catena-Poly[[bis­(μ-3-carboxy­benzoato)bis­(1,10-phenanthroline)tricopper(II)]-di-μ3-isophthalato]

An, Y.; Li, X.-F.; Dong, L.-H.; Yin, Y.-S.

doi:10.1107/S1600536808036908

catena-Poly[[bis(μ-3-carboxybenzoato)bis(1,10-phenanthroline)tricopper(II)]-di-μ₃-isophthalato]

Y. An, X.-F. Li, L.-H. Dong and Y.-S. Yin

The title copper coordination polymer, [Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]_n, was synthesized by reacting Cu(NO₃)₂, isophthalic acid and 1,10-phenanthroline under hydrothermal conditions. The trinuclear unit presents a central almost planar CuO₄ chromophore with the cation on a symmetry center, and two symmetry-related CuN₂O₃ groups with the metal centre in a distorted square-pyramidal environment. These units are bridged by isophthalate ligands into one-dimensional double-chain coordination polymers which are, in turn, connected by various π–π stacking interactions (face-to-face distance ca 3.45 Å) and O—H

O hydrogen bonds, forming a three-dimensional supramolecular network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808036908/bg2210sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808036908/bg2210Isup2.hkl Contains datablock I

CCDC reference: 712320

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.031
wR factor = 0.089
Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    --  O5      ..       7.28 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    --  N1      ..       6.13 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    --  N2      ..       5.52 su
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.

Alert level G
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          6
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 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

Comment top

The design and construction of coordination polymers has attracted much attention owing to their intriguing topologies and potential applications as functional materials (Han et al., 2008, Ma et al., 2007). Many networks with various structural motifs have been documented in the past decade (Amabilino et al., 1995). Unlike pyridine 2,4-, 3,4- 2,5- and 2,6-dicarboxylic acids which were widely reported as bridging ligands to assemble various coordination polymers, isophthalic acid (H₂ip) has been reported only scarcely in the role of multicarboxylate ligand (Han et al., 2007). We report here the synthesis and structure of the title copper(II) coordination polymer [Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)]_n,assembled from isophthalic acid, 1,10-phenanthroline(phen) and copper(II), (I).

In I, there is one and a half Cu(II) ions (Cu1 lies on center of symmetry), one ip, one Hip and one phen ligand in each independent crystallographic unit. Each Cu2 ion is coordinated by three oxygen atoms from two ip ligands and one Hip ligand in a mono-bidentate and bidentate coordination modes and two nitrogen atoms from a chelate phen ligand to furnish a distorted square pyramidal geometry. On the other hand, each Cu1 atom is four-coordinated by four oxygen atoms, forming a slightly distorted square geometry. (Fig.1 and Table 1).

The carboxylate oxygen atoms bridge three copper atoms (Cu2, Cu1 and Cu2ⁱ) via the syn–anti O,O-bridges to form a trinuclear [Cu₃(ip)₂(Hip)₂(phen)₂] subunit (Fig. 1), which are interconnected through the bridging ip groups to form an infinite one-dimensional double chain with Cu···Cu distances of 3.755 (3) and 9.994 (3) Å (Fig. 2). The lateral phen ligands from adjacent double-chains are paired to furnish moderately strong π—π stacking interactions (face-face distance ca 3.45 (1) Å) (He et al.,2007, Han et al., 2005), which extend the double-chains into two-dimensional wavelike layers parallel to the ab plane in the lattice. These layers are further linked via strong hydrogen bonds between uncoordinated carboxylate oxygen atoms of ip ligands (Table 2), forming a three-dimensional supramolecular network.

Related literature top

For related literature on the design and construction of coordination polymers, see: Amabilino & Stoddart (1995); Han et al. (2005, 2007, 2008); He & Han (2007); Ma et al. (2007).

Experimental top

A mixture of Cu(NO₃)₂.2H₂O (0.5 mmol, 0.120 g), isophthalic acid (0.5 mmol, 0.084 g), NaOH (1 mmol, 0.04 g), and water (10 ml) was mixed in a 23 ml Teflon reactor, which was heated at 453 K for six days and then cooled to room temperature at a rate of 5 K h^-1. Yield: 48%. CH&N analysis for C₂₀H₁₇N₂O₈Cu_1.5 (found/calc): C, 47.05(47.22), H, 2.64(3.37), N, 5.73%(5.51%).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. A trinuclear [Cu₃(ip)₂(Hip)₂(phen)₂] subunit with thermal ellipsoids at 30% probability. Symmetry transformations used to generate equivalent atoms: (i) -x+1,-y,-z+1; (ii) -x+1,-y,-z+2; (iii) x,y,z-1.
	Fig. 2. Packing view of I drawn along c and depicting the double chain fragment.

catena-Poly[[bis(µ-3-carboxybenzoato)bis(1,10-phenanthroline)tricopper(II)]- di-µ₃-isophthalato] top

Crystal data top

[Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]	Z = 1
M_r = 1209.5	F(000) = 613
Triclinic, P1	D_x = 1.644 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.383 (1) Å	Cell parameters from 2356 reflections
b = 10.659 (1) Å	θ = 2.3–25.0°
c = 11.754 (1) Å	µ = 1.38 mm⁻¹
α = 83.147 (1)°	T = 293 K
β = 86.191 (1)°	Block, green
γ = 71.134 (1)°	0.37 × 0.32 × 0.23 mm
V = 1221.6 (2) Å³

Data collection top

Bruker SMART APEX area-detector diffractometer	4741 independent reflections
Radiation source: fine-focus sealed tube	4241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.631, T_max = 0.738	k = −13→13
9575 measured reflections	l = −12→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0453P)² + 0.1215P] where P = (F_o² + 2F_c²)/3
4741 reflections	(Δ/σ)_max = 0.001
358 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]	γ = 71.134 (1)°
M_r = 1209.5	V = 1221.6 (2) Å³
Triclinic, P1	Z = 1
a = 10.383 (1) Å	Mo Kα radiation
b = 10.659 (1) Å	µ = 1.38 mm⁻¹
c = 11.754 (1) Å	T = 293 K
α = 83.147 (1)°	0.37 × 0.32 × 0.23 mm
β = 86.191 (1)°

Data collection top

Bruker SMART APEX area-detector diffractometer	4741 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4241 reflections with I > 2σ(I)
T_min = 0.631, T_max = 0.738	R_int = 0.063
9575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.09	Δρ_max = 0.43 e Å⁻³
4741 reflections	Δρ_min = −0.35 e Å⁻³
358 parameters

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
Cu1	0.5000	0.0000	0.5000	0.02502 (10)
Cu2	0.76902 (2)	−0.22278 (2)	0.697826 (19)	0.03033 (10)
C1	0.57791 (19)	0.04808 (18)	0.70129 (16)	0.0290 (4)
C2	0.57869 (19)	0.09529 (18)	0.81581 (16)	0.0281 (4)
C3	0.7018 (2)	0.0843 (2)	0.86308 (19)	0.0404 (5)
H3	0.7831	0.0514	0.8219	0.048*
C4	0.7030 (2)	0.1222 (3)	0.9707 (2)	0.0493 (6)
H4	0.7852	0.1171	1.0012	0.059*
C5	0.5830 (2)	0.1680 (2)	1.03389 (18)	0.0402 (5)
H5	0.5850	0.1920	1.1071	0.048*
C6	0.46010 (18)	0.17821 (17)	0.98864 (16)	0.0278 (4)
C7	0.45796 (18)	0.14417 (17)	0.87873 (16)	0.0268 (4)
H7	0.3752	0.1541	0.8468	0.032*
C8	0.3300 (2)	0.22144 (19)	1.06009 (16)	0.0316 (4)
C9	0.47836 (18)	−0.22297 (18)	0.61761 (15)	0.0280 (4)
C10	0.41202 (18)	−0.30677 (18)	0.69616 (16)	0.0282 (4)
C11	0.4890 (2)	−0.4306 (2)	0.74662 (19)	0.0376 (5)
H11	0.5811	−0.4645	0.7271	0.045*
C12	0.4301 (2)	−0.5038 (2)	0.8255 (2)	0.0470 (6)
H12	0.4824	−0.5871	0.8582	0.056*
C13	0.2936 (2)	−0.4538 (2)	0.8561 (2)	0.0419 (5)
H13	0.2541	−0.5030	0.9096	0.050*
C14	0.21559 (19)	−0.32961 (19)	0.80667 (16)	0.0315 (4)
C15	0.27491 (18)	−0.25778 (19)	0.72611 (16)	0.0287 (4)
H15	0.2221	−0.1757	0.6917	0.034*
C16	0.0685 (2)	−0.2698 (2)	0.83842 (17)	0.0358 (4)
C17	0.9058 (2)	−0.1207 (2)	0.48733 (18)	0.0392 (5)
H17	0.8308	−0.0438	0.4813	0.047*
C18	1.0192 (2)	−0.1282 (3)	0.4132 (2)	0.0484 (6)
H18	1.0188	−0.0570	0.3590	0.058*
C19	1.1296 (2)	−0.2400 (3)	0.4213 (2)	0.0512 (6)
H19	1.2060	−0.2444	0.3739	0.061*
C20	1.1287 (2)	−0.3489 (2)	0.5008 (2)	0.0435 (5)
C21	1.2363 (2)	−0.4740 (3)	0.5150 (2)	0.0554 (7)
H21	1.3160	−0.4853	0.4705	0.067*
C22	1.2253 (2)	−0.5748 (3)	0.5903 (2)	0.0536 (7)
H22	1.2964	−0.6550	0.5957	0.064*
C23	1.1066 (2)	−0.5616 (2)	0.6627 (2)	0.0451 (6)
C24	1.0861 (3)	−0.6618 (2)	0.7445 (2)	0.0533 (6)
H24	1.1520	−0.7454	0.7528	0.064*
C25	0.9713 (3)	−0.6371 (2)	0.8110 (2)	0.0554 (7)
H25	0.9574	−0.7037	0.8643	0.066*
C26	0.8730 (3)	−0.5104 (2)	0.7994 (2)	0.0435 (5)
H26	0.7956	−0.4937	0.8471	0.052*
C27	1.00094 (19)	−0.4393 (2)	0.65414 (18)	0.0348 (4)
C28	1.01068 (19)	−0.3337 (2)	0.57116 (17)	0.0334 (4)
N1	0.90243 (16)	−0.22039 (16)	0.56575 (14)	0.0318 (4)
N2	0.88699 (17)	−0.41398 (17)	0.72270 (14)	0.0345 (4)
O1	0.68897 (14)	−0.03047 (14)	0.66264 (12)	0.0370 (3)
O2	0.47142 (14)	0.08815 (14)	0.64570 (11)	0.0363 (3)
O3	0.34517 (15)	0.22533 (15)	1.16551 (12)	0.0386 (3)
O4	0.22068 (15)	0.25058 (19)	1.01149 (13)	0.0511 (4)
O5	0.60479 (13)	−0.26213 (14)	0.60173 (12)	0.0346 (3)
O6	0.40038 (13)	−0.11313 (13)	0.57278 (12)	0.0352 (3)
O7	0.02655 (15)	−0.34182 (18)	0.92198 (14)	0.0495 (4)
H7A	−0.0540	−0.3045	0.9375	0.074*
O8	−0.00380 (15)	−0.16831 (17)	0.78902 (15)	0.0524 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02711 (17)	0.02716 (17)	0.01884 (17)	−0.00744 (13)	0.00295 (12)	−0.00007 (12)
Cu2	0.03051 (15)	0.03137 (15)	0.02253 (14)	−0.00187 (10)	0.00550 (10)	−0.00313 (10)
C1	0.0350 (10)	0.0269 (9)	0.0239 (9)	−0.0098 (8)	0.0072 (8)	−0.0022 (7)
C2	0.0332 (10)	0.0256 (9)	0.0233 (9)	−0.0073 (7)	0.0041 (7)	−0.0027 (7)
C3	0.0300 (10)	0.0534 (13)	0.0360 (11)	−0.0096 (9)	0.0087 (8)	−0.0137 (10)
C4	0.0313 (11)	0.0773 (17)	0.0428 (13)	−0.0178 (11)	0.0010 (9)	−0.0201 (12)
C5	0.0427 (12)	0.0531 (13)	0.0272 (11)	−0.0156 (10)	0.0017 (9)	−0.0143 (9)
C6	0.0324 (9)	0.0240 (8)	0.0244 (9)	−0.0072 (7)	0.0063 (7)	−0.0019 (7)
C7	0.0287 (9)	0.0254 (9)	0.0236 (9)	−0.0064 (7)	0.0017 (7)	0.0000 (7)
C8	0.0367 (10)	0.0292 (9)	0.0256 (10)	−0.0084 (8)	0.0083 (8)	−0.0014 (8)
C9	0.0328 (10)	0.0300 (9)	0.0229 (9)	−0.0120 (8)	0.0034 (7)	−0.0057 (7)
C10	0.0307 (9)	0.0292 (9)	0.0261 (9)	−0.0118 (8)	0.0020 (7)	−0.0035 (7)
C11	0.0293 (10)	0.0335 (10)	0.0447 (12)	−0.0058 (8)	0.0044 (9)	0.0019 (9)
C12	0.0408 (12)	0.0332 (11)	0.0579 (15)	−0.0059 (9)	0.0016 (10)	0.0124 (10)
C13	0.0416 (11)	0.0403 (11)	0.0437 (13)	−0.0181 (9)	0.0045 (10)	0.0073 (9)
C14	0.0315 (10)	0.0371 (10)	0.0286 (10)	−0.0148 (8)	0.0012 (8)	−0.0042 (8)
C15	0.0295 (9)	0.0299 (9)	0.0258 (9)	−0.0087 (7)	0.0001 (7)	−0.0016 (7)
C16	0.0318 (10)	0.0483 (12)	0.0290 (10)	−0.0154 (9)	0.0015 (8)	−0.0050 (9)
C17	0.0418 (11)	0.0409 (11)	0.0333 (11)	−0.0121 (9)	0.0054 (9)	−0.0052 (9)
C18	0.0521 (14)	0.0549 (14)	0.0419 (13)	−0.0237 (11)	0.0148 (11)	−0.0100 (11)
C19	0.0429 (13)	0.0716 (17)	0.0460 (14)	−0.0258 (12)	0.0184 (11)	−0.0227 (12)
C20	0.0322 (11)	0.0585 (14)	0.0417 (12)	−0.0116 (10)	0.0052 (9)	−0.0240 (11)
C21	0.0298 (11)	0.0708 (17)	0.0608 (16)	−0.0020 (11)	0.0083 (11)	−0.0329 (14)
C22	0.0359 (12)	0.0541 (15)	0.0596 (16)	0.0092 (11)	−0.0062 (11)	−0.0264 (13)
C23	0.0415 (12)	0.0417 (12)	0.0465 (13)	0.0019 (10)	−0.0133 (10)	−0.0183 (10)
C24	0.0591 (15)	0.0371 (12)	0.0533 (15)	0.0052 (11)	−0.0219 (13)	−0.0109 (11)
C25	0.0806 (19)	0.0386 (12)	0.0422 (14)	−0.0110 (12)	−0.0198 (13)	0.0021 (10)
C26	0.0534 (13)	0.0417 (12)	0.0312 (11)	−0.0092 (10)	−0.0035 (10)	−0.0026 (9)
C27	0.0295 (10)	0.0385 (11)	0.0329 (11)	−0.0020 (8)	−0.0058 (8)	−0.0124 (8)
C28	0.0256 (9)	0.0413 (11)	0.0325 (10)	−0.0056 (8)	0.0001 (8)	−0.0151 (9)
N1	0.0282 (8)	0.0355 (9)	0.0305 (9)	−0.0069 (7)	0.0037 (7)	−0.0099 (7)
N2	0.0363 (9)	0.0350 (9)	0.0285 (9)	−0.0054 (7)	−0.0022 (7)	−0.0052 (7)
O1	0.0430 (8)	0.0321 (7)	0.0273 (7)	−0.0019 (6)	0.0116 (6)	−0.0055 (6)
O2	0.0366 (7)	0.0459 (8)	0.0253 (7)	−0.0103 (6)	0.0030 (6)	−0.0096 (6)
O3	0.0442 (8)	0.0455 (8)	0.0239 (7)	−0.0119 (7)	0.0103 (6)	−0.0078 (6)
O4	0.0315 (8)	0.0806 (12)	0.0331 (8)	−0.0077 (8)	0.0078 (7)	−0.0072 (8)
O5	0.0279 (7)	0.0439 (8)	0.0324 (8)	−0.0122 (6)	0.0072 (6)	−0.0075 (6)
O6	0.0332 (7)	0.0342 (7)	0.0350 (8)	−0.0104 (6)	0.0052 (6)	0.0047 (6)
O7	0.0308 (7)	0.0736 (11)	0.0401 (9)	−0.0171 (7)	0.0085 (6)	0.0055 (8)
O8	0.0360 (8)	0.0567 (10)	0.0538 (10)	−0.0048 (7)	0.0072 (8)	0.0032 (8)

Geometric parameters (Å, º) top

Cu1—O6	1.923 (1)	C13—C14	1.390 (3)
Cu1—O2ⁱ	2.010 (1)	C13—H13	0.93
Cu1—O2	2.010 (1)	C14—C15	1.384 (3)
Cu2—O3ⁱⁱ	1.935 (1)	C14—C16	1.493 (3)
Cu2—O1	1.951 (1)	C15—H15	0.93
Cu2—N2	2.008 (2)	C16—O8	1.205 (3)
Cu2—N1	2.014 (2)	C16—O7	1.313 (3)
Cu2—O5	2.278 (1)	C17—N1	1.328 (3)
C1—O2	1.247 (2)	C17—C18	1.404 (3)
C1—O1	1.278 (2)	C17—H17	0.93
C1—C2	1.494 (3)	C18—C19	1.360 (3)
C2—C7	1.391 (2)	C18—H18	0.93
C2—C3	1.392 (3)	C19—C20	1.403 (4)
C3—C4	1.375 (3)	C19—H19	0.93
C3—H3	0.93	C20—C28	1.407 (3)
C4—C5	1.383 (3)	C20—C21	1.436 (3)
C4—H4	0.9300	C21—C22	1.337 (4)
C5—C6	1.382 (3)	C21—H21	0.93
C5—H5	0.93	C22—C23	1.429 (4)
C6—C7	1.386 (3)	C22—H22	0.93
C6—C8	1.510 (2)	C23—C27	1.404 (3)
C7—H7	0.93	C23—C24	1.409 (4)
C8—O4	1.236 (2)	C24—C25	1.351 (4)
C8—O3	1.266 (2)	C24—H24	0.93
C9—O5	1.251 (2)	C25—C26	1.402 (3)
C9—O6	1.265 (2)	C25—H25	0.93
C9—C10	1.497 (3)	C26—N2	1.322 (3)
C10—C15	1.386 (2)	C26—H26	0.93
C10—C11	1.388 (3)	C27—N2	1.357 (3)
C11—C12	1.380 (3)	C27—C28	1.424 (3)
C11—H11	0.9300	C28—N1	1.356 (2)
C12—C13	1.383 (3)	O3—Cu2ⁱⁱ	1.9349 (14)
C12—H12	0.9300	O7—H7A	0.82

O6—Cu1—O2ⁱ	92.30 (6)	C14—C15—C10	120.78 (17)
O6ⁱ—Cu1—O2	92.30 (6)	C14—C15—H15	119.6
O6—Cu1—O2	87.70 (6)	C10—C15—H15	119.6
O3ⁱⁱ—Cu2—O1	92.66 (6)	O8—C16—O7	124.33 (19)
O3ⁱⁱ—Cu2—N2	96.52 (7)	O8—C16—C14	122.77 (19)
O1—Cu2—N2	168.29 (7)	O7—C16—C14	112.85 (18)
O3ⁱⁱ—Cu2—N1	174.37 (6)	N1—C17—C18	122.0 (2)
O1—Cu2—N1	88.24 (6)	N1—C17—H17	119.0
N2—Cu2—N1	81.94 (7)	C18—C17—H17	119.0
O3ⁱⁱ—Cu2—O5	87.08 (6)	C19—C18—C17	119.6 (2)
O1—Cu2—O5	91.79 (6)	C19—C18—H18	120.2
N2—Cu2—O5	95.92 (6)	C17—C18—H18	120.2
N1—Cu2—O5	98.46 (6)	C18—C19—C20	120.2 (2)
O2—C1—O1	122.29 (17)	C18—C19—H19	119.9
O2—C1—C2	119.67 (16)	C20—C19—H19	119.9
O1—C1—C2	118.02 (17)	C19—C20—C28	116.6 (2)
C7—C2—C3	119.32 (17)	C19—C20—C21	125.7 (2)
C7—C2—C1	120.71 (17)	C28—C20—C21	117.8 (2)
C3—C2—C1	119.89 (17)	C22—C21—C20	121.9 (2)
C4—C3—C2	119.93 (18)	C22—C21—H21	119.0
C4—C3—H3	120.0	C20—C21—H21	119.0
C2—C3—H3	120.0	C21—C22—C23	121.3 (2)
C3—C4—C5	120.5 (2)	C21—C22—H22	119.3
C3—C4—H4	119.7	C23—C22—H22	119.3
C5—C4—H4	119.7	C27—C23—C24	116.2 (2)
C6—C5—C4	120.24 (19)	C27—C23—C22	118.5 (2)
C6—C5—H5	119.9	C24—C23—C22	125.3 (2)
C4—C5—H5	119.9	C25—C24—C23	120.3 (2)
C5—C6—C7	119.43 (17)	C25—C24—H24	119.8
C5—C6—C8	120.12 (17)	C23—C24—H24	119.8
C7—C6—C8	120.41 (17)	C24—C25—C26	119.6 (2)
C6—C7—C2	120.50 (18)	C24—C25—H25	120.2
C6—C7—H7	119.7	C26—C25—H25	120.2
C2—C7—H7	119.7	N2—C26—C25	122.1 (2)
O4—C8—O3	126.40 (18)	N2—C26—H26	118.9
O4—C8—C6	118.12 (17)	C25—C26—H26	118.9
O3—C8—C6	115.48 (18)	N2—C27—C23	123.3 (2)
O5—C9—O6	123.92 (17)	N2—C27—C28	116.57 (17)
O5—C9—C10	119.67 (17)	C23—C27—C28	120.1 (2)
O6—C9—C10	116.40 (15)	N1—C28—C20	123.2 (2)
C15—C10—C11	118.97 (17)	N1—C28—C27	116.50 (17)
C15—C10—C9	120.43 (16)	C20—C28—C27	120.31 (19)
C11—C10—C9	120.43 (16)	C17—N1—C28	118.42 (17)
C12—C11—C10	120.60 (18)	C17—N1—Cu2	129.29 (14)
C12—C11—H11	119.7	C28—N1—Cu2	111.69 (14)
C10—C11—H11	119.7	C26—N2—C27	118.37 (18)
C11—C12—C13	120.21 (19)	C26—N2—Cu2	129.40 (15)
C11—C12—H12	119.9	C27—N2—Cu2	112.03 (14)
C13—C12—H12	119.9	C1—O1—Cu2	129.14 (13)
C12—C13—C14	119.75 (19)	C1—O2—Cu1	110.19 (11)
C12—C13—H13	120.1	C8—O3—Cu2ⁱⁱ	134.22 (14)
C14—C13—H13	120.1	C9—O5—Cu2	129.50 (12)
C15—C14—C13	119.68 (18)	C9—O6—Cu1	112.10 (11)
C15—C14—C16	118.41 (18)	C16—O7—H7A	109.5
C13—C14—C16	121.91 (18)

O2—C1—C2—C7	22.0 (3)	C19—C20—C28—C27	179.90 (19)
O1—C1—C2—C7	−159.56 (17)	C21—C20—C28—C27	0.7 (3)
O2—C1—C2—C3	−161.19 (19)	N2—C27—C28—N1	−2.8 (3)
O1—C1—C2—C3	17.2 (3)	C23—C27—C28—N1	177.86 (17)
C7—C2—C3—C4	−0.3 (3)	N2—C27—C28—C20	176.54 (18)
C1—C2—C3—C4	−177.1 (2)	C23—C27—C28—C20	−2.8 (3)
C2—C3—C4—C5	1.7 (4)	C18—C17—N1—C28	−2.1 (3)
C3—C4—C5—C6	−1.1 (4)	C18—C17—N1—Cu2	168.21 (16)
C4—C5—C6—C7	−1.0 (3)	C20—C28—N1—C17	2.6 (3)
C4—C5—C6—C8	176.8 (2)	C27—C28—N1—C17	−178.15 (18)
C5—C6—C7—C2	2.4 (3)	C20—C28—N1—Cu2	−169.34 (16)
C8—C6—C7—C2	−175.41 (16)	C27—C28—N1—Cu2	9.9 (2)
C3—C2—C7—C6	−1.8 (3)	O1—Cu2—N1—C17	−7.31 (18)
C1—C2—C7—C6	174.98 (16)	N2—Cu2—N1—C17	179.07 (19)
C5—C6—C8—O4	168.3 (2)	O5—Cu2—N1—C17	84.24 (18)
C7—C6—C8—O4	−13.9 (3)	O1—Cu2—N1—C28	163.50 (13)
C5—C6—C8—O3	−11.0 (3)	N2—Cu2—N1—C28	−10.12 (13)
C7—C6—C8—O3	166.82 (17)	O5—Cu2—N1—C28	−104.95 (13)
O5—C9—C10—C15	171.84 (17)	C25—C26—N2—C27	−0.5 (3)
O6—C9—C10—C15	−6.6 (3)	C25—C26—N2—Cu2	−174.86 (16)
O5—C9—C10—C11	−3.4 (3)	C23—C27—N2—C26	−1.9 (3)
O6—C9—C10—C11	178.12 (18)	C28—C27—N2—C26	178.76 (19)
C15—C10—C11—C12	−0.1 (3)	C23—C27—N2—Cu2	173.43 (15)
C9—C10—C11—C12	175.2 (2)	C28—C27—N2—Cu2	−5.9 (2)
C10—C11—C12—C13	−0.7 (4)	O3ⁱⁱ—Cu2—N2—C26	8.8 (2)
C11—C12—C13—C14	0.3 (4)	O1—Cu2—N2—C26	150.2 (3)
C12—C13—C14—C15	0.8 (3)	N1—Cu2—N2—C26	−176.6 (2)
C12—C13—C14—C16	−178.7 (2)	O5—Cu2—N2—C26	−78.90 (19)
C13—C14—C15—C10	−1.6 (3)	O3ⁱⁱ—Cu2—N2—C27	−165.84 (13)
C16—C14—C15—C10	177.98 (17)	O1—Cu2—N2—C27	−24.5 (4)
C11—C10—C15—C14	1.2 (3)	N1—Cu2—N2—C27	8.70 (13)
C9—C10—C15—C14	−174.09 (17)	O5—Cu2—N2—C27	106.44 (13)
C15—C14—C16—O8	7.6 (3)	O2—C1—O1—Cu2	−100.2 (2)
C13—C14—C16—O8	−172.9 (2)	C2—C1—O1—Cu2	81.5 (2)
C15—C14—C16—O7	−174.78 (18)	O3ⁱⁱ—Cu2—O1—C1	−16.66 (17)
C13—C14—C16—O7	4.8 (3)	N2—Cu2—O1—C1	−158.3 (3)
N1—C17—C18—C19	−0.1 (4)	N1—Cu2—O1—C1	168.91 (17)
C17—C18—C19—C20	1.9 (4)	O5—Cu2—O1—C1	70.49 (17)
C18—C19—C20—C28	−1.4 (3)	O1—C1—O2—Cu1	4.6 (2)
C18—C19—C20—C21	177.7 (2)	C2—C1—O2—Cu1	−177.06 (13)
C19—C20—C21—C22	−177.6 (2)	O6ⁱ—Cu1—O2—C1	−76.87 (13)
C28—C20—C21—C22	1.5 (3)	O6—Cu1—O2—C1	103.13 (13)
C20—C21—C22—C23	−1.6 (4)	O4—C8—O3—Cu2ⁱⁱ	21.2 (3)
C21—C22—C23—C27	−0.6 (3)	C6—C8—O3—Cu2ⁱⁱ	−159.55 (13)
C21—C22—C23—C24	−179.8 (2)	O6—C9—O5—Cu2	87.4 (2)
C27—C23—C24—C25	−1.3 (3)	C10—C9—O5—Cu2	−91.0 (2)
C22—C23—C24—C25	178.0 (2)	O3ⁱⁱ—Cu2—O5—C9	34.20 (17)
C23—C24—C25—C26	−0.8 (4)	O1—Cu2—O5—C9	−58.37 (17)
C24—C25—C26—N2	1.8 (4)	N2—Cu2—O5—C9	130.45 (17)
C24—C23—C27—N2	2.8 (3)	N1—Cu2—O5—C9	−146.85 (17)
C22—C23—C27—N2	−176.6 (2)	O5—C9—O6—Cu1	−10.3 (2)
C24—C23—C27—C28	−177.90 (19)	C10—C9—O6—Cu1	168.13 (12)
C22—C23—C27—C28	2.8 (3)	O2ⁱ—Cu1—O6—C9	84.72 (13)
C19—C20—C28—N1	−0.8 (3)	O2—Cu1—O6—C9	−95.28 (13)
C21—C20—C28—N1	179.97 (19)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ⁱⁱⁱ	0.82	1.73	2.539 (2)	170

Symmetry code: (iii) −x, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu₃(C₈H₄O₄)₂(C₈H₅O₄)₂(C₁₀H₈N₂)₂]
M_r	1209.5
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.383 (1), 10.659 (1), 11.754 (1)
α, β, γ (°)	83.147 (1), 86.191 (1), 71.134 (1)
V (Å³)	1221.6 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.38
Crystal size (mm)	0.37 × 0.32 × 0.23

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.631, 0.738
No. of measured, independent and observed [I > 2σ(I)] reflections	9575, 4741, 4241
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.09
No. of reflections	4741
No. of parameters	358
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.35

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O6	1.923 (1)	Cu2—N2	2.008 (2)
Cu1—O2	2.010 (1)	Cu2—N1	2.014 (2)
Cu2—O3ⁱ	1.935 (1)	Cu2—O5	2.278 (1)
Cu2—O1	1.951 (1)

O6—Cu1—O2ⁱⁱ	92.30 (6)	N2—Cu2—N1	81.94 (7)
O6—Cu1—O2	87.70 (6)	O1—Cu2—O5	91.79 (6)
O3ⁱ—Cu2—O1	92.66 (6)	N1—Cu2—O5	98.46 (6)
O1—Cu2—N2	168.29 (7)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1.