A nanoporous three dimensional metal coordination polymer {(NH4)2Zn[C6H2(COO)4]·8H2O}n

metal-organic papers

m540

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

A nanoporous three-dimensional metal coordination

polymer {(NH

)

Zn[C

H

(COO)

]

8H

O}

Yan-Qiong Sun, Jie Zhang and Guo-Yu Yang*

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China

Correspondence e-mail: ygy@ms.fjirsm.ac.cn

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.003 AÊ H-atom completeness 39% Disorder in solvent or counterion

Rfactor = 0.032

wRfactor = 0.097

Data-to-parameter ratio = 13.5

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, poly[ammonium zinc- -benzene-1,2,4,5-tetracarboxylate octahydrate] {(NH4)2Zn[C6H2(COO)4]

-8H2O}n, forms a three-dimensional network containing one-dimensional nanoporous rhomboid channels along thecaxis, accommodating guest water molecules and the ammonium cations. The dimensions of the large channel are 11.555 (2)

15.00 (1) AÊ. The network consists of [Zn(C6H2(COO)4]2ÿ

anions containing tetrahedral Zn atoms bonded to four carboxylate groups. The Zn O distances range from 1.974 (2) to 1.978 (2) AÊ. The ammonium cations and the water molecules are associated in a centrosymmetric network by intermolecular hydrogen bonds. The hydrogen bonding is essential to stabilize the crystal structure.

Comment

Aromatic polycarboxylate ligands have versatile coordination modes as they can form bridges between metallic centers, generating various molecular topologies and architectures, as well as having potential application as functional materials. They ®nd widespread application in heterogeneous catalysis, chemical absorption and magnetism. Owing to their wide-spread utility (Yaghi & Li, 1996), a considerable number of reports based on metal±aromatic polycarboxylate coordin-ation polymers have appeared over the past few years (Yaghi et al., 1997). 1,2,4,5-Benzenetetracarboxylic acid (H4btec) has

four carboxyl groups, with eight O-donor atoms that may be completely or partly deprotonated, inducing rich coordination modes and allowing novel structures with up to three-dimensional networks. It has been reported that an increase in pH results in a higher connectivity level of the ligands, which in turn leads to a higher dimensionality of the crystal structure

(Pan et al., 2001). We adjusted the pH value to 9±10 with

NH3H2O and obtained the title compound, (I).

{(NH4)2Zn[C6H2(COO)4]8H2O}n is a three-dimensional polymer containing one-dimensional nanoporous channels along thec axis, accommodating guest water molecules and the ammonium cation. All the carboxyl groups of H4btec are

deprotonated, in agreement with the IR data, in which no absorption peaks are observed around 1700 cmÿ1_{for COOH.}

There is a strong absorption peak at 1603 cmÿ1_for as(CO).

Only one type of coordination mode of btec4ÿ_{is present in} the structure. Each carboxylate group adopts a monodentate mode, coordinating one Zn atom. Therefore, each btec4ÿ_acts as an4-bridge, linking four Zn centers, and each Zn atom

attaches to four btec4ÿ _{ligands, forming a slightly distorted} tetrahedron around Zn2+_{, with ZnÐO bond lengths ranging}

from 1.974 (2) to 1.978 (2) AÊ, similar to other related ZnÐO distances (Robl, 1992). Zn2+_{is situated on the twofold axis and}

the four coordinated O atoms are related to each other in pairs by the twofold axis; the btec4ÿ_{phenyl ring is centrosymmetric.} The closest Zn Zn distance is 5.538 (1) AÊ, indicating the lack of any direct metal±metal interaction. The macrocyclic unit [Zn4(btec)4]12ÿ, which forms a rhomboid sheet, with a

Zn Zn distance of 9.587 (1) AÊ, constitutes the basic building block of the structure. Every building block is linked together through ZnÐO bonds to generate a three-dimensional structure with a nanoporous rhomboid channel along the c axis. The dimensions of this large channel are 11.555 (2)

15.100 (3) AÊ. It accommodates ammonium cations and water molecules associated into a centrosymmetric network by intermolecular hydrogen bonds. Different kinds of hydrogen bonding are observed in the structure: (a) hydrogen bonding among water molecules [O O distance: 1.845 (2)± 3.039 (2) AÊ]; (b) hydrogen bonding of water molecules and carboxylate O atoms [O O distance: 2.725 (8)±3.028 (1) AÊ]; (c) hydrogen bonding between the ammonium cations and

carboxylate O atoms [N O distance: 2.847 (2)±3.016 (2) AÊ]; (d) hydrogen bonding between the ammonium cations and water molecules [N O distance: 2.894(2)±3.058 (2) AÊ]. The guest water molecules and ammonium cations are obviously essential to stabilize the crystal structure.

Experimental

A mixture of Zn(CH3COO)23H2O (0.043 g, 0.2 mmol),

1,2,4,5-benzenetetracarboxylic dianhydride (0.043 g, 0.2 mmol), NH3H2O

(1 ml) and H2O (6 ml) with a molar ratio of 1:1:278:1667 (solution pH

= 8±9) was heated in a stainless steel reactor with a Te¯on liner at 433 K for three days. It produced a colorless solution. After evaporation for several days at room temperature, colorless rhom-boidal crystals were obtained.

Crystal data

[Zn(C10H2O8)](NH4)28H2O Mr= 495.70

Monoclinic,C2=c a= 11.555 (2) AÊ

b= 15.300 (3) AÊ

c= 11.072 (2) AÊ

= 91.97 (3)

V= 1956.4 (7) AÊ3 Z= 4

Dx= 1.683 Mg mÿ3 Mo Kradiation Cell parameters from 50

re¯ections

= 2.2±27.5

= 1.34 mmÿ1 T= 293 (2) K Rhomboidal, colorless 0.200.190.10 mm

Data collection

Siemems SMART CCD diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.762,Tmax= 0.877

4233 measured re¯ections

2242 independent re¯ections 2015 re¯ections withI> 2(I)

Rint= 0.010 max= 27.5

h=ÿ14!14

k=ÿ19!18

l=ÿ14!14

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.032} wR(F2_{) = 0.097} S= 0.98 2242 re¯ections 166 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0773P)2 + 1.4324P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.66 e AÊÿ3 min=ÿ0.59 e AÊÿ3

Acta Cryst.(2002). E58, m540±m542 Sun, Zhang and Yang [Zn(C₁₀H₂O₈)](NH₄)₂8H₂O

m541

metal-organic papers

Figure 1

The Zn2+_{coordination environment in the title compound and the}

atom-labeling scheme, Displacement ellipsoids are shown at the 30% probability level [symmetry codes: (i) 1ÿx, y,ÿz+1

2; (ii)x+12,yÿ12,

z; (iii)ÿx+1

2,yÿ12,ÿz+12].

Figure 2

metal-organic papers

m542

Table 1

Selected geometric parameters (AÊ,_).

Zn1ÐO4i _{1.9744 (14)}

Zn1ÐO1 1.9789 (14)

O1ÐC1 1.276 (2)

O2ÐC1 1.235 (3)

O3ÐC5 1.237 (3)

O4ÐC5 1.268 (2)

O4ii_ÐZn1ÐO4i _{123.02 (9)}

O4ii_{ÐZn1ÐO1 103.79 (6)}

O4i_{ÐZn1ÐO1 104.91 (6)}

O1iii_{ÐZn1ÐO1 117.40 (8)}

O2ÐC1ÐO1 124.74 (17)

O3ÐC5ÐO4 123.50 (18)

Symmetry codes: (i)1

2ÿx;yÿ12;12ÿz; (ii)12‡x;yÿ12;z; (iii) 1ÿx;y;12ÿz.

The phenyl ring and ammonium H atoms were located in a difference Fourier map and their positions and isotropic displacement parameters were re®ned. Atom O3wis equally disordered over two positions (O3wÐO3w0 _{distance: 1.523 AÊ). The occupancy of atom}

O5wre®ned to 0.496 and was ®xed at 0.5. The re®nement is unstable if the occupancy of O5wis set to 1. The H atoms of the water O atoms were not located in the difference Fourier map, and were not included, owing to the complexities of the structure.

Data collection:SMART(Bruker, 1999); data reduction:SAINT

(Bruker, 1999);cell re®nement:SMART; data reduction:SHELXTL

(Bruker, 1997); program(s) used to solve structure: SHELXS97

(Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

This work was supported by the Ministry of Finance of China, the National Science Foundation of China (Grant No.20171045) and the Talents Program of the Chinese Academy of Sciences.

References

Bruker. (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker. (1999).SMART(Version 5.054) andSAINT(Version 5.054). Bruker AXS Inc., Madison, Wisconsin, USA.

Pan, L., Frydel, T., Sander, M. B., Huang, X. Y. & Li, J. (2001).Inorg. Chem.40, 1271±1283.

Robl, C. (1992).Mater. Res. Bull.27, 99±107. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Yaghi, O. M., Li, H. L., Groy & T. L. (1996).J. Am. Chem. Soc.118, 9096±9101. Yaghi, O. M., Charles, E. D., Li, G. M., Li & H. L. (1997).J. Am. Chem. Soc.

supporting information

sup-1

Acta Cryst. (2002). E58, m540–m542

supporting information

Acta Cryst. (2002). E58, m540–m542 [doi:10.1107/S1600536802015994]

A nanoporous three-dimensional metal coordination polymer

{(NH

)

Zn[C

H

(COO)

]

·

8H

O}

Yan-Qiong Sun, Jie Zhang and Guo-Yu Yang

S1. Comment

Aromatic poly-carboxylic ligands have a versatile coordination modes as they can form bridges between metallic centers,

generating various molecular topologies and architectures, as well as having potential application as functional materials.

They find widespread application in heterogeneous catalysis, chemical absorption and magnetism. Owing to their

widespread utility (Yaghi et al., 1996), a considerable number of reports based on metal–aromatic poly-carboxylic

coordination polymers have appeared over the past few years (Yaghi et al., 1997). 1,2,4,5-Benzenetetracarboxylic acid

(H4btec) has four carboxyl groups, eight O-donor atoms that may be completely or partly deprotonated, inducing rich

coordination modes and allowing novel structure with higher dimensions. It has been reported that an increase in pH

results in a higher connectivity level of the ligands, which in turn leads to a higher dimensionality of the crystal structure

(Pan et al., 2001). We adjusted the PH value to 9 ~10 by NH3·H2O and fortunately obtained the title compound, (I).

{(NH4)2Zn[C6H2(COO)4]·8H2O}n is a three-dimensional polymer containing one-dimensional nanoporous channels

along the c axis with guest water molecules and the ammonium cation. All the carboxyl groups of H4btec are

deprotonated, in agreement with the IR data in which no absorption peaks are observed around 1700 cm−1 _{for COOH.}

There is a strong absorption peak at 1603 cm−1 _{for υ} as(CO).

Only one type of coordination mode of btec4− _{is present in the structure. Each carboxylate group adopts a monodentate}

chelating mode, coordinating one Zn atom. Therefore, each btec4− _{acts as a µ4-bridge linking four Zn centers and each}

central Zn atom attaches to four btec4− _{ligands, forming a slightly distorted tetrahedron around Zn}2+_{, with Zn···O bond}

lengths ranging from 1.974 (2) to 1.978 (2) Å, similar to other related Zn···O distances (Robl.,1992). Zn2+ _{is situated on}

the twofold axis and the four O atoms in a pair are related to each other by the twofold axis; the btec4− _{phenyl ring is}

centrosymmetric. The closest Zn···Zn distance is 5.538 (1) Å, indicating the lack of any direct metal–metal interaction.

The macrocyclic unit [Zn4(btec)4]12−, which forms a rhombus sheet, with a Zn···Zn distance of 9.587 (1) Å, constitutes the

basic building block of the structure. Every building block is linked together through Zn···O bonds to generate a

three-dimensional structure with a nanoporous rhomboid channel along the c axis. The dimensions of this large channel are

11.555 (2) Å × 15.100 (3) Å. It accommodates ammonium cations and water molecules associated into a

centrosymmetric network by intermolecular hydrogen bonds. Different kinds of hydrogen bonding are observed in the

structure: (a) hydrogen bonding among water molecules [O···O distance: 1.845 (2)–3.039 (2) Å]; (b) hydrogen bonding

of water molecules and carboxylate oxygen atoms [O···O distance: 2.725 (8)–3.028 (1) Å]; (c) hydrogen bonding between

the ammonium cation and carboxylate oxygen atoms [N···O distance: 2.847 (2)–3.016 (2) Å]; (d) hydrogen bonding

between the ammonium cation and water molecules [N···O distance:2.894 (2)–3.058 (2) Å]. The guest water molecules

supporting information

sup-2

Acta Cryst. (2002). E58, m540–m542

S2. Experimental

A mixture of Zn(CH3COO)2·3H2O (0.043 g, 0.2 mmol), 1,2,4,5-benzenetetracarboxylic dianhydride (0.043 g, 0.2 mmol),

NH3·H2O (1 ml) and H2O (6 ml) with a molar ratio of 1:1:278:1667 (solution PH=8 ~9) was heated in a stainless steel

reactor with a Teflon liner at 433 K for three d. It produced a colorless solution. After evaporation for several days at

room temperature, colorless diamond-like crystals were obtained.

S3. Refinement

The phenyl ring and ammonium hydrogen atoms were located in a difference Fourier map and their positions and

isotropic displacement parameters were refined. Atom O3w is equally disordered over two positions (O3w—O3w′

distance: 1.523 Å). The occupancy of atom O5w is 0.496 and assigned to 0.5. The refinement is unstable if the occupancy

of O5w is assigned to 1. The hydrogen atoms of the water O atoms were not located in the difference Fourier map, and

supporting information

sup-3

Acta Cryst. (2002). E58, m540–m542

Figure 1

The Zn2+ _{coordination environment in the title compound and the atom-labeling scheme, Displacement ellipsoids are}

shown at the 30% probability level [symmetry codes: (i) 1 − x, y, −z + 0.5; (ii) x + 0.5, y − 0.5, z; (iii) −x + 0.5, y − 0.5, −z

supporting information

sup-4

Acta Cryst. (2002). E58, m540–m542

Figure 2

Packing diagram, viewed down the [001] diagonal of the unit cell, showing hydrogen-bond interactions.

poly[Ammonium Zinc-µ-benzene-1,2,4,5- tetracarboxylato-octahydrate

Crystal data

[Zn(C10H2O8)](NH4)2·8H2O

Mr = 495.70 Monoclinic, C2/c Hall symbol: -C 2yc a = 11.555 (2) Å b = 15.300 (3) Å c = 11.072 (2) Å β = 91.97 (3)° V = 1956.4 (7) Å3

Z = 4

F(000) = 1032 Dx = 1.683 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 50 reflections θ = 2.2–27.5°

µ = 1.34 mm−1

T = 293 K

Diamond, colorless 0.20 × 0.19 × 0.10 mm

Data collection

Siemems SMART CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.762, Tmax = 0.877

4233 measured reflections 2242 independent reflections 2015 reflections with I > 2σ(I) Rint = 0.010

θmax = 27.5°, θmin = 2.2°

h = −14→14 k = −19→18 l = −14→14

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.032}

wR(F2_{) = 0.097}

S = 0.98

2242 reflections 166 parameters 0 restraints

supporting information

sup-5

Acta Cryst. (2002). E58, m540–m542

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0773P)2 + 1.4324P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.66 e Å−3

Δρmin = −0.59 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of}

F2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq Occ. (<1)

Zn1 0.5000 0.494950 (16) 0.2500 0.01785 (13)

O1 0.38370 (12) 0.56214 (9) 0.15306 (13) 0.0270 (3)

O2 0.52526 (13) 0.65120 (11) 0.09969 (16) 0.0366 (4)

O3 0.1452 (2) 0.84669 (13) 0.27795 (15) 0.0538 (5)

O4 0.08978 (13) 0.93339 (9) 0.12755 (14) 0.0292 (3)

C1 0.42225 (17) 0.62977 (12) 0.10034 (17) 0.0235 (4)

C2 0.33176 (16) 0.68962 (11) 0.04435 (17) 0.0221 (4)

C3 0.27625 (18) 0.74539 (13) 0.12211 (18) 0.0257 (4)

C4 0.19476 (16) 0.80621 (12) 0.07962 (17) 0.0226 (4)

C5 0.13959 (17) 0.86542 (13) 0.16921 (18) 0.0267 (4)

N 0.7271 (3) 0.5761 (2) 0.0020 (3) 0.0574 (6)

O1W 0.1645 (4) 0.5424 (5) 0.2555 (6) 0.177 (2)

O2W 0.0000 0.5920 (11) 0.7500 0.361 (10)

O3W 0.3966 (5) 0.2159 (4) 0.0572 (6) 0.0801 (16) 0.50

O3W′ 0.4277 (6) 0.1764 (5) −0.0637 (11) 0.137 (4) 0.50

O4W 0.4212 (7) 0.9401 (5) 0.012 (2) 0.517 (16)

O5W 0.4706 (12) 0.1707 (6) 0.1937 (10) 0.162 (5) 0.50

H1 0.302 (3) 0.748 (2) 0.212 (3) 0.050 (8)*

H11 0.774 (6) 0.630 (5) 0.020 (6) 0.15 (2)*

H12 0.741 (9) 0.520 (6) 0.044 (11) 0.22 (4)*

H13 0.668 (7) 0.587 (4) 0.046 (7) 0.16 (3)*

H14 0.695 (8) 0.573 (5) −0.088 (9) 0.23 (4)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Zn1 0.02137 (18) 0.01547 (17) 0.01684 (18) 0.000 0.00242 (11) 0.000

O1 0.0313 (7) 0.0220 (6) 0.0275 (7) 0.0057 (5) −0.0006 (6) 0.0048 (5)

O2 0.0272 (8) 0.0402 (9) 0.0424 (9) 0.0038 (6) −0.0003 (6) 0.0083 (7)

O3 0.0826 (14) 0.0575 (11) 0.0215 (8) 0.0381 (10) 0.0065 (8) −0.0012 (8)

O4 0.0384 (8) 0.0225 (7) 0.0272 (7) 0.0115 (5) 0.0081 (6) −0.0019 (5)

supporting information

sup-6

Acta Cryst. (2002). E58, m540–m542

C2 0.0261 (9) 0.0178 (8) 0.0224 (9) 0.0059 (6) 0.0005 (7) 0.0012 (7)

C3 0.0340 (10) 0.0248 (9) 0.0180 (8) 0.0087 (7) −0.0001 (7) −0.0007 (7)

C4 0.0281 (9) 0.0201 (8) 0.0198 (9) 0.0066 (7) 0.0038 (7) −0.0011 (6)

C5 0.0325 (10) 0.0256 (9) 0.0222 (9) 0.0077 (7) 0.0030 (7) −0.0042 (7)

N 0.0534 (15) 0.0608 (17) 0.0581 (17) −0.0100 (12) 0.0052 (13) −0.0016 (13)

O1W 0.096 (3) 0.241 (6) 0.197 (6) −0.005 (4) 0.052 (4) −0.027 (6)

O2W 0.300 (18) 0.292 (18) 0.48 (3) 0.000 −0.125 (18) 0.000

O3W 0.100 (4) 0.061 (3) 0.079 (4) −0.036 (3) −0.007 (3) 0.007 (3)

O3W′ 0.085 (5) 0.067 (4) 0.258 (13) −0.027 (3) 0.005 (6) 0.038 (6)

O4W 0.191 (9) 0.168 (7) 1.18 (5) −0.034 (6) −0.075 (16) 0.164 (16)

O5W 0.191 (12) 0.128 (6) 0.174 (12) −0.019 (7) 0.086 (11) −0.025 (6)

Geometric parameters (Å, º)

Zn1—O4i _{1.9744 (14) C2—C4}v _{1.398 (3)}

Zn1—O4ii _{1.9744 (14) C3—C4 1.394 (3)}

Zn1—O1iii _{1.9789 (14) C3—H1 1.04 (3)}

Zn1—O1 1.9789 (14) C4—C2v _{1.398 (3)}

O1—C1 1.276 (2) C4—C5 1.501 (2)

O2—C1 1.235 (3) N—H11 1.01 (7)

O3—C5 1.237 (3) N—H12 0.99 (10)

O4—C5 1.268 (2) N—H13 0.86 (8)

O4—Zn1iv _{1.9744 (14) N—H14 1.05 (10)}

C1—C2 1.507 (2) O3W—O3W′ 1.523 (12)

C2—C3 1.385 (3) O5W—O5Wiii _{1.40 (2)}

O4i_—Zn1—O4ii _{123.02 (9) C2—C3—H1 120.2 (17)}

O4i_—Zn1—O1iii _{104.91 (6) C4—C3—H1 117.8 (17)}

O4ii_—Zn1—O1iii _{103.79 (6) C3—C4—C2}v _{118.99 (17)}

O4i_{—Zn1—O1 103.79 (6) C3—C4—C5 118.49 (17)}

O4ii_{—Zn1—O1 104.91 (6) C2}v_{—C4—C5 122.52 (16)}

O1iii_{—Zn1—O1 117.40 (8) O3—C5—O4 123.50 (18)}

C1—O1—Zn1 115.35 (12) O3—C5—C4 119.60 (17)

C5—O4—Zn1iv _{112.59 (13) O4—C5—C4 116.89 (17)}

O2—C1—O1 124.74 (17) H11—N—H12 124 (6)

O2—C1—C2 119.43 (17) H11—N—H13 99 (5)

O1—C1—C2 115.64 (17) H12—N—H13 91 (6)

C3—C2—C4v _{119.46 (16) H11—N—H14 113 (6)}

C3—C2—C1 116.62 (17) H12—N—H14 116 (7)

C4v_{—C2—C1 123.87 (16) H13—N—H14 107 (6)}

C2—C3—C4 121.55 (18)