Poly[(μ-3,5-dinitro-2-oxidobenzoato)(μ-3-hydroxy-pyridine)copper(II)].

A new coordination polymer, [Cu(C(7)H(2)N(2)O(7))(C(5)H(5)NO)](n), exhibits a double-chain structure, in which 3,5-dinitro-2-oxidobenzoate and 3-hydroxy-pyridine both act as bridging ligands, -connecting adjacent copper(II) centers to form an infinite double-stranded chain. The asymmetric unit contains one Cu(II) ion, one 3,5-dinitro-2-oxidobenzoate ligand and a 3-hydroxy-pyridine ligand. Coordination by one N atom and three O atoms from two different 3,5-dinitro-2-oxidobenzoate ligands and a 3-hydroxy-pyridine ligand creates a square-planar Cu(II) center, which is augmented by a less tightly bonded fifth phenol O atom to form a square-pyramidal five-coordinate complex with an essentially planar base. The double-stranded chains are stabilized by intra-chain π-π inter-actions [the centroid-to-centroid distance between adjacent aromatic rings is 3.719 (7) Å], and further linked through O-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular network.

Related literature

For related literature, see: Bradshaw et al. (2005 ▶); Eddaoudi et al. (2001 ▶); Fujita et al. (1994 ▶); Gable et al. (1990 ▶); Gao et al. (2005 ▶); He et al. (2006 ▶); Li et al. (1999 ▶); Losier & Zaworotko (1996 ▶); Moulton & Zaworotko (2001 ▶); Song & Xi (2006 ▶) Song et al., 2006 ▶; Song, Guo & Guo, 2007 ▶; Song, Guo & He, 2007 ▶; Song, Guo & Zhang, 2007 ▶; Song, Yan et al., 2007 ▶); Stang & Olenyuk (1997 ▶); Withersby et al. (1999 ▶); Yaghi & Li (1995 ▶).

Experimental

Crystal data

[Cu(C7n class="Species">H2N2O7)(C5H5NO)]

M = 384.75

Monoclinic,

a = 8.1055 (3) Å

b = 6.2208 (2) Å

c = 26.9837 (9) Å

β = 94.030 (3)°

V = 1357.23 (8) Å3

Z = 4

Mo Kα radiation

μ = 1.66 mm−1

T = 296 (2) K

0.25 × 0.16 × 0.09 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.681, T max = 0.865

12917 measured reflections

3094 independent reflections

2275 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.092

S = 1.03

3094 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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, 2001 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009392/zl2099sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009392/zl2099Isup2.hkl

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

[Cu(C7H2N2O7)(C5H5NO)]	F000 = 772
Mr = 384.75	Dx = 1.883 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2895 reflections
a = 8.1055 (3) Å	θ = 2.4–27.9º
b = 6.2208 (2) Å	µ = 1.66 mm−1
c = 26.9837 (9) Å	T = 296 (2) K
β = 94.030 (3)º	Plate, blue
V = 1357.23 (8) Å3	0.25 × 0.16 × 0.09 mm
Z = 4

Bruker APEXII area-detector diffractometer	3094 independent reflections
Radiation source: fine-focus sealed tube	2275 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.061
T = 296(2) K	θmax = 27.5º
φ and ω scans	θmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.681, Tmax = 0.865	k = −8→8
12917 measured reflections	l = −31→34

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.0416P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3094 reflections	Δρmax = 0.38 e Å−3
218 parameters	Δρmin = −0.45 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Cu1	0.12663 (5)	0.27589 (5)	0.187438 (14)	0.02720 (13)
O1	0.2121 (3)	0.3893 (3)	0.12851 (7)	0.0336 (5)
C3	0.4627 (4)	0.8652 (4)	0.15767 (12)	0.0300 (7)
H3	0.5168	0.9353	0.1846	0.036*
C7	0.2967 (4)	0.5637 (4)	0.12445 (11)	0.0266 (6)
C2	0.3785 (4)	0.6762 (4)	0.16517 (11)	0.0257 (6)
C6	0.3114 (4)	0.6587 (4)	0.07688 (11)	0.0303 (7)
C5	0.3921 (4)	0.8497 (5)	0.06963 (12)	0.0339 (7)
H5	0.3957	0.9089	0.0381	0.041*
C4	0.4673 (4)	0.9503 (4)	0.11085 (12)	0.0319 (7)
N2	0.2313 (3)	0.5572 (4)	0.03232 (10)	0.0383 (7)
N3	0.5560 (3)	1.1514 (4)	0.10454 (13)	0.0432 (7)
O5	0.5735 (3)	1.2190 (4)	0.06299 (10)	0.0593 (8)
O4	0.6093 (3)	1.2453 (3)	0.14266 (11)	0.0569 (7)
O6	0.1611 (3)	0.6731 (4)	0.00078 (10)	0.0580 (7)
O7	0.2381 (4)	0.3631 (4)	0.02875 (9)	0.0591 (7)
N1	0.0150 (3)	0.0378 (3)	0.14852 (9)	0.0280 (6)
C10	−0.1449 (4)	−0.2943 (4)	0.09616 (13)	0.0354 (8)
H10	−0.1983	−0.4056	0.0785	0.043*
C8	−0.0260 (4)	−0.1437 (4)	0.17174 (12)	0.0308 (7)
H8	−0.0007	−0.1566	0.2058	0.037*
C9	−0.1048 (4)	−0.3115 (4)	0.14630 (12)	0.0294 (7)
C12	−0.0227 (4)	0.0547 (4)	0.09966 (12)	0.0335 (7)
H12	0.0064	0.1790	0.0832	0.040*
C11	−0.1036 (4)	−0.1078 (5)	0.07304 (13)	0.0377 (8)
H11	−0.1303	−0.0907	0.0392	0.045*
O8	−0.1323 (3)	−0.4927 (3)	0.17369 (9)	0.0429 (6)
H8A	−0.2046	−0.5657	0.1591	0.064*
C1	0.3686 (4)	0.6059 (4)	0.21742 (11)	0.0272 (7)
O2	0.2620 (3)	0.4681 (3)	0.22901 (8)	0.0378 (5)
O3	0.4641 (2)	0.6940 (3)	0.25017 (8)	0.0290 (5)

	U11	U22	U33	U12	U13	U23
Cu1	0.0369 (2)	0.02288 (17)	0.0209 (2)	−0.00557 (14)	−0.00425 (16)	0.00164 (14)
O1	0.0472 (14)	0.0299 (10)	0.0231 (12)	−0.0138 (9)	−0.0003 (10)	−0.0021 (8)
C3	0.0300 (17)	0.0254 (13)	0.034 (2)	−0.0014 (11)	−0.0011 (14)	−0.0047 (12)
C7	0.0291 (17)	0.0262 (13)	0.0241 (17)	−0.0016 (11)	−0.0008 (13)	−0.0019 (11)
C2	0.0298 (17)	0.0255 (13)	0.0215 (17)	−0.0004 (11)	−0.0002 (13)	−0.0009 (11)
C6	0.0342 (18)	0.0365 (15)	0.0195 (18)	−0.0052 (12)	−0.0021 (14)	−0.0005 (12)
C5	0.0335 (19)	0.0391 (15)	0.0294 (19)	−0.0064 (13)	0.0038 (15)	0.0076 (14)
C4	0.0291 (17)	0.0282 (13)	0.038 (2)	−0.0066 (12)	0.0038 (15)	0.0039 (13)
N2	0.0425 (17)	0.0507 (16)	0.0216 (16)	−0.0148 (13)	0.0006 (13)	−0.0006 (12)
N3	0.0349 (17)	0.0343 (13)	0.060 (2)	−0.0077 (12)	0.0038 (16)	0.0058 (14)
O5	0.0653 (19)	0.0535 (14)	0.060 (2)	−0.0221 (12)	0.0112 (15)	0.0213 (13)
O4	0.0575 (17)	0.0447 (13)	0.068 (2)	−0.0267 (11)	0.0005 (15)	−0.0063 (12)
O6	0.0634 (19)	0.0757 (17)	0.0321 (16)	−0.0060 (14)	−0.0154 (13)	0.0153 (13)
O7	0.090 (2)	0.0474 (14)	0.0379 (17)	−0.0132 (13)	−0.0070 (15)	−0.0116 (12)
N1	0.0331 (15)	0.0236 (11)	0.0265 (15)	−0.0028 (9)	−0.0037 (11)	0.0018 (10)
C10	0.0395 (19)	0.0282 (14)	0.037 (2)	−0.0087 (12)	−0.0082 (16)	−0.0089 (13)
C8	0.0362 (18)	0.0258 (13)	0.0291 (19)	−0.0049 (12)	−0.0072 (15)	0.0043 (12)
C9	0.0279 (17)	0.0246 (13)	0.035 (2)	−0.0017 (11)	−0.0038 (14)	0.0030 (12)
C12	0.0430 (19)	0.0294 (14)	0.0269 (19)	−0.0071 (13)	−0.0052 (15)	−0.0006 (12)
C11	0.045 (2)	0.0382 (16)	0.0282 (19)	−0.0047 (14)	−0.0052 (16)	−0.0036 (14)
O8	0.0481 (16)	0.0281 (10)	0.0501 (16)	−0.0143 (9)	−0.0124 (12)	0.0091 (10)
C1	0.0321 (17)	0.0246 (13)	0.0242 (18)	0.0024 (11)	−0.0024 (14)	−0.0046 (11)
O2	0.0511 (15)	0.0399 (11)	0.0214 (12)	−0.0187 (10)	−0.0040 (10)	0.0005 (9)
O3	0.0315 (12)	0.0313 (10)	0.0231 (12)	−0.0031 (8)	−0.0055 (9)	−0.0073 (8)

Cu1—O1	1.9132 (19)	N3—O5	1.215 (4)
Cu1—O2	1.929 (2)	N3—O4	1.234 (4)
Cu1—O3i	1.952 (2)	N1—C12	1.336 (4)
Cu1—N1	1.996 (2)	N1—C8	1.344 (3)
O1—C7	1.292 (3)	C10—C11	1.370 (4)
C3—C4	1.373 (4)	C10—C9	1.373 (5)
C3—C2	1.382 (4)	C10—H10	0.9300
C3—H3	0.9300	C8—C9	1.381 (4)
C7—C6	1.426 (4)	C8—H8	0.9300
C7—C2	1.426 (4)	C9—O8	1.375 (3)
C2—C1	1.484 (4)	C12—C11	1.379 (4)
C6—C5	1.377 (4)	C12—H12	0.9300
C6—N2	1.468 (4)	C11—H11	0.9300
C5—C4	1.380 (4)	O8—H8A	0.8200
C5—H5	0.9300	C1—O3	1.259 (3)
C4—N3	1.459 (3)	C1—O2	1.271 (3)
N2—O7	1.213 (3)	O3—Cu1ii	1.952 (2)
N2—O6	1.224 (3)
O1—Cu1—O2	91.74 (8)	O5—N3—O4	123.3 (3)
O1—Cu1—O3i	173.49 (8)	O5—N3—C4	119.7 (3)
O2—Cu1—O3i	83.90 (8)	O4—N3—C4	117.1 (3)
O1—Cu1—N1	90.78 (9)	C12—N1—C8	118.6 (2)
O2—Cu1—N1	169.99 (10)	C12—N1—Cu1	121.62 (18)
O3i—Cu1—N1	94.34 (9)	C8—N1—Cu1	119.7 (2)
C7—O1—Cu1	127.25 (19)	C11—C10—C9	117.8 (3)
C4—C3—C2	120.6 (3)	C11—C10—H10	121.1
C4—C3—H3	119.7	C9—C10—H10	121.1
C2—C3—H3	119.7	N1—C8—C9	121.6 (3)
O1—C7—C6	120.2 (3)	N1—C8—H8	119.2
O1—C7—C2	124.6 (3)	C9—C8—H8	119.2
C6—C7—C2	115.2 (2)	C10—C9—O8	123.9 (3)
C3—C2—C7	120.8 (3)	C10—C9—C8	120.0 (3)
C3—C2—C1	116.8 (3)	O8—C9—C8	116.1 (3)
C7—C2—C1	122.3 (2)	N1—C12—C11	121.6 (3)
C5—C6—C7	123.8 (3)	N1—C12—H12	119.2
C5—C6—N2	116.2 (3)	C11—C12—H12	119.2
C7—C6—N2	119.9 (2)	C10—C11—C12	120.4 (3)
C6—C5—C4	117.7 (3)	C10—C11—H11	119.8
C6—C5—H5	121.2	C12—C11—H11	119.8
C4—C5—H5	121.2	C9—O8—H8A	109.5
C3—C4—C5	121.8 (3)	O3—C1—O2	121.0 (3)
C3—C4—N3	118.9 (3)	O3—C1—C2	117.9 (3)
C5—C4—N3	119.2 (3)	O2—C1—C2	121.0 (3)
O7—N2—O6	123.5 (3)	C1—O2—Cu1	130.1 (2)
O7—N2—C6	118.2 (3)	C1—O3—Cu1ii	117.95 (19)
O6—N2—C6	118.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O4iii	0.82	1.94	2.738 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O4i	0.82	1.94	2.738 (3)	165

Symmetry code: (i) .