Tetra-kis(μ3-2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}-6-nitro-pheno-lato)tetra-copper(II).

The title cluster, [Cu4(C11H12N2O6)4], was obtained from the Cu(0)-FeCl2·4H2O-H4 L-Et3N-DMF reaction system (in air), where H4 L is 2-hy-droxy-methyl-2{[(2-hy-droxy-3-nitro-phen-yl)methyl-idene]amino}-propane-1,3-diol and DMF is di-methyl-formamide. The asymmetric unit consists of one Cu(2+) ion and one dianionic ligand; a -4 symmetry element generates the cluster, which contains a {Cu4O4} cubane-like core. The metal ion has an elongated square-based pyramidal CuNO4 coordination geometry with the N atom in a basal site. An intra-molecular O-H⋯O hydrogen bond is observed. The solvent mol-ecules were found to be highly disordered and their contribution to the scattering was removed with the SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155], which indicated a solvent cavity of volume 3131 Å(3) containing approximately 749 electrons. These solvent molecules are not considered in the given chemical formula.

Related literature

For general background to direct synthesis (DS), see: Kokozay & Shevchenko (2005 ▶). For related structures, see: Dey et al. (2002 ▶); Dong et al. (2007 ▶); Guo et al. (2008 ▶). For successful realisation of n class="Chemical">DS, see: Chygorin et al. (2012 ▶); Nesterov et al. (2012 ▶).

Experimental

Crystal data

[Cu4(C11H12N2O6)4]

M = 1327.06

Tetragonal,

a = 20.5587 (14) Å

c = 18.010 (2) Å

V = 7612.0 (11) Å3

Z = 4

Mo Kα radiation

μ = 1.17 mm−1

T = 173 K

0.40 × 0.40 × 0.30 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) ▶ T min = 0.653, T max = 0.721

3349 measured reflections

3349 independent reflections

1395 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.075

wR(F 2) = 0.184

S = 0.80

3349 reflections

182 parameters

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CrysAlis CCD (Agilent, 2012 ▶); cell refinement: CrysAlis RED (Agilent, 2012 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814000798/hb7174sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000798/hb7174Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu4(C11H12N2O6)4]	Dx = 1.158 Mg m−3
Mr = 1327.06	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 462 reflections
Hall symbol: -I 4ad	θ = 3.0–25.0°
a = 20.5587 (14) Å	µ = 1.17 mm−1
c = 18.010 (2) Å	T = 173 K
V = 7612.0 (11) Å3	Block, brown
Z = 4	0.40 × 0.40 × 0.30 mm
F(000) = 2704

Agilent Xcalibur Sapphire3 diffractometer	3349 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 16.1827 pixels mm-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −16→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = 0→24
Tmin = 0.653, Tmax = 0.721	l = 0→21
3349 measured reflections

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184	H-atom parameters constrained
S = 0.80	w = 1/[σ2(Fo2) + (0.060P)2] where P = (Fo2 + 2Fc2)/3
3349 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.94 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.48941 (4)	0.66864 (4)	0.06731 (4)	0.0396 (3)
O1	0.5536 (2)	0.6041 (2)	0.0524 (3)	0.0451 (13)
N1	0.4460 (3)	0.6539 (3)	−0.0276 (3)	0.0406 (16)
C1	0.5204 (4)	0.5693 (4)	−0.0716 (4)	0.047 (2)
N2	0.6541 (4)	0.5153 (3)	0.0538 (4)	0.0542 (19)
O2	0.6303 (3)	0.5101 (3)	0.1159 (3)	0.0611 (17)
C2	0.5608 (4)	0.5690 (4)	−0.0063 (5)	0.047 (2)
O3	0.7144 (3)	0.5100 (3)	0.0436 (3)	0.0751 (19)
C3	0.6141 (4)	0.5230 (4)	−0.0096 (5)	0.050 (2)
O4	0.4358 (3)	0.7332 (3)	−0.1606 (3)	0.0761 (19)
H4A	0.4728	0.7401	−0.1646	0.114*	0.50
H4C	0.4145	0.7014	−0.1769	0.114*	0.50
C4	0.6276 (4)	0.4875 (4)	−0.0723 (5)	0.061 (2)
H4B	0.6644	0.4596	−0.0728	0.073*
O5	0.2776 (3)	0.7029 (3)	−0.0736 (4)	0.0732 (18)
H5A	0.2430	0.6816	−0.0784	0.110*
C5	0.5890 (4)	0.4913 (4)	−0.1342 (5)	0.061 (3)
H5B	0.5991	0.4672	−0.1777	0.073*
O6	0.4282 (2)	0.7408 (2)	0.0779 (2)	0.0369 (12)
C6	0.5353 (4)	0.5310 (4)	−0.1317 (4)	0.052 (2)
H6A	0.5071	0.5320	−0.1735	0.063*
C7	0.4659 (4)	0.6122 (4)	−0.0773 (4)	0.048 (2)
H7A	0.4416	0.6101	−0.1220	0.057*
C8	0.3906 (4)	0.6972 (4)	−0.0412 (4)	0.047 (2)
C9	0.4121 (4)	0.7530 (4)	−0.0911 (4)	0.057 (2)
H9A	0.3747	0.7826	−0.0989	0.069*
H9B	0.4465	0.7780	−0.0653	0.069*
C10	0.3319 (4)	0.6594 (4)	−0.0737 (5)	0.058 (2)
H10A	0.3415	0.6448	−0.1249	0.069*
H10B	0.3223	0.6206	−0.0430	0.069*
C11	0.3712 (4)	0.7262 (4)	0.0359 (4)	0.0436 (19)
H11A	0.3454	0.7663	0.0285	0.052*
H11B	0.3440	0.6945	0.0633	0.052*

	U11	U22	U33	U12	U13	U23
Cu1	0.0337 (6)	0.0344 (6)	0.0509 (5)	0.0009 (5)	−0.0021 (5)	−0.0018 (4)
O1	0.044 (3)	0.029 (3)	0.062 (3)	−0.005 (3)	−0.002 (3)	−0.015 (3)
N1	0.039 (4)	0.037 (4)	0.046 (3)	−0.005 (3)	−0.001 (3)	−0.006 (3)
C1	0.032 (5)	0.046 (5)	0.064 (5)	0.001 (4)	0.007 (4)	−0.004 (5)
N2	0.053 (5)	0.038 (4)	0.071 (5)	0.012 (4)	−0.004 (4)	−0.017 (4)
O2	0.059 (4)	0.040 (4)	0.084 (4)	0.008 (3)	−0.019 (4)	−0.004 (3)
C2	0.034 (5)	0.022 (4)	0.084 (6)	−0.001 (4)	0.003 (5)	−0.009 (4)
O3	0.032 (4)	0.077 (5)	0.116 (5)	0.013 (3)	−0.001 (3)	−0.026 (4)
C3	0.039 (5)	0.041 (5)	0.071 (5)	−0.023 (4)	−0.002 (5)	−0.018 (5)
O4	0.082 (5)	0.088 (5)	0.059 (3)	−0.014 (4)	0.006 (3)	0.006 (3)
C4	0.039 (5)	0.045 (6)	0.098 (6)	−0.004 (5)	0.005 (5)	−0.024 (5)
O5	0.038 (4)	0.065 (4)	0.116 (5)	0.001 (3)	−0.020 (4)	0.000 (4)
C5	0.037 (5)	0.051 (6)	0.094 (6)	−0.004 (5)	0.020 (5)	−0.033 (5)
O6	0.019 (3)	0.029 (3)	0.063 (3)	0.002 (2)	−0.007 (2)	0.004 (2)
C6	0.040 (5)	0.054 (6)	0.062 (5)	−0.012 (5)	0.005 (4)	−0.016 (5)
C7	0.044 (5)	0.048 (5)	0.051 (5)	−0.013 (4)	−0.001 (4)	0.010 (4)
C8	0.032 (5)	0.043 (5)	0.067 (5)	0.005 (4)	−0.013 (4)	0.004 (4)
C9	0.048 (6)	0.063 (6)	0.062 (5)	−0.010 (5)	−0.017 (4)	0.010 (5)
C10	0.041 (5)	0.061 (6)	0.071 (5)	0.005 (5)	0.000 (5)	−0.007 (5)
C11	0.030 (5)	0.041 (5)	0.059 (4)	0.000 (4)	0.003 (4)	−0.002 (4)

Cu1—O1	1.892 (5)	C4—C5	1.371 (11)
Cu1—O6i	1.940 (5)	C4—H4B	0.9500
Cu1—N1	1.952 (6)	O5—C10	1.430 (9)
Cu1—O6	1.954 (4)	O5—H5A	0.8400
Cu1—O6ii	2.524 (5)	C5—C6	1.374 (11)
O1—C2	1.288 (8)	C5—H5B	0.9500
N1—C7	1.304 (9)	O6—C11	1.428 (8)
N1—C8	1.467 (9)	O6—Cu1iii	1.940 (5)
C1—C6	1.373 (10)	C6—H6A	0.9500
C1—C7	1.428 (10)	C7—H7A	0.9500
C1—C2	1.440 (10)	C8—C9	1.524 (10)
N2—O2	1.224 (8)	C8—C10	1.551 (10)
N2—O3	1.259 (8)	C8—C11	1.562 (10)
N2—C3	1.417 (10)	C9—H9A	0.9900
C2—C3	1.449 (10)	C9—H9B	0.9900
C3—C4	1.373 (10)	C10—H10A	0.9900
O4—C9	1.403 (9)	C10—H10B	0.9900
O4—H4A	0.7773	C11—H11A	0.9900
O4—H4C	0.8400	C11—H11B	0.9900
O1—Cu1—O6i	93.6 (2)	C6—C5—H5B	120.9
O1—Cu1—N1	94.9 (2)	C11—O6—Cu1iii	118.5 (4)
O6i—Cu1—N1	164.4 (2)	C11—O6—Cu1	108.5 (4)
O1—Cu1—O6	174.8 (2)	Cu1iii—O6—Cu1	108.6 (2)
O6i—Cu1—O6	87.9 (2)	C1—C6—C5	123.1 (8)
O1—Cu1—O6ii	93.45 (18)	C1—C6—H6A	118.5
O6i—Cu1—O6ii	73.19 (17)	C5—C6—H6A	118.5
N1—Cu1—O6ii	119.2 (2)	N1—C7—C1	127.0 (7)
O6—Cu1—O6ii	82.22 (17)	N1—C7—H7A	116.5
N1—Cu1—O6	84.8 (2)	C1—C7—H7A	116.5
C2—O1—Cu1	126.0 (5)	N1—C8—C9	109.3 (6)
C7—N1—C8	121.9 (6)	N1—C8—C10	111.3 (6)
C7—N1—Cu1	124.0 (5)	C9—C8—C10	112.3 (6)
C8—N1—Cu1	114.0 (5)	N1—C8—C11	106.4 (6)
C6—C1—C7	118.2 (8)	C9—C8—C11	108.1 (7)
C6—C1—C2	120.9 (8)	C10—C8—C11	109.2 (6)
C7—C1—C2	120.8 (7)	O4—C9—C8	114.1 (7)
O2—N2—O3	121.3 (7)	O4—C9—H9A	108.7
O2—N2—C3	120.9 (7)	C8—C9—H9A	108.7
O3—N2—C3	117.6 (7)	O4—C9—H9B	108.7
O1—C2—C1	127.1 (7)	C8—C9—H9B	108.7
O1—C2—C3	119.0 (7)	H9A—C9—H9B	107.6
C1—C2—C3	113.9 (7)	O5—C10—C8	107.0 (6)
C4—C3—N2	119.1 (8)	O5—C10—H10A	110.3
C4—C3—C2	122.3 (8)	C8—C10—H10A	110.3
N2—C3—C2	118.6 (7)	O5—C10—H10B	110.3
C9—O4—H4A	111.7	C8—C10—H10B	110.3
C9—O4—H4C	110.9	H10A—C10—H10B	108.6
H4A—O4—H4C	128.4	O6—C11—C8	110.0 (6)
C5—C4—C3	121.4 (8)	O6—C11—H11A	109.7
C5—C4—H4B	119.3	C8—C11—H11A	109.7
C3—C4—H4B	119.3	O6—C11—H11B	109.7
C10—O5—H5A	109.5	C8—C11—H11B	109.7
C4—C5—C6	118.2 (8)	H11A—C11—H11B	108.2
C4—C5—H5B	120.9
O6i—Cu1—O1—C2	170.0 (6)	O6i—Cu1—O6—C11	−139.6 (4)
N1—Cu1—O1—C2	3.0 (6)	N1—Cu1—O6—C11	26.7 (4)
O6—Cu1—O1—C2	−84 (2)	O1—Cu1—O6—Cu1iii	−116 (2)
O6ii—Cu1—O1—C2	−116.7 (6)	O6i—Cu1—O6—Cu1iii	−9.5 (2)
O1—Cu1—N1—C7	−2.5 (6)	N1—Cu1—O6—Cu1iii	156.7 (3)
O6i—Cu1—N1—C7	−125.4 (8)	C7—C1—C6—C5	175.5 (7)
O6—Cu1—N1—C7	172.3 (6)	C2—C1—C6—C5	−0.9 (12)
O6ii—Cu1—N1—C7	94.2 (6)	C4—C5—C6—C1	3.4 (13)
O1—Cu1—N1—C8	−178.6 (5)	C8—N1—C7—C1	177.6 (7)
O6i—Cu1—N1—C8	58.5 (11)	Cu1—N1—C7—C1	1.8 (11)
O6—Cu1—N1—C8	−3.8 (5)	C6—C1—C7—N1	−177.0 (7)
O6ii—Cu1—N1—C8	−81.9 (5)	C2—C1—C7—N1	−0.6 (12)
Cu1—O1—C2—C1	−2.8 (11)	C7—N1—C8—C9	−77.3 (8)
Cu1—O1—C2—C3	178.0 (5)	Cu1—N1—C8—C9	98.9 (6)
C6—C1—C2—O1	177.4 (7)	C7—N1—C8—C10	47.3 (9)
C7—C1—C2—O1	1.0 (12)	Cu1—N1—C8—C10	−136.5 (5)
C6—C1—C2—C3	−3.4 (11)	C7—N1—C8—C11	166.2 (6)
C7—C1—C2—C3	−179.7 (7)	Cu1—N1—C8—C11	−17.6 (7)
O2—N2—C3—C4	−135.5 (8)	N1—C8—C9—O4	59.8 (8)
O3—N2—C3—C4	40.2 (11)	C10—C8—C9—O4	−64.2 (9)
O2—N2—C3—C2	45.5 (10)	C11—C8—C9—O4	175.3 (6)
O3—N2—C3—C2	−138.8 (8)	N1—C8—C10—O5	170.8 (6)
O1—C2—C3—C4	−175.1 (7)	C9—C8—C10—O5	−66.3 (8)
C1—C2—C3—C4	5.5 (11)	C11—C8—C10—O5	53.6 (8)
O1—C2—C3—N2	3.8 (11)	Cu1iii—O6—C11—C8	−167.6 (4)
C1—C2—C3—N2	−175.5 (7)	Cu1—O6—C11—C8	−43.2 (6)
N2—C3—C4—C5	177.6 (8)	N1—C8—C11—O6	39.5 (8)
C2—C3—C4—C5	−3.5 (13)	C9—C8—C11—O6	−77.8 (7)
C3—C4—C5—C6	−1.2 (13)	C10—C8—C11—O6	159.8 (6)
O1—Cu1—O6—C11	114 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O4ii	0.78	1.96	2.729 (9)	171

Table 1

Selected bond lengths (Å)

Cu1—O1	1.892 (5)
Cu1—O6i	1.940 (5)
Cu1—N1	1.952 (6)
Cu1—O6	1.954 (4)
Cu1—O6ii	2.524 (5)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O4ii	0.78	1.96	2.729 (9)	171

Symmetry code: (ii) .