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

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.027
• wR factor = 0.065
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br1    --  Cu2     ..      28.32 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br2    --  Cu2     ..      28.36 su
PLAT416_ALERT_2_B Short Intra D-H..H-D       H6B    ..  H6C     ..       1.41 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O4     -  *H4     ...          ?

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Tm1
PLAT301_ALERT_3_C Main Residue  Disorder .........................       3.00 Perc.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H5     ..  H6C     ..       2.13 Ang.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        CU1
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .         H4

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.920
            Tmax scaled      0.503 Tmin scaled      0.313
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions, with C—H distances of 0.93 Å. All other H atoms were located in a difference Fourier map and treated as riding, with fixed U_iso(H) = 1.2U_eq(O). The H4 and H6C atoms lie close to a mirror plane, and were treated as disordered with constrained site occupancy factors of 0.25 and 0.5, respectively. Atom Cu1 was refined as disordered over two positions, each with 50% site occupancy.

Computing details

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

	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)]

Crystal data

[Cu4Tm2Br3(C6H4NO2)6(OH)(H2O)4]	F(000) = 3144
Mr = 1653.43	Dx = 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) Å^3	Block, yellow
Z = 4	0.16 × 0.09 × 0.08 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0288P)^2 + 11.1134P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2408 reflections	Δρmax = 0.83 e Å^−3
179 parameters	Δρmin = −0.87 e Å^−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00119 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Tm1—O4	2.197 (2)	O3—C10	1.243 (3)
Tm1—O1^i	2.208 (2)	O4—Tm1^ix	2.197 (2)
Tm1—O1^ii	2.208 (2)	O4—H4	1.0867
Tm1—O5	2.284 (4)	O5—H5	0.8127
Tm1—O3^iii	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—O1^i	109.97 (10)	Cu1'^vi—Br1—Cu1'^iv	161.3 (7)
O4—Tm1—O1^ii	109.97 (10)	Cu1'^vii—Br1—Cu1'^iv	180.000 (4)
O1^i—Tm1—O1^ii	113.85 (14)	Cu2^vi—Br1—Cu1^vi	90.0
O4—Tm1—O5	159.04 (17)	Cu2—Br1—Cu1^vi	90.000 (2)
O1^i—Tm1—O5	80.41 (9)	Cu1'—Br1—Cu1^vi	170.7 (3)
O1^ii—Tm1—O5	80.41 (9)	Cu1'^iv—Br1—Cu1^vi	170.7 (3)
O4—Tm1—O3^iii	83.02 (12)	Cu2^vi—Br1—Cu1	90.000 (2)
O1^i—Tm1—O3^iii	154.05 (11)	Cu2—Br1—Cu1	90.0
O1^ii—Tm1—O3^iii	80.34 (10)	Cu1'^vi—Br1—Cu1	170.7 (3)
O5—Tm1—O3^iii	80.85 (11)	Cu1'^vii—Br1—Cu1	170.7 (3)
O4—Tm1—O3	83.02 (12)	Cu1^vi—Br1—Cu1	180.000 (1)
O1^i—Tm1—O3	80.34 (10)	Cu2—Br2—Cu2^v	64.51 (4)
O1^ii—Tm1—O3	154.05 (11)	C1—O1—Tm1^viii	154.2 (3)
O5—Tm1—O3	80.85 (11)	C10—O3—Tm1	139.8 (3)
O3^iii—Tm1—O3	79.09 (15)	Tm1—O4—Tm1^ix	135.8 (3)
O4—Tm1—O6	72.25 (17)	Tm1—O4—H4	110.9
O1^i—Tm1—O6	72.46 (9)	Tm1^ix—O4—H4	110.9
O1^ii—Tm1—O6	72.46 (9)	Tm1—O5—H5	120.2
O5—Tm1—O6	128.71 (15)	Tm1—O6—H6B	60.9
O3^iii—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)
O1^i—Tm1—H6B	64.0	O2—C1—C2	117.9 (3)
O1^ii—Tm1—H6B	64.0	O1—C1—C2	115.9 (3)
O5—Tm1—H6B	108.8	C5—C2—C3	118.0 (3)
O3^iii—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)

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.