catena-Poly[[tetra-μ-benzoato-κ8O:O′-dicopper(II)]-μ-[N-(pyridin-4-yl)nicotin­amide]-κ2N:N′-[dibenzoato-κ2O-copper(II)]-μ-[N-(pyridin-4-yl)nicotin­amide]-κ2N:N′]

Kraft, P.E.; LaDuca, R.L.

doi:10.1107/S1600536812030437

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1049-m1050

https://doi.org/10.1107/S1600536812030437

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catena-Poly[[tetra-μ-benzoato-κ⁸O:O′-dicopper(II)]-μ-[N-(pyridin-4-yl)nicotinamide]-κ²N:N′-[dibenzoato-κ²O-copper(II)]-μ-[N-(pyridin-4-yl)nicotinamide]-κ²N:N′]

Peter E. Kraft ^a and Robert L. LaDuca ^b ^*

^aMunster High School, Munster, IN 46321, USA, and ^bLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 3 July 2012; accepted 3 July 2012; online 10 July 2012)

In the polymeric title compound, [Cu₃(C₇H₅O₂)₆(C₁₁H₉N₃O)₂]_n, square-planar-coordinated Cu^II ions on crystallographic inversion centres are bound by two monodentate benzoate anions. The resulting [Cu(benzoate)]₂ fragments are joined to centrosymmetic [Cu₂(benzoate)₄] paddlewheel clusters [Cu⋯Cu = 2.6331 (5) Å] by means of bridging N-(pyridin-4-yl)nicotinamide (4-pna) ligands [dihedral angle between the aromatic rings = 39.18 (12)°], thereby forming [Cu₃(benzoate)₆(4-pna)₂]_n coordination-polymer chains that are arranged parallel to the [30-1] crystal direction. These polymeric chains are anchored into supramolecular layers by N—H⋯O hydrogen bonding between neighboring 4-pna ligands. These layers aggregate by crystal packing forces to afford the crystal structure of the title compound.

Related literature

For the preparation of N-(pyridin-4-yl)nicotinamide, see: Gardner et al. (1954 ). For the preparation of other coordination polymers containing N-(pyridin-4-yl)nicotinamide, see: Kumar (2009 ).

Experimental

Crystal data

[Cu₃(C₇H₅O₂)₆(C₁₁H₉N₃O)₂]
M_r = 1315.70
Triclinic, $[P \overline 1]$
a = 8.9183 (7) Å
b = 11.3348 (9) Å
c = 15.5534 (12) Å
α = 85.471 (1)°
β = 75.804 (1)°
γ = 75.007 (1)°
V = 1472.1 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 173 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.725, T_max = 0.803
24050 measured reflections
5372 independent reflections
4042 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.02
5372 reflections
397 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9481 (18)
Cu1—N1	2.014 (2)
Cu2—O4ⁱ	1.9543 (19)
Cu2—O6ⁱ	1.962 (2)
Cu2—O3	1.9727 (19)
Cu2—O5	1.973 (2)
Cu2—N3	2.196 (2)
Symmetry code: (i) -x+3, -y+1, -z-1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2ⁱⁱ	0.86 (2)	2.01 (2)	2.867 (3)	177 (3)
Symmetry code: (ii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812030437/hb6888sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030437/hb6888Isup2.hkl

checkCIF report

Comment top

In comparison to divalent metal coordination polymers containing rigid rod dipyridine ligands such as 4,4'-bipyridine, related materials containing the kinked dipodal ligand N-(pyridin-4-yl)nicotinamide (4-pna) are much less common (Kumar, 2009). The title compound was obtained as blue crystals through the hydrothermal reaction of copper nitrate, benzoic acid, and 4-pna.

The asymmetric unit of the title compound (Fig. 1) contains two copper atoms, one of which (Cu1) lies on a crystallographic inversion centre, a 4-pna ligand, and three benzoate ligands. Cu1 is square planar coordinated by trans 4-pyridyl N atom donors from two 4-pna ligands and trans O atom donors from monodentate carboxylate groups belonging to two benzoate ligands. The other copper atom (Cu2) is square pyramidally coordinated, with its apical position occupied by a N atom donor from the nicotinamide end of a 4-pna ligand and its basal positions filled by O atom donors from four benzoate ligands.

Pairs of Cu2 atoms are linked into dinuclear [Cu₂(benzoate)₄] paddlewheel clusters by four syn-syn bridging benzoate ligands, with crystallographic inversion centres at the centroids of the clusters. Within these [Cu₂(benzoate)₄] clusters, the Cu···Cu through-space distance is 2.633 (2) Å. The 4-pna ligands projecting out of the apical positions of the Cu2 atoms within the dinuclear paddlewheel clusters connect to Cu1 atoms, generating one-dimensional [Cu₃(benzoate)₆(4-pna)₂]_n polymer chains along the [3 0 1] crystal direction (Fig. 2).

Each individual chain is anchored to two others via N—H···O hydrogen bonding (Table 1) between amide moieties of neighboring 4-pna ligands. In this manner, supramolecular two-dimensional layers are constructed (Fig. 3); these lie parallel to the ac crystal planes. The three-dimensional structure of the title compound results from crystal packing forces between these layers, which stack along the b crystal direction. (Fig. 4).

Related literature top

For the preparation of N-(pyridin-4-yl)nicotinamide, see: Gardner et al. (1954). For the preparation of other coordination polymers containing N-(pyridin-4-yl)nicotinamide, see: Kumar (2009).

Experimental top

Copper(II) nitrate hydrate and benzoic acid were obtained commercially. N-(Pyridin-4-yl)nicotinamide (4-pna) was prepared via a published procedure (Gardner et al., 1954). A mixture of copper nitrate hydrate (89 mg, 0.37 mmol), benzoic acid (45 mg, 0.37 mmol), 4-pna (74 mg, 0.37 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 393 K for 24 h. Blue blocks of the title compound were obtained.

Structure description top

For the preparation of N-(pyridin-4-yl)nicotinamide, see: Gardner et al. (1954). For the preparation of other coordination polymers containing N-(pyridin-4-yl)nicotinamide, see: Kumar (2009).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability ellipsoids, complete coordination environments, and atom numbering scheme. Hydrogen atom positions are shown as grey sticks with the exception of the amide group hydrogen atom. Color codes: dark blue Cu, red O, light blue N, black C, pink H. Symmetry codes: (i) -x, -y + 1, -z; (ii) -x + 3, -y + 1, -z - 1.
	Fig. 2. A single [Cu₃(benzoate)₆(4-pna)₂]_n coordination polymer chain.
	Fig. 3. Supramolecular layer of [Cu₃(benzoate)₆(4-pna)₂]_n chains. N—H···O hydrogen bonding is shown as dashed lines.
	Fig. 4. Stacking of supramolecular layers within the title compound.

catena-Poly[[tetra-µ-benzoato-κ⁸O:O'-dicopper(II)]- µ-[N-(pyridin-4-yl)nicotinamide]-κ²N:N'- [dibenzoato-κ²O-copper(II)]-µ-[N- (pyridin-4-yl)nicotinamide]-κ²N:N'] top

Crystal data top

[Cu₃(C₇H₅O₂)₆(C₁₁H₉N₃O)₂]	Z = 1
M_r = 1315.70	F(000) = 673
Triclinic, P1	D_x = 1.484 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9183 (7) Å	Cell parameters from 24050 reflections
b = 11.3348 (9) Å	θ = 1.9–25.4°
c = 15.5534 (12) Å	µ = 1.15 mm⁻¹
α = 85.471 (1)°	T = 173 K
β = 75.804 (1)°	Block, blue
γ = 75.007 (1)°	0.30 × 0.20 × 0.20 mm
V = 1472.1 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	5372 independent reflections
Radiation source: fine-focus sealed tube	4042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω–φ scans	θ_max = 25.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.725, T_max = 0.803	k = −13→13
24050 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0281P)² + 1.0621P] where P = (F_o² + 2F_c²)/3
5372 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.38 e Å⁻³
1 restraint	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu₃(C₇H₅O₂)₆(C₁₁H₉N₃O)₂]	γ = 75.007 (1)°
M_r = 1315.70	V = 1472.1 (2) Å³
Triclinic, P1	Z = 1
a = 8.9183 (7) Å	Mo Kα radiation
b = 11.3348 (9) Å	µ = 1.15 mm⁻¹
c = 15.5534 (12) Å	T = 173 K
α = 85.471 (1)°	0.30 × 0.20 × 0.20 mm
β = 75.804 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5372 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4042 reflections with I > 2σ(I)
T_min = 0.725, T_max = 0.803	R_int = 0.053
24050 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.38 e Å⁻³
5372 reflections	Δρ_min = −0.31 e Å⁻³
397 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	0.0000	0.5000	0.0000	0.02146 (13)
Cu2	1.36616 (4)	0.54604 (3)	−0.44207 (2)	0.02392 (11)
O1	0.0790 (2)	0.35964 (17)	−0.07773 (12)	0.0266 (5)
O2	0.2143 (3)	0.29187 (19)	0.02586 (14)	0.0394 (5)
O3	1.4882 (2)	0.66396 (18)	−0.43039 (13)	0.0323 (5)
O4	1.7183 (2)	0.58342 (18)	−0.52675 (13)	0.0295 (5)
O5	1.4691 (2)	0.43007 (18)	−0.35983 (13)	0.0284 (5)
O6	1.7006 (2)	0.35647 (18)	−0.45767 (13)	0.0329 (5)
O7	0.7243 (2)	0.5482 (2)	−0.28967 (13)	0.0373 (5)
N1	0.1981 (3)	0.5589 (2)	−0.05294 (14)	0.0218 (5)
N2	0.6435 (3)	0.6367 (2)	−0.15343 (15)	0.0231 (5)
H2N	0.684 (3)	0.661 (2)	−0.1152 (16)	0.028*
N3	1.1596 (3)	0.6361 (2)	−0.33950 (14)	0.0227 (5)
C1	0.2737 (3)	0.5403 (2)	−0.13860 (18)	0.0244 (6)
H1	0.2240	0.5075	−0.1753	0.029*
C2	0.2702 (3)	0.6069 (2)	−0.00283 (18)	0.0237 (6)
H2	0.2170	0.6245	0.0573	0.028*
C3	0.4166 (3)	0.6317 (2)	−0.03425 (18)	0.0226 (6)
H3	0.4645	0.6631	0.0041	0.027*
C4	0.4948 (3)	0.6105 (2)	−0.12310 (17)	0.0207 (6)
C5	0.4182 (3)	0.5656 (2)	−0.17648 (18)	0.0238 (6)
H5	0.4651	0.5529	−0.2379	0.029*
C6	0.7466 (3)	0.6081 (3)	−0.23565 (18)	0.0248 (6)
C7	0.8914 (3)	0.6583 (3)	−0.25392 (17)	0.0222 (6)
C8	1.0264 (3)	0.5974 (3)	−0.31442 (18)	0.0239 (6)
H8	1.0235	0.5243	−0.3392	0.029*
C9	1.1613 (3)	0.7396 (3)	−0.30381 (18)	0.0298 (7)
H9	1.2558	0.7681	−0.3207	0.036*
C10	1.0331 (3)	0.8063 (3)	−0.2440 (2)	0.0327 (7)
H10	1.0392	0.8791	−0.2202	0.039*
C11	0.8949 (3)	0.7656 (3)	−0.21908 (19)	0.0283 (7)
H11	0.8038	0.8107	−0.1786	0.034*
C12	1.6289 (3)	0.6623 (3)	−0.47145 (19)	0.0270 (7)
C13	1.6959 (4)	0.7642 (3)	−0.45442 (19)	0.0306 (7)
C14	1.8593 (4)	0.7500 (3)	−0.47238 (19)	0.0313 (7)
H14	1.9295	0.6754	−0.4957	0.038*
C15	1.9208 (4)	0.8441 (3)	−0.4565 (2)	0.0396 (8)
H15	2.0332	0.8336	−0.4688	0.047*
C16	1.8214 (5)	0.9517 (3)	−0.4232 (2)	0.0566 (11)
H16	1.8646	1.0162	−0.4130	0.068*
C17	1.6585 (5)	0.9670 (4)	−0.4045 (3)	0.0756 (15)
H17	1.5888	1.0419	−0.3812	0.091*
C18	1.5972 (4)	0.8726 (3)	−0.4199 (3)	0.0623 (12)
H18	1.4848	0.8829	−0.4065	0.075*
C19	1.6096 (3)	0.3635 (3)	−0.38105 (19)	0.0271 (7)
C20	1.6740 (3)	0.2846 (3)	−0.31014 (19)	0.0275 (7)
C21	1.5723 (4)	0.2589 (3)	−0.2323 (2)	0.0342 (7)
H21	1.4603	0.2916	−0.2235	0.041*
C22	1.6334 (4)	0.1856 (3)	−0.1674 (2)	0.0453 (9)
H22	1.5631	0.1666	−0.1147	0.054*
C23	1.7952 (5)	0.1399 (3)	−0.1787 (2)	0.0519 (10)
H23	1.8370	0.0905	−0.1337	0.062*
C24	1.8963 (4)	0.1663 (3)	−0.2558 (3)	0.0511 (10)
H24	2.0084	0.1350	−0.2639	0.061*
C25	1.8364 (4)	0.2375 (3)	−0.3211 (2)	0.0402 (8)
H25	1.9073	0.2544	−0.3743	0.048*
C26	0.1744 (3)	0.2772 (3)	−0.04270 (19)	0.0263 (7)
C27	0.3730 (5)	−0.0630 (4)	−0.1756 (3)	0.0698 (13)
H27	0.4193	−0.1385	−0.2053	0.084*
C28	0.3120 (5)	0.0550 (3)	−0.0454 (3)	0.0555 (10)
H28	0.3169	0.0601	0.0145	0.067*
C29	0.2334 (4)	0.1471 (3)	−0.1756 (2)	0.0368 (8)
H29	0.1829	0.2163	−0.2058	0.044*
C30	0.2388 (4)	0.1566 (3)	−0.0885 (2)	0.0326 (7)
C31	0.3782 (6)	−0.0545 (4)	−0.0896 (3)	0.0787 (14)
H31	0.4278	−0.1244	−0.0596	0.094*
C32	0.3013 (4)	0.0368 (3)	−0.2192 (3)	0.0514 (10)
H32	0.2980	0.0309	−0.2793	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0145 (2)	0.0247 (3)	0.0243 (3)	−0.0074 (2)	0.0022 (2)	−0.0077 (2)
Cu2	0.01624 (19)	0.0281 (2)	0.0262 (2)	−0.00850 (15)	0.00295 (14)	−0.00849 (15)
O1	0.0183 (10)	0.0285 (11)	0.0325 (11)	−0.0079 (9)	0.0004 (9)	−0.0107 (9)
O2	0.0537 (15)	0.0391 (13)	0.0320 (12)	−0.0183 (11)	−0.0145 (11)	−0.0026 (10)
O3	0.0212 (11)	0.0328 (12)	0.0422 (13)	−0.0136 (9)	0.0051 (9)	−0.0123 (10)
O4	0.0211 (11)	0.0349 (12)	0.0336 (12)	−0.0133 (9)	0.0016 (9)	−0.0109 (10)
O5	0.0205 (11)	0.0332 (12)	0.0298 (11)	−0.0065 (9)	−0.0002 (9)	−0.0082 (9)
O6	0.0234 (11)	0.0386 (13)	0.0314 (12)	−0.0043 (9)	0.0019 (9)	−0.0065 (10)
O7	0.0288 (12)	0.0510 (14)	0.0341 (12)	−0.0216 (11)	0.0079 (9)	−0.0220 (11)
N1	0.0179 (12)	0.0237 (13)	0.0232 (12)	−0.0074 (10)	−0.0001 (10)	−0.0051 (10)
N2	0.0163 (12)	0.0310 (14)	0.0224 (13)	−0.0101 (10)	0.0012 (10)	−0.0068 (11)
N3	0.0182 (12)	0.0272 (13)	0.0220 (12)	−0.0088 (10)	0.0008 (10)	−0.0036 (10)
C1	0.0191 (15)	0.0285 (16)	0.0260 (16)	−0.0066 (12)	−0.0036 (12)	−0.0060 (12)
C2	0.0206 (15)	0.0227 (15)	0.0241 (15)	−0.0041 (12)	0.0020 (12)	−0.0056 (12)
C3	0.0176 (14)	0.0257 (16)	0.0262 (15)	−0.0086 (12)	−0.0028 (12)	−0.0069 (12)
C4	0.0159 (14)	0.0195 (14)	0.0250 (15)	−0.0045 (11)	−0.0012 (12)	−0.0013 (12)
C5	0.0203 (15)	0.0299 (16)	0.0201 (15)	−0.0074 (13)	−0.0006 (12)	−0.0037 (12)
C6	0.0205 (15)	0.0260 (16)	0.0271 (16)	−0.0085 (12)	−0.0001 (12)	−0.0034 (13)
C7	0.0176 (14)	0.0267 (15)	0.0207 (14)	−0.0084 (12)	0.0021 (11)	−0.0024 (12)
C8	0.0211 (15)	0.0246 (15)	0.0247 (15)	−0.0073 (12)	0.0004 (12)	−0.0059 (12)
C9	0.0242 (16)	0.0379 (18)	0.0288 (16)	−0.0156 (14)	0.0015 (13)	−0.0071 (14)
C10	0.0305 (17)	0.0300 (17)	0.0364 (18)	−0.0144 (14)	0.0053 (14)	−0.0122 (14)
C11	0.0230 (16)	0.0306 (17)	0.0271 (16)	−0.0066 (13)	0.0043 (13)	−0.0075 (13)
C12	0.0228 (16)	0.0312 (17)	0.0297 (16)	−0.0137 (13)	−0.0033 (13)	−0.0030 (14)
C13	0.0301 (17)	0.0326 (18)	0.0309 (17)	−0.0170 (14)	0.0007 (13)	−0.0061 (14)
C14	0.0293 (17)	0.0373 (18)	0.0308 (17)	−0.0174 (14)	−0.0030 (13)	−0.0026 (14)
C15	0.043 (2)	0.052 (2)	0.0340 (18)	−0.0301 (18)	−0.0080 (15)	0.0037 (16)
C16	0.068 (3)	0.052 (2)	0.058 (2)	−0.043 (2)	0.003 (2)	−0.014 (2)
C17	0.060 (3)	0.045 (2)	0.116 (4)	−0.026 (2)	0.018 (3)	−0.046 (2)
C18	0.036 (2)	0.045 (2)	0.100 (3)	−0.0187 (18)	0.015 (2)	−0.032 (2)
C19	0.0240 (16)	0.0270 (16)	0.0336 (17)	−0.0112 (13)	−0.0044 (14)	−0.0105 (13)
C20	0.0265 (16)	0.0263 (16)	0.0316 (17)	−0.0066 (13)	−0.0076 (13)	−0.0083 (13)
C21	0.0302 (18)	0.0311 (18)	0.0398 (19)	−0.0069 (14)	−0.0057 (15)	−0.0022 (15)
C22	0.049 (2)	0.043 (2)	0.039 (2)	−0.0082 (18)	−0.0059 (17)	0.0021 (17)
C23	0.069 (3)	0.045 (2)	0.044 (2)	−0.003 (2)	−0.028 (2)	−0.0031 (17)
C24	0.035 (2)	0.061 (3)	0.059 (2)	−0.0002 (18)	−0.0238 (19)	−0.011 (2)
C25	0.0311 (19)	0.051 (2)	0.041 (2)	−0.0112 (16)	−0.0095 (15)	−0.0088 (17)
C26	0.0228 (16)	0.0294 (17)	0.0273 (16)	−0.0131 (13)	0.0015 (13)	−0.0055 (13)
C27	0.083 (3)	0.037 (2)	0.087 (3)	0.006 (2)	−0.030 (3)	−0.030 (2)
C28	0.080 (3)	0.034 (2)	0.052 (2)	−0.008 (2)	−0.021 (2)	−0.0035 (18)
C29	0.0276 (17)	0.0356 (19)	0.048 (2)	−0.0015 (14)	−0.0128 (15)	−0.0141 (16)
C30	0.0291 (17)	0.0278 (17)	0.0411 (19)	−0.0067 (14)	−0.0059 (14)	−0.0100 (14)
C31	0.118 (4)	0.029 (2)	0.088 (3)	0.003 (2)	−0.044 (3)	−0.004 (2)
C32	0.047 (2)	0.048 (2)	0.060 (2)	0.0019 (18)	−0.0214 (19)	−0.0288 (19)

Geometric parameters (Å, º) top

Cu1—O1	1.9481 (18)	C10—C11	1.384 (4)
Cu1—O1ⁱ	1.9481 (18)	C10—H10	0.9500
Cu1—N1ⁱ	2.014 (2)	C11—H11	0.9500
Cu1—N1	2.014 (2)	C12—C13	1.497 (4)
Cu2—O4ⁱⁱ	1.9543 (19)	C13—C18	1.374 (4)
Cu2—O6ⁱⁱ	1.962 (2)	C13—C14	1.384 (4)
Cu2—O3	1.9727 (19)	C14—C15	1.382 (4)
Cu2—O5	1.973 (2)	C14—H14	0.9500
Cu2—N3	2.196 (2)	C15—C16	1.362 (5)
O1—C26	1.276 (3)	C15—H15	0.9500
O2—C26	1.239 (3)	C16—C17	1.377 (5)
O3—C12	1.257 (3)	C16—H16	0.9500
O4—C12	1.262 (3)	C17—C18	1.382 (5)
O4—Cu2ⁱⁱ	1.9543 (18)	C17—H17	0.9500
O5—C19	1.263 (3)	C18—H18	0.9500
O6—C19	1.262 (3)	C19—C20	1.495 (4)
O6—Cu2ⁱⁱ	1.962 (2)	C20—C25	1.381 (4)
O7—C6	1.203 (3)	C20—C21	1.384 (4)
N1—C1	1.343 (3)	C21—C22	1.382 (4)
N1—C2	1.346 (3)	C21—H21	0.9500
N2—C6	1.386 (3)	C22—C23	1.372 (5)
N2—C4	1.394 (3)	C22—H22	0.9500
N2—H2N	0.861 (17)	C23—C24	1.376 (5)
N3—C8	1.331 (3)	C23—H23	0.9500
N3—C9	1.341 (3)	C24—C25	1.371 (5)
C1—C5	1.373 (4)	C24—H24	0.9500
C1—H1	0.9500	C25—H25	0.9500
C2—C3	1.370 (4)	C26—C30	1.501 (4)
C2—H2	0.9500	C27—C31	1.362 (6)
C3—C4	1.395 (4)	C27—C32	1.366 (5)
C3—H3	0.9500	C27—H27	0.9500
C4—C5	1.392 (4)	C28—C30	1.381 (5)
C5—H5	0.9500	C28—C31	1.385 (5)
C6—C7	1.499 (4)	C28—H28	0.9500
C7—C11	1.380 (4)	C29—C30	1.380 (4)
C7—C8	1.389 (4)	C29—C32	1.389 (4)
C8—H8	0.9500	C29—H29	0.9500
C9—C10	1.374 (4)	C31—H31	0.9500
C9—H9	0.9500	C32—H32	0.9500

O1—Cu1—O1ⁱ	180.0	O3—C12—O4	125.9 (3)
O1—Cu1—N1ⁱ	89.20 (8)	O3—C12—C13	117.2 (3)
O1ⁱ—Cu1—N1ⁱ	90.80 (8)	O4—C12—C13	116.9 (2)
O1—Cu1—N1	90.80 (8)	C18—C13—C14	118.7 (3)
O1ⁱ—Cu1—N1	89.20 (8)	C18—C13—C12	120.9 (3)
N1ⁱ—Cu1—N1	180.0	C14—C13—C12	120.4 (3)
O4ⁱⁱ—Cu2—O6ⁱⁱ	88.63 (8)	C15—C14—C13	120.2 (3)
O4ⁱⁱ—Cu2—O3	168.50 (8)	C15—C14—H14	119.9
O6ⁱⁱ—Cu2—O3	89.13 (9)	C13—C14—H14	119.9
O4ⁱⁱ—Cu2—O5	88.78 (8)	C16—C15—C14	120.4 (3)
O6ⁱⁱ—Cu2—O5	168.47 (8)	C16—C15—H15	119.8
O3—Cu2—O5	91.18 (8)	C14—C15—H15	119.8
O4ⁱⁱ—Cu2—N3	99.17 (8)	C15—C16—C17	120.1 (3)
O6ⁱⁱ—Cu2—N3	96.15 (8)	C15—C16—H16	120.0
O3—Cu2—N3	92.29 (8)	C17—C16—H16	120.0
O5—Cu2—N3	95.35 (8)	C16—C17—C18	119.4 (4)
C26—O1—Cu1	108.01 (17)	C16—C17—H17	120.3
C12—O3—Cu2	126.41 (18)	C18—C17—H17	120.3
C12—O4—Cu2ⁱⁱ	119.08 (17)	C13—C18—C17	121.1 (3)
C19—O5—Cu2	123.94 (19)	C13—C18—H18	119.4
C19—O6—Cu2ⁱⁱ	121.68 (19)	C17—C18—H18	119.4
C1—N1—C2	116.7 (2)	O6—C19—O5	125.6 (3)
C1—N1—Cu1	121.09 (18)	O6—C19—C20	116.7 (3)
C2—N1—Cu1	121.88 (18)	O5—C19—C20	117.7 (3)
C6—N2—C4	126.4 (2)	C25—C20—C21	119.0 (3)
C6—N2—H2N	115.0 (19)	C25—C20—C19	120.3 (3)
C4—N2—H2N	117.6 (19)	C21—C20—C19	120.7 (3)
C8—N3—C9	117.4 (2)	C22—C21—C20	120.1 (3)
C8—N3—Cu2	123.03 (18)	C22—C21—H21	120.0
C9—N3—Cu2	119.43 (18)	C20—C21—H21	120.0
N1—C1—C5	124.1 (3)	C23—C22—C21	120.4 (3)
N1—C1—H1	117.9	C23—C22—H22	119.8
C5—C1—H1	117.9	C21—C22—H22	119.8
N1—C2—C3	123.3 (3)	C22—C23—C24	119.5 (3)
N1—C2—H2	118.4	C22—C23—H23	120.2
C3—C2—H2	118.4	C24—C23—H23	120.2
C2—C3—C4	119.4 (2)	C25—C24—C23	120.4 (3)
C2—C3—H3	120.3	C25—C24—H24	119.8
C4—C3—H3	120.3	C23—C24—H24	119.8
C5—C4—N2	123.9 (2)	C24—C25—C20	120.6 (3)
C5—C4—C3	117.8 (2)	C24—C25—H25	119.7
N2—C4—C3	118.3 (2)	C20—C25—H25	119.7
C1—C5—C4	118.7 (3)	O2—C26—O1	123.7 (3)
C1—C5—H5	120.7	O2—C26—C30	119.6 (3)
C4—C5—H5	120.7	O1—C26—C30	116.7 (3)
O7—C6—N2	123.9 (3)	C31—C27—C32	120.1 (4)
O7—C6—C7	121.2 (2)	C31—C27—H27	120.0
N2—C6—C7	114.9 (2)	C32—C27—H27	120.0
C11—C7—C8	118.2 (2)	C30—C28—C31	119.8 (4)
C11—C7—C6	124.0 (2)	C30—C28—H28	120.1
C8—C7—C6	117.7 (2)	C31—C28—H28	120.1
N3—C8—C7	123.4 (3)	C30—C29—C32	120.3 (3)
N3—C8—H8	118.3	C30—C29—H29	119.8
C7—C8—H8	118.3	C32—C29—H29	119.8
N3—C9—C10	123.2 (3)	C29—C30—C28	119.1 (3)
N3—C9—H9	118.4	C29—C30—C26	120.6 (3)
C10—C9—H9	118.4	C28—C30—C26	120.2 (3)
C9—C10—C11	118.8 (3)	C27—C31—C28	120.7 (4)
C9—C10—H10	120.6	C27—C31—H31	119.6
C11—C10—H10	120.6	C28—C31—H31	119.6
C7—C11—C10	118.9 (3)	C27—C32—C29	119.9 (3)
C7—C11—H11	120.5	C27—C32—H32	120.1
C10—C11—H11	120.5	C29—C32—H32	120.1

N1ⁱ—Cu1—O1—C26	−97.42 (18)	C6—C7—C11—C10	−176.8 (3)
N1—Cu1—O1—C26	82.58 (18)	C9—C10—C11—C7	1.1 (5)
O4ⁱⁱ—Cu2—O3—C12	−7.5 (6)	Cu2—O3—C12—O4	−1.2 (4)
O6ⁱⁱ—Cu2—O3—C12	−86.3 (2)	Cu2—O3—C12—C13	177.83 (19)
O5—Cu2—O3—C12	82.2 (2)	Cu2ⁱⁱ—O4—C12—O3	2.9 (4)
N3—Cu2—O3—C12	177.6 (2)	Cu2ⁱⁱ—O4—C12—C13	−176.08 (19)
O4ⁱⁱ—Cu2—O5—C19	91.6 (2)	O3—C12—C13—C18	−20.6 (5)
O6ⁱⁱ—Cu2—O5—C19	14.5 (5)	O4—C12—C13—C18	158.5 (3)
O3—Cu2—O5—C19	−76.9 (2)	O3—C12—C13—C14	158.7 (3)
N3—Cu2—O5—C19	−169.4 (2)	O4—C12—C13—C14	−22.2 (4)
O1—Cu1—N1—C1	32.9 (2)	C18—C13—C14—C15	−0.6 (5)
O1ⁱ—Cu1—N1—C1	−147.1 (2)	C12—C13—C14—C15	−179.9 (3)
O1—Cu1—N1—C2	−140.1 (2)	C13—C14—C15—C16	−0.2 (5)
O1ⁱ—Cu1—N1—C2	39.9 (2)	C14—C15—C16—C17	0.6 (6)
O4ⁱⁱ—Cu2—N3—C8	0.9 (2)	C15—C16—C17—C18	−0.2 (7)
O6ⁱⁱ—Cu2—N3—C8	90.5 (2)	C14—C13—C18—C17	1.0 (6)
O3—Cu2—N3—C8	179.9 (2)	C12—C13—C18—C17	−179.7 (4)
O5—Cu2—N3—C8	−88.7 (2)	C16—C17—C18—C13	−0.6 (7)
O4ⁱⁱ—Cu2—N3—C9	−174.6 (2)	Cu2ⁱⁱ—O6—C19—O5	0.8 (4)
O6ⁱⁱ—Cu2—N3—C9	−85.0 (2)	Cu2ⁱⁱ—O6—C19—C20	179.98 (17)
O3—Cu2—N3—C9	4.4 (2)	Cu2—O5—C19—O6	−3.9 (4)
O5—Cu2—N3—C9	95.8 (2)	Cu2—O5—C19—C20	176.99 (17)
C2—N1—C1—C5	0.8 (4)	O6—C19—C20—C25	19.3 (4)
Cu1—N1—C1—C5	−172.5 (2)	O5—C19—C20—C25	−161.5 (3)
C1—N1—C2—C3	−2.8 (4)	O6—C19—C20—C21	−161.4 (3)
Cu1—N1—C2—C3	170.4 (2)	O5—C19—C20—C21	17.8 (4)
N1—C2—C3—C4	2.1 (4)	C25—C20—C21—C22	−0.8 (4)
C6—N2—C4—C5	−9.2 (4)	C19—C20—C21—C22	179.8 (3)
C6—N2—C4—C3	171.6 (3)	C20—C21—C22—C23	1.4 (5)
C2—C3—C4—C5	0.6 (4)	C21—C22—C23—C24	−0.9 (5)
C2—C3—C4—N2	179.9 (2)	C22—C23—C24—C25	−0.1 (5)
N1—C1—C5—C4	1.8 (4)	C23—C24—C25—C20	0.6 (5)
N2—C4—C5—C1	178.3 (3)	C21—C20—C25—C24	−0.1 (5)
C3—C4—C5—C1	−2.5 (4)	C19—C20—C25—C24	179.2 (3)
C4—N2—C6—O7	−5.6 (5)	Cu1—O1—C26—O2	−4.5 (3)
C4—N2—C6—C7	174.1 (2)	Cu1—O1—C26—C30	175.13 (19)
O7—C6—C7—C11	149.7 (3)	C32—C29—C30—C28	−0.3 (5)
N2—C6—C7—C11	−30.0 (4)	C32—C29—C30—C26	176.3 (3)
O7—C6—C7—C8	−25.7 (4)	C31—C28—C30—C29	−0.1 (6)
N2—C6—C7—C8	154.6 (3)	C31—C28—C30—C26	−176.8 (4)
C9—N3—C8—C7	0.0 (4)	O2—C26—C30—C29	−162.1 (3)
Cu2—N3—C8—C7	−175.6 (2)	O1—C26—C30—C29	18.2 (4)
C11—C7—C8—N3	1.0 (4)	O2—C26—C30—C28	14.5 (4)
C6—C7—C8—N3	176.6 (3)	O1—C26—C30—C28	−165.1 (3)
C8—N3—C9—C10	−0.5 (4)	C32—C27—C31—C28	−0.3 (8)
Cu2—N3—C9—C10	175.3 (2)	C30—C28—C31—C27	0.4 (7)
N3—C9—C10—C11	−0.1 (5)	C31—C27—C32—C29	−0.1 (7)
C8—C7—C11—C10	−1.5 (4)	C30—C29—C32—C27	0.5 (5)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+3, −y+1, −z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2ⁱⁱⁱ	0.86 (2)	2.01 (2)	2.867 (3)	177 (3)

Symmetry code: (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu₃(C₇H₅O₂)₆(C₁₁H₉N₃O)₂]
M_r	1315.70
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.9183 (7), 11.3348 (9), 15.5534 (12)
α, β, γ (°)	85.471 (1), 75.804 (1), 75.007 (1)
V (Å³)	1472.1 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.725, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	24050, 5372, 4042
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.02
No. of reflections	5372
No. of parameters	397
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Crystal Maker (Palmer, 2007).

Selected bond lengths (Å) top

Cu1—O1	1.9481 (18)	Cu2—O3	1.9727 (19)
Cu1—N1	2.014 (2)	Cu2—O5	1.973 (2)
Cu2—O4ⁱ	1.9543 (19)	Cu2—N3	2.196 (2)
Cu2—O6ⁱ	1.962 (2)

Symmetry code: (i) −x+3, −y+1, −z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2ⁱⁱ	0.861 (17)	2.007 (18)	2.867 (3)	177 (3)

Symmetry code: (ii) −x+1, −y+1, −z.

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for supporting this work. PEK thanks the Michigan State University High School Honors Science Program for his participation in this research project.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gardner, T. S., Wenis, E. & Lee, J. (1954). J. Org. Chem. 19, 753–757. CrossRef CAS Web of Science Google Scholar
Kumar, D. K. (2009). Inorg. Chim. Acta, 362, 1767–1771. Web of Science CSD CrossRef Google Scholar
Palmer, D. (2007). Crystal Maker. Version 7.2. PO Box 183, Bicester, Oxfordshire OX26 3TA, England. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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