research communications Acta Cryst. (2019). E75, 1069–1075 https://doi.org/10.1107/S2056989019008922 1069 Received 11 June 2019 Accepted 21 June 2019 Edited by J. Simpson, University of Otago, New Zealand Keywords: crystal structure; copper complex; coordination polymer; open-cube structure. CCDC references: 1935842; 1935841 Supporting information: this article has supporting information at journals.iucr.org/e Crystal structures of two Cu II compounds: catena- poly[[chloridocopper(II)]-l-N-[ethoxy(pyridin-2- yl)methylidene]-N 0 -[oxido(pyridin-3-yl)methyl- idene]hydrazine-j 4 N,N 0 ,O:N 00 ] and di-l-chlorido- 1:4j 2 Cl:Cl-2:3j 2 Cl:Cl-dichlorido-2jCl,4jCl-bis- [l 3 -ethoxy(pyridin-2-yl)methanolato-1:2:3j 3 O:- N,O:O;1:3:4j 3 O:O:N,O]bis[l 2 -ethoxy(pyridin-2- yl)methanolato-1:2j 3 N,O:O;3:4j 3 N,O:O]tetra- copper(II) Ousmane Sall, a Farba Bouyagui Tamboura, b Adama Sy, a Aliou Hamady Barry, c Elhadj Ibrahima Thiam, a Mohamed Gaye a * and Javier Ellena d a De ´partement de Chimie, Faculte ´ des Sciences et Techniques, Universite ´ Cheikh Anta Diop, Dakar, Senegal, b De ´partement de Chimie, Faculte ´ des Sciences et Techniques, Universite ´ Alioune Diop, Bambey, Senegal, c De ´partement de Chimie, Faculte ´ des Sciences et Techniques, Universite ´ de Nouakchott, Nouakchott, Mauritania, and d Instituto de Fı ´sica de Sa ˜o Carlos, Universidade de Sa ˜o Paulo, CP 369, 13.560-970 – Sa ˜o Carlos, SP, Brazil. *Correspondence e-mail: [email protected]Two Cu II complexes [Cu(C 14 H 13 N 4 O 2 )Cl] n , I, and [Cu 4 (C 8 H 10 NO 2 ) 4 Cl 4 ] n , II, have been synthesized. In the structure of the mononuclear complex I, each ligand is coordinated to two metal centers. The basal plane around the Cu II cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitrogen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitrogen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by intermolecular C—HO and C—HCl interactions, leading to a three-dimensional network structure. The tetranuclear complex II lies about a crystallographic inversion centre and has one core in which two Cu II metal centers are mutually interconnected via two enolato oxygen atoms while the other two Cu II cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which the two open-cube units, with seven vertices each, share a side composed of two Cu II ions bridged by two enolato oxygen atoms acting in a 3 -mode. The Cu II atoms in each of the two CuO 3 NCl units are connected by one 2 -O and two 3 -O atoms from deprotonated hydroxyl groups and one chloride anion to the three other Cu II centres. Each of the pentacoordinated Cu II cations has a distorted NO 3 Cl square-pyramidal environment. The Cu II atoms in each of the two CuO 2 NCl 2 units are connected by 2 -O and 3 -O atoms from deprotonated alcohol hydroxy groups and one chloride anion to two other Cu II ions. Each of the pentacoordinated Cu II cations has a distorted NO 2 Cl 2 square-pyramidal environment. In the crystal, a series of intramolecular C—HO and C—HCl hydrogen bonds are observed in each tetranuclear monomeric unit, which is connected to four tetranuclear monomeric units by intermolecular C—HO hydrogen bonds, thus forming a planar two-dimensional structure in the ( 101) plane. 1. Chemical context Picolinic acid esters (Gonza ´ lez-Duarte et al. , 1996, 1998; Hay & Clark, 1979; Luo et al. , 2002; Paul et al., 1974) as well as ISSN 2056-9890
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Crystal structures of two CuII compounds: catena-poly[[chloridocopper(II)]-l-N-[ethoxy(pyridin-2-yl)methylidene]-N000-[oxido(pyridin-3-yl)methyl-idene]hydrazine-j4N,N000,O:N000000] and di-l-chlorido-1:4j2Cl:Cl-2:3j2Cl:Cl-dichlorido-2jCl,4jCl-bis-[l3-ethoxy(pyridin-2-yl)methanolato-1:2:3j3O:-N,O:O;1:3:4j3O:O:N,O]bis[l2-ethoxy(pyridin-2-yl)methanolato-1:2j3N,O:O;3:4j3N,O:O]tetra-copper(II)
Ousmane Sall,a Farba Bouyagui Tamboura,b Adama Sy,a Aliou Hamady Barry,c
Elhadj Ibrahima Thiam,a Mohamed Gayea* and Javier Ellenad
aDepartement de Chimie, Faculte des Sciences et Techniques, Universite Cheikh Anta Diop, Dakar, Senegal,bDepartement de Chimie, Faculte des Sciences et Techniques, Universite Alioune Diop, Bambey, Senegal, cDepartement
de Chimie, Faculte des Sciences et Techniques, Universite de Nouakchott, Nouakchott, Mauritania, and dInstituto de
Fısica de Sao Carlos, Universidade de Sao Paulo, CP 369, 13.560-970 – Sao Carlos, SP, Brazil. *Correspondence e-mail:
nicotinic acid hydrazide (Bharati et al., 2015; Galic et al., 2011;
Nakanishi & Sato, 2017) are widely used in coordination
chemistry for their ability to bind metals through the amino
and/or the ester functional groups (Hay & Clark, 1979).
Complexes formed by ethyl picolinate (EP) with various
divalent metal thiocyanates (Paul et al., 1975), chlorides
(Gonzalez-Duarte et al., 1996) and perchlorates (Natun et al.,
1995) have been prepared and characterized. Several modes of
coordination are observed, depending on the conformation of
the molecule. Ethyl picolinate acts as a bidentate ligand
coordinating through the ring nitrogen and the carbonyl
oxygen. The carboxylic ester function can coordinate in
several ways, while the pyridine nitrogen atom can also
coordinate in a unidentate fashion. The nicotinic acid hydra-
zide can coordinate through the hydrazino moiety as well as
through the pyridine nitrogen atom (Lumme et al., 1984;
Shahverdizadeh et al., 2011a,b). These facts make these
ligands and their analogues very attractive and they have been
used in several studies. Many polynuclear complexes of tran-
sition metals with various structures can be generated,
depending on the disposition of the metal ions and the donor
sites (N or O). Trimers (Zhang et al., 2009), square shapes
(Aouaidjia et al., 2017), cyclic forms (Acevedo-Chavez et al.,
2002) and cubans (Shit et al., 2013) have been reported that
have potential applications in the field of magnetism (Shit et
al., 2013), catalysis (Okeke et al., 2018) and biomimetic
synthesis (Wu et al., 2004). By extension, the introduction of
an ethoxy-carbonyl group in the ortho position of the pyridine
gives a ligand that can have a similar behavior to �-amino acid
esters. It has been shown that the presence of metal ions
promotes the hydrolysis of the ester function of the picolinic
ester (Xue et al., 2016). A condensation can then occur
between nicotinic acid hydrazide and the hydrolysed picolinic
ester, to generate two organic ligands with a large number of
coordination sites in situ, in the presence of copper(II) ions.
These ligands then coordinate to the copper(II) cations to
yield the two complexes that are reported here.
2. Structural commentary
The condensation reaction of pyridine-2-carbaldehyde and
nicotinic acid hydrazide in ethanol in the presence of copper
acetate yields two different complexes whose ligands are
respectively a hemiacetal [ethoxy(pyridine-2-yl)methanol]
and a condensation product [({1-[1-ethoxy-1-(pyridin-2-yl)-
methylene]}-2-(oxonicotinyl))hydrazine]. It has been shown
(Papaefstathiou et al., 2000; Boudalis et al., 2008; Mautner et
al., 2010) that the presence of a metal can induce a nucleo-
philic attack of the ethanol molecule on the carbonyl group to
give a hemiacetal. This reaction can also occur when a frag-
ment such as a pyridyl nitrogen atom is present that is capable
of inducing the polarization of the carbonyl function
(Papaefstathiou et al., 2000). It is under these conditions that
the complexes I and II were formed in situ.
In the crystal structure of the coordination polymer
[CuCl(C14H13N4O2)]n, I, the repeat unit of which is shown in
(Fig. 1), the CuII center is pentacoordinated by one chloride
atom, one enolate oxygen atom of the mono deprotonated
organic ligand, one pyridine, one imino nitrogen atom, and by
a pyridine nitrogen atom of a ligand from an adjacent complex
1070 Sall et al. � [Cu(C14H13N4O2)Cl] and [Cu4(C8H10NO2)4Cl4] Acta Cryst. (2019). E75, 1069–1075
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Figure 1An ORTEP view of the repeat unit of the coordination polymer I,showing the atom-numbering scheme. Displacement ellipsoids are drawnat the 50% probability level. Symmetry codes: (i) 3
2 � x, �12 + y, 3
2 � z; (ii)32 � x, 1
2 + y, 32 � z.
molecule. This latter contact bridges the CuII cations to form a
one-dimensional coordination polymer along the b-axis
direction (Fig. 2). Intermolecular C—H� � �O and C—H� � �Cl
hydrogen bonds, (Table 1), link the polymers into a three-
dimensional network (Fig. 3). The coordination environment
can be best described as strongly distorted square pyramidal.
The basal plane around the CuII ion is formed by the Cl2 anion
with a Cu1—Cl2 distance of 2.2707 (6) A, an O16 atom with a
Cu1—O16 distance of 1.9808 (15) A and the N11 and N22
atoms from the same ligand with a Cu—N distances of
1.9437 (17) and 2.0444 (17) A (Table 2). These bond lengths
are similar to the values found in related complexes (Datta et
al., 2011a,b; Da Silva et al., 2013). The apical position of the
distorted square pyramid is occupied by one pyridine N3 atom
of a neighbouring unit with a Cu—N distance of 2.2009 (17) A.
This distance is shorter than that found in similar compound
(Roztocki et al., 2015). The ligand, which acts in a tridentate
fashion, forms two five-membered rings upon coordination
with the CuII centre: OCNNCu and NCCNCu, with the N11
atom common to both. The five-membered chelate rings
impose large distortions on the ideal angles of a regular square
pyramid, with bite angles in the range 79.11 (7)–79.40 (7)�,
which are slightly smaller than those found in similar
compounds (Roztocki et al., 2015). The transoid angles in the
basal plane O16—Cu1—N22 and N11—Cu1—Cl2 deviate
severely from linearity with values of 158.51 (7)� and
146.17 (6)� (Table 2). These two largest angles around the CuII
ion give a � parameter of 0.206, which is indicative of a
distorted square-pyramidal environment around the CuII ion
(Addison et al., 1984).
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Acta Cryst. (2019). E75, 1069–1075 Sall et al. � [Cu(C14H13N4O2)Cl] and [Cu4(C8H10NO2)4Cl4] 1071
Figure 2The polymer expansion of complex I, showing an infinite chainpropagating along the b-axis direction. In this and subsequent figures,hydrogen bonds are drawn as dashed lines.
Figure 4The structure of II with ellipsoids drawn at the 50% probability level.Unlabelled atoms are generated by the symmetry operation 1 � x, 1 � y,1 � z.
In II, the tetranuclear open-cube complex lies about a
crystallographic inversion centre, with each mono deproto-
nated ethoxy(pyridin-2-yl)methanolate ligand coordinating to
each Cu atom through its imine nitrogen atom and its alco-
Crystal data, data collection and structure refinement details
are summarized in Table 5. All H atoms were refined using a
riding model with d(C—H) = 0.93 A for aromatic, d(C—H) =
0.97 A for methylene and d(C—H) = 0.98 A for methine H
atoms with Uiso(H) = 1.2Ueq(C) and d(C—H) = 0.96 A and
Uiso(H) = 1.5Ueq(C) for methyl H atoms. One reflection with
Fo <<< Fc that was likely to have been affected by the
beamstop was omitted from the final refinement cycles.
Acknowledgements
The authors are grateful to the Sonatel Foundation for
financial support.
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Table 5Experimental details.
I II
Crystal dataChemical formula [Cu(C14H13N4O2)Cl] [Cu4(C8H10NO2)4Cl4]Mr 368.27 1004.68Crystal system, space group Monoclinic, P21/n Monoclinic, P21/nTemperature (K) 293 293a, b, c (A) 11.1472 (9), 9.9573 (6), 14.4904 (11) 11.5150 (4), 13.1051 (5), 12.8066 (6)� (�) 111.595 (9) 100.066 (4)V (A3) 1495.5 (2) 1902.83 (13)Z 4 2Radiation type Mo K� Mo K�� (mm�1) 1.65 2.54Crystal size (mm) 0.3 � 0.2 � 0.1 0.22 � 0.2 � 0.05
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research communications
Acta Cryst. (2019). E75, 1069–1075 Sall et al. � [Cu(C14H13N4O2)Cl] and [Cu4(C8H10NO2)4Cl4] 1075
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrainedw = 1/[σ2(Fo
2) + (0.0492P)2 + 0.1803P] where P = (Fo
2 + 2Fc2)/3
(Δ/σ)max = 0.001Δρmax = 0.40 e Å−3
Δρmin = −0.41 e Å−3
Special details
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrainedw = 1/[σ2(Fo
2) + (0.0422P)2 + 0.4202P] where P = (Fo
2 + 2Fc2)/3
(Δ/σ)max = 0.001Δρmax = 0.46 e Å−3
Δρmin = −0.43 e Å−3
Special details
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.
supporting information
sup-6Acta Cryst. (2019). E75, 1069-1075
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)