Di-μ4-succinato-tetra­kis[aqua­phenanthrolinecopper(II)] tetra­nitrate tetra­hydrate

Kitiphaisalnont, P.; Siripaisarnpipat, S.; Chaichit, N.

doi:10.1107/S1600536809039580

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1284

https://doi.org/10.1107/S1600536809039580

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Di-μ₄-succinato-tetrakis[aquaphenanthrolinecopper(II)] tetranitrate tetrahydrate

Panana Kitiphaisalnont,^a Sutatip Siripaisarnpipat ^a ^* and Narongsak Chaichit ^b

^aDepartment of Chemistry, Kasetsart University, Bangkok 10903, Thailand, and ^bDepartment of Physics, Thammasat University, Rangsit, Pathumthani 12121, Thailand
^*Correspondence e-mail: fscists@ku.ac.th

(Received 21 September 2009; accepted 29 September 2009; online 3 October 2009)

In the title compound, [Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O, the complete tetracation is generated by crystallographic inversion symmetry. Both unique Cu²⁺ ions are coordinated by an N,N′-bidentate phenanthroline molecule, two O-monodentate bis-bridging succinate dianions and a water molecule, resulting in distorted CuN₂O₃ square-based pyramidal geometries for the metal ions, with the water molecule occupying the apical site. In the crystal, the components are linked by O—H⋯O hydrogen bonds and aromatic π–π stacking interactions [minimum centroid–centroid separation = 3.537 (2) Å].

Related literature

For related structures, see: McCann et al. (1998 ); Padmanabhan et al. (2005 ); Ghosh et al. (2007 ).

Experimental

Crystal data

[Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O
M_r = 1599.29
Monoclinic, P 2₁ /c
a = 8.9180 (1) Å
b = 34.1090 (2) Å
c = 10.3620 (2) Å
β = 96.031 (1)°
V = 3134.51 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.10 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: none
23089 measured reflections
8980 independent reflections
7772 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.191
S = 1.05
8980 reflections
463 parameters
101 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.88 e Å⁻³
Δρ_min = −1.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O2	1.948 (3)
Cu1—O5	1.966 (3)
Cu1—N2	2.011 (3)
Cu1—N1	2.015 (3)
Cu1—O4	2.240 (3)
Cu2—O1	1.946 (3)
Cu2—O6	1.952 (3)
Cu2—N4	2.007 (3)
Cu2—N3	2.025 (3)
Cu2—O3	2.160 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H4⋯O14	0.73 (7)	1.99 (7)	2.707 (7)	169 (7)
O3—H16⋯O13	0.70 (6)	2.07 (6)	2.772 (6)	177 (9)
O4—H23⋯O12	0.82 (6)	2.27 (6)	3.015 (7)	153 (5)
O4—H24⋯O10ⁱ	0.82 (5)	2.03 (6)	2.816 (6)	161 (8)
O13—H13C⋯O5ⁱⁱ	0.77 (7)	2.24 (7)	3.000 (5)	167 (7)
O13—H13D⋯O10ⁱⁱⁱ	0.71 (7)	2.23 (7)	2.899 (7)	159 (8)
O14—H14B⋯O9^iv	0.83 (7)	2.15 (6)	2.846 (13)	142 (6)
O14—H14C⋯O7^v	0.82 (9)	2.10 (9)	2.874 (14)	158 (10)
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z; (iii) x+1, y, z-1; (iv) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) x+1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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 I, global. DOI: https://doi.org/10.1107/S1600536809039580/hb5112sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039580/hb5112Isup2.hkl

checkCIF report

Comment top

The moleculular structure of the title compound, (I), consists of a tetranuclear [Cu₄(phen)₄(suc)₂(H₂O)₄].⁴⁺ species and uncoordinated water molecules and nitrate anions. Each Cu(II) ion (Table 1) exhibits a distorted square pyramidal coordination geometry through one apical water oxygen atom, two phen N atoms and two carboxylate O atoms from two succinate dianions which act as bis bridging ligands toward the Cu1 and Cu2 atoms (Fig. 1). The Cu1···Cu2 distance is 3.0318 (4) Å. The succinate ions also bridge two Cu(II) ions (Cu1' and Cu2'). The Cu1 and Cu2' distance separated by the bridging succinate anion is 6.396 Å. The face-to-face π-π interactions between the phenanthroline ring enhance the stability of the structure.

The apical water molecules form hydrogen bonds with nitrate O atoms (O···O distances of 2.810–2.920 Å) and uncoordinated water O atoms (O···O distances of 2.709–2.768Å): Table 2.

Related literature top

For related structures, see: McCann et al. (1998); Padmanabhan et al. (2005); Ghosh et al. (2007).

Experimental top

The solvothermal systhesis was carried out in telflon-lined stainless steel autoclave. A mixture of Cu(NO₃)₂.2H₂O, phenantholine and succinic acid (mole ratio 1:1:1) in (H₂O)/MeOH (2:1) was heated at 423 K for 72 h. Green slabs of (I) in a green solution were obtained.

Structure description top

The apical water molecules form hydrogen bonds with nitrate O atoms (O···O distances of 2.810–2.920 Å) and uncoordinated water O atoms (O···O distances of 2.709–2.768Å): Table 2.

For related structures, see: McCann et al. (1998); Padmanabhan et al. (2005); Ghosh et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (I), with 50% probability displacement ellipsoids for non-H atoms.

Di-µ₄-succinato-tetrakis[aquaphenanthrolinecopper(II)] tetranitrate tetrahydrate top

Crystal data top

[Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O	Z = 2
M_r = 1599.29	F(000) = 1632
Monoclinic, P2₁/c	D_x = 1.694 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.9180 (1) Å	Cell parameters from 23295 reflections
b = 34.1090 (2) Å	µ = 1.44 mm⁻¹
c = 10.3620 (2) Å	T = 293 K
β = 96.031 (1)°	Slab, green
V = 3134.51 (7) Å³	0.20 × 0.19 × 0.10 mm

Data collection top

Bruker SMART 1K CCD diffractometer	7772 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 30.5°, θ_min = 1.2°
ω scans	h = −12→9
23089 measured reflections	k = −37→48
8980 independent reflections	l = −13→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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1023P)² + 8.0138P] where P = (F_o² + 2F_c²)/3
8980 reflections	(Δ/σ)_max < 0.001
463 parameters	Δρ_max = 2.88 e Å⁻³
101 restraints	Δρ_min = −1.59 e Å⁻³

Crystal data top

[Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O	V = 3134.51 (7) Å³
M_r = 1599.29	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9180 (1) Å	µ = 1.44 mm⁻¹
b = 34.1090 (2) Å	T = 293 K
c = 10.3620 (2) Å	0.20 × 0.19 × 0.10 mm
β = 96.031 (1)°

Data collection top

Bruker SMART 1K CCD diffractometer	7772 reflections with I > 2σ(I)
23089 measured reflections	R_int = 0.018
8980 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	101 restraints
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 2.88 e Å⁻³
8980 reflections	Δρ_min = −1.59 e Å⁻³
463 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	0.28697 (5)	0.045902 (12)	0.25937 (4)	0.02773 (12)
Cu2	0.45414 (5)	0.092420 (12)	0.07025 (4)	0.02759 (12)
O1	0.5954 (3)	0.05491 (8)	0.1565 (3)	0.0403 (6)
O2	0.4661 (3)	0.01290 (8)	0.2689 (3)	0.0384 (6)
O3	0.6118 (4)	0.11127 (12)	−0.0618 (3)	0.0431 (7)
O4	0.1350 (5)	0.01289 (11)	0.3799 (4)	0.0577 (9)
O5	0.2091 (3)	0.02148 (9)	0.0939 (3)	0.0366 (6)
O6	0.3553 (4)	0.05135 (8)	−0.0390 (3)	0.0396 (6)
O7	−0.1911 (12)	0.2391 (4)	0.0691 (10)	0.191 (2)
O8	−0.1382 (12)	0.2708 (4)	0.2187 (10)	0.191 (2)
O9	−0.3494 (12)	0.2700 (4)	0.1619 (9)	0.191 (2)
O10	−0.0018 (6)	0.06202 (15)	0.6390 (5)	0.0804 (7)
O11	−0.1232 (6)	0.11331 (15)	0.5928 (5)	0.0804 (7)
O12	−0.0996 (6)	0.07141 (15)	0.4439 (5)	0.0804 (7)
O13	0.8466 (5)	0.06449 (13)	−0.1270 (4)	0.0529 (8)
O14	0.6181 (10)	0.18964 (17)	−0.1023 (7)	0.105 (2)
N1	0.1424 (3)	0.09146 (9)	0.2426 (3)	0.0281 (5)
N2	0.3661 (3)	0.07455 (9)	0.4221 (3)	0.0299 (6)
N3	0.2987 (3)	0.13232 (9)	−0.0008 (3)	0.0313 (6)
N4	0.5046 (3)	0.13445 (8)	0.2033 (3)	0.0285 (5)
N5	−0.0754 (7)	0.08168 (19)	0.5574 (6)	0.0804 (7)
N6	−0.2256 (16)	0.2581 (4)	0.1483 (12)	0.191 (2)
C1	0.0277 (4)	0.09854 (12)	0.1527 (4)	0.0348 (7)
H1	0.0070	0.0806	0.0856	0.042*
C2	−0.0628 (5)	0.13195 (14)	0.1556 (5)	0.0442 (9)
H2	−0.1422	0.1359	0.0912	0.053*
C3	−0.0343 (5)	0.15882 (13)	0.2536 (5)	0.0441 (9)
H3	−0.0919	0.1815	0.2547	0.053*
C4	0.0829 (4)	0.15163 (11)	0.3524 (4)	0.0357 (7)
C5	0.1192 (6)	0.17666 (13)	0.4627 (5)	0.0502 (11)
H5	0.0631	0.1993	0.4711	0.060*
C6	0.2326 (6)	0.16796 (14)	0.5539 (4)	0.0524 (11)
H6	0.2540	0.1849	0.6237	0.063*
C7	0.3218 (5)	0.13296 (12)	0.5464 (4)	0.0396 (8)
C8	0.4391 (6)	0.12140 (15)	0.6398 (4)	0.0508 (11)
H8	0.4656	0.1369	0.7124	0.061*
C9	0.5138 (6)	0.08717 (15)	0.6231 (4)	0.0507 (11)
H9	0.5903	0.0790	0.6852	0.061*
C10	0.4754 (5)	0.06441 (13)	0.5126 (4)	0.0404 (8)
H10	0.5284	0.0413	0.5021	0.049*
C11	0.2887 (4)	0.10818 (11)	0.4393 (3)	0.0302 (6)
C12	0.1680 (4)	0.11755 (10)	0.3420 (3)	0.0287 (6)
C13	0.1976 (5)	0.12984 (14)	−0.1039 (4)	0.0409 (8)
H13	0.1950	0.1075	−0.1555	0.049*
C14	0.0944 (5)	0.16024 (16)	−0.1369 (5)	0.0503 (11)
H14	0.0256	0.1580	−0.2105	0.060*
C15	0.0946 (5)	0.19314 (14)	−0.0612 (5)	0.0495 (10)
H15	0.0250	0.2131	−0.0818	0.059*
C16	0.2019 (5)	0.19638 (12)	0.0489 (4)	0.0401 (8)
C17	0.2115 (6)	0.22905 (12)	0.1378 (5)	0.0513 (11)
H17	0.1425	0.2495	0.1242	0.062*
C18	0.3176 (6)	0.23065 (12)	0.2398 (6)	0.0529 (11)
H18	0.3224	0.2524	0.2941	0.063*
C19	0.4237 (5)	0.19925 (11)	0.2661 (4)	0.0385 (8)
C20	0.5367 (6)	0.19841 (13)	0.3722 (5)	0.0478 (10)
H20	0.5482	0.2194	0.4295	0.057*
C21	0.6289 (5)	0.16652 (14)	0.3902 (4)	0.0446 (9)
H21	0.7046	0.1660	0.4591	0.053*
C22	0.6097 (4)	0.13465 (12)	0.3049 (4)	0.0346 (7)
H22	0.6723	0.1129	0.3195	0.042*
C23	0.4138 (4)	0.16638 (10)	0.1835 (4)	0.0300 (6)
C24	0.3028 (4)	0.16508 (10)	0.0740 (3)	0.0303 (6)
C25	0.5830 (4)	0.02380 (10)	0.2196 (3)	0.0288 (6)
C26	0.7229 (4)	−0.00119 (11)	0.2433 (3)	0.0307 (7)
C27	0.2562 (4)	0.02685 (10)	−0.0151 (3)	0.0276 (6)
C28	0.1862 (4)	0.00277 (12)	−0.1284 (4)	0.0319 (7)
H13D	0.865 (7)	0.0669 (19)	−0.191 (7)	0.054 (19)*
H13C	0.840 (8)	0.042 (2)	−0.128 (7)	0.07 (2)*
H4	0.624 (7)	0.132 (2)	−0.075 (6)	0.055 (18)*
H16	0.671 (7)	0.0999 (18)	−0.081 (6)	0.047 (16)*
H24	0.101 (10)	−0.0089 (12)	0.393 (9)	0.11 (3)*
H23	0.080 (6)	0.0256 (17)	0.422 (5)	0.065 (19)*
H28B	0.173 (7)	−0.0210 (18)	−0.092 (6)	0.057 (16)*
H26B	0.704 (7)	−0.0255 (19)	0.270 (6)	0.058 (16)*
H26A	0.773 (6)	0.0080 (14)	0.316 (5)	0.039 (12)*
H28A	0.098 (7)	0.0156 (19)	−0.140 (6)	0.065 (18)*
H14B	0.669 (8)	0.200 (2)	−0.155 (6)	0.10 (3)*
H14C	0.679 (10)	0.198 (3)	−0.044 (8)	0.09 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0279 (2)	0.0305 (2)	0.0247 (2)	0.00133 (15)	0.00241 (15)	−0.00501 (15)
Cu2	0.0291 (2)	0.0243 (2)	0.0287 (2)	0.00061 (14)	−0.00019 (15)	−0.00122 (14)
O1	0.0387 (14)	0.0304 (13)	0.0505 (16)	0.0070 (11)	−0.0019 (12)	0.0056 (11)
O2	0.0359 (13)	0.0400 (14)	0.0402 (14)	0.0100 (11)	0.0079 (11)	0.0007 (11)
O3	0.0407 (16)	0.0469 (19)	0.0435 (16)	0.0031 (14)	0.0136 (13)	0.0056 (14)
O4	0.072 (2)	0.0434 (18)	0.063 (2)	−0.0140 (17)	0.0327 (19)	−0.0013 (16)
O5	0.0366 (13)	0.0438 (15)	0.0298 (12)	−0.0025 (11)	0.0053 (10)	−0.0122 (11)
O6	0.0477 (16)	0.0338 (13)	0.0368 (14)	−0.0110 (11)	0.0018 (12)	−0.0077 (11)
O7	0.146 (4)	0.276 (7)	0.139 (4)	0.073 (4)	−0.043 (3)	−0.078 (4)
O8	0.146 (4)	0.276 (7)	0.139 (4)	0.073 (4)	−0.043 (3)	−0.078 (4)
O9	0.146 (4)	0.276 (7)	0.139 (4)	0.073 (4)	−0.043 (3)	−0.078 (4)
O10	0.0886 (18)	0.0729 (15)	0.0775 (16)	0.0048 (13)	−0.0016 (13)	−0.0012 (13)
O11	0.0886 (18)	0.0729 (15)	0.0775 (16)	0.0048 (13)	−0.0016 (13)	−0.0012 (13)
O12	0.0886 (18)	0.0729 (15)	0.0775 (16)	0.0048 (13)	−0.0016 (13)	−0.0012 (13)
O13	0.062 (2)	0.051 (2)	0.048 (2)	0.0071 (17)	0.0155 (17)	−0.0016 (16)
O14	0.169 (7)	0.059 (3)	0.089 (4)	−0.035 (4)	0.023 (5)	0.007 (3)
N1	0.0273 (13)	0.0322 (14)	0.0246 (12)	−0.0023 (10)	0.0023 (10)	−0.0017 (10)
N2	0.0325 (14)	0.0333 (14)	0.0235 (12)	−0.0018 (11)	0.0004 (11)	−0.0009 (11)
N3	0.0293 (14)	0.0331 (14)	0.0307 (14)	0.0010 (11)	−0.0004 (11)	0.0028 (11)
N4	0.0275 (13)	0.0258 (13)	0.0316 (14)	0.0000 (10)	0.0008 (11)	−0.0001 (10)
N5	0.0886 (18)	0.0729 (15)	0.0775 (16)	0.0048 (13)	−0.0016 (13)	−0.0012 (13)
N6	0.146 (4)	0.276 (7)	0.139 (4)	0.073 (4)	−0.043 (3)	−0.078 (4)
C1	0.0276 (16)	0.0421 (19)	0.0333 (17)	−0.0040 (14)	−0.0037 (13)	−0.0033 (14)
C2	0.0297 (18)	0.053 (2)	0.048 (2)	0.0044 (16)	−0.0056 (16)	0.0041 (19)
C3	0.0336 (18)	0.038 (2)	0.060 (3)	0.0081 (15)	0.0050 (17)	0.0029 (18)
C4	0.0380 (18)	0.0296 (16)	0.0399 (19)	0.0033 (14)	0.0060 (15)	−0.0033 (14)
C5	0.064 (3)	0.0328 (19)	0.055 (3)	0.0055 (19)	0.010 (2)	−0.0127 (18)
C6	0.076 (3)	0.041 (2)	0.040 (2)	0.001 (2)	0.004 (2)	−0.0183 (18)
C7	0.052 (2)	0.0382 (19)	0.0274 (16)	−0.0061 (16)	0.0000 (15)	−0.0065 (14)
C8	0.067 (3)	0.055 (3)	0.0281 (18)	−0.009 (2)	−0.0080 (18)	−0.0079 (17)
C9	0.057 (3)	0.060 (3)	0.0311 (19)	−0.001 (2)	−0.0140 (18)	0.0008 (18)
C10	0.044 (2)	0.045 (2)	0.0307 (17)	0.0021 (16)	−0.0045 (15)	0.0051 (15)
C11	0.0355 (17)	0.0324 (16)	0.0225 (14)	−0.0036 (13)	0.0025 (12)	−0.0024 (12)
C12	0.0289 (15)	0.0295 (15)	0.0279 (15)	−0.0003 (12)	0.0043 (12)	−0.0034 (12)
C13	0.0392 (19)	0.051 (2)	0.0314 (17)	0.0005 (17)	−0.0034 (15)	0.0014 (16)
C14	0.043 (2)	0.065 (3)	0.040 (2)	0.004 (2)	−0.0099 (17)	0.010 (2)
C15	0.044 (2)	0.048 (2)	0.054 (3)	0.0117 (19)	−0.0056 (19)	0.015 (2)
C16	0.0401 (19)	0.0319 (18)	0.048 (2)	0.0054 (15)	0.0032 (16)	0.0113 (16)
C17	0.056 (3)	0.0281 (18)	0.068 (3)	0.0121 (17)	0.001 (2)	0.0058 (19)
C18	0.062 (3)	0.0242 (17)	0.072 (3)	0.0041 (17)	0.004 (2)	−0.0074 (19)
C19	0.042 (2)	0.0251 (16)	0.048 (2)	−0.0041 (14)	0.0037 (16)	−0.0028 (15)
C20	0.053 (2)	0.040 (2)	0.049 (2)	−0.0090 (18)	−0.0010 (19)	−0.0123 (18)
C21	0.041 (2)	0.050 (2)	0.040 (2)	−0.0082 (17)	−0.0066 (16)	−0.0077 (17)
C22	0.0298 (16)	0.0386 (18)	0.0343 (17)	−0.0006 (13)	−0.0018 (13)	0.0008 (14)
C23	0.0308 (16)	0.0243 (14)	0.0346 (16)	−0.0019 (12)	0.0018 (13)	0.0015 (12)
C24	0.0302 (15)	0.0274 (15)	0.0335 (16)	0.0011 (12)	0.0044 (13)	0.0052 (12)
C25	0.0325 (16)	0.0280 (15)	0.0248 (14)	0.0066 (12)	−0.0026 (12)	−0.0060 (11)
C26	0.0326 (16)	0.0332 (17)	0.0250 (15)	0.0076 (13)	−0.0036 (12)	−0.0022 (13)
C27	0.0254 (14)	0.0275 (15)	0.0287 (15)	0.0053 (11)	−0.0021 (11)	−0.0070 (12)
C28	0.0272 (15)	0.0353 (17)	0.0320 (16)	0.0006 (13)	−0.0024 (12)	−0.0101 (14)

Geometric parameters (Å, º) top

Cu1—O2	1.948 (3)	C4—C12	1.398 (5)
Cu1—O5	1.966 (3)	C4—C5	1.437 (6)
Cu1—N2	2.011 (3)	C5—C6	1.342 (7)
Cu1—N1	2.015 (3)	C5—H5	0.9300
Cu1—O4	2.240 (3)	C6—C7	1.441 (6)
Cu1—Cu2	3.0322 (6)	C6—H6	0.9300
Cu2—O1	1.946 (3)	C7—C11	1.401 (5)
Cu2—O6	1.952 (3)	C7—C8	1.405 (6)
Cu2—N4	2.007 (3)	C8—C9	1.364 (7)
Cu2—N3	2.025 (3)	C8—H8	0.9300
Cu2—O3	2.160 (3)	C9—C10	1.396 (6)
O1—C25	1.258 (5)	C9—H9	0.9300
O2—C25	1.264 (5)	C10—H10	0.9300
O3—H4	0.73 (7)	C11—C12	1.432 (5)
O3—H16	0.70 (6)	C13—C14	1.405 (6)
O4—H24	0.82 (5)	C13—H13	0.9300
O4—H23	0.82 (6)	C14—C15	1.369 (7)
O5—C27	1.259 (4)	C14—H14	0.9300
O6—C27	1.260 (5)	C15—C16	1.415 (6)
O7—N6	1.114 (14)	C15—H15	0.9300
O8—N6	1.099 (14)	C16—C24	1.403 (5)
O9—N6	1.199 (14)	C16—C17	1.443 (7)
O10—N5	1.216 (8)	C17—C18	1.344 (7)
O11—N5	1.231 (8)	C17—H17	0.9300
O12—N5	1.224 (8)	C18—C19	1.436 (6)
O13—H13D	0.70 (7)	C18—H18	0.9300
O13—H13C	0.75 (8)	C19—C23	1.407 (5)
O14—H14B	0.83 (7)	C19—C20	1.411 (6)
O14—H14C	0.82 (8)	C20—C21	1.364 (7)
N1—C1	1.331 (4)	C20—H20	0.9300
N1—C12	1.362 (4)	C21—C22	1.400 (6)
N2—C10	1.326 (5)	C21—H21	0.9300
N2—C11	1.360 (5)	C22—H22	0.9300
N3—C13	1.327 (5)	C23—C24	1.426 (5)
N3—C24	1.358 (5)	C25—C26	1.510 (5)
N4—C22	1.334 (5)	C26—C28ⁱ	1.510 (5)
N4—C23	1.359 (4)	C26—H26B	0.90 (6)
C1—C2	1.399 (6)	C26—H26A	0.89 (5)
C1—H1	0.9300	C27—C28	1.513 (4)
C2—C3	1.371 (7)	C28—C26ⁱ	1.510 (5)
C2—H2	0.9300	C28—H28B	0.91 (6)
C3—C4	1.406 (6)	C28—H28A	0.90 (7)
C3—H3	0.9300

O2—Cu1—O5	90.69 (12)	C5—C6—C7	121.6 (4)
O2—Cu1—N2	91.42 (12)	C5—C6—H6	119.2
O5—Cu1—N2	175.95 (12)	C7—C6—H6	119.2
O2—Cu1—N1	164.53 (12)	C11—C7—C8	117.1 (4)
O5—Cu1—N1	95.00 (12)	C11—C7—C6	118.1 (4)
N2—Cu1—N1	82.10 (12)	C8—C7—C6	124.8 (4)
O2—Cu1—O4	102.84 (14)	C9—C8—C7	119.4 (4)
O5—Cu1—O4	95.40 (14)	C9—C8—H8	120.3
N2—Cu1—O4	87.49 (14)	C7—C8—H8	120.3
N1—Cu1—O4	90.95 (14)	C8—C9—C10	120.0 (4)
O2—Cu1—Cu2	83.04 (9)	C8—C9—H9	120.0
O5—Cu1—Cu2	79.10 (9)	C10—C9—H9	120.0
N2—Cu1—Cu2	97.73 (9)	N2—C10—C9	122.3 (4)
N1—Cu1—Cu2	83.93 (8)	N2—C10—H10	118.9
O4—Cu1—Cu2	172.09 (12)	C9—C10—H10	118.9
O1—Cu2—O6	91.46 (13)	N2—C11—C7	123.0 (3)
O1—Cu2—N4	93.81 (12)	N2—C11—C12	116.7 (3)
O6—Cu2—N4	164.98 (13)	C7—C11—C12	120.2 (3)
O1—Cu2—N3	173.84 (13)	N1—C12—C4	123.5 (3)
O6—Cu2—N3	91.23 (13)	N1—C12—C11	116.2 (3)
N4—Cu2—N3	82.25 (12)	C4—C12—C11	120.3 (3)
O1—Cu2—O3	93.07 (14)	N3—C13—C14	121.4 (4)
O6—Cu2—O3	97.50 (14)	N3—C13—H13	119.3
N4—Cu2—O3	96.25 (14)	C14—C13—H13	119.3
N3—Cu2—O3	92.07 (14)	C15—C14—C13	120.3 (4)
O1—Cu2—Cu1	72.40 (9)	C15—C14—H14	119.9
O6—Cu2—Cu1	77.09 (9)	C13—C14—H14	119.9
N4—Cu2—Cu1	91.12 (9)	C14—C15—C16	119.1 (4)
N3—Cu2—Cu1	102.83 (9)	C14—C15—H15	120.5
O3—Cu2—Cu1	164.16 (11)	C16—C15—H15	120.5
C25—O1—Cu2	134.9 (3)	C24—C16—C15	117.2 (4)
C25—O2—Cu1	121.1 (2)	C24—C16—C17	118.4 (4)
Cu2—O3—H4	122 (5)	C15—C16—C17	124.4 (4)
Cu2—O3—H16	125 (5)	C18—C17—C16	121.5 (4)
H4—O3—H16	110 (7)	C18—C17—H17	119.2
Cu1—O4—H24	144 (7)	C16—C17—H17	119.2
Cu1—O4—H23	118 (5)	C17—C18—C19	121.0 (4)
H24—O4—H23	98 (7)	C17—C18—H18	119.5
C27—O5—Cu1	126.8 (2)	C19—C18—H18	119.5
C27—O6—Cu2	130.2 (2)	C23—C19—C20	116.8 (4)
H13D—O13—H13C	97 (7)	C23—C19—C18	118.7 (4)
H14B—O14—H14C	88 (8)	C20—C19—C18	124.4 (4)
C1—N1—C12	117.8 (3)	C21—C20—C19	119.6 (4)
C1—N1—Cu1	129.7 (3)	C21—C20—H20	120.2
C12—N1—Cu1	112.5 (2)	C19—C20—H20	120.2
C10—N2—C11	118.2 (3)	C20—C21—C22	120.0 (4)
C10—N2—Cu1	129.3 (3)	C20—C21—H21	120.0
C11—N2—Cu1	112.4 (2)	C22—C21—H21	120.0
C13—N3—C24	119.2 (3)	N4—C22—C21	122.1 (4)
C13—N3—Cu2	129.1 (3)	N4—C22—H22	119.0
C24—N3—Cu2	111.7 (2)	C21—C22—H22	119.0
C22—N4—C23	118.2 (3)	N4—C23—C19	123.3 (3)
C22—N4—Cu2	129.3 (3)	N4—C23—C24	116.6 (3)
C23—N4—Cu2	112.4 (2)	C19—C23—C24	120.1 (3)
O10—N5—O12	122.5 (7)	N3—C24—C16	122.8 (3)
O10—N5—O11	117.0 (6)	N3—C24—C23	117.0 (3)
O12—N5—O11	120.4 (6)	C16—C24—C23	120.1 (3)
O8—N6—O7	119.1 (16)	O1—C25—O2	125.4 (3)
O8—N6—O9	112.7 (14)	O1—C25—C26	116.4 (3)
O7—N6—O9	127.8 (14)	O2—C25—C26	118.1 (3)
N1—C1—C2	122.4 (4)	C25—C26—C28ⁱ	113.2 (3)
N1—C1—H1	118.8	C25—C26—H26B	113 (4)
C2—C1—H1	118.8	C28ⁱ—C26—H26B	110 (4)
C3—C2—C1	119.9 (4)	C25—C26—H26A	106 (3)
C3—C2—H2	120.1	C28ⁱ—C26—H26A	114 (3)
C1—C2—H2	120.1	H26B—C26—H26A	99 (5)
C2—C3—C4	119.2 (4)	O5—C27—O6	125.5 (3)
C2—C3—H3	120.4	O5—C27—C28	117.9 (3)
C4—C3—H3	120.4	O6—C27—C28	116.6 (3)
C12—C4—C3	117.2 (4)	C26ⁱ—C28—C27	114.8 (3)
C12—C4—C5	118.5 (4)	C26ⁱ—C28—H28B	114 (4)
C3—C4—C5	124.3 (4)	C27—C28—H28B	103 (4)
C6—C5—C4	121.3 (4)	C26ⁱ—C28—H28A	116 (4)
C6—C5—H5	119.4	C27—C28—H28A	97 (4)
C4—C5—H5	119.4	H28B—C28—H28A	110 (5)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4···O14	0.73 (7)	1.99 (7)	2.707 (7)	169 (7)
O3—H16···O13	0.70 (6)	2.07 (6)	2.772 (6)	177 (9)
O4—H23···O12	0.82 (6)	2.27 (6)	3.015 (7)	153 (5)
O4—H24···O10ⁱⁱ	0.82 (5)	2.03 (6)	2.816 (6)	161 (8)
O13—H13C···O5ⁱ	0.77 (7)	2.24 (7)	3.000 (5)	167 (7)
O13—H13D···O10ⁱⁱⁱ	0.71 (7)	2.23 (7)	2.899 (7)	159 (8)
O14—H14B···O9^iv	0.83 (7)	2.15 (6)	2.846 (13)	142 (6)
O14—H14C···O7^v	0.82 (9)	2.10 (9)	2.874 (14)	158 (10)

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

Experimental details

Crystal data
Chemical formula	[Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O
M_r	1599.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.9180 (1), 34.1090 (2), 10.3620 (2)
β (°)	96.031 (1)
V (Å³)	3134.51 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.20 × 0.19 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	23089, 8980, 7772
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.191, 1.05
No. of reflections	8980
No. of parameters	463
No. of restraints	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.88, −1.59

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O2	1.948 (3)	Cu2—O1	1.946 (3)
Cu1—O5	1.966 (3)	Cu2—O6	1.952 (3)
Cu1—N2	2.011 (3)	Cu2—N4	2.007 (3)
Cu1—N1	2.015 (3)	Cu2—N3	2.025 (3)
Cu1—O4	2.240 (3)	Cu2—O3	2.160 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4···O14	0.73 (7)	1.99 (7)	2.707 (7)	169 (7)
O3—H16···O13	0.70 (6)	2.07 (6)	2.772 (6)	177 (9)
O4—H23···O12	0.82 (6)	2.27 (6)	3.015 (7)	153 (5)
O4—H24···O10ⁱ	0.82 (5)	2.03 (6)	2.816 (6)	161 (8)
O13—H13C···O5ⁱⁱ	0.77 (7)	2.24 (7)	3.000 (5)	167 (7)
O13—H13D···O10ⁱⁱⁱ	0.71 (7)	2.23 (7)	2.899 (7)	159 (8)
O14—H14B···O9^iv	0.83 (7)	2.15 (6)	2.846 (13)	142 (6)
O14—H14C···O7^v	0.82 (9)	2.10 (9)	2.874 (14)	158 (10)

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

Acknowledgements

The authors thank the Royal Golden Jubilee PhD Program (RGJ) for financial support.

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ghosh, A. K., Ghoshal, D., Zangrando, E., Ribas, J. & Chaudhuri, N. R. (2007). Inorg. Chem. 46, 3057–3071. Web of Science CSD CrossRef PubMed CAS Google Scholar
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