Poly[[aqua­[μ-1,4-bis­(3-pyridylmeth­yl)piperazine-κ2N:N′](μ-isophthalato-κ2O1:O3)copper(II)]

Gandolfo, C.M.; LaDuca, R.L.

doi:10.1107/S160053681000632X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m318

doi:10.1107/S160053681000632X

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Poly[[aqua[μ-1,4-bis(3-pyridylmethyl)piperazine-κ²N:N′](μ-isophthalato-κ²O¹:O³)copper(II)]

Chaun M. Gandolfo ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825 USA
^*Correspondence e-mail: laduca@msu.edu

(Received 16 February 2010; accepted 17 February 2010; online 20 February 2010)

In the title compound, [Cu(C₈H₄O₄)(C₁₆H₂₀N₄)(H₂O)]_n, square-pyramidally coordinated Cu^II ions are linked into [Cu(H₂O)(isophthalate)]_n coordination polymer chains by isophthalate dianions. These chains are connected into undulating [Cu(H₂O)(isophthalate)(3-bpmp)]_n [3-bmp is bis(3-pyridylmethyl)piperazine] layers by 3-bpmp tethering ligands. The pseudo three-dimensional structure of the title compound is fostered by interlayer O—H⋯O hydrogen bonding between the aqua ligands and unligated isophthalate O atoms. The selected crystal was non-merohedrally twinned. Only reflections from the major twin component were used in the solution and refinement.

Related literature

For other divalent copper aromatic dicarboxylate coordination polymers containing bis(3-pyridylmethyl)piperazine, see: Johnston et al. (2008 ). For the synthesis of bis(3-pyridylmethyl)piperazine, see: Pocic et al. (2005 ). The twin law was determined using CELLNOW (Sheldrick, 2009 ).

Experimental

Crystal data

[Cu(C₈H₄O₄)(C₁₆H₂₀N₄)(H₂O)]
M_r = 514.03
Triclinic, $[P \overline 1]$
a = 6.9122 (4) Å
b = 10.0328 (5) Å
c = 16.7456 (9) Å
α = 86.822 (1)°
β = 84.210 (1)°
γ = 80.771 (1)°
V = 1139.49 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 173 K
0.34 × 0.18 × 0.17 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2003 ) T_min = 0.729, T_max = 0.850
31818 measured reflections
4141 independent reflections
3681 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.117
S = 1.16
4141 reflections
313 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1ⁱ	0.82 (2)	1.96 (2)	2.778 (3)	174 (3)
O5—H5B⋯O3ⁱⁱ	0.83 (2)	2.02 (2)	2.805 (3)	158 (3)
Symmetry codes: (i) x+1, y, z; (ii) x, 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, pub. DOI: 10.1107/S160053681000632X/ng2734sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000632X/ng2734Isup2.hkl

checkCIF report

Comment top

The title compound (I) was prepared by the hydrothermal reaction of copper nitrate, isophthalic acid and bis(3-pyridylmethyl)piperazine (3-bpmp). Its asymmetric unit (Fig. 1) contains a divalent copper atom, an aqua ligand, a fully deprotonated isophthalate ligand, and halves of two crystallographically independent 3-bpmp ligands whose central piperazinyl rings contain crystallographic inversion centers. In contrast to the previously reported phase {[Cu(H₂O)(isophthalate)(3-bpmp)]^.2H₂O}_n (Johnston, et al., 2008) no water molecules of crystallization are present in the title compound.

The basal plane of the distorted square pyramidal {CuO₃N₂} coordination sphere contains two trans pyridyl N atom donors from crystallographically distinct 3-bpmp ligands and two trans O atom donors from different isophthalate ligands. The apical position is occupied by the aqua ligand.

Isophthalate ligands in a bis(monodentate) bridging mode link the Cu^II ions into one-dimensional [Cu(H₂O)(isophthalate)]_n coordination polymer chains arranged along the b crystal direction. The Cu···Cu distance through the isophthalate ligands measures 10.0328 (5) Å, defining the b lattice parameter. In turn, these chains are connected into undulating [Cu(H₂O)(isophthalate)(3-bpmp)]_n coordination polymer layers by 3-bpmp tethering ligands (Fig. 2). These layers are arranged parallel to the bc crystal planes. The crystallographically distinct 3-bpmp ligands promote two different through-ligand Cu···Cu contact distances, 12.394 (6) and 12.830 (6) Å. The "wavelength" of the undulations in the layer motifs is 16.7456 (9) Å, which defines the c lattice parameter. Intralayer hydrogen bonding between the aqua ligands and unligated isophthalate O atoms provides additional stabilization of the layer motifs.

Adjacent [Cu(H₂O)(isophthalate)(3-bpmp)]_n layers stack in an AAA pattern along the a crystal direction. Interlayer hydrogen bonding between the aqua ligands and unligated isophthalate O atoms provides the supramolecular interactions necessary to generate the pseudo three-dimensional structure of the title compound.

Related literature top

For other divalent copper aromatic dicarboxylate coordination polymers containing bis(3-pyridylmethyl)piperazine, see: Johnston et al. (2008). For the synthesis of bis(3-pyridylmethyl)piperazine, see: Pocic et al. (2005). The twin law was determined using CELLNOW (Sheldrick, 2009).

Experimental top

All starting materials were obtained commercially, except for 3-bpmp, which was prepared according to a literature procedure (Pocic, et al., 2005). A mixture of Cu(NO₃)₂^.2.5H₂O (72 mg, 0.30 mmol), isophthalic acid (49 mg, 0.30 mmol), and 3-bpmp (79 mg, 0.30 mmol) and 10.0 g water (550 mmol) was placed into a 15 ml borosilicate glass vial, which was then sealed and heated under autogenous pressure at 363 K for 120 h. Blue-green blocks of the title compound were obtained along with a green polycrystalline material.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (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 and atom numbering scheme. Hydrogen atom positions are shown as grey sticks. Color codes: dark blue Cu, light blue N, red O, black C. Symmetry codes: (i) x, y, z.
	Fig. 2. Face-on view of the coordination polymer layer motif in the title compound.
	Fig. 3. Stacking diagram for the title compound, viewed down the b axis.

Poly[[aqua[µ-1,4-bis(3-pyridylmethyl)piperazine- κ²N:N'](µ-isophthalato- κ²O¹:O³)copper(II)] top

Crystal data top

[Cu(C₈H₄O₄)(C₁₆H₂₀N₄)(H₂O)]	Z = 2
M_r = 514.03	F(000) = 534
Triclinic, P1	D_x = 1.498 Mg m⁻³
a = 6.9122 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0328 (5) Å	Cell parameters from 4141 reflections
c = 16.7456 (9) Å	θ = 1.2–25.3°
α = 86.822 (1)°	µ = 1.00 mm⁻¹
β = 84.210 (1)°	T = 173 K
γ = 80.771 (1)°	Block, blue-green
V = 1139.49 (11) Å³	0.34 × 0.18 × 0.17 mm

Data collection top

Bruker APEXII diffractometer	4141 independent reflections
Radiation source: fine-focus sealed tube	3681 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ω–ϕ scans	θ_max = 25.3°, θ_min = 1.2°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2003)	h = −8→8
T_min = 0.729, T_max = 0.850	k = −11→12
31818 measured reflections	l = 0→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.038P)² + 0.3004P] where P = (F_o² + 2F_c²)/3
4141 reflections	(Δ/σ)_max < 0.001
313 parameters	Δρ_max = 0.44 e Å⁻³
3 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Cu(C₈H₄O₄)(C₁₆H₂₀N₄)(H₂O)]	γ = 80.771 (1)°
M_r = 514.03	V = 1139.49 (11) Å³
Triclinic, P1	Z = 2
a = 6.9122 (4) Å	Mo Kα radiation
b = 10.0328 (5) Å	µ = 1.00 mm⁻¹
c = 16.7456 (9) Å	T = 173 K
α = 86.822 (1)°	0.34 × 0.18 × 0.17 mm
β = 84.210 (1)°

Data collection top

Bruker APEXII diffractometer	4141 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 2003)	3681 reflections with I > 2σ(I)
T_min = 0.729, T_max = 0.850	R_int = 0.077
31818 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 0.44 e Å⁻³
4141 reflections	Δρ_min = −0.56 e Å⁻³
313 parameters

Special details top

Experimental. The selected crystal was non-merohedrally twinned. The twin law was determined using CELLNOW (Sheldrick, 2009). Only reflections from the major twin component were used in the solution and refinement.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.06345 (5)	0.16501 (3)	0.247474 (17)	0.03608 (14)
O1	−0.2554 (3)	0.07048 (19)	0.26910 (13)	0.0497 (5)
O2	−0.0541 (3)	−0.64683 (17)	0.24333 (11)	0.0407 (4)
O3	0.1918 (3)	−0.53485 (19)	0.26226 (12)	0.0481 (5)
O4	0.0528 (3)	−0.03315 (17)	0.25491 (10)	0.0378 (4)
O5	0.3884 (3)	0.2070 (2)	0.22304 (13)	0.0468 (5)
H5A	0.489 (4)	0.165 (3)	0.2398 (18)	0.056*
H5B	0.362 (5)	0.2875 (19)	0.2338 (19)	0.056*
N1	−0.2981 (4)	0.4364 (2)	−0.00903 (14)	0.0450 (6)
N2	−0.3058 (4)	0.4306 (2)	0.50868 (14)	0.0459 (6)
N3	0.0735 (3)	0.1569 (2)	0.12699 (13)	0.0369 (5)
N4	0.0851 (3)	0.1613 (2)	0.36631 (13)	0.0364 (5)
C1	−0.1526 (5)	0.3472 (3)	0.55036 (17)	0.0522 (7)
H1A	−0.2147	0.2988	0.5967	0.063*
H1B	−0.0697	0.4063	0.5715	0.063*
C2	−0.1293 (5)	0.3582 (3)	−0.05256 (17)	0.0543 (8)
H2A	−0.0398	0.4206	−0.0763	0.065*
H2B	−0.1754	0.3150	−0.0973	0.065*
C3	0.1232 (4)	0.1509 (3)	−0.03844 (18)	0.0516 (7)
H3	0.1412	0.1486	−0.0954	0.062*
C4	−0.4673 (4)	0.3578 (3)	0.49701 (18)	0.0492 (7)
H4A	−0.5319	0.3322	0.5498	0.059*
H4B	−0.4150	0.2741	0.4683	0.059*
C5	0.2344 (4)	0.0554 (3)	0.00767 (18)	0.0505 (7)
H5	0.3287	−0.0133	−0.0168	0.061*
C6	−0.4586 (4)	0.3589 (3)	0.01158 (18)	0.0486 (7)
H6A	−0.4119	0.2774	0.0446	0.058*
H6B	−0.5022	0.3290	−0.0381	0.058*
C7	−0.0140 (4)	0.2497 (3)	−0.00209 (17)	0.0447 (7)
C8	−0.3847 (4)	0.5539 (3)	0.55103 (17)	0.0471 (7)
H8A	−0.2761	0.6037	0.5592	0.056*
H8B	−0.4486	0.5304	0.6044	0.056*
C9	−0.3711 (4)	0.5567 (3)	−0.05738 (17)	0.0490 (7)
H9A	−0.4137	0.5290	−0.1078	0.059*
H9B	−0.2640	0.6109	−0.0716	0.059*
C10	0.1134 (5)	0.1464 (3)	0.53032 (18)	0.0484 (7)
H10	0.1234	0.1402	0.5866	0.058*
C11	−0.0233 (4)	0.2453 (3)	0.49772 (16)	0.0429 (6)
C12	−0.3987 (4)	−0.1727 (3)	0.24824 (15)	0.0399 (6)
H12	−0.4912	−0.0917	0.2477	0.048*
C13	0.2053 (4)	0.0623 (3)	0.09015 (17)	0.0444 (6)
H13	0.2822	−0.0029	0.1221	0.053*
C14	−0.1298 (4)	−0.4115 (3)	0.25201 (14)	0.0351 (6)
C15	−0.3263 (4)	−0.4149 (3)	0.24274 (17)	0.0422 (6)
H15	−0.3696	−0.4990	0.2377	0.051*
C16	0.2351 (4)	0.0567 (3)	0.48069 (18)	0.0478 (7)
H16	0.3297	−0.0113	0.5024	0.057*
C17	−0.4595 (4)	−0.2960 (3)	0.24079 (17)	0.0438 (6)
H17	−0.5936	−0.2992	0.2343	0.053*
C18	−0.0310 (4)	0.2481 (3)	0.41507 (16)	0.0395 (6)
H18	−0.1241	0.3154	0.3918	0.047*
C19	−0.1320 (4)	−0.0336 (3)	0.26089 (15)	0.0378 (6)
C20	−0.2003 (4)	−0.1679 (2)	0.25656 (14)	0.0339 (5)
C21	0.2174 (4)	0.0674 (3)	0.39949 (17)	0.0431 (6)
H21	0.3021	0.0059	0.3655	0.052*
C22	−0.0351 (4)	0.2482 (3)	0.08150 (16)	0.0387 (6)
H22	−0.1307	0.3146	0.1075	0.046*
C23	−0.0687 (4)	−0.2874 (3)	0.25844 (15)	0.0354 (6)
H23	0.0658	−0.2846	0.2642	0.042*
C24	0.0186 (4)	−0.5397 (3)	0.25266 (14)	0.0372 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0415 (2)	0.0285 (2)	0.0384 (2)	−0.00438 (14)	−0.00604 (14)	−0.00113 (13)
O1	0.0404 (11)	0.0330 (10)	0.0747 (14)	0.0028 (9)	−0.0121 (10)	−0.0069 (9)
O2	0.0470 (11)	0.0290 (9)	0.0466 (11)	−0.0040 (8)	−0.0094 (8)	−0.0024 (8)
O3	0.0392 (11)	0.0355 (11)	0.0691 (13)	−0.0008 (8)	−0.0099 (9)	−0.0049 (9)
O4	0.0375 (11)	0.0304 (9)	0.0458 (10)	−0.0047 (8)	−0.0059 (8)	−0.0023 (8)
O5	0.0368 (11)	0.0431 (11)	0.0589 (12)	0.0013 (9)	−0.0076 (9)	−0.0044 (10)
N1	0.0413 (13)	0.0499 (14)	0.0436 (13)	−0.0085 (11)	−0.0062 (10)	0.0074 (11)
N2	0.0458 (14)	0.0469 (14)	0.0449 (13)	−0.0048 (11)	−0.0044 (10)	−0.0075 (11)
N3	0.0350 (12)	0.0339 (12)	0.0426 (12)	−0.0071 (9)	−0.0040 (9)	−0.0024 (9)
N4	0.0352 (12)	0.0328 (11)	0.0418 (12)	−0.0066 (9)	−0.0056 (9)	0.0016 (9)
C1	0.0559 (19)	0.0586 (19)	0.0410 (15)	−0.0030 (15)	−0.0063 (13)	−0.0072 (13)
C2	0.0533 (19)	0.066 (2)	0.0407 (16)	−0.0018 (16)	−0.0055 (13)	0.0061 (14)
C3	0.0456 (17)	0.067 (2)	0.0419 (16)	−0.0055 (15)	−0.0038 (13)	−0.0053 (14)
C4	0.0495 (18)	0.0454 (16)	0.0527 (17)	−0.0073 (14)	−0.0024 (13)	−0.0080 (13)
C5	0.0420 (16)	0.0569 (19)	0.0507 (17)	−0.0013 (14)	−0.0009 (13)	−0.0115 (14)
C6	0.0517 (18)	0.0451 (16)	0.0506 (16)	−0.0115 (14)	−0.0112 (13)	0.0081 (13)
C7	0.0392 (15)	0.0537 (18)	0.0421 (15)	−0.0096 (13)	−0.0056 (12)	0.0015 (13)
C8	0.0461 (17)	0.0499 (17)	0.0462 (16)	−0.0089 (13)	−0.0024 (13)	−0.0101 (13)
C9	0.0476 (17)	0.0522 (18)	0.0477 (16)	−0.0113 (14)	−0.0086 (13)	0.0127 (13)
C10	0.0508 (18)	0.0531 (18)	0.0429 (15)	−0.0105 (14)	−0.0099 (13)	0.0021 (13)
C11	0.0417 (15)	0.0468 (16)	0.0413 (15)	−0.0095 (13)	−0.0055 (12)	−0.0004 (12)
C12	0.0352 (14)	0.0391 (15)	0.0431 (15)	0.0011 (11)	−0.0025 (11)	−0.0034 (11)
C13	0.0416 (16)	0.0442 (16)	0.0472 (16)	−0.0043 (12)	−0.0062 (12)	−0.0029 (12)
C14	0.0395 (14)	0.0354 (14)	0.0304 (12)	−0.0058 (11)	−0.0024 (10)	−0.0013 (10)
C15	0.0434 (16)	0.0361 (14)	0.0478 (15)	−0.0091 (12)	−0.0020 (12)	−0.0037 (12)
C16	0.0427 (16)	0.0483 (17)	0.0521 (17)	−0.0059 (13)	−0.0116 (13)	0.0102 (13)
C17	0.0337 (14)	0.0458 (16)	0.0531 (16)	−0.0079 (12)	−0.0056 (12)	−0.0040 (12)
C18	0.0405 (15)	0.0362 (14)	0.0412 (14)	−0.0047 (12)	−0.0045 (11)	−0.0001 (11)
C19	0.0414 (15)	0.0341 (14)	0.0376 (13)	−0.0021 (12)	−0.0095 (11)	−0.0004 (11)
C20	0.0380 (14)	0.0312 (13)	0.0321 (12)	−0.0039 (11)	−0.0030 (10)	−0.0009 (10)
C21	0.0402 (15)	0.0407 (15)	0.0476 (15)	−0.0033 (12)	−0.0045 (12)	−0.0018 (12)
C22	0.0395 (15)	0.0373 (14)	0.0395 (14)	−0.0068 (12)	−0.0041 (11)	−0.0015 (11)
C23	0.0350 (14)	0.0358 (14)	0.0352 (13)	−0.0035 (11)	−0.0050 (10)	−0.0023 (10)
C24	0.0448 (16)	0.0319 (14)	0.0338 (13)	−0.0031 (12)	−0.0028 (11)	−0.0012 (10)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.9322 (18)	C5—H5	0.9500
Cu1—O4	1.9978 (18)	C6—C9ⁱⁱⁱ	1.503 (4)
Cu1—N4	2.009 (2)	C6—H6A	0.9900
Cu1—N3	2.017 (2)	C6—H6B	0.9900
Cu1—O5	2.343 (2)	C7—C22	1.392 (4)
O1—C19	1.242 (3)	C8—C4ⁱⁱ	1.508 (4)
O2—C24	1.280 (3)	C8—H8A	0.9900
O3—C24	1.233 (3)	C8—H8B	0.9900
O4—C19	1.272 (3)	C9—C6ⁱⁱⁱ	1.503 (4)
O5—H5A	0.820 (18)	C9—H9A	0.9900
O5—H5B	0.825 (17)	C9—H9B	0.9900
N1—C2	1.451 (4)	C10—C16	1.380 (4)
N1—C6	1.458 (4)	C10—C11	1.385 (4)
N1—C9	1.465 (3)	C10—H10	0.9500
N2—C1	1.452 (4)	C11—C18	1.389 (4)
N2—C8	1.461 (4)	C12—C17	1.384 (4)
N2—C4	1.462 (4)	C12—C20	1.401 (4)
N3—C13	1.337 (4)	C12—H12	0.9500
N3—C22	1.341 (3)	C13—H13	0.9500
N4—C18	1.338 (3)	C14—C15	1.389 (4)
N4—C21	1.342 (3)	C14—C23	1.390 (4)
C1—C11	1.506 (4)	C14—C24	1.511 (4)
C1—H1A	0.9900	C15—C17	1.386 (4)
C1—H1B	0.9900	C15—H15	0.9500
C2—C7	1.513 (4)	C16—C21	1.374 (4)
C2—H2A	0.9900	C16—H16	0.9500
C2—H2B	0.9900	C17—H17	0.9500
C3—C7	1.379 (4)	C18—H18	0.9500
C3—C5	1.381 (4)	C19—C20	1.505 (4)
C3—H3	0.9500	C20—C23	1.385 (4)
C4—C8ⁱⁱ	1.508 (4)	C21—H21	0.9500
C4—H4A	0.9900	C22—H22	0.9500
C4—H4B	0.9900	C23—H23	0.9500
C5—C13	1.380 (4)

O2ⁱ—Cu1—O4	153.48 (8)	C22—C7—C2	122.2 (3)
O2ⁱ—Cu1—N4	93.47 (8)	N2—C8—C4ⁱⁱ	110.0 (2)
O4—Cu1—N4	89.57 (8)	N2—C8—H8A	109.7
O2ⁱ—Cu1—N3	91.23 (8)	C4ⁱⁱ—C8—H8A	109.7
O4—Cu1—N3	88.28 (8)	N2—C8—H8B	109.7
N4—Cu1—N3	173.41 (8)	C4ⁱⁱ—C8—H8B	109.7
O2ⁱ—Cu1—O5	95.11 (8)	H8A—C8—H8B	108.2
O4—Cu1—O5	111.24 (7)	N1—C9—C6ⁱⁱⁱ	110.4 (2)
N4—Cu1—O5	90.05 (8)	N1—C9—H9A	109.6
N3—Cu1—O5	84.93 (8)	C6ⁱⁱⁱ—C9—H9A	109.6
C24—O2—Cu1^iv	130.85 (17)	N1—C9—H9B	109.6
C19—O4—Cu1	101.25 (15)	C6ⁱⁱⁱ—C9—H9B	109.6
Cu1—O5—H5A	129 (2)	H9A—C9—H9B	108.1
Cu1—O5—H5B	95 (2)	C16—C10—C11	119.7 (3)
H5A—O5—H5B	116 (3)	C16—C10—H10	120.1
C2—N1—C6	112.3 (2)	C11—C10—H10	120.1
C2—N1—C9	110.0 (2)	C10—C11—C18	117.2 (3)
C6—N1—C9	108.5 (2)	C10—C11—C1	120.6 (3)
C1—N2—C8	111.6 (2)	C18—C11—C1	122.1 (2)
C1—N2—C4	112.1 (2)	C17—C12—C20	119.7 (2)
C8—N2—C4	109.2 (2)	C17—C12—H12	120.1
C13—N3—C22	118.3 (2)	C20—C12—H12	120.1
C13—N3—Cu1	118.38 (18)	N3—C13—C5	122.7 (3)
C22—N3—Cu1	123.13 (18)	N3—C13—H13	118.7
C18—N4—C21	117.8 (2)	C5—C13—H13	118.7
C18—N4—Cu1	122.48 (18)	C15—C14—C23	119.1 (2)
C21—N4—Cu1	119.72 (18)	C15—C14—C24	121.1 (2)
N2—C1—C11	113.3 (2)	C23—C14—C24	119.8 (2)
N2—C1—H1A	108.9	C17—C15—C14	120.2 (3)
C11—C1—H1A	108.9	C17—C15—H15	119.9
N2—C1—H1B	108.9	C14—C15—H15	119.9
C11—C1—H1B	108.9	C21—C16—C10	119.0 (3)
H1A—C1—H1B	107.7	C21—C16—H16	120.5
N1—C2—C7	114.5 (2)	C10—C16—H16	120.5
N1—C2—H2A	108.6	C12—C17—C15	120.6 (3)
C7—C2—H2A	108.6	C12—C17—H17	119.7
N1—C2—H2B	108.6	C15—C17—H17	119.7
C7—C2—H2B	108.6	N4—C18—C11	123.7 (2)
H2A—C2—H2B	107.6	N4—C18—H18	118.2
C7—C3—C5	120.2 (3)	C11—C18—H18	118.2
C7—C3—H3	119.9	O1—C19—O4	123.2 (3)
C5—C3—H3	119.9	O1—C19—C20	119.6 (2)
N2—C4—C8ⁱⁱ	109.8 (2)	O4—C19—C20	117.2 (2)
N2—C4—H4A	109.7	C23—C20—C12	119.1 (2)
C8ⁱⁱ—C4—H4A	109.7	C23—C20—C19	121.0 (2)
N2—C4—H4B	109.7	C12—C20—C19	119.9 (2)
C8ⁱⁱ—C4—H4B	109.7	N4—C21—C16	122.5 (3)
H4A—C4—H4B	108.2	N4—C21—H21	118.7
C13—C5—C3	118.4 (3)	C16—C21—H21	118.7
C13—C5—H5	120.8	N3—C22—C7	122.9 (3)
C3—C5—H5	120.8	N3—C22—H22	118.6
N1—C6—C9ⁱⁱⁱ	110.4 (2)	C7—C22—H22	118.6
N1—C6—H6A	109.6	C20—C23—C14	121.3 (3)
C9ⁱⁱⁱ—C6—H6A	109.6	C20—C23—H23	119.4
N1—C6—H6B	109.6	C14—C23—H23	119.4
C9ⁱⁱⁱ—C6—H6B	109.6	O3—C24—O2	125.9 (2)
H6A—C6—H6B	108.1	O3—C24—C14	120.1 (2)
C3—C7—C22	117.6 (3)	O2—C24—C14	114.0 (2)
C3—C7—C2	120.2 (3)

O2ⁱ—Cu1—O4—C19	−1.3 (3)	C22—N3—C13—C5	0.3 (4)
N4—Cu1—O4—C19	95.58 (16)	Cu1—N3—C13—C5	−174.6 (2)
N3—Cu1—O4—C19	−90.64 (16)	C3—C5—C13—N3	0.4 (4)
O5—Cu1—O4—C19	−174.53 (15)	C23—C14—C15—C17	−0.7 (4)
O2ⁱ—Cu1—N3—C13	156.3 (2)	C24—C14—C15—C17	−178.8 (2)
O4—Cu1—N3—C13	−50.2 (2)	C11—C10—C16—C21	−0.2 (4)
O5—Cu1—N3—C13	61.3 (2)	C20—C12—C17—C15	1.0 (4)
O2ⁱ—Cu1—N3—C22	−18.4 (2)	C14—C15—C17—C12	−0.2 (4)
O4—Cu1—N3—C22	135.1 (2)	C21—N4—C18—C11	−0.6 (4)
O5—Cu1—N3—C22	−113.4 (2)	Cu1—N4—C18—C11	178.0 (2)
O2ⁱ—Cu1—N4—C18	24.1 (2)	C10—C11—C18—N4	0.0 (4)
O4—Cu1—N4—C18	−129.5 (2)	C1—C11—C18—N4	178.2 (3)
O5—Cu1—N4—C18	119.3 (2)	Cu1—O4—C19—O1	−7.3 (3)
O2ⁱ—Cu1—N4—C21	−157.3 (2)	Cu1—O4—C19—C20	171.84 (18)
O4—Cu1—N4—C21	49.1 (2)	C17—C12—C20—C23	−1.0 (4)
O5—Cu1—N4—C21	−62.1 (2)	C17—C12—C20—C19	177.2 (2)
C8—N2—C1—C11	−161.2 (3)	O1—C19—C20—C23	−171.1 (2)
C4—N2—C1—C11	75.9 (3)	O4—C19—C20—C23	9.6 (4)
C6—N1—C2—C7	−72.1 (3)	O1—C19—C20—C12	10.7 (4)
C9—N1—C2—C7	166.9 (3)	O4—C19—C20—C12	−168.6 (2)
C1—N2—C4—C8ⁱⁱ	−176.4 (2)	C18—N4—C21—C16	0.8 (4)
C8—N2—C4—C8ⁱⁱ	59.3 (3)	Cu1—N4—C21—C16	−177.8 (2)
C7—C3—C5—C13	−0.4 (5)	C10—C16—C21—N4	−0.5 (4)
C2—N1—C6—C9ⁱⁱⁱ	179.3 (2)	C13—N3—C22—C7	−1.1 (4)
C9—N1—C6—C9ⁱⁱⁱ	−58.8 (3)	Cu1—N3—C22—C7	173.6 (2)
C5—C3—C7—C22	−0.3 (4)	C3—C7—C22—N3	1.1 (4)
C5—C3—C7—C2	177.2 (3)	C2—C7—C22—N3	−176.4 (3)
N1—C2—C7—C3	166.5 (3)	C12—C20—C23—C14	0.2 (4)
N1—C2—C7—C22	−16.1 (4)	C19—C20—C23—C14	−178.0 (2)
C1—N2—C8—C4ⁱⁱ	176.0 (2)	C15—C14—C23—C20	0.6 (4)
C4—N2—C8—C4ⁱⁱ	−59.4 (3)	C24—C14—C23—C20	178.8 (2)
C2—N1—C9—C6ⁱⁱⁱ	−177.9 (3)	Cu1^iv—O2—C24—O3	4.6 (4)
C6—N1—C9—C6ⁱⁱⁱ	58.8 (3)	Cu1^iv—O2—C24—C14	−174.75 (15)
C16—C10—C11—C18	0.4 (4)	C15—C14—C24—O3	−178.8 (2)
C16—C10—C11—C1	−177.8 (3)	C23—C14—C24—O3	3.1 (4)
N2—C1—C11—C10	−171.6 (3)	C15—C14—C24—O2	0.6 (4)
N2—C1—C11—C18	10.3 (4)	C23—C14—C24—O2	−177.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1^v	0.82 (2)	1.96 (2)	2.778 (3)	174 (3)
O5—H5B···O3ⁱ	0.83 (2)	2.02 (2)	2.805 (3)	158 (3)

Symmetry codes: (i) x, y+1, z; (v) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₄O₄)(C₁₆H₂₀N₄)(H₂O)]
M_r	514.03
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.9122 (4), 10.0328 (5), 16.7456 (9)
α, β, γ (°)	86.822 (1), 84.210 (1), 80.771 (1)
V (Å³)	1139.49 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.34 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (TWINABS; Sheldrick, 2003)
T_min, T_max	0.729, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	31818, 4141, 3681
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.117, 1.16
No. of reflections	4141
No. of parameters	313
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.56

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1ⁱ	0.820 (18)	1.962 (18)	2.778 (3)	174 (3)
O5—H5B···O3ⁱⁱ	0.825 (17)	2.02 (2)	2.805 (3)	158 (3)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work. CMG thanks the Michigan State University Honors College for funding his Professorial Assistantship.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Johnston, L. L., Martin, D. P. & LaDuca, R. L. (2008). Inorg. Chim. Acta, 361, 2887–2894. Web of Science CSD CrossRef CAS Google Scholar
Palmer, D. (2007). CrystalMaker. CrystalMaker Software Ltd, Yarnton, England. Google Scholar
Pocic, D., Planeix, J.-M., Kyritsakas, N., Jouaiti, A. & Husseini, M. W. (2005). CrystEngComm, 7, 624–628. Web of Science CSD CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2009). CELLNOW. University of Göttingen, Germany. Google Scholar

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