Poly[tetra­aqua-μ4-bromido-di-μ2-bromido-μ2-hydroxido-di-μ3-iso­nicotinato-tetra-μ2-isonicotinato-tetra­copper(I)dithulium(III)]

Wang, G.-M.; Li, Z.-X.; Zheng, Q.-H.; Liu, H.-L.

doi:10.1107/S1600536808028675

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1260-m1261

doi:10.1107/S1600536808028675

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Poly[tetraaqua-μ₄-bromido-di-μ₂-bromido-μ₂-hydroxido-di-μ₃-isonicotinato-tetra-μ₂-isonicotinato-tetracopper(I)dithulium(III)]

Guo-Ming Wang,^a ^* Zeng-Xin Li,^a Qing-Hua Zheng ^a and Hui-Luan Liu ^a

^aDepartment of Chemistry, Teachers College of Qingdao University, Qingdao, Shandong 266071, People's Republic of China
^*Correspondence e-mail: gmwang_pub@163.com

(Received 1 September 2008; accepted 8 September 2008; online 13 September 2008)

A new thulium(III)–copper(I) heterometallic coordination polymer, [Cu₄Tm₂Br₃(C₆H₄NO₂)₆(OH)(H₂O)₄]_n, has been prepared by a hydrothermal 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 CuBrN₂ and tetrahedral CuBr₃N 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 [Tm₂(μ₂-OH(IN)₆(H₂O)₄] cores (IN = isonicotinate) and one-dimensional inorganic [Cu₄Br₃]_n chains, which are linked together, forming heterometallic Cu–halide–lanthanide–organic layers.

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_r = 1653.43
Orthorhombic, C m c m
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[F² > 2σ(F²)] = 0.027
wR(F²) = 0.064
S = 1.11
2408 reflections
179 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028675/sj2536sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028675/sj2536Isup2.hkl

checkCIF report

Comment top

The rational design and synthesis of heterometallic lanthanide(Ln)–transition metal(TM) compounds have attracted increasing attention in recent years, not only because of their intriguing variety of architectures and topologies but also owing to their potential applications in luminescence, magnetism, bimetallic catalysis, and molecular adsorption. (Benelli & Gatteschi, 2002; Shibasaki & Yoshikawa, 2002; Zhao et al., 2004a,b; Guillou et al., 2006; Wang et al., 2006). So far, most work has been focused on the assembly of homometallic Ln and TM compounds, while the construction of heterometallic Ln–TM extented architectures is still a challenge (Ren et al., 2003; Prasad et al., 2007; Cheng et al., 2008). This may be attributed to the different competitive reactions of Ln and TM metals with the same ligand, which often results in the formation of the homometallic compounds rather than heterometallic ones. Generally, the Ln ions prefer O-donors, while TM ions have stronger tendency to coordinate to N-donors. Therefore, isonicotinic acid (HIN) has been chosen here as the multifunctional bridging ligand to construct new hetero-Ln–TM complexes. The title compound [Tm₂Cu₄Br₃(µ2-OH)(C₆H₄NO₂)₆(H₂O)₄]_n (1) is reported here and displays novel two-dimensional coordination features.

In the asymmetric unit, the Tm1 atom, occupying a special position on a mirror plane (Fig. 1), is seven-coordinated and has a capped trigonal–prismatic coordination environment comprising two coordinated water molecules, one µ₂-OH and four carboxylate oxygen atoms from four IN^- ligands. The Tm—O bond lengths range from 2.193 (2) to 2.449 (5) Å. Both Cu1 and Cu2 atoms occupy special positions on two crystallographic mirror planes, one perpendicular (z = 0) and the other parallel to the c axis. The Cu1 atom is three-coordinate with one µ₄-Br1 and two N atoms from two bridging IN^- moieties, while the Cu2 center is coordinated to one µ₄-Br1, two µ₂-Br2 atoms and one N atom from one IN^- ligand that defines a distorted tetrahedral geometry. The Cu—N and Cu—Br distances are in the range 1.928 (3)–2.020 (4) Å and 2.518 (9)–2.688 (7) Å, respectively. Although copper(II) salts were used as starting materials, the Cu centers in the product are in the +1 oxidation state. This is attributed to a reduction reaction occurring under the hydrothermal conditions used.

The framework of 1 is constructed from two subunits, dimeric [Tm₂(µ₂-OH)(IN^-)₆] (Tm₂) cores and inorganic [Cu₄Br₃]_n chains. As shown in Fig. 2, two crystallographically identical Tm(III) ions are linked by one bridging hydroxo group and six IN^- ligands to form the dimeric Tm₂ fragment, in which the IN^- ligand adopts two different coordination modes. The Tm···Tm distance is 4.071 (1) Å. The Cu(I) centers, however, are bridged by µ₄-Br and µ₂-Br atoms to form one-dimensional inorganic [Cu₄Br₃]_n chains (Fig. 3). Interestingly, such one-dimensional copper halide chains appear to be constructed directly from corner- and edge-sharing tetrahedral Cu(2)Br₃N units, decorated by the trigonal Cu(1)BrN₂ groups protruding outside the chain. In addition, the Cu···Cu distance within the copper(I) halide chains is 2.688 (7) Å, less than twice the van der Waals radius of the Cu(I) ion (1.4) Å), indicating a strong Cu···Cu interaction. The linkages between dimeric Tm₂ and inorganic [Cu₄Br₃]_n motifs through N—Cu bonds give rise to a novel two-dimensional hetero-Tm—Cu framework (Fig. 4). Adjacent sheets are further packed to form a three-dimensional supramolecular framework through O—H···O hydrogen bonds.

Related literature top

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 top

The title compound was synthesized under mild hydrothermal conditions. Typically, a mixture of Tm₂O₃ (0.5 mmol, 0.193 g), CuBr₂ (0.089 g, 0.40 mmol), HIN (2.00 mmol, 0.247 g) and H₂O (8 ml) was sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 8 days. The yellow block-like crystals obtained were recovered by filtration, washed with distilled water and dried in air.

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of 1, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, y, z; (ii) x, y, 1/2 - z; (iii) x, 1 - y, 1 - z; (iv) x, 1 - y, -1/2 + z; (v) x, 2 - y, 1 - z; (vi) -x, 1 - y, 1 - z].
	Fig. 2. Dimeric [Tm₂(µ2-OH)(IN)₆] fragment and the coordination modes of IN^- found in 1.
	Fig. 3. One-dimensional infinite [Cu₄Br₃]_n chains along b axis (a), and polyhedral view of the [Cu₄Br₃N₆]_n chains. [Symmetry codes: (i) -x, 2 - y, 1 - z; (ii) x, 1 - y, 1 - z; (iii) -x, 1 - y, 1 - z; (iv) x, -1 + y, z].
	Fig. 4. View of the two-dimensional layer structure of 1.

Poly[tetraaqua-µ₄-bromido-di-µ₂-bromido-µ₂-hydroxido-di-µ₃- isonicotinato-tetra-µ₂-isonicotinato-tetracopper(I)dithulium(III)] top

Crystal data top

[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

Data collection top

Bruker APEXII area-detector diffractometer	2408 independent reflections
Radiation source: fine-focus sealed tube	2090 reflections with I > 2σ(I)
Graphite monochromator	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 top

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)

Crystal data top

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

Data collection top

Bruker APEXII area-detector diffractometer	2408 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2090 reflections with I > 2σ(I)
T_min = 0.341, T_max = 0.547	R_int = 0.037
17231 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	6 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0288P)² + 11.1134P] where P = (F_o² + 2F_c²)/3
2408 reflections	Δρ_max = 0.83 e Å⁻³
179 parameters	Δρ_min = −0.87 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) x, −y+1, −z+1; (ii) x, −y+1, z−1/2; (iii) x, y, −z+1/2; (iv) x, −y+2, −z+1; (v) −x, −y+1, −z+1; (vi) −x, −y+2, −z+1; (vii) −x, y, z; (viii) x, −y+1, z+1/2; (ix) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (x) −x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₄Tm₂Br₃(C₆H₄NO₂)₆(OH)(H₂O)₄]
M_r	1653.43
Crystal system, space group	Orthorhombic, Cmcm
Temperature (K)	295
a, b, c (Å)	19.1815 (2), 6.6973 (4), 34.7044 (5)
V (Å³)	4458.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.58
Crystal size (mm)	0.16 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.341, 0.547
No. of measured, independent and observed [I > 2σ(I)] reflections	17231, 2408, 2090
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.11
No. of reflections	2408
No. of parameters	179
No. of restraints	6
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0288P)² + 11.1134P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.87

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱ	0.81	1.86	2.667 (3)	174.5

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Acknowledgements

This work was supported by the Qingdao University Research Fund (No. 063-06300522).

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