (17)	0.0411 (6)
H4	0.1026	−0.1797	0.5068	0.049*
C5	0.14154 (18)	0.5409 (4)	0.2821 (2)	0.0499 (7)
C6	0.2275 (3)	0.7161 (6)	0.2379 (5)	0.123 (2)
H6A	0.2177	0.8342	0.2379	0.148*
H6B	0.2623	0.6929	0.1973	0.148*
C7	0.2605 (2)	0.6587 (6)	0.3262 (5)	0.119 (2)
H7A	0.2711	0.7506	0.3671	0.143*
H7B	0.3080	0.5972	0.3264	0.143*
C8	0.0982 (4)	0.6567 (8)	0.1358 (3)	0.145 (2)
H8A	0.1209	0.7198	0.0943	0.217*
H8B	0.0560	0.7178	0.1519	0.217*
H8C	0.0793	0.5535	0.1094	0.217*
C9	0.2002 (4)	0.4805 (7)	0.4328 (3)	0.138 (2)
H9A	0.2485	0.5044	0.4710	0.206*
H9B	0.1938	0.3629	0.4266	0.206*
H9C	0.1583	0.5257	0.4575	0.206*
N1	0.15590 (19)	0.6252 (4)	0.2134 (2)	0.0794 (10)
N2	0.19989 (19)	0.5522 (4)	0.3487 (3)	0.0834 (10)
O1	0.08341 (11)	0.0970 (3)	0.30113 (13)	0.0528 (5)
O2	−0.02943 (11)	0.2381 (2)	0.36978 (12)	0.0447 (4)
O3	0.08044 (12)	0.4612 (3)	0.28274 (14)	0.0596 (6)
O4	0.16535 (14)	−0.0572 (4)	0.39070 (16)	0.0871 (9)
Zr1	0.0000	0.26734 (5)	0.2500	0.03931 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0396 (16)	0.0571 (18)	0.0517 (16)	0.0091 (13)	0.0210 (13)	0.0038 (13)
C2	0.0318 (14)	0.0452 (15)	0.0397 (13)	0.0033 (11)	0.0117 (11)	−0.0024 (11)
C3	0.0352 (14)	0.0391 (15)	0.0400 (13)	0.0023 (11)	0.0105 (11)	−0.0030 (11)
C4	0.0327 (14)	0.0481 (16)	0.0448 (14)	0.0084 (12)	0.0135 (11)	−0.0006 (12)
C5	0.0468 (17)	0.0397 (16)	0.0657 (19)	0.0011 (13)	0.0169 (15)	−0.0060 (14)
C6	0.085 (4)	0.077 (3)	0.232 (8)	−0.017 (3)	0.090 (5)	−0.004 (4)
C7	0.041 (2)	0.080 (3)	0.232 (7)	−0.007 (2)	0.014 (3)	−0.057 (4)
C8	0.199 (7)	0.143 (5)	0.090 (4)	−0.003 (5)	0.021 (4)	0.057 (4)
C9	0.185 (6)	0.136 (5)	0.071 (3)	0.039 (4)	−0.033 (3)	−0.023 (3)
N1	0.081 (2)	0.065 (2)	0.103 (3)	−0.0082 (17)	0.046 (2)	0.0122 (17)
N2	0.062 (2)	0.074 (2)	0.105 (3)	−0.0014 (17)	−0.0073 (19)	−0.0117 (19)
O1	0.0457 (12)	0.0672 (14)	0.0519 (11)	0.0144 (10)	0.0262 (9)	0.0110 (10)
O2	0.0443 (11)	0.0482 (11)	0.0451 (10)	0.0089 (9)	0.0177 (8)	0.0031 (8)
O3	0.0546 (13)	0.0640 (14)	0.0624 (13)	−0.0195 (11)	0.0167 (10)	−0.0042 (11)
O4	0.0589 (15)	0.133 (2)	0.0792 (17)	0.0487 (16)	0.0389 (13)	0.0420 (16)
Zr1	0.0351 (2)	0.0449 (3)	0.0405 (2)	0.000	0.01366 (15)	0.000

Geometric parameters (Å, º) top

C1—O4	1.206 (3)	C7—H7A	0.9700
C1—O1	1.300 (3)	C7—H7B	0.9700
C1—C2	1.509 (3)	C8—N1	1.442 (6)
C2—C4	1.383 (4)	C8—H8A	0.9600
C2—C3	1.407 (3)	C8—H8B	0.9600
C3—O2	1.348 (3)	C8—H8C	0.9600
C3—C4ⁱ	1.391 (3)	C9—N2	1.419 (6)
C4—C3ⁱ	1.391 (3)	C9—H9A	0.9600
C4—H4	0.9300	C9—H9B	0.9600
C5—O3	1.253 (3)	C9—H9C	0.9600
C5—N2	1.314 (4)	Zr1—O1	2.058 (2)
C5—N1	1.322 (4)	Zr1—O2	2.0215 (17)
C6—N1	1.445 (6)	Zr1—O3	2.108 (2)
C6—C7	1.455 (8)	Zr1—O2ⁱⁱ	2.0215 (17)
C6—H6A	0.9700	Zr1—O1ⁱⁱ	2.058 (2)
C6—H6B	0.9700	Zr1—O3ⁱⁱ	2.108 (2)
C7—N2	1.458 (6)

O4—C1—O1	121.9 (2)	H8B—C8—H8C	109.5
O4—C1—C2	120.5 (3)	N2—C9—H9A	109.5
O1—C1—C2	117.6 (2)	N2—C9—H9B	109.5
C4—C2—C3	119.6 (2)	H9A—C9—H9B	109.5
C4—C2—C1	117.7 (2)	N2—C9—H9C	109.5
C3—C2—C1	122.7 (2)	H9A—C9—H9C	109.5
O2—C3—C4ⁱ	119.5 (2)	H9B—C9—H9C	109.5
O2—C3—C2	122.6 (2)	C5—N1—C8	123.3 (4)
C4ⁱ—C3—C2	117.9 (2)	C5—N1—C6	109.7 (4)
C2—C4—C3ⁱ	122.5 (2)	C8—N1—C6	124.9 (5)
C2—C4—H4	118.7	C5—N2—C9	123.9 (4)
C3ⁱ—C4—H4	118.7	C5—N2—C7	110.6 (4)
O3—C5—N2	125.1 (3)	C9—N2—C7	125.3 (5)
O3—C5—N1	124.1 (3)	C1—O1—Zr1	137.87 (16)
N2—C5—N1	110.8 (3)	C3—O2—Zr1	133.46 (15)
N1—C6—C7	105.1 (4)	C5—O3—Zr1	156.5 (2)
N1—C6—H6A	110.7	O2—Zr1—O2ⁱⁱ	166.56 (10)
C7—C6—H6A	110.7	O2—Zr1—O1ⁱⁱ	89.38 (7)
N1—C6—H6B	110.7	O2ⁱⁱ—Zr1—O1ⁱⁱ	81.62 (7)
C7—C6—H6B	110.7	O2—Zr1—O1	81.62 (7)
H6A—C6—H6B	108.8	O2ⁱⁱ—Zr1—O1	89.38 (7)
C6—C7—N2	103.2 (4)	O1ⁱⁱ—Zr1—O1	96.05 (12)
C6—C7—H7A	111.1	O2—Zr1—O3	98.06 (8)
N2—C7—H7A	111.1	O2ⁱⁱ—Zr1—O3	91.94 (8)
C6—C7—H7B	111.1	O1ⁱⁱ—Zr1—O3	170.80 (8)
N2—C7—H7B	111.1	O1—Zr1—O3	90.42 (9)
H7A—C7—H7B	109.1	O2—Zr1—O3ⁱⁱ	91.94 (8)
N1—C8—H8A	109.5	O2ⁱⁱ—Zr1—O3ⁱⁱ	98.06 (8)
N1—C8—H8B	109.5	O1ⁱⁱ—Zr1—O3ⁱⁱ	90.42 (9)
H8A—C8—H8B	109.5	O1—Zr1—O3ⁱⁱ	170.80 (8)
N1—C8—H8C	109.5	O3—Zr1—O3ⁱⁱ	83.95 (13)
H8A—C8—H8C	109.5

O4—C1—C2—C4	−14.8 (4)	C6—C7—N2—C9	−172.3 (5)
O1—C1—C2—C4	165.3 (3)	O4—C1—O1—Zr1	−166.5 (3)
O4—C1—C2—C3	164.4 (3)	C2—C1—O1—Zr1	13.3 (5)
O1—C1—C2—C3	−15.4 (4)	C4ⁱ—C3—O2—Zr1	−160.28 (19)
C4—C2—C3—O2	179.3 (2)	C2—C3—O2—Zr1	20.8 (4)
C1—C2—C3—O2	0.1 (4)	N2—C5—O3—Zr1	−108.5 (6)
C4—C2—C3—C4ⁱ	0.4 (4)	N1—C5—O3—Zr1	71.3 (7)
C1—C2—C3—C4ⁱ	−178.8 (3)	C3—O2—Zr1—O2ⁱⁱ	29.7 (2)
C3—C2—C4—C3ⁱ	−0.4 (5)	C3—O2—Zr1—O1ⁱⁱ	77.5 (2)
C1—C2—C4—C3ⁱ	178.9 (3)	C3—O2—Zr1—O1	−18.7 (2)
N1—C6—C7—N2	−6.1 (5)	C3—O2—Zr1—O3	−108.0 (2)
O3—C5—N1—C8	10.0 (6)	C3—O2—Zr1—O3ⁱⁱ	167.9 (2)
N2—C5—N1—C8	−170.2 (4)	C1—O1—Zr1—O2	0.7 (3)
O3—C5—N1—C6	174.0 (3)	C1—O1—Zr1—O2ⁱⁱ	−169.3 (3)
N2—C5—N1—C6	−6.1 (4)	C1—O1—Zr1—O1ⁱⁱ	−87.7 (3)
C7—C6—N1—C5	7.7 (5)	C1—O1—Zr1—O3	98.8 (3)
C7—C6—N1—C8	171.5 (5)	C1—O1—Zr1—O3ⁱⁱ	46.7 (6)
O3—C5—N2—C9	−2.9 (6)	C5—O3—Zr1—O2	139.9 (6)
N1—C5—N2—C9	177.3 (4)	C5—O3—Zr1—O2ⁱⁱ	−31.1 (6)
O3—C5—N2—C7	−178.2 (3)	C5—O3—Zr1—O1ⁱⁱ	−76.5 (8)
N1—C5—N2—C7	1.9 (4)	C5—O3—Zr1—O1	58.3 (6)
C6—C7—N2—C5	2.9 (5)	C5—O3—Zr1—O3ⁱⁱ	−129.0 (6)

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

Experimental details

Crystal data
Chemical formula	[Zr(C₈H₂O₆)(C₅H₁₀N₂O)₂]
M_r	513.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	17.550 (3), 8.0828 (12), 15.425 (2)
β (°)	100.558 (2)
V (Å³)	2151.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.946, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	5721, 2448, 1958
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.03
No. of reflections	2448
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.34

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zr1—O1	2.058 (2)	Zr1—O3	2.108 (2)
Zr1—O2	2.0215 (17)

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2003). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chavan, S., Vitillo, J. G., Gianolio, D., Zavorotynska, O., Civalleri, B., Jakobsen, S., Nilsen, M. H., Valenzano, L., Lamberti, C., Lillerud, K. P. & Bordiga, S. (2012). Phys. Chem. Chem. Phys. 14, 1614–1626. Web of Science CrossRef CAS PubMed Google Scholar
Dietzel, P. D. C., Morita, Y., Blom, R. & Fjellvåg, H. (2005). Angew. Chem. Int. Ed. 44, 6354–6358. Web of Science CSD CrossRef CAS Google Scholar
Dietzel, P. D. C., Panella, B., Hirscher, M., Blom, R. & Fjellvåg, H. (2006). Chem. Commun. pp. 959–961. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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