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One naphthalene-1,4-dicarboxyl­ate dianion in the title compound, [Cu2(C12H6O4)2(C14H8N4)2]·4H2O, bridges two N-heterocycle-chelated Cu atoms whereas the other one bridges four N-heterocycle-chelated Cu atoms, linking them into a flat carboxyl­ate-bridged layer. The two independent Cu atoms show square-pyramidal coordination. Water mol­ecules occupy the space between adjacent layers; they are possibly disordered, and their H atoms were not located.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056310/bt2581sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056310/bt2581Isup2.hkl
Contains datablock I

CCDC reference: 672638

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.007 Å
  • H-atom completeness 78%
  • R factor = 0.055
  • wR factor = 0.190
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT220_ALERT_2_A Large Non-Solvent O Ueq(max)/Ueq(min) ... 4.65 Ratio
Author Response: The lattice water molecules are disordered, but the disorder was not treated.
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W
Author Response: Hydrogen atoms for the four water molecules are not placed.
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O2W
Author Response: Hydrogen atoms for the four water molecules are not placed.
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O3W
Author Response: Hydrogen atoms for the four water molecules are not placed.
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O4W
Author Response: Hydrogen atoms for the four water molecules are not placed.

Alert level B PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2 .. 2.80 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O3W .. O4W .. 2.61 Ang.
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.88 PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.04 PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 2346.00 Ang-3 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 2000 Deg. PLAT213_ALERT_2_C Atom O6 has ADP max/min Ratio ............. 3.30 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.68 Ratio
Author Response: The lattice water molecules are disordered, but the disorder was not treated.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT430_ALERT_2_C Short Inter D...A Contact  O4     ..  O4W     ..       2.86 Ang.

Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C52 H36 Cu2 N8 O12 Atom count from the _atom_site data: C52 H28 Cu2 N8 O12 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C52 H36 Cu2 N8 O12 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 104.00 104.00 0.00 H 72.00 56.00 16.00 Cu 4.00 4.00 0.00 N 16.00 16.00 0.00 O 24.00 24.00 0.00 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.06 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2 (2) 2.12 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 436
5 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 13 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check

Comment top

The Cambridge Structural Database (Version 5.28, November 2006) lists several examples of metal(II) naphthalene-1,4-dicarboxylates (Maji et al., 2005; Zheng et al., 2004). The dicarboxylate group is rigid, like terephthalic acid. The copper terephthalate complex of the title heterocycle (Wang et al., 2006) has water in the coordination enviroment of the cadmium atom; the compound exists as a linear chain; one carboxyl end is chelating whereas the other is unidentate.

Related literature top

The Cambridge Structural Database (Version 5.28, November 2006) lists several examples of metal(II) naphthalene-1,4-dicarboxylates. For hydrated diaqua(4,4'-bipyridine)-cobalt, -nickel and -copper compounds, see: Maji et al. (2005); Zheng et al. (2004). For the hydrated 1,2-bis(4-pyridyl)ethanecopper compound, see: Maji et al. (2005). For the crystal structure of naphthalene-1,4-dicarboxylic acid, see: Derissen et al. (1979). For the copper terephthalate complex of the N-heterocycle, see: Wang et al. (2006).

Experimental top

Copper chloride dihydrate (0.1 mmol), naphthalene-1,4-dicarboxylic acid (0.1 mmol), pyrazino[2,3-f][1,10]phenanthroline and water (12 ml) were sealed in a 23-ml Teflon-lined Parr bomb, which was heated at 423 K for two days. Blue block crystals were picked from the cool solution by hand in about 30% yield.

Refinement top

As all C–, N– and O-atoms showed somewhat elongated ellipsoids, their anisotropic temperature factors were restrained to be nearly isotropic. The O2, O4, O6 and O8 atoms, which are not involved in coordination, showed large displacement parameters. An attempt was made to refine each atom as two atoms of half site-occupancy each, with the pairs of C–O double-bond distances restrained to within 0.01 Å of each other. However, this treatment required the carboxyl –CO2 group to be approximately planar, so that the O1, O3, O5 and O7 atoms that are involved in coordination would have to be split into two. As the treatment led to only a minor separation between the disorder components, the structure was refined without disorder.

Carbon-bound H atoms were placed in calculated positions [C—H 0.93–0.97 Å and Uiso(H) 1.2–1.5Ueq(C)], and were included in the refinement in the riding-model approximation. The water H-atoms could not be placed in chemically sensible positions on the basis of hydrogen bonding, and were not included.

The final difference Fourier map had a large peak near O3w.

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of a portion of the chain structure; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius. (Symmetry codes are given in Table 1.)
[Figure 2] Fig. 2. OLEX (Dolomanov et al., 2003) representation of the layer network.
Poly[[(µ4-naphthalene-1,4-dicarboxylato- κ4O:O:O:O')(µ2-naphthalene-1,4- dicarboxylato-κ2O:O')bis(pyrazino[2,3-f][1,10]phenanthroline-κ2N,N')dicopper(II)] tetrahydrate] top
Crystal data top
[Cu2(C12H6O4)2(C14H8N4)2]·4H2OZ = 2
Mr = 1091.97F(000) = 1116
Triclinic, P1Dx = 1.546 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.679 (5) ÅCell parameters from 15645 reflections
b = 14.690 (6) Åθ = 3.0–27.5°
c = 14.833 (7) ŵ = 0.98 mm1
α = 69.37 (2)°T = 295 K
β = 82.05 (2)°Block, blue
γ = 65.13 (2)°0.38 × 0.27 × 0.16 mm
V = 2346 (2) Å3
Data collection top
Rigaku RAXIS-RAPID
diffractometer
10535 independent reflections
Radiation source: fine-focus sealed tube6887 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω–scansh = 1616
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1819
Tmin = 0.618, Tmax = 0.859l = 1919
22789 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.1132P)2]
where P = (Fo2 + 2Fc2)/3
10535 reflections(Δ/σ)max = 0.001
667 parametersΔρmax = 1.03 e Å3
436 restraintsΔρmin = 0.51 e Å3
Crystal data top
[Cu2(C12H6O4)2(C14H8N4)2]·4H2Oγ = 65.13 (2)°
Mr = 1091.97V = 2346 (2) Å3
Triclinic, P1Z = 2
a = 12.679 (5) ÅMo Kα radiation
b = 14.690 (6) ŵ = 0.98 mm1
c = 14.833 (7) ÅT = 295 K
α = 69.37 (2)°0.38 × 0.27 × 0.16 mm
β = 82.05 (2)°
Data collection top
Rigaku RAXIS-RAPID
diffractometer
10535 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
6887 reflections with I > 2σ(I)
Tmin = 0.618, Tmax = 0.859Rint = 0.032
22789 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055436 restraints
wR(F2) = 0.190H-atom parameters constrained
S = 1.09Δρmax = 1.03 e Å3
10535 reflectionsΔρmin = 0.51 e Å3
667 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.40502 (3)0.45832 (4)0.46309 (3)0.03280 (15)
Cu21.08859 (3)0.04876 (3)0.02766 (3)0.03177 (15)
O10.5140 (2)0.4239 (2)0.3639 (2)0.0448 (7)
O20.4999 (3)0.2724 (3)0.3878 (3)0.0798 (12)
O30.9640 (2)0.1145 (3)0.1032 (2)0.0484 (7)
O40.9801 (3)0.2685 (3)0.0434 (3)0.0950 (14)
O50.5321 (2)0.4001 (2)0.55622 (19)0.0403 (6)
O60.5128 (5)0.2520 (4)0.6161 (4)0.166 (3)
O70.9755 (2)0.0895 (2)0.92765 (18)0.0358 (6)
O81.0457 (3)0.1950 (3)0.8171 (3)0.0884 (14)
O1W0.4320 (7)0.1517 (6)0.3165 (6)0.172 (3)
O2W0.4226 (10)0.0548 (8)0.4733 (8)0.264 (5)
O3W0.2273 (10)0.2971 (9)0.1769 (10)0.269 (5)
O4W0.0234 (8)0.4201 (7)0.0950 (7)0.199 (3)
N10.2756 (3)0.5119 (3)0.5508 (2)0.0365 (7)
N20.1416 (3)0.6969 (3)0.5521 (3)0.0618 (11)
N30.1518 (3)0.6744 (3)0.3731 (3)0.0564 (11)
N40.2664 (3)0.5018 (3)0.3791 (2)0.0374 (7)
N51.2335 (3)0.0271 (3)0.0366 (2)0.0370 (7)
N61.6504 (3)0.2026 (4)0.0081 (4)0.0778 (15)
N71.6236 (4)0.1483 (4)0.1776 (4)0.0813 (16)
N81.2092 (3)0.0200 (3)0.1218 (2)0.0419 (8)
C10.5436 (3)0.3354 (4)0.3488 (3)0.0456 (10)
C20.6396 (4)0.3128 (3)0.2770 (3)0.0410 (9)
C30.6428 (3)0.3867 (3)0.1860 (3)0.0412 (9)
C40.5545 (4)0.4905 (4)0.1521 (3)0.0542 (11)
H40.49290.51220.19240.065*
C50.5566 (5)0.5586 (5)0.0639 (4)0.0773 (17)
H50.49630.62560.04390.093*
C60.6494 (5)0.5291 (5)0.0019 (4)0.0838 (18)
H60.65090.57670.05890.101*
C70.7375 (5)0.4303 (5)0.0309 (4)0.0701 (15)
H70.79800.41150.01110.084*
C80.7392 (4)0.3555 (4)0.1236 (3)0.0448 (10)
C90.8284 (4)0.2514 (4)0.1551 (3)0.0446 (10)
C100.8216 (4)0.1838 (4)0.2438 (3)0.0497 (11)
H100.88050.11610.26460.060*
C110.7283 (4)0.2133 (4)0.3046 (3)0.0475 (10)
H110.72610.16480.36470.057*
C120.9324 (3)0.2109 (4)0.0949 (3)0.0519 (11)
C130.5642 (3)0.3075 (4)0.6105 (3)0.0597 (14)
C140.6719 (4)0.2660 (3)0.6709 (3)0.0467 (11)
C150.7829 (4)0.2141 (4)0.6364 (3)0.0525 (12)
C160.7986 (5)0.1958 (5)0.5469 (4)0.0658 (14)
H160.73370.21810.50940.079*
C170.9053 (6)0.1467 (5)0.5149 (4)0.0778 (17)
H170.91330.13560.45590.093*
C181.0043 (5)0.1124 (5)0.5705 (5)0.0752 (16)
H181.07770.07790.54850.090*
C190.9937 (4)0.1291 (4)0.6554 (4)0.0594 (13)
H191.06040.10670.69070.071*
C200.8835 (4)0.1799 (3)0.6927 (3)0.0458 (10)
C210.8679 (3)0.1958 (3)0.7835 (3)0.0451 (11)
C220.7598 (4)0.2426 (4)0.8150 (3)0.0497 (11)
H220.75070.25000.87560.060*
C230.6608 (4)0.2801 (4)0.7583 (4)0.0533 (12)
H230.58750.31460.78040.064*
C240.9719 (3)0.1584 (3)0.8466 (3)0.0448 (10)
C250.2843 (4)0.5114 (4)0.6399 (3)0.0494 (11)
H250.35740.48080.66860.059*
C260.1866 (4)0.5557 (4)0.6905 (3)0.0559 (12)
H260.19530.55340.75260.067*
C270.0786 (4)0.6022 (4)0.6508 (4)0.0523 (11)
H270.01350.63270.68460.063*
C280.0674 (3)0.6034 (3)0.5569 (3)0.0418 (9)
C290.1678 (3)0.5570 (3)0.5106 (3)0.0341 (8)
C300.0446 (3)0.6484 (3)0.5075 (3)0.0437 (10)
C310.2407 (4)0.7337 (4)0.5027 (5)0.0748 (17)
H310.31030.76970.52880.090*
C320.2450 (4)0.7213 (4)0.4169 (5)0.0688 (16)
H320.31710.74710.38810.083*
C330.0489 (3)0.6382 (3)0.4184 (3)0.0431 (10)
C340.0568 (3)0.5868 (3)0.3719 (3)0.0372 (9)
C350.1630 (3)0.5495 (3)0.4170 (3)0.0344 (8)
C360.0581 (4)0.5722 (4)0.2839 (3)0.0485 (11)
H360.01100.59660.25100.058*
C370.1624 (4)0.5215 (4)0.2462 (3)0.0545 (12)
H370.16470.50980.18820.065*
C380.2649 (4)0.4877 (4)0.2954 (3)0.0461 (10)
H380.33520.45390.26880.055*
C391.2428 (4)0.0517 (4)0.1160 (3)0.0507 (11)
H391.17520.03200.14900.061*
C401.3496 (4)0.1059 (5)0.1521 (4)0.0703 (16)
H401.35220.11870.20970.084*
C411.4494 (4)0.1399 (4)0.1038 (4)0.0653 (14)
H411.52060.17740.12680.078*
C421.4433 (3)0.1176 (4)0.0183 (4)0.0500 (11)
C431.3335 (3)0.0605 (3)0.0128 (3)0.0413 (9)
C441.5449 (4)0.1491 (4)0.0385 (4)0.0564 (13)
C451.7391 (5)0.2288 (5)0.0639 (6)0.092 (2)
H451.81380.26630.04610.110*
C461.7261 (5)0.2040 (5)0.1441 (5)0.083 (2)
H461.79280.22680.17970.100*
C471.5308 (4)0.1213 (4)0.1220 (4)0.0596 (14)
C481.4168 (4)0.0613 (4)0.1527 (3)0.0505 (12)
C491.3201 (3)0.0329 (3)0.0982 (3)0.0400 (9)
C501.3978 (5)0.0324 (4)0.2340 (4)0.0670 (16)
H501.46030.04860.27150.080*
C511.2862 (5)0.0203 (5)0.2597 (4)0.0687 (15)
H511.27240.03920.31520.082*
C521.1935 (4)0.0454 (4)0.2016 (3)0.0564 (12)
H521.11810.08110.21950.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0200 (2)0.0465 (3)0.0297 (2)0.00772 (19)0.00046 (17)0.0166 (2)
Cu20.0223 (2)0.0404 (3)0.0325 (3)0.00717 (19)0.00198 (18)0.0176 (2)
O10.0337 (14)0.064 (2)0.0453 (16)0.0163 (13)0.0082 (12)0.0347 (15)
O20.083 (3)0.069 (3)0.095 (3)0.041 (2)0.049 (2)0.039 (2)
O30.0386 (15)0.059 (2)0.0553 (18)0.0118 (14)0.0079 (13)0.0397 (15)
O40.080 (3)0.075 (3)0.131 (4)0.035 (2)0.065 (3)0.053 (3)
O50.0303 (13)0.0463 (17)0.0372 (14)0.0089 (12)0.0103 (11)0.0097 (12)
O60.147 (4)0.117 (4)0.211 (5)0.098 (4)0.135 (4)0.081 (4)
O70.0293 (13)0.0411 (15)0.0345 (13)0.0118 (11)0.0063 (11)0.0097 (11)
O80.066 (2)0.099 (3)0.084 (3)0.057 (2)0.035 (2)0.032 (2)
O1W0.197 (6)0.211 (6)0.183 (6)0.103 (5)0.048 (5)0.141 (5)
O2W0.328 (9)0.227 (8)0.238 (8)0.108 (7)0.058 (7)0.058 (7)
O3W0.299 (9)0.204 (7)0.322 (10)0.126 (7)0.007 (7)0.078 (7)
O4W0.228 (7)0.191 (7)0.233 (7)0.109 (6)0.009 (6)0.096 (5)
N10.0255 (15)0.052 (2)0.0351 (16)0.0147 (14)0.0023 (13)0.0198 (15)
N20.0331 (19)0.062 (3)0.081 (3)0.0132 (17)0.0146 (19)0.025 (2)
N30.0281 (18)0.054 (2)0.075 (3)0.0136 (16)0.0103 (18)0.006 (2)
N40.0279 (16)0.049 (2)0.0358 (16)0.0146 (14)0.0005 (13)0.0153 (15)
N50.0241 (15)0.0434 (19)0.0405 (17)0.0082 (13)0.0024 (13)0.0160 (14)
N60.0276 (19)0.069 (3)0.107 (4)0.0112 (19)0.006 (2)0.002 (3)
N70.049 (2)0.093 (3)0.081 (3)0.039 (2)0.029 (2)0.019 (3)
N80.0455 (19)0.047 (2)0.0385 (17)0.0212 (16)0.0095 (15)0.0123 (15)
C10.037 (2)0.060 (3)0.042 (2)0.017 (2)0.0058 (18)0.024 (2)
C20.039 (2)0.050 (2)0.041 (2)0.0161 (18)0.0030 (17)0.0263 (18)
C30.038 (2)0.048 (2)0.039 (2)0.0114 (17)0.0058 (17)0.0254 (18)
C40.043 (2)0.051 (3)0.055 (3)0.008 (2)0.010 (2)0.019 (2)
C50.075 (4)0.055 (3)0.067 (3)0.004 (3)0.005 (3)0.010 (3)
C60.087 (4)0.073 (4)0.059 (3)0.021 (3)0.015 (3)0.006 (3)
C70.072 (3)0.075 (4)0.051 (3)0.024 (3)0.020 (2)0.022 (3)
C80.043 (2)0.053 (3)0.043 (2)0.0166 (19)0.0082 (18)0.0264 (19)
C90.039 (2)0.051 (3)0.049 (2)0.0126 (18)0.0089 (18)0.032 (2)
C100.050 (2)0.043 (2)0.051 (2)0.0058 (19)0.006 (2)0.027 (2)
C110.050 (2)0.052 (3)0.038 (2)0.013 (2)0.0053 (18)0.0219 (19)
C120.042 (2)0.059 (3)0.056 (3)0.016 (2)0.015 (2)0.031 (2)
C130.045 (2)0.055 (3)0.069 (3)0.026 (2)0.033 (2)0.012 (2)
C140.038 (2)0.038 (2)0.052 (2)0.0141 (18)0.0200 (19)0.0060 (18)
C150.051 (3)0.054 (3)0.048 (2)0.030 (2)0.019 (2)0.005 (2)
C160.064 (3)0.084 (4)0.053 (3)0.034 (3)0.012 (2)0.016 (3)
C170.090 (4)0.088 (4)0.062 (3)0.041 (3)0.007 (3)0.022 (3)
C180.067 (3)0.072 (4)0.080 (4)0.023 (3)0.007 (3)0.027 (3)
C190.052 (3)0.057 (3)0.062 (3)0.023 (2)0.011 (2)0.005 (2)
C200.038 (2)0.045 (2)0.047 (2)0.0190 (18)0.0133 (19)0.0008 (18)
C210.032 (2)0.042 (2)0.049 (2)0.0174 (17)0.0159 (18)0.0078 (18)
C220.040 (2)0.053 (3)0.050 (2)0.0193 (19)0.0116 (19)0.004 (2)
C230.033 (2)0.047 (3)0.068 (3)0.0118 (18)0.015 (2)0.005 (2)
C240.031 (2)0.048 (2)0.045 (2)0.0144 (18)0.0130 (18)0.0004 (18)
C250.033 (2)0.083 (3)0.043 (2)0.026 (2)0.0028 (17)0.030 (2)
C260.048 (3)0.093 (4)0.048 (2)0.034 (2)0.011 (2)0.043 (2)
C270.042 (2)0.067 (3)0.064 (3)0.026 (2)0.021 (2)0.041 (2)
C280.0299 (19)0.047 (2)0.051 (2)0.0175 (17)0.0084 (17)0.0198 (19)
C290.0256 (17)0.041 (2)0.0377 (19)0.0150 (15)0.0030 (15)0.0147 (16)
C300.0262 (18)0.039 (2)0.061 (3)0.0124 (16)0.0056 (18)0.0135 (19)
C310.021 (2)0.073 (4)0.104 (4)0.005 (2)0.008 (3)0.019 (3)
C320.030 (2)0.064 (3)0.093 (4)0.014 (2)0.011 (3)0.006 (3)
C330.0269 (19)0.038 (2)0.057 (2)0.0139 (16)0.0053 (18)0.0034 (18)
C340.0268 (18)0.040 (2)0.0400 (19)0.0135 (16)0.0072 (16)0.0044 (16)
C350.0279 (18)0.037 (2)0.0366 (19)0.0146 (15)0.0003 (15)0.0075 (16)
C360.044 (2)0.059 (3)0.042 (2)0.026 (2)0.0122 (19)0.0059 (19)
C370.057 (3)0.077 (3)0.036 (2)0.031 (2)0.007 (2)0.017 (2)
C380.036 (2)0.070 (3)0.035 (2)0.021 (2)0.0015 (17)0.0209 (19)
C390.035 (2)0.068 (3)0.058 (3)0.017 (2)0.0049 (19)0.036 (2)
C400.042 (3)0.099 (4)0.085 (4)0.024 (3)0.018 (3)0.060 (3)
C410.034 (2)0.068 (3)0.095 (4)0.012 (2)0.016 (2)0.045 (3)
C420.0228 (19)0.046 (2)0.071 (3)0.0091 (17)0.0041 (19)0.012 (2)
C430.0266 (18)0.040 (2)0.052 (2)0.0137 (16)0.0056 (17)0.0069 (18)
C440.029 (2)0.044 (3)0.078 (3)0.0104 (18)0.012 (2)0.000 (2)
C450.033 (3)0.083 (4)0.117 (5)0.015 (3)0.013 (3)0.009 (4)
C460.037 (3)0.088 (4)0.107 (5)0.028 (3)0.031 (3)0.005 (3)
C470.033 (2)0.053 (3)0.077 (3)0.023 (2)0.027 (2)0.013 (2)
C480.048 (2)0.048 (3)0.052 (2)0.025 (2)0.021 (2)0.002 (2)
C490.035 (2)0.038 (2)0.045 (2)0.0155 (17)0.0133 (18)0.0042 (17)
C500.071 (3)0.071 (3)0.067 (3)0.040 (3)0.029 (3)0.006 (3)
C510.087 (4)0.085 (4)0.049 (3)0.039 (3)0.015 (3)0.028 (3)
C520.061 (3)0.067 (3)0.050 (2)0.026 (2)0.006 (2)0.025 (2)
Geometric parameters (Å, º) top
Cu1—O11.924 (3)C15—C161.416 (7)
Cu1—O51.965 (2)C15—C201.427 (5)
Cu1—O5i2.440 (3)C16—C171.349 (8)
Cu1—N12.012 (3)C16—H160.9300
Cu1—N42.037 (3)C17—C181.404 (8)
Cu2—O31.916 (3)C17—H170.9300
Cu2—O7ii1.964 (2)C18—C191.345 (8)
Cu2—O7iii2.348 (3)C18—H180.9300
Cu2—N52.017 (3)C19—C201.419 (7)
Cu2—N82.024 (3)C19—H190.9300
O1—C11.287 (5)C20—C211.421 (6)
O2—C11.209 (5)C21—C221.352 (6)
O3—C121.262 (6)C21—C241.511 (5)
O4—C121.230 (6)C22—C231.404 (6)
O5—C131.232 (5)C22—H220.9300
O5—Cu1i2.440 (3)C23—H230.9300
O6—C131.216 (6)C25—C261.390 (6)
O7—C241.262 (5)C25—H250.9300
O7—Cu2iv1.964 (2)C26—C271.357 (6)
O7—Cu2iii2.348 (3)C26—H260.9300
O8—C241.224 (5)C27—C281.414 (6)
N1—C251.339 (5)C27—H270.9300
N1—C291.360 (5)C28—C291.384 (6)
N2—C311.347 (6)C28—C301.464 (6)
N2—C301.353 (6)C29—C351.441 (5)
N3—C321.308 (7)C30—C331.393 (6)
N3—C331.357 (5)C31—C321.359 (8)
N4—C381.332 (5)C31—H310.9300
N4—C351.352 (5)C32—H320.9300
N5—C391.325 (5)C33—C341.449 (6)
N5—C431.367 (5)C34—C361.393 (6)
N6—C451.329 (7)C34—C351.391 (5)
N6—C441.344 (7)C36—C371.370 (7)
N7—C461.349 (9)C36—H360.9300
N7—C471.366 (5)C37—C381.389 (6)
N8—C521.329 (6)C37—H370.9300
N8—C491.357 (5)C38—H380.9300
C1—C21.508 (6)C39—C401.396 (6)
C2—C111.376 (6)C39—H390.9300
C2—C31.412 (6)C40—C411.354 (7)
C3—C41.418 (6)C40—H400.9300
C3—C81.441 (6)C41—C421.402 (7)
C4—C51.342 (7)C41—H410.9300
C4—H40.9300C42—C431.402 (6)
C5—C61.404 (8)C42—C441.451 (6)
C5—H50.9300C43—C491.429 (6)
C6—C71.367 (8)C44—C471.403 (8)
C6—H60.9300C45—C461.334 (10)
C7—C81.422 (7)C45—H450.9300
C7—H70.9300C46—H460.9300
C8—C91.423 (6)C47—C481.450 (7)
C9—C101.358 (7)C48—C501.373 (7)
C9—C121.511 (6)C48—C491.391 (5)
C10—C111.396 (6)C50—C511.373 (8)
C10—H100.9300C50—H500.9300
C11—H110.9300C51—C521.396 (6)
C13—C141.515 (5)C51—H510.9300
C14—C231.363 (7)C52—H520.9300
C14—C151.412 (7)
O1—Cu1—O591.2 (1)C20—C19—H19119.1
O1—Cu1—N1171.5 (1)C21—C20—C19123.7 (4)
O5—Cu1—N196.2 (1)C21—C20—C15118.5 (4)
O1—Cu1—N492.4 (1)C19—C20—C15117.7 (4)
O5—Cu1—N4171.8 (1)C22—C21—C20120.1 (4)
N1—Cu1—N480.8 (1)C22—C21—C24119.6 (4)
O1—Cu1—O5i86.7 (1)C20—C21—C24120.3 (3)
O5—Cu1—O5i72.8 (1)C21—C22—C23121.6 (5)
N1—Cu1—O5i91.5 (1)C21—C22—H22119.2
N4—Cu1—O5i114.8 (1)C23—C22—H22119.2
O7ii—Cu2—O389.5 (1)C14—C23—C22120.1 (4)
O7ii—Cu2—N598.1 (1)C14—C23—H23120.0
O3—Cu2—N5172.4 (1)C22—C23—H23120.0
O7ii—Cu2—N8173.9 (1)O8—C24—O7124.7 (3)
O3—Cu2—N891.7 (1)O8—C24—C21119.6 (4)
N5—Cu2—N880.8 (1)O7—C24—C21115.7 (3)
O7ii—Cu2—O7iii74.6 (1)N1—C25—C26121.4 (4)
O3—Cu2—O7iii87.0 (1)N1—C25—H25119.3
N5—Cu2—O7iii94.3 (1)C26—C25—H25119.3
N8—Cu2—O7iii111.4 (1)C27—C26—C25121.1 (4)
C1—O1—Cu1120.8 (3)C27—C26—H26119.5
C12—O3—Cu2120.9 (3)C25—C26—H26119.5
C13—O5—Cu1120.1 (3)C26—C27—C28118.4 (4)
C13—O5—Cu1i132.6 (2)C26—C27—H27120.8
Cu1—O5—Cu1i107.22 (12)C28—C27—H27120.8
C24—O7—Cu2iv121.6 (2)C29—C28—C27117.8 (4)
C24—O7—Cu2iii129.8 (2)C29—C28—C30118.6 (4)
Cu2iv—O7—Cu2iii105.40 (11)C27—C28—C30123.5 (4)
C25—N1—C29118.1 (3)N1—C29—C28123.1 (4)
C25—N1—Cu1128.0 (3)N1—C29—C35115.7 (3)
C29—N1—Cu1113.8 (2)C28—C29—C35121.1 (3)
C31—N2—C30114.0 (5)N2—C30—C33122.1 (4)
C32—N3—C33116.1 (5)N2—C30—C28118.0 (4)
C38—N4—C35117.6 (3)C33—C30—C28119.9 (4)
C38—N4—Cu1129.1 (3)N2—C31—C32123.8 (5)
C35—N4—Cu1113.3 (2)N2—C31—H31118.1
C39—N5—C43117.6 (4)C32—C31—H31118.1
C39—N5—Cu2128.9 (3)N3—C32—C31122.7 (5)
C43—N5—Cu2113.5 (3)N3—C32—H32118.7
C45—N6—C44115.2 (6)C31—C32—H32118.7
C46—N7—C47113.0 (6)N3—C33—C30121.2 (4)
C52—N8—C49117.4 (4)N3—C33—C34118.0 (4)
C52—N8—Cu2128.8 (3)C30—C33—C34120.8 (3)
C49—N8—Cu2113.8 (3)C36—C34—C35117.7 (4)
O2—C1—O1124.3 (4)C36—C34—C33123.5 (4)
O2—C1—C2120.3 (4)C35—C34—C33118.8 (4)
O1—C1—C2115.4 (4)N4—C35—C34123.4 (4)
C11—C2—C3119.7 (4)N4—C35—C29116.0 (3)
C11—C2—C1116.2 (4)C34—C35—C29120.6 (4)
C3—C2—C1124.1 (4)C37—C36—C34119.2 (4)
C2—C3—C4123.1 (4)C37—C36—H36120.4
C2—C3—C8118.9 (4)C34—C36—H36120.4
C4—C3—C8118.0 (4)C36—C37—C38119.5 (4)
C5—C4—C3122.4 (5)C36—C37—H37120.3
C5—C4—H4118.8C38—C37—H37120.3
C3—C4—H4118.8N4—C38—C37122.6 (4)
C4—C5—C6120.3 (5)N4—C38—H38118.7
C4—C5—H5119.9C37—C38—H38118.7
C6—C5—H5119.9N5—C39—C40122.8 (4)
C7—C6—C5120.0 (6)N5—C39—H39118.6
C7—C6—H6120.0C40—C39—H39118.6
C5—C6—H6120.0C41—C40—C39120.3 (5)
C6—C7—C8121.8 (5)C41—C40—H40119.9
C6—C7—H7119.1C39—C40—H40119.9
C8—C7—H7119.1C40—C41—C42118.7 (4)
C7—C8—C9123.2 (4)C40—C41—H41120.6
C7—C8—C3117.5 (4)C42—C41—H41120.6
C9—C8—C3119.3 (4)C41—C42—C43118.1 (4)
C10—C9—C8119.4 (4)C41—C42—C44123.3 (4)
C10—C9—C12117.3 (4)C43—C42—C44118.6 (5)
C8—C9—C12123.3 (4)N5—C43—C42122.4 (4)
C9—C10—C11121.7 (4)N5—C43—C49116.0 (4)
C9—C10—H10119.2C42—C43—C49121.6 (4)
C11—C10—H10119.2N6—C44—C47121.9 (4)
C2—C11—C10121.1 (4)N6—C44—C42118.7 (5)
C2—C11—H11119.5C47—C44—C42119.4 (4)
C10—C11—H11119.5N6—C45—C46123.2 (6)
O4—C12—O3124.6 (4)N6—C45—H45118.4
O4—C12—C9121.6 (4)C46—C45—H45118.4
O3—C12—C9113.8 (4)C45—C46—N7124.9 (5)
O6—C13—O5122.5 (4)C45—C46—H46117.6
O6—C13—C14121.4 (4)N7—C46—H46117.6
O5—C13—C14116.1 (4)N7—C47—C44121.8 (5)
C23—C14—C15120.5 (4)N7—C47—C48116.9 (5)
C23—C14—C13119.3 (4)C44—C47—C48121.3 (4)
C15—C14—C13120.2 (4)C50—C48—C49117.6 (5)
C14—C15—C16122.5 (4)C50—C48—C47123.9 (4)
C14—C15—C20119.1 (4)C49—C48—C47118.6 (4)
C16—C15—C20118.4 (5)N8—C49—C48123.7 (4)
C17—C16—C15121.6 (5)N8—C49—C43115.8 (3)
C17—C16—H16119.2C48—C49—C43120.5 (4)
C15—C16—H16119.2C51—C50—C48119.8 (4)
C16—C17—C18120.1 (6)C51—C50—H50120.1
C16—C17—H17119.9C48—C50—H50120.1
C18—C17—H17119.9C50—C51—C52119.3 (5)
C19—C18—C17120.3 (6)C50—C51—H51120.3
C19—C18—H18119.8C52—C51—H51120.3
C17—C18—H18119.8N8—C52—C51122.3 (5)
C18—C19—C20121.8 (5)N8—C52—H52118.8
C18—C19—H19119.1C51—C52—H52118.8
O5—Cu1—O1—C193.3 (2)Cu2iii—O7—C24—C2133.8 (3)
N4—Cu1—O1—C179.3 (2)C22—C21—C24—O8120.2 (4)
O5i—Cu1—O1—C1166.0 (2)C20—C21—C24—O861.2 (4)
O7ii—Cu2—O3—C1290.6 (2)C22—C21—C24—O760.2 (4)
N8—Cu2—O3—C1283.4 (2)C20—C21—C24—O7118.5 (4)
O7iii—Cu2—O3—C12165.2 (2)C29—N1—C25—C260.2 (7)
O1—Cu1—O5—C1394.3 (3)Cu1—N1—C25—C26177.2 (4)
N1—Cu1—O5—C1389.8 (3)N1—C25—C26—C270.8 (8)
O5i—Cu1—O5—C13179.4 (3)C25—C26—C27—C280.9 (8)
O1—Cu1—O5—Cu1i86.21 (14)C26—C27—C28—C290.1 (7)
N1—Cu1—O5—Cu1i89.68 (14)C26—C27—C28—C30178.1 (4)
O5i—Cu1—O5—Cu1i0.0C25—N1—C29—C280.9 (6)
O5—Cu1—N1—C254.6 (4)Cu1—N1—C29—C28176.8 (3)
N4—Cu1—N1—C25176.9 (4)C25—N1—C29—C35176.4 (4)
O5i—Cu1—N1—C2568.3 (4)Cu1—N1—C29—C355.9 (4)
O5—Cu1—N1—C29178.0 (3)C27—C28—C29—N10.8 (6)
N4—Cu1—N1—C295.7 (3)C30—C28—C29—N1179.1 (4)
O5i—Cu1—N1—C29109.2 (3)C27—C28—C29—C35176.4 (4)
O1—Cu1—N4—C3811.1 (4)C30—C28—C29—C352.0 (6)
N1—Cu1—N4—C38174.0 (4)C31—N2—C30—C330.1 (7)
O5i—Cu1—N4—C3898.6 (4)C31—N2—C30—C28178.6 (4)
O1—Cu1—N4—C35170.4 (3)C29—C28—C30—N2177.6 (4)
N1—Cu1—N4—C354.5 (3)C27—C28—C30—N24.1 (7)
O5i—Cu1—N4—C3582.9 (3)C29—C28—C30—C333.8 (6)
O7ii—Cu2—N5—C397.6 (4)C27—C28—C30—C33174.4 (4)
N8—Cu2—N5—C39178.5 (4)C30—N2—C31—C321.8 (8)
O7iii—Cu2—N5—C3967.5 (4)C33—N3—C32—C310.0 (8)
O7ii—Cu2—N5—C43175.6 (3)N2—C31—C32—N31.9 (9)
N8—Cu2—N5—C431.6 (3)C32—N3—C33—C301.7 (6)
O7iii—Cu2—N5—C43109.4 (3)C32—N3—C33—C34179.3 (4)
O3—Cu2—N8—C521.7 (4)N2—C30—C33—N31.7 (7)
N5—Cu2—N8—C52179.9 (4)C28—C30—C33—N3176.8 (4)
O7iii—Cu2—N8—C5289.1 (4)N2—C30—C33—C34179.3 (4)
O3—Cu2—N8—C49178.0 (3)C28—C30—C33—C342.2 (6)
N5—Cu2—N8—C490.4 (3)N3—C33—C34—C360.4 (6)
O7iii—Cu2—N8—C4990.5 (3)C30—C33—C34—C36178.6 (4)
Cu1—O1—C1—O26.7 (3)N3—C33—C34—C35179.8 (4)
Cu1—O1—C1—C2173.3 (2)C30—C33—C34—C351.2 (6)
O2—C1—C2—C1147.7 (4)C38—N4—C35—C342.0 (6)
O1—C1—C2—C11132.3 (4)Cu1—N4—C35—C34179.3 (3)
O2—C1—C2—C3132.6 (4)C38—N4—C35—C29176.0 (4)
O1—C1—C2—C347.4 (4)Cu1—N4—C35—C292.7 (4)
C11—C2—C3—C4179.7 (4)C36—C34—C35—N41.1 (6)
C1—C2—C3—C40.6 (6)C33—C34—C35—N4179.1 (4)
C11—C2—C3—C80.5 (6)C36—C34—C35—C29176.8 (4)
C1—C2—C3—C8179.8 (3)C33—C34—C35—C293.1 (6)
C2—C3—C4—C5177.5 (5)N1—C29—C35—N42.1 (5)
C8—C3—C4—C51.7 (7)C28—C29—C35—N4179.5 (4)
C3—C4—C5—C61.2 (10)N1—C29—C35—C34175.9 (3)
C4—C5—C6—C70.6 (11)C28—C29—C35—C341.5 (6)
C5—C6—C7—C80.6 (10)C35—C34—C36—C370.6 (6)
C6—C7—C8—C9178.7 (5)C33—C34—C36—C37179.2 (4)
C6—C7—C8—C31.2 (8)C34—C36—C37—C381.4 (7)
C2—C3—C8—C7177.6 (4)C35—N4—C38—C371.1 (7)
C4—C3—C8—C71.6 (6)Cu1—N4—C38—C37179.6 (3)
C2—C3—C8—C90.1 (6)C36—C37—C38—N40.5 (7)
C4—C3—C8—C9179.3 (4)C43—N5—C39—C402.5 (7)
C7—C8—C9—C10178.1 (5)Cu2—N5—C39—C40179.3 (4)
C3—C8—C9—C100.6 (6)N5—C39—C40—C412.9 (9)
C7—C8—C9—C122.1 (7)C39—C40—C41—C421.4 (9)
C3—C8—C9—C12179.6 (3)C40—C41—C42—C430.2 (8)
C8—C9—C10—C110.8 (7)C40—C41—C42—C44179.1 (5)
C12—C9—C10—C11179.3 (4)C39—N5—C43—C420.8 (6)
C3—C2—C11—C100.3 (6)Cu2—N5—C43—C42178.1 (3)
C1—C2—C11—C10180.0 (4)C39—N5—C43—C49179.8 (4)
C9—C10—C11—C20.4 (7)Cu2—N5—C43—C492.6 (4)
Cu2—O3—C12—O43.8 (3)C41—C42—C43—N50.5 (7)
Cu2—O3—C12—C9176.4 (2)C44—C42—C43—N5179.5 (4)
C10—C9—C12—O4142.3 (4)C41—C42—C43—C49178.8 (4)
C8—C9—C12—O437.5 (4)C44—C42—C43—C490.2 (6)
C10—C9—C12—O337.5 (4)C45—N6—C44—C471.4 (7)
C8—C9—C12—O3142.7 (4)C45—N6—C44—C42179.9 (5)
Cu1—O5—C13—O67.4 (4)C41—C42—C44—N60.2 (7)
Cu1i—O5—C13—O6171.9 (4)C43—C42—C44—N6179.1 (4)
Cu1—O5—C13—C14172.7 (3)C41—C42—C44—C47178.6 (5)
Cu1i—O5—C13—C148.0 (4)C43—C42—C44—C470.4 (6)
O6—C13—C14—C2391.8 (5)C44—N6—C45—C460.4 (9)
O5—C13—C14—C2388.0 (5)N6—C45—C46—N71.4 (11)
O6—C13—C14—C1588.7 (5)C47—N7—C46—C451.9 (9)
O5—C13—C14—C1591.4 (5)C46—N7—C47—C440.8 (7)
C23—C14—C15—C16178.7 (5)C46—N7—C47—C48179.9 (5)
C13—C14—C15—C161.8 (7)N6—C44—C47—N70.8 (7)
C23—C14—C15—C202.2 (7)C42—C44—C47—N7179.5 (4)
C13—C14—C15—C20177.2 (4)N6—C44—C47—C48178.5 (4)
C14—C15—C16—C17179.5 (5)C42—C44—C47—C480.3 (7)
C20—C15—C16—C170.5 (8)N7—C47—C48—C501.1 (7)
C15—C16—C17—C180.0 (9)C44—C47—C48—C50179.6 (5)
C16—C17—C18—C190.7 (9)N7—C47—C48—C49179.7 (4)
C17—C18—C19—C201.0 (9)C44—C47—C48—C491.1 (7)
C18—C19—C20—C21177.7 (5)C52—N8—C49—C480.1 (6)
C18—C19—C20—C150.5 (7)Cu2—N8—C49—C48179.8 (3)
C14—C15—C20—C212.4 (6)C52—N8—C49—C43178.9 (4)
C16—C15—C20—C21178.5 (4)Cu2—N8—C49—C430.8 (5)
C14—C15—C20—C19179.3 (4)C50—C48—C49—N80.9 (7)
C16—C15—C20—C190.2 (7)C47—C48—C49—N8177.7 (4)
C19—C20—C21—C22178.3 (4)C50—C48—C49—C43179.9 (4)
C15—C20—C21—C220.1 (6)C47—C48—C49—C431.2 (6)
C19—C20—C21—C240.3 (6)N5—C43—C49—N82.2 (5)
C15—C20—C21—C24178.5 (4)C42—C43—C49—N8178.4 (4)
C20—C21—C22—C232.4 (7)N5—C43—C49—C48178.7 (4)
C24—C21—C22—C23178.9 (4)C42—C43—C49—C480.6 (6)
C15—C14—C23—C220.3 (7)C49—C48—C50—C511.5 (7)
C13—C14—C23—C22179.7 (4)C47—C48—C50—C51177.1 (5)
C21—C22—C23—C142.7 (7)C48—C50—C51—C521.0 (8)
Cu2iv—O7—C24—O810.8 (3)C49—N8—C52—C510.6 (7)
Cu2iii—O7—C24—O8145.8 (3)Cu2—N8—C52—C51179.8 (4)
Cu2iv—O7—C24—C21169.6 (2)C50—C51—C52—N80.0 (8)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1; (iii) x+2, y, z+1; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Cu2(C12H6O4)2(C14H8N4)2]·4H2O
Mr1091.97
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)12.679 (5), 14.690 (6), 14.833 (7)
α, β, γ (°)69.37 (2), 82.05 (2), 65.13 (2)
V3)2346 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.98
Crystal size (mm)0.38 × 0.27 × 0.16
Data collection
DiffractometerRigaku RAXIS-RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.618, 0.859
No. of measured, independent and
observed [I > 2σ(I)] reflections
22789, 10535, 6887
Rint0.032
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.190, 1.09
No. of reflections10535
No. of parameters667
No. of restraints436
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.03, 0.51

Computer programs: RAPID-AUTO (Rigaku Corporation, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001); OLEX (Dolomanov et al., 2003), publCIF (Westrip, 2007).

Selected bond lengths (Å) top
Cu1—O11.924 (3)Cu1—N42.037 (3)
Cu1—O51.965 (2)Cu2—O31.916 (3)
Cu1—O5i2.440 (3)Cu2—O7ii1.964 (2)
Cu1—N12.012 (3)Cu2—O7iii2.348 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1; (iii) x+2, y, z+1.
 

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