Literature DB >> 21201015

Poly[tetra-aqua-μ(4)-bromido-di-μ(2)-bromido-μ(2)-hydroxido-di-μ(3)-iso-nicotinato-tetra-μ(2)-isonicotinato-tetra-copper(I)dithulium(III)].

Guo-Ming Wang¹, Zeng-Xin Li, Qing-Hua Zheng, Hui-Luan Liu.

Abstract

A new thulium(III)-copper(I) heterometallic coordination polymer, [Cu(4)Tm(2)Br(3)(C(6)H(4)NO(2))(6)(OH)(H(2)O)(4)](n), has been prepared by a hydro-thermal method. The Tm and both Cu atoms lie on mirror planes. The Tm atom is seven-coordinate with a capped distorted trigonal-prismatic coordination geometry, while the Cu atoms adopt trigonal CuBrN(2) and tetra-hedral CuBr(3)N coordination modes, respectively. The Cu atom in the trigonal coordination environment is disordered over two sites of equal occupancy. The crystal structure is constructed from two distinct units of dimeric [Tm(2)(μ(2)-OH(IN)(6)(H(2)O)(4)] cores (IN = isonicotinate) and one-dimensional inorganic [Cu(4)Br(3)](n) chains, which are linked together, forming heterometallic Cu-halide-lanthanide-organic layers.

Entities: Chemical Disease Species

Year: 2008 PMID： 21201015 PMCID： PMC2959303 DOI： 10.1107/S1600536808028675

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For background to the structures and applications of heterometallic lanthanide–transition metal polymers, see: Benelli & Gatteschi (2002 ▶); Shibasaki & Yoshikawa (2002 ▶); Zhao et al. (2004a ▶,b ▶); Guillou et al. (2006 ▶); Wang et al. (2006 ▶). For some examples of heterometallic lanthanide–transition metal extended architectures, see: Ren et al. (2003 ▶); Prasad et al. (2007 ▶); Cheng et al. (2008 ▶).

Experimental

Crystal data

[Cu4Tm2Br3(C6H4NO2)6(OH)(H2O)4] M = 1653.43 Orthorhombic, a = 19.1815 (2) Å b = 6.6973 (4) Å c = 34.7044 (5) Å V = 4458.3 (3) Å3 Z = 4 Mo Kα radiation μ = 8.58 mm−1 T = 295 (2) K 0.16 × 0.09 × 0.08 mm

Data collection

Bruker APEXII area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.341, T max = 0.547 (expected range = 0.313–0.503) 17231 measured reflections 2408 independent reflections 2090 reflections with I > 2σ(I) R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.027 wR(F 2) = 0.064 S = 1.11 2408 reflections 179 parameters 6 restraints H-atom parameters constrained Δρmax = 0.83 e Å−3 Δρmin = −0.87 e Å−3 Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028675/sj2536sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028675/sj2536Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu₄Tm₂Br₃(C₆H₄NO₂)₆(OH)(H₂O)₄]	F(000) = 3144
M_r = 1653.43	D_x = 2.463 Mg m⁻³
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 6070 reflections
a = 19.1815 (2) Å	θ = 2.1–26.5°
b = 6.6973 (4) Å	µ = 8.58 mm⁻¹
c = 34.7044 (5) Å	T = 295 K
V = 4458.3 (3) Å³	Block, yellow
Z = 4	0.16 × 0.09 × 0.08 mm

Bruker APEXII area-detector diffractometer	2408 independent reflections
Radiation source: fine-focus sealed tube	2090 reflections with I > 2σ(I)
graphite	R_int = 0.037
φ and ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
T_min = 0.341, T_max = 0.547	k = −8→8
17231 measured reflections	l = −43→42

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0288P)² + 11.1134P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
2408 reflections	Δρ_max = 0.83 e Å⁻³
179 parameters	Δρ_min = −0.87 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00119 (4)

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	U_iso*/U_eq	Occ. (<1)
Tm1	0.106107 (10)	−0.00154 (3)	0.2500	0.01935 (10)
Cu1	0.1384 (6)	1.0000	0.5000	0.037 (3)	0.50
Cu1'	0.1361 (6)	1.064 (2)	0.4997 (8)	0.038 (2)	0.25
Cu2	0.0000	0.63637 (13)	0.47157 (2)	0.0465 (2)
Br1	0.0000	1.0000	0.5000	0.0344 (2)
Br2	0.11106 (3)	0.5000	0.5000	0.04244 (17)
O1	0.16098 (14)	1.0892 (4)	0.69667 (7)	0.0352 (6)
O2	0.27354 (15)	1.1077 (5)	0.68216 (7)	0.0475 (8)
O3	0.05791 (13)	0.2265 (5)	0.29248 (8)	0.0390 (7)
O4	0.0000	−0.1250 (8)	0.2500	0.0389 (13)
H4	0.0000	−0.2788	0.2600	0.047*	0.50
O5	0.19308 (19)	0.2314 (6)	0.2500	0.0365 (9)
H5	0.2041	0.2871	0.2699	0.044*
O6	0.1159 (2)	−0.3688 (7)	0.2500	0.0647 (15)
H6B	0.1529	−0.2988	0.2500	0.078*
H6C	0.1278	−0.4859	0.2380	0.078*	0.50
C1	0.2117 (2)	1.0891 (6)	0.67359 (9)	0.0278 (8)
C2	0.19342 (19)	1.0649 (5)	0.63145 (9)	0.0244 (7)
C3	0.1278 (2)	1.0044 (6)	0.62013 (11)	0.0307 (8)
H3A	0.0932	0.9823	0.6384	0.037*
C4	0.1139 (2)	0.9771 (6)	0.58161 (12)	0.0344 (10)
H4A	0.0702	0.9295	0.5744	0.041*
C5	0.2424 (2)	1.0999 (6)	0.60318 (10)	0.0303 (8)
H5A	0.2873	1.1397	0.6098	0.036*
C6	0.2246 (2)	1.0755 (6)	0.56502 (10)	0.0323 (8)
H6A	0.2580	1.1008	0.5462	0.039*
C7	0.0597 (2)	0.5415 (6)	0.39568 (11)	0.0307 (9)
H7A	0.1015	0.5754	0.4076	0.037*
C8	0.06218 (19)	0.4538 (5)	0.35956 (11)	0.0260 (8)
H8A	0.1047	0.4302	0.3475	0.031*
C9	0.0000	0.4016 (7)	0.34159 (13)	0.0216 (10)
C10	0.0000	0.2775 (8)	0.30518 (13)	0.0240 (10)
N1	0.16080 (18)	1.0165 (5)	0.55395 (9)	0.0340 (8)
N2	0.0000	0.5802 (7)	0.41440 (12)	0.0275 (9)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tm1	0.01730 (14)	0.02826 (15)	0.01249 (13)	0.00208 (9)	0.000	0.000
Cu1	0.0466 (19)	0.052 (8)	0.0131 (15)	0.000	0.000	0.000 (8)
Cu1'	0.047 (2)	0.051 (7)	0.0145 (17)	−0.004 (4)	0.0008 (16)	0.001 (5)
Cu2	0.0465 (4)	0.0686 (6)	0.0243 (4)	0.000	0.000	−0.0111 (4)
Br1	0.0271 (4)	0.0500 (5)	0.0260 (4)	0.000	0.000	−0.0129 (3)
Br2	0.0286 (3)	0.0619 (4)	0.0368 (4)	0.000	0.000	0.0074 (3)
O1	0.0438 (16)	0.0448 (16)	0.0171 (13)	−0.0065 (14)	0.0069 (11)	0.0009 (12)
O2	0.0406 (17)	0.081 (2)	0.0212 (14)	−0.0224 (17)	−0.0013 (12)	−0.0077 (15)
O3	0.0250 (13)	0.0570 (18)	0.0348 (15)	0.0037 (13)	0.0023 (11)	−0.0254 (13)
O4	0.023 (3)	0.033 (3)	0.061 (4)	0.000	0.000	0.000
O5	0.046 (2)	0.051 (2)	0.0127 (17)	−0.021 (2)	0.000	0.000
O6	0.053 (3)	0.027 (2)	0.113 (5)	0.008 (2)	0.000	0.000
C1	0.039 (2)	0.031 (2)	0.0138 (16)	−0.0086 (17)	0.0020 (15)	0.0005 (15)
C2	0.034 (2)	0.0235 (16)	0.0161 (16)	−0.0035 (15)	−0.0005 (14)	−0.0006 (14)
C3	0.0290 (18)	0.042 (2)	0.0207 (18)	−0.0027 (17)	0.0035 (15)	0.0043 (15)
C4	0.030 (2)	0.050 (3)	0.024 (2)	−0.0011 (18)	−0.0018 (16)	−0.0005 (17)
C5	0.0307 (19)	0.039 (2)	0.0211 (18)	−0.0088 (17)	0.0013 (15)	−0.0008 (17)
C6	0.033 (2)	0.045 (2)	0.0188 (18)	−0.0045 (18)	0.0048 (15)	−0.0001 (17)
C7	0.028 (2)	0.040 (2)	0.024 (2)	−0.0044 (16)	−0.0016 (15)	−0.0091 (16)
C8	0.0226 (18)	0.032 (2)	0.0229 (18)	−0.0003 (14)	0.0006 (14)	−0.0065 (15)
C9	0.029 (2)	0.018 (2)	0.018 (2)	0.000	0.000	0.0000 (19)
C10	0.024 (2)	0.028 (3)	0.020 (2)	0.000	0.000	−0.003 (2)
N1	0.0339 (18)	0.051 (2)	0.0176 (15)	0.0022 (15)	0.0003 (13)	0.0007 (14)
N2	0.034 (2)	0.030 (2)	0.018 (2)	0.000	0.000	−0.0048 (19)

Tm1—O4	2.197 (2)	O3—C10	1.243 (3)
Tm1—O1ⁱ	2.208 (2)	O4—Tm1^ix	2.197 (2)
Tm1—O1ⁱⁱ	2.208 (2)	O4—H4	1.0867
Tm1—O5	2.284 (4)	O5—H5	0.8127
Tm1—O3ⁱⁱⁱ	2.315 (2)	O6—H6B	0.8504
Tm1—O3	2.315 (2)	O6—H6C	0.9163
Tm1—O6	2.467 (5)	C1—C2	1.512 (5)
Tm1—H6B	2.1833	C2—C5	1.379 (5)
Cu1—N1	1.924 (4)	C2—C3	1.380 (5)
Cu1—N1^iv	1.924 (4)	C3—C4	1.375 (5)
Cu1—Br1	2.654 (12)	C3—H3A	0.9300
Cu1'—N1	1.97 (3)	C4—N1	1.342 (5)
Cu1'—N1^iv	2.00 (3)	C4—H4A	0.9300
Cu1'—Br1	2.645 (12)	C5—C6	1.377 (5)
Cu2—N2	2.020 (4)	C5—H5A	0.9300
Cu2—Br2	2.5191 (7)	C6—N1	1.342 (5)
Cu2—Br2^v	2.5191 (7)	C6—H6A	0.9300
Cu2—Br1	2.6275 (9)	C7—N2	1.341 (4)
Cu2—Cu2^v	2.6889 (17)	C7—C8	1.385 (6)
Br1—Cu2^vi	2.6276 (9)	C7—H7A	0.9300
Br1—Cu1'^vi	2.645 (12)	C8—C9	1.391 (4)
Br1—Cu1'^vii	2.645 (12)	C8—H8A	0.9300
Br1—Cu1'^iv	2.645 (12)	C9—C8^vii	1.391 (4)
Br1—Cu1^vi	2.654 (12)	C9—C10	1.512 (7)
Br2—Cu2^v	2.5191 (7)	C10—O3^vii	1.243 (3)
O1—C1	1.260 (4)	N1—Cu1'^iv	2.00 (3)
O1—Tm1^viii	2.208 (2)	N2—C7^vii	1.341 (4)
O2—C1	1.230 (5)

O4—Tm1—O1ⁱ	109.97 (10)	Cu1'^vi—Br1—Cu1'^iv	161.3 (7)
O4—Tm1—O1ⁱⁱ	109.97 (10)	Cu1'^vii—Br1—Cu1'^iv	180.000 (4)
O1ⁱ—Tm1—O1ⁱⁱ	113.85 (14)	Cu2^vi—Br1—Cu1^vi	90.0
O4—Tm1—O5	159.04 (17)	Cu2—Br1—Cu1^vi	90.000 (2)
O1ⁱ—Tm1—O5	80.41 (9)	Cu1'—Br1—Cu1^vi	170.7 (3)
O1ⁱⁱ—Tm1—O5	80.41 (9)	Cu1'^iv—Br1—Cu1^vi	170.7 (3)
O4—Tm1—O3ⁱⁱⁱ	83.02 (12)	Cu2^vi—Br1—Cu1	90.000 (2)
O1ⁱ—Tm1—O3ⁱⁱⁱ	154.05 (11)	Cu2—Br1—Cu1	90.0
O1ⁱⁱ—Tm1—O3ⁱⁱⁱ	80.34 (10)	Cu1'^vi—Br1—Cu1	170.7 (3)
O5—Tm1—O3ⁱⁱⁱ	80.85 (11)	Cu1'^vii—Br1—Cu1	170.7 (3)
O4—Tm1—O3	83.02 (12)	Cu1^vi—Br1—Cu1	180.000 (1)
O1ⁱ—Tm1—O3	80.34 (10)	Cu2—Br2—Cu2^v	64.51 (4)
O1ⁱⁱ—Tm1—O3	154.05 (11)	C1—O1—Tm1^viii	154.2 (3)
O5—Tm1—O3	80.85 (11)	C10—O3—Tm1	139.8 (3)
O3ⁱⁱⁱ—Tm1—O3	79.09 (15)	Tm1—O4—Tm1^ix	135.8 (3)
O4—Tm1—O6	72.25 (17)	Tm1—O4—H4	110.9
O1ⁱ—Tm1—O6	72.46 (9)	Tm1^ix—O4—H4	110.9
O1ⁱⁱ—Tm1—O6	72.46 (9)	Tm1—O5—H5	120.2
O5—Tm1—O6	128.71 (15)	Tm1—O6—H6B	60.9
O3ⁱⁱⁱ—Tm1—O6	133.49 (10)	Tm1—O6—H6C	150.7
O3—Tm1—O6	133.49 (10)	H6B—O6—H6C	105.4
O4—Tm1—H6B	92.1	O2—C1—O1	126.2 (3)
O1ⁱ—Tm1—H6B	64.0	O2—C1—C2	117.9 (3)
O1ⁱⁱ—Tm1—H6B	64.0	O1—C1—C2	115.9 (3)
O5—Tm1—H6B	108.8	C5—C2—C3	118.0 (3)
O3ⁱⁱⁱ—Tm1—H6B	140.0	C5—C2—C1	120.8 (3)
O3—Tm1—H6B	140.0	C3—C2—C1	121.2 (3)
O6—Tm1—H6B	19.9	C4—C3—C2	119.5 (4)
Cu1'^iv—Cu1—N1	93 (4)	C4—C3—H3A	120.2
Cu1'^iv—Cu1—N1^iv	89 (4)	C2—C3—H3A	120.2
N1—Cu1—N1^iv	154.2 (7)	N1—C4—C3	122.6 (4)
Cu1'^iv—Cu1—Br1	84 (3)	N1—C4—H4A	118.7
N1—Cu1—Br1	102.9 (4)	C3—C4—H4A	118.7
N1^iv—Cu1—Br1	102.9 (4)	C6—C5—C2	119.7 (3)
Cu1'^iv—Cu1'—N1	79 (4)	C6—C5—H5A	120.2
Cu1'^iv—Cu1'—N1^iv	76 (4)	C2—C5—H5A	120.2
N1—Cu1'—N1^iv	142.3 (6)	N1—C6—C5	122.4 (4)
Cu1'^iv—Cu1'—Br1	80.7 (3)	N1—C6—H6A	118.8
N1—Cu1'—Br1	102.0 (9)	C5—C6—H6A	118.8
N1^iv—Cu1'—Br1	101.2 (9)	N2—C7—C8	123.3 (4)
N2—Cu2—Br2	108.50 (6)	N2—C7—H7A	118.3
N2—Cu2—Br2^v	108.50 (7)	C8—C7—H7A	118.3
Br2—Cu2—Br2^v	115.49 (4)	C7—C8—C9	118.9 (4)
N2—Cu2—Br1	122.79 (14)	C7—C8—H8A	120.6
Br2—Cu2—Br1	100.894 (19)	C9—C8—H8A	120.6
Br2^v—Cu2—Br1	100.894 (19)	C8—C9—C8^vii	118.1 (5)
N2—Cu2—Cu2^v	126.47 (15)	C8—C9—C10	120.8 (2)
Br2—Cu2—Cu2^v	57.744 (18)	C8^vii—C9—C10	120.8 (2)
Br2^v—Cu2—Cu2^v	57.744 (18)	O3—C10—O3^vii	126.7 (5)
Br1—Cu2—Cu2^v	110.74 (4)	O3—C10—C9	116.6 (2)
Cu2^vi—Br1—Cu2	180.0	O3^vii—C10—C9	116.6 (2)
Cu2^vi—Br1—Cu1'^vi	98.6 (4)	C4—N1—C6	117.7 (3)
Cu2—Br1—Cu1'^vi	81.4 (4)	C4—N1—Cu1	122.3 (4)
Cu2^vi—Br1—Cu1'^vii	81.4 (4)	C6—N1—Cu1	119.9 (4)
Cu2—Br1—Cu1'^vii	98.6 (4)	C4—N1—Cu1'	123.7 (5)
Cu2^vi—Br1—Cu1'	81.4 (4)	C6—N1—Cu1'	116.5 (5)
Cu2—Br1—Cu1'	98.6 (4)	C4—N1—Cu1'^iv	117.0 (5)
Cu1'^vi—Br1—Cu1'	180.0 (13)	C6—N1—Cu1'^iv	124.3 (5)
Cu1'^vii—Br1—Cu1'	161.3 (7)	C7—N2—C7^vii	117.2 (4)
Cu2^vi—Br1—Cu1'^iv	98.6 (4)	C7—N2—Cu2	120.8 (2)
Cu2—Br1—Cu1'^iv	81.4 (4)	C7^vii—N2—Cu2	120.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2^x	0.81	1.86	2.667 (3)	175.

10 in total

1. Magnetism of lanthanides in molecular materials with transition-metal ions and organic radicals.

Authors: Cristiano Benelli; Dante Gatteschi
Journal: Chem Rev Date: 2002-06 Impact factor: 60.622

2. Lanthanide complexes in multifunctional asymmetric catalysis.

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Journal: Chem Rev Date: 2002-06 Impact factor: 60.622

3. Coordination polymers containing 1D channels as selective luminescent probes.

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Journal: J Am Chem Soc Date: 2004-12-01 Impact factor: 15.419

4. A cubic 3d-4f structure with only ferromagnetic Gd-Mn interactions.

Authors: Thazhe K Prasad; Melath V Rajasekharan; Jean-Pierre Costes
Journal: Angew Chem Int Ed Engl Date: 2007 Impact factor: 15.336

5. Linking two distinct layered networks of nanosized {Ln18} and {Cu24} wheels through isonicotinate ligands.

Authors: Jian-Wen Cheng; Jie Zhang; Shou-Tian Zheng; Guo-Yu Yang
Journal: Chemistry Date: 2008 Impact factor: 5.236

6. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

7. New 3-D La(III)-Cu(II)-containing coordination polymer with a high potential porosity.

Authors: Olivier Guillou; Carole Daiguebonne; Magatte Camara; Nicolas Kerbellec
Journal: Inorg Chem Date: 2006-10-16 Impact factor: 5.165

8. A sodalite-like framework based on octacyanomolybdate and neodymium with guest methanol molecules and neodymium octahydrate ions.

Authors: Zhao-Xi Wang; Xiao-Fei Shen; Jun Wang; Peng Zhang; Yi-Zhi Li; Emmanuel N Nfor; You Song; Shin-ichi Ohkoshi; Kazuhito Hashimoto; Xiao-Zeng You
Journal: Angew Chem Int Ed Engl Date: 2006-05-12 Impact factor: 15.336

9. Design and synthesis of 3d-4f metal-based zeolite-type materials with a 3D nanotubular structure encapsulated "water" pipe.

Authors: Bin Zhao; Peng Cheng; Xiaoyan Chen; Cai Cheng; Wei Shi; Daizheng Liao; Shiping Yan; Zonghui Jiang
Journal: J Am Chem Soc Date: 2004-03-17 Impact factor: 15.419

10. Nanoporous lanthanide-copper(II) coordination polymers: syntheses and crystal structures of [[M2(Cu3(iminodiacetate)6)].8 H2O]n (M=La, Nd, Eu).

Authors: Yan-Ping Ren; La-Sheng Long; Bing-Wei Mao; You-Zhu Yuan; Rong-Bin Huang; Lan-Sun Zheng
Journal: Angew Chem Int Ed Engl Date: 2003-02-03 Impact factor: 15.336

10 in total

1 in total

1. Poly[tetra-aqua-μ(3)-benzene-1,2-di-carboxyl-ato-μ(3)-bromido-penta-μ(2)-bromido-octa-μ(3)-isonicotinato-hepta-copper(I)trilanthanum(III)].

Authors: Guo-Ming Wang; Zeng-Xin Li; Shu-Yun Xue; Hui-Luan Liu
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2009-04-22

1 in total