metal-organic papers
m158
Xiaoet al. [Cu(C8H3NO6)(C10H8N2)] doi:10.1107/S1600536804032970 Acta Cryst.(2005). E61, m158±m159 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
catena
-Poly[[(2,2
000-bipyridine)copper(II)]-l
-5-nitroisophthalato]
Hong-Ping Xiao,* Xin-Hua Li and Ya-Qian Cheng
School of Chemistry and Materials Science, Wenzhou Normal College, Zhejiang Wenzhou, 325027, People's Republic of China
Correspondence e-mail: hp_xiao@wznc.zj.cn
Key indicators
Single-crystal X-ray study
T= 298 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.040
wRfactor = 0.097
Data-to-parameter ratio = 14.7
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, [Cu(C8H3NO6)(C10H8N2)]n, the Cu
atom exists in a four-coordinate environment de®ned by two carboxyl O atoms belonging to two 5-nitroisophthalate dianions and two N atoms from a 2,20-bipyridine molecule. The 5-nitroisophthalate dianion acts as a bridge between two Cu atoms in a tris-monodentate coordination mode, resulting in a zigzag coordination polymer.
Comment
Following reports on the synthesis of one- and three-dimen-sional metal coordination polymers by using multicarboxylic acid ligands (Liuet al., 2002; Luet al., 2001; O0Keeffeet al., 2000; Yaghi et al., 2003) such as terephthalic acid (Zhuet al., 2004), isophthalic acid (Xiao et al., 2004) and 1,2,4,5-benzenetetracarboxylic acid (Longet al., 2003), we have used 5-nitroisophthalic acid in the synthesis of a coordination polymer, (I), of a copper(II) derivative in which the metal atom is chelated by 2,20-bipyridine. The CuIIatom has a
four-coordinate environment de®ned by two carboxyl O atoms belonging to two 5-nitroisophthalate dianions and two N atoms from the heterocycle (Fig. 1); the geometry is square planar. The 5-nitroisophthalate dianion functions as a bridge between two Cu atoms, giving rise to a zigzag chain (Fig. 2). The motif is similar to those of {[Cu(phen)(phth)(H2O)]
-H2ODMF}n (phen is 1,10-phenanthroline and phth is
isophthalate; Xiao et al., 2004) and {[Cu(2,20 -bipy)-(tp)(H2O)]H2ODMF}n(tp is terephthalate and 2,20-bipy is
2,20-bipyridine; Xiao & Zhu, 2003). The structure differs in the mode of bonding as well as the deprotonation of the carboxyl groups of the 5-nitroisophthalate anion compared with those noted in [CuCl(phen)2](C8H4NO6)2H2O (Yeet al., 2004). In
(I), the two carboxyl groups are deprotoned and they are involved in coordination to the Cu atoms, whereas in [CuCl(phen)2](C8H4NO6)2H2O, only one carboxyl group is
deprotoned.
Experimental
The title compound was synthesized by the hydrothermal method from a mixture of 5-nitroisophthalic acid (0.3 mmol), Cu(CH3
-COO)2H2O (0.3 mmol), 2,2-bipyridine (0.3 mmol) and water
(8.0 ml) in a 15.0 ml telfon-lined stainless steel reactor. The solution was heated at 423 K for four days. After reaction, the vessel was slowly cooled to room temperature to give blue crystals.
Crystal data
[Cu(C8H3NO6)(C10H8N2)]
Mr= 428.84
Monoclinic,P21/c
a= 9.5529 (11) AÊ
b= 12.6089 (14) AÊ
c= 13.7463 (16) AÊ
= 95.238 (2)
V= 1648.8 (3) AÊ3
Z= 4
Dx= 1.728 Mg mÿ3
MoKradiation Cell parameters from 3556
re¯ections
= 2.2±28.0
= 1.37 mmÿ1
T= 298 (2) K Block, blue
0.300.220.13 mm Data collection
Bruker APEX area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2002)
Tmin= 0.684,Tmax= 0.842
9984 measured re¯ections
3713 independent re¯ections 3266 re¯ections withI> 2(I)
Rint= 0.024
max= 27.5
h=ÿ12!12
k=ÿ7!16
l=ÿ17!17 Refinement
Re®nement onF2
R[F2> 2(F2)] = 0.040
wR(F2) = 0.097
S= 1.05 3713 re¯ections 253 parameters
w= 1/[2(F
o2) + (0.0472P)2
+ 0.9168P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.36 e AÊÿ3 min=ÿ0.26 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Cu1ÐO2 1.9149 (17)
Cu1ÐO3i 1.9538 (16) Cu1ÐN1Cu1ÐN2 2.0046 (19)2.017 (2)
O2ÐCu1ÐO3i 98.71 (7)
O2ÐCu1ÐN1 91.11 (7) O3iÐCu1ÐN1 170.18 (7)
O2ÐCu1ÐN2 168.97 (8) O3iÐCu1ÐN2 89.94 (7)
N1ÐCu1ÐN2 80.32 (8)
Symmetry code: (i)x;ÿy1 2;z12.
H atoms were included in the re®nement in calculated positions in the riding-model approximation [CÐH = 0.93 AÊ and Uiso(H) =
1.2Ueq(C)].
Data collection:SMART(Bruker, 2002); cell re®nement:SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.
We acknowledge ®nancial support by the Wenzhou Science and Technology Project of China (No. S2003A008).
References
Bruker (2002).SMART(Version 5.618),SAINT(Version 6.02a),SADABS
(Version 2.03) andXP. Bruker AXS Inc., Madison, Wisconsin, USA. Liu, G. F., Qiao, Z. P., Wang, H. Z., Chen, X. M. & Yang, G. (2002).New J.
Chem.26, 791±795.
Long, L. S., Ren, Y. P., Ma, L. H., Jiang, Y. B., Huang, R. B. & Zheng, L. S. (2003).Inorg. Chem. Commun.6, 690±693.
Lu, J. Y., Norman, C., Abboud, K. A. & Ison, A. (2001). Inorg. Chem. Commun.4, 459±461.
O'Keeffe, M., Eddaoudi, M., Li, H., Reineke, T. & Yaghi, O. M. (2000).J. Solid State Chem.152, 3±20.
Sheldrick, G. M. (1997).SHELX97. University of GoÈttingen, Germany. Xiao, H. P., Li, X. H. & Hu, M. L (2004).Acta Cryst.E60, m468±m470. Xiao, H. P. & Zhu, L. G. (2003).Chin. J. Inorg. Chem.19, 1179±1183. Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim,
J. (2003).Nature(London),423, 705±714.
Ye, M. D., Xiao, H. P. & Hu, M. L. (2004).Acta Cryst.E60, m1516±m1518. Zhu, L. G., Xiao, H. P. & Lu, J. Y. (2004).Inorg. Chem. Commun.7, 94±96.
Figure 2
View of the zigzag chain of (I).
Figure 1
The coordination environment of the Cu atom in (I), with atom numbering, showing displacement ellipsoids at the 30% probability level [symmetry code: (i)x,ÿy+3
supporting information
sup-1
Acta Cryst. (2005). E61, m158–m159
supporting information
Acta Cryst. (2005). E61, m158–m159 [https://doi.org/10.1107/S1600536804032970]
catena
-Poly[[(2,2
′
-bipyridine)copper(II)]-
µ
-5-nitroisophthalato]
Hong-Ping Xiao, Xin-Hua Li and Ya-Qian Cheng
catena-Poly[[(2,2′-bipyridine)copper(II)]-µ-5-nitroisophthalato]
Crystal data
[Cu(C8H3NO6)(C10H8N2)] Mr = 428.84
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 9.5529 (11) Å
b = 12.6089 (14) Å
c = 13.7463 (16) Å
β = 95.238 (2)°
V = 1648.8 (3) Å3 Z = 4
F(000) = 868
Dx = 1.728 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3556 reflections
θ = 2.2–28.0°
µ = 1.37 mm−1 T = 298 K Block, blue
0.30 × 0.22 × 0.13 mm
Data collection
Bruker APEX area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: integration (SADABS; Bruker, 2002)
Tmin = 0.684, Tmax = 0.842
9984 measured reflections 3713 independent reflections 3266 reflections with I > 2σ(I)
Rint = 0.024
θmax = 27.5°, θmin = 2.1° h = −12→12
k = −7→16
l = −17→17
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.040 wR(F2) = 0.097 S = 1.05 3713 reflections 253 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters not defined?
w = 1/[σ2(F
o2) + (0.0472P)2 + 0.9168P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.36 e Å−3
Δρmin = −0.26 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cu1 0.63928 (3) 0.49329 (2) 0.439222 (19) 0.02441 (11)
O1 0.69814 (19) 0.36958 (18) 0.27940 (14) 0.0496 (5)
O3 0.54050 (18) 0.12488 (13) −0.00557 (11) 0.0316 (4)
O4 0.4132 (2) 0.20218 (17) −0.13129 (14) 0.0586 (6)
O5 0.2053 (2) 0.61591 (18) 0.05076 (16) 0.0626 (7)
O6 0.1410 (3) 0.5108 (2) −0.06762 (17) 0.0803 (10)
N1 0.75910 (19) 0.61592 (15) 0.40514 (13) 0.0255 (4)
N2 0.7737 (2) 0.49919 (15) 0.56109 (15) 0.0295 (5)
N3 0.2168 (3) 0.5340 (2) 0.00489 (16) 0.0424 (6)
C1 0.7367 (2) 0.67571 (19) 0.32486 (17) 0.0313 (5)
H1 0.6605 0.6603 0.2801 0.038*
C2 0.8230 (3) 0.7593 (2) 0.3064 (2) 0.0431 (7)
H2 0.8053 0.8001 0.2502 0.052*
C3 0.9360 (3) 0.7813 (2) 0.3728 (2) 0.0509 (8)
H3 0.9970 0.8365 0.3612 0.061*
C4 0.9584 (3) 0.7214 (2) 0.4562 (2) 0.0416 (6)
H4 1.0334 0.7363 0.5022 0.050*
C5 0.8678 (2) 0.63852 (19) 0.47103 (16) 0.0275 (5)
C6 0.8790 (2) 0.56972 (19) 0.55786 (16) 0.0279 (5)
C7 0.9881 (2) 0.5748 (2) 0.63163 (18) 0.0349 (6)
H7 1.0607 0.6234 0.6282 0.042*
C8 0.9876 (3) 0.5067 (2) 0.70998 (19) 0.0405 (7)
H8 1.0615 0.5071 0.7590 0.049*
C9 0.8762 (3) 0.4379 (2) 0.71497 (19) 0.0434 (7)
H9 0.8723 0.3930 0.7683 0.052*
C10 0.7707 (3) 0.4371 (2) 0.63936 (18) 0.0390 (6)
H10 0.6948 0.3915 0.6432 0.047*
C11 0.5921 (2) 0.42224 (19) 0.25698 (16) 0.0295 (5)
C12 0.5083 (2) 0.40583 (18) 0.15967 (16) 0.0265 (5)
C13 0.4049 (3) 0.47762 (19) 0.12727 (17) 0.0290 (5)
H13 0.3879 0.5373 0.1641 0.035*
C14 0.3277 (2) 0.4589 (2) 0.03931 (17) 0.0292 (5)
C15 0.3491 (2) 0.37116 (19) −0.01775 (16) 0.0289 (5)
H15 0.2952 0.3609 −0.0768 0.035*
C16 0.4521 (2) 0.29879 (18) 0.01453 (16) 0.0253 (5)
C17 0.5311 (2) 0.31728 (18) 0.10303 (16) 0.0274 (5)
H17 0.6009 0.2692 0.1248 0.033*
C18 0.4699 (3) 0.20208 (19) −0.04856 (17) 0.0306 (5)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cu1 0.02518 (17) 0.02655 (17) 0.02028 (16) −0.00525 (11) −0.00451 (11) 0.00048 (10)
O1 0.0341 (10) 0.0678 (14) 0.0433 (11) 0.0121 (10) −0.0161 (8) −0.0090 (10)
O2 0.0382 (10) 0.0291 (9) 0.0224 (8) −0.0058 (7) −0.0079 (7) −0.0012 (6)
O3 0.0389 (9) 0.0287 (9) 0.0259 (8) 0.0109 (7) −0.0042 (7) −0.0025 (7)
O4 0.0857 (16) 0.0521 (13) 0.0325 (10) 0.0363 (12) −0.0251 (10) −0.0152 (9)
O5 0.0792 (16) 0.0522 (13) 0.0526 (13) 0.0394 (12) −0.0136 (11) −0.0133 (11)
O6 0.090 (2) 0.089 (2) 0.0523 (15) 0.0562 (15) −0.0422 (15) −0.0247 (12)
supporting information
sup-3
Acta Cryst. (2005). E61, m158–m159
N2 0.0292 (11) 0.0350 (12) 0.0232 (10) −0.0003 (8) −0.0048 (8) 0.0006 (8)
N3 0.0479 (14) 0.0461 (13) 0.0312 (12) 0.0224 (11) −0.0064 (10) −0.0008 (10)
C1 0.0298 (12) 0.0313 (13) 0.0317 (12) −0.0033 (10) −0.0025 (10) 0.0006 (10) C2 0.0478 (16) 0.0374 (15) 0.0429 (15) −0.0093 (12) −0.0029 (12) 0.0102 (12) C3 0.0526 (17) 0.0399 (16) 0.0586 (18) −0.0227 (13) −0.0045 (15) 0.0066 (14) C4 0.0372 (14) 0.0418 (15) 0.0431 (15) −0.0154 (12) −0.0102 (12) −0.0038 (12)
C5 0.0239 (11) 0.0283 (12) 0.0295 (11) −0.0007 (9) −0.0017 (9) −0.0079 (9)
C6 0.0250 (11) 0.0321 (13) 0.0263 (11) 0.0014 (9) 0.0003 (9) −0.0099 (9)
C7 0.0258 (12) 0.0448 (15) 0.0327 (13) 0.0019 (11) −0.0060 (10) −0.0133 (11)
C8 0.0372 (15) 0.0559 (18) 0.0261 (12) 0.0111 (12) −0.0103 (11) −0.0116 (11) C9 0.0472 (16) 0.0569 (18) 0.0248 (12) 0.0098 (14) −0.0045 (11) 0.0030 (12) C10 0.0409 (14) 0.0456 (16) 0.0293 (13) −0.0023 (12) −0.0025 (11) 0.0044 (11) C11 0.0296 (12) 0.0328 (13) 0.0247 (11) −0.0082 (10) −0.0048 (9) 0.0004 (10) C12 0.0262 (11) 0.0294 (12) 0.0230 (11) −0.0018 (9) −0.0030 (9) −0.0001 (9) C13 0.0344 (13) 0.0265 (12) 0.0255 (11) 0.0012 (10) −0.0014 (10) −0.0032 (9) C14 0.0313 (12) 0.0284 (12) 0.0267 (11) 0.0071 (10) −0.0038 (10) 0.0026 (10)
C15 0.0327 (12) 0.0327 (13) 0.0200 (10) 0.0025 (10) −0.0051 (9) 0.0008 (9)
C16 0.0277 (11) 0.0247 (11) 0.0230 (11) 0.0004 (9) −0.0008 (9) 0.0005 (9)
C17 0.0266 (11) 0.0266 (12) 0.0278 (11) 0.0015 (9) −0.0039 (9) 0.0014 (9)
C18 0.0332 (12) 0.0310 (13) 0.0264 (12) 0.0049 (10) −0.0032 (10) −0.0030 (10)
Geometric parameters (Å, º)
Cu1—O2 1.9149 (17) C4—C5 1.383 (3)
Cu1—O3i 1.9538 (16) C4—H4 0.9300
Cu1—N1 2.0046 (19) C5—C6 1.471 (3)
Cu1—N2 2.017 (2) C6—C7 1.388 (3)
O1—C11 1.227 (3) C7—C8 1.377 (4)
O2—C11 1.281 (3) C7—H7 0.9300
O3—C18 1.296 (3) C8—C9 1.379 (4)
O3—Cu1ii 1.9538 (16) C8—H8 0.9300
O4—C18 1.214 (3) C9—C10 1.380 (4)
O5—N3 1.220 (3) C9—H9 0.9300
O6—N3 1.213 (3) C10—H10 0.9300
N1—C1 1.338 (3) C11—C12 1.509 (3)
N1—C5 1.345 (3) C12—C13 1.383 (3)
N2—C10 1.333 (3) C12—C17 1.390 (3)
N2—C6 1.346 (3) C13—C14 1.378 (3)
N3—C14 1.467 (3) C13—H13 0.9300
C1—C2 1.376 (3) C14—C15 1.382 (3)
C1—H1 0.9300 C15—C16 1.385 (3)
C2—C3 1.377 (4) C15—H15 0.9300
C2—H2 0.9300 C16—C17 1.392 (3)
C3—C4 1.374 (4) C16—C18 1.515 (3)
C3—H3 0.9300 C17—H17 0.9300
O2—Cu1—O3i 98.71 (7) C8—C7—H7 120.4
O3i—Cu1—N1 170.18 (7) C7—C8—C9 119.2 (2)
O2—Cu1—N2 168.97 (8) C7—C8—H8 120.4
O3i—Cu1—N2 89.94 (7) C9—C8—H8 120.4
N1—Cu1—N2 80.32 (8) C8—C9—C10 118.8 (3)
C11—O2—Cu1 111.11 (15) C8—C9—H9 120.6
C18—O3—Cu1ii 130.20 (15) C10—C9—H9 120.6
C1—N1—C5 119.5 (2) N2—C10—C9 122.3 (3)
C1—N1—Cu1 125.16 (15) N2—C10—H10 118.8
C5—N1—Cu1 115.37 (15) C9—C10—H10 118.8
C10—N2—C6 119.1 (2) O1—C11—O2 125.0 (2)
C10—N2—Cu1 126.14 (18) O1—C11—C12 120.5 (2)
C6—N2—Cu1 114.70 (16) O2—C11—C12 114.5 (2)
O6—N3—O5 123.6 (2) C13—C12—C17 119.3 (2)
O6—N3—C14 117.9 (2) C13—C12—C11 120.1 (2)
O5—N3—C14 118.5 (2) C17—C12—C11 120.6 (2)
N1—C1—C2 122.1 (2) C14—C13—C12 118.7 (2)
N1—C1—H1 119.0 C14—C13—H13 120.7
C2—C1—H1 119.0 C12—C13—H13 120.7
C1—C2—C3 118.6 (3) C13—C14—C15 122.7 (2)
C1—C2—H2 120.7 C13—C14—N3 119.0 (2)
C3—C2—H2 120.7 C15—C14—N3 118.3 (2)
C4—C3—C2 119.7 (3) C14—C15—C16 118.9 (2)
C4—C3—H3 120.1 C14—C15—H15 120.6
C2—C3—H3 120.1 C16—C15—H15 120.6
C3—C4—C5 119.1 (2) C15—C16—C17 118.9 (2)
C3—C4—H4 120.4 C15—C16—C18 117.43 (19)
C5—C4—H4 120.4 C17—C16—C18 123.7 (2)
N1—C5—C4 121.1 (2) C12—C17—C16 121.6 (2)
N1—C5—C6 114.5 (2) C12—C17—H17 119.2
C4—C5—C6 124.4 (2) C16—C17—H17 119.2
N2—C6—C7 121.3 (2) O4—C18—O3 126.7 (2)
N2—C6—C5 114.67 (19) O4—C18—C16 118.1 (2)
C7—C6—C5 124.0 (2) O3—C18—C16 115.13 (19)
C8—C7—C6 119.1 (2)