Poly[bis-(1,3-dimethyl-1,3-diazinan-2-one)(2,5-dioxidoterephthalato)zirconium(IV)].

In the title coordination polymer, [Zr(C8H2O6)(C6H12N2O)2] n , the Zr(IV) atom, which lies on a crystallographic twofold rotation axis, is coordinated by two O,O'-bidentate 2,5-dioxidoterephthalate (DHTP(4-)) ligands and two O-bonded 1,3-dimethyl-1,3-diazinan-2-one (DMPU) ligands (the latter in a cis orientation) in a distorted ZrO6 octa-hedral geometry. The deprotonated hy-droxy and carb-oxy O atoms of the DHTP(4-) ligand chelate the Zr(IV) ion via a six-membered ring; the dihedral angle between the carboxyl-ate group and the aromatic ring is 19.94 (11)°. The DHTP(4-) ligand is completed by crystallographic inversion symmetry and coordinates to two Zr(IV) atoms, thereby forming polymeric zigzag chains propagating in the c-axis direction.

Related literature

For examples of DHTP-containing MOFs, see: Dietzel et al. (2005 ▶, 2006 ▶). For examples of zirconium MOFs, see: Chavan et al. (2012 ▶). For a related structure, see: Maercz et al. (2013 ▶).

Experimental

Crystal data

[Zr(C8H2O6)(C6H12N2O)2]

M = 541.67

Monoclinic,

a = 18.761 (2) Å

b = 8.4049 (10) Å

c = 14.8816 (17) Å

β = 102.239 (1)°

V = 2293.3 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.53 mm−1

T = 293 K

0.10 × 0.08 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.949, T max = 0.969

8477 measured reflections

2730 independent reflections

2437 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.096

S = 1.07

2730 reflections

150 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.32 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813003437/hb7026sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003437/hb7026Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zr(C8H2O6)(C6H12N2O)2]	F(000) = 1112
Mr = 541.67	Dx = 1.569 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.761 (2) Å	Cell parameters from 2840 reflections
b = 8.4049 (10) Å	θ = 2.8–24.3°
c = 14.8816 (17) Å	µ = 0.53 mm−1
β = 102.239 (1)°	T = 293 K
V = 2293.3 (5) Å3	Block, colourless
Z = 4	0.10 × 0.08 × 0.06 mm

Bruker SMART CCD diffractometer	2730 independent reflections
Radiation source: fine-focus sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 28.8°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −24→25
Tmin = 0.949, Tmax = 0.969	k = −10→10
8477 measured reflections	l = −19→20

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 = 1.07	w = 1/[σ2(Fo2) + (0.0462P)2 + 2.0694P] where P = (Fo2 + 2Fc2)/3
2730 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.01168 (12)	0.8750 (3)	0.06523 (15)	0.0370 (5)
C2	−0.04708 (11)	0.9809 (3)	0.06010 (16)	0.0389 (5)
C3	−0.10053 (13)	0.9651 (4)	0.12208 (19)	0.0494 (6)
C4	0.05755 (12)	0.8979 (3)	0.00446 (16)	0.0409 (5)
H4	0.0968	0.8292	0.0072	0.049*
C5	0.13245 (14)	0.4514 (3)	0.28509 (18)	0.0460 (6)
C6	0.1951 (3)	0.2463 (6)	0.2172 (4)	0.1152 (19)
H6A	0.1811	0.1438	0.2380	0.138*
H6B	0.2043	0.2328	0.1559	0.138*
C7	0.2608 (3)	0.3007 (6)	0.2785 (6)	0.137 (3)
H7A	0.2813	0.3874	0.2491	0.164*
H7B	0.2961	0.2146	0.2880	0.164*
C8	0.25001 (19)	0.3551 (5)	0.3685 (4)	0.0998 (15)
H8A	0.2447	0.2635	0.4061	0.120*
H8B	0.2927	0.4139	0.3993	0.120*
C9	0.1770 (2)	0.5490 (5)	0.4385 (2)	0.0860 (12)
H9A	0.2201	0.5396	0.4862	0.129*
H9B	0.1357	0.5104	0.4607	0.129*
H9C	0.1694	0.6587	0.4211	0.129*
C10	0.0730 (3)	0.3413 (7)	0.1388 (3)	0.1198 (18)
H10A	0.0849	0.2712	0.0932	0.180*
H10B	0.0594	0.4435	0.1117	0.180*
H10C	0.0331	0.2977	0.1617	0.180*
N1	0.18563 (12)	0.4566 (3)	0.35990 (19)	0.0583 (6)
N2	0.13613 (17)	0.3589 (3)	0.2142 (2)	0.0732 (8)
O1	0.07673 (10)	0.5374 (2)	0.28218 (12)	0.0532 (5)
O2	−0.07967 (9)	0.8873 (2)	0.19808 (13)	0.0519 (5)
O3	0.02342 (9)	0.7526 (2)	0.12481 (12)	0.0424 (4)
O4	−0.16069 (11)	1.0250 (4)	0.10048 (17)	0.0870 (9)
Zr1	0.0000	0.72101 (4)	0.2500	0.03776 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0321 (10)	0.0424 (14)	0.0359 (11)	0.0017 (9)	0.0060 (8)	−0.0032 (9)
C2	0.0295 (10)	0.0489 (15)	0.0387 (12)	0.0026 (10)	0.0086 (9)	−0.0011 (10)
C3	0.0397 (13)	0.0587 (17)	0.0531 (15)	0.0122 (12)	0.0173 (11)	0.0085 (12)
C4	0.0306 (10)	0.0495 (15)	0.0432 (12)	0.0076 (10)	0.0095 (9)	0.0001 (10)
C5	0.0470 (13)	0.0399 (14)	0.0542 (15)	0.0022 (11)	0.0176 (11)	0.0035 (11)
C6	0.145 (5)	0.082 (3)	0.140 (5)	0.039 (3)	0.078 (4)	−0.006 (3)
C7	0.083 (3)	0.077 (3)	0.277 (9)	0.013 (2)	0.098 (5)	−0.021 (4)
C8	0.0489 (19)	0.069 (3)	0.169 (5)	0.0175 (18)	−0.004 (2)	0.017 (3)
C9	0.086 (2)	0.094 (3)	0.062 (2)	0.013 (2)	−0.0200 (18)	−0.0037 (19)
C10	0.172 (5)	0.107 (4)	0.069 (3)	0.012 (4)	0.001 (3)	−0.037 (3)
N1	0.0422 (12)	0.0490 (15)	0.0787 (17)	0.0082 (10)	0.0014 (11)	0.0044 (12)
N2	0.097 (2)	0.0551 (17)	0.0735 (18)	0.0136 (16)	0.0320 (16)	−0.0102 (14)
O1	0.0458 (10)	0.0629 (13)	0.0478 (10)	0.0151 (9)	0.0028 (8)	−0.0043 (9)
O2	0.0445 (9)	0.0666 (13)	0.0492 (10)	0.0150 (9)	0.0205 (8)	0.0134 (9)
O3	0.0408 (9)	0.0467 (11)	0.0410 (9)	0.0073 (7)	0.0117 (7)	0.0035 (7)
O4	0.0529 (12)	0.134 (2)	0.0840 (16)	0.0459 (14)	0.0373 (11)	0.0487 (16)
Zr1	0.03075 (17)	0.0470 (2)	0.03504 (18)	0.000	0.00586 (12)	0.000

C1—O3	1.346 (3)	C7—H7B	0.9700
C1—C4	1.388 (3)	C8—N1	1.462 (4)
C1—C2	1.406 (3)	C8—H8A	0.9700
C2—C4i	1.386 (3)	C8—H8B	0.9700
C2—C3	1.505 (3)	C9—N1	1.442 (4)
C3—O4	1.215 (3)	C9—H9A	0.9600
C3—O2	1.293 (3)	C9—H9B	0.9600
C4—C2i	1.386 (3)	C9—H9C	0.9600
C4—H4	0.9300	C10—N2	1.456 (5)
C5—O1	1.264 (3)	C10—H10A	0.9600
C5—N2	1.325 (4)	C10—H10B	0.9600
C5—N1	1.329 (3)	C10—H10C	0.9600
C6—C7	1.443 (8)	Zr1—O1	2.0955 (18)
C6—N2	1.449 (5)	Zr2—O2	2.0723 (18)
C6—H6A	0.9700	Zr3—O3	2.0203 (17)
C6—H6B	0.9700	Zr1—O3ii	2.0203 (17)
C7—C8	1.470 (8)	Zr1—O2ii	2.0723 (18)
C7—H7A	0.9700	Zr1—O1ii	2.0955 (18)
O3—C1—C4	119.9 (2)	H9A—C9—H9B	109.5
O3—C1—C2	122.5 (2)	N1—C9—H9C	109.5
C4—C1—C2	117.7 (2)	H9A—C9—H9C	109.5
C4i—C2—C1	119.8 (2)	H9B—C9—H9C	109.5
C4i—C2—C3	118.3 (2)	N2—C10—H10A	109.5
C1—C2—C3	121.8 (2)	N2—C10—H10B	109.5
O4—C3—O2	122.2 (2)	H10A—C10—H10B	109.5
O4—C3—C2	120.2 (2)	N2—C10—H10C	109.5
O2—C3—C2	117.6 (2)	H10A—C10—H10C	109.5
C2i—C4—C1	122.5 (2)	H10B—C10—H10C	109.5
C2i—C4—H4	118.7	C5—N1—C9	120.3 (2)
C1—C4—H4	118.7	C5—N1—C8	120.9 (3)
O1—C5—N2	119.4 (3)	C9—N1—C8	118.4 (3)
O1—C5—N1	118.6 (2)	C5—N2—C6	121.8 (4)
N2—C5—N1	122.0 (3)	C5—N2—C10	120.2 (3)
C7—C6—N2	110.9 (4)	C6—N2—C10	116.7 (4)
C7—C6—H6A	109.5	C5—O1—Zr1	162.17 (19)
N2—C6—H6A	109.5	C3—O2—Zr1	136.71 (16)
C7—C6—H6B	109.5	C1—O3—Zr1	132.13 (15)
N2—C6—H6B	109.5	O3—Zr1—O3ii	164.90 (10)
H6A—C6—H6B	108.0	O3—Zr1—O2ii	88.54 (7)
C6—C7—C8	114.2 (4)	O3ii—Zr1—O2ii	81.27 (7)
C6—C7—H7A	108.7	O3—Zr1—O2	81.27 (7)
C8—C7—H7A	108.7	O3ii—Zr1—O2	88.54 (7)
C6—C7—H7B	108.7	O2ii—Zr1—O2	95.19 (12)
C8—C7—H7B	108.7	O3—Zr1—O1ii	99.16 (7)
H7A—C7—H7B	107.6	O3ii—Zr1—O1ii	91.97 (7)
N1—C8—C7	111.9 (4)	O2ii—Zr1—O1ii	171.16 (7)
N1—C8—H8A	109.2	O2—Zr1—O1ii	90.30 (8)
C7—C8—H8A	109.2	O3—Zr1—O1	91.97 (7)
N1—C8—H8B	109.2	O3ii—Zr1—O1	99.16 (7)
C7—C8—H8B	109.2	O2ii—Zr1—O1	90.30 (8)
H8A—C8—H8B	107.9	O2—Zr1—O1	171.16 (7)
N1—C9—H9A	109.5	O1ii—Zr1—O1	85.13 (11)
N1—C9—H9B	109.5
O3—C1—C2—C4i	−178.2 (2)	C7—C6—N2—C10	164.6 (5)
C4—C1—C2—C4i	0.3 (4)	N2—C5—O1—Zr1	−75.3 (7)
O3—C1—C2—C3	0.7 (4)	N1—C5—O1—Zr1	104.9 (6)
C4—C1—C2—C3	179.2 (2)	O4—C3—O2—Zr1	160.2 (3)
C4i—C2—C3—O4	20.1 (4)	C2—C3—O2—Zr1	−20.1 (4)
C1—C2—C3—O4	−158.8 (3)	C4—C1—O3—Zr1	152.68 (18)
C4i—C2—C3—O2	−159.5 (3)	C2—C1—O3—Zr1	−28.8 (3)
C1—C2—C3—O2	21.6 (4)	C1—O3—Zr1—O3ii	−23.03 (19)
O3—C1—C4—C2i	178.2 (2)	C1—O3—Zr1—O2ii	−70.4 (2)
C2—C1—C4—C2i	−0.3 (4)	C1—O3—Zr1—O2	25.1 (2)
N2—C6—C7—C8	47.7 (6)	C1—O3—Zr1—O1ii	114.0 (2)
C6—C7—C8—N1	−44.6 (6)	C1—O3—Zr1—O1	−160.7 (2)
O1—C5—N1—C9	4.8 (4)	C3—O2—Zr1—O3	0.6 (3)
N2—C5—N1—C9	−175.0 (3)	C3—O2—Zr1—O3ii	169.4 (3)
O1—C5—N1—C8	177.6 (3)	C3—O2—Zr1—O2ii	88.3 (3)
N2—C5—N1—C8	−2.2 (5)	C3—O2—Zr1—O1ii	−98.6 (3)
C7—C8—N1—C5	21.3 (5)	C3—O2—Zr1—O1	−39.9 (6)
C7—C8—N1—C9	−165.7 (4)	C5—O1—Zr1—O3	29.7 (6)
O1—C5—N2—C6	−173.7 (3)	C5—O1—Zr1—O3ii	−140.1 (6)
N1—C5—N2—C6	6.0 (5)	C5—O1—Zr1—O2ii	−58.9 (6)
O1—C5—N2—C10	−7.7 (5)	C5—O1—Zr1—O2	69.6 (9)
N1—C5—N2—C10	172.1 (4)	C5—O1—Zr1—O1ii	128.7 (6)
C7—C6—N2—C5	−28.8 (6)

Table 1

Selected bond lengths (Å)

Zr1—O1	2.0955 (18)
Zr2—O2	2.0723 (18)
Zr3—O3	2.0203 (17)