trans-Bis(4,7-diphenyl-1,10-phenanthroline-κ2N,N′)bis­(nitrato-κ2O,O′)zinc(II)

Fernandes, J.A.; Almeida Paz, F.A.; Liu, F.-Y.; Cunha-Silva, L.; Carlos, L.D.; Rocha, J.

doi:10.1107/S1600536810047161

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1608-m1609

https://doi.org/10.1107/S1600536810047161

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trans-Bis(4,7-diphenyl-1,10-phenanthroline-κ²N,N′)bis(nitrato-κ²O,O′)zinc(II)

José A. Fernandes,^a Filipe A. Almeida Paz,^a ^* Feng-Yi Liu,^a,^b Luís Cunha-Silva,^a ‡ Luís D. Carlos ^b and João Rocha ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bDepartment of Physics, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 11 November 2010; accepted 14 November 2010; online 20 November 2010)

The title compound, [Zn(NO₃)₂(C₂₄H₁₆N₂)₂], is a twofold axially symmetric coordination compound. Given that the Zn—O interactions [2.4926 (15) and 2.6673 (15) Å] can be considered as weakly bonding and the nitrate ions share the same C₂ axis of the Zn(dpp)₂ fragment (dpp is 4,7-diphenyl-1,10-phenanthroline), these anions belong to the coordination sphere of Zn²⁺, leading to a complex with an overall coordination number of 8 for the metal ion.

Related literature

For an isotypic compound containing copper(II), see: Moreno et al. (2006 ). For structures with eight-coordinate Zn²⁺ ions containing crown ethers, see: Nurtaeva & Holt (2002 ); Doxsee et al. (1994 ); Junk et al. (2001 ). For structures with eight-coordinate Zn²⁺ ions containing a calyxarene, see: Beer et al. (1995 ). For structures with eight-coordinate Zn²⁺ ions containing nidoboranes, see: Greenwood et al. (1971 ); Allmann et al. (1976 ). For compounds containing the tetranitratozincate(II) anion, see: Bellito et al. (1976 ); Chekhlov (2007 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For geometrical aspects of C—H⋯π contacts, see: Babu (2003 ). For background research from our group focused on the use of hydrothermal synthesis to prepare metastable hybrid compounds, see: Paz & Klinowski (2003 , 2004 , 2007 ); Paz et al. (2005 ).

Experimental

Crystal data

[Zn(NO₃)₂(C₂₄H₁₆N₂)₂]
M_r = 854.17
Monoclinic, C 2/c
a = 20.5074 (4) Å
b = 17.4116 (3) Å
c = 12.7089 (3) Å
β = 124.035 (1)°
V = 3760.56 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 180 K
0.40 × 0.28 × 0.15 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.762, T_max = 0.900
36092 measured reflections
4283 independent reflections
3824 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.06
4283 reflections
278 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047161/cv2797sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047161/cv2797Isup2.hkl

checkCIF report

Comment top

Some features of the zinc element, namely small radius and a fully occupied electron d-layer make this element unsuitable for preparing compounds with large coordination numbers. A survey in the Cambridge Structural Database (Allen, 2002) revealed, however, some zinc compounds which could be classified as having a coordination number of 8. Nevertheless, most of these compounds comprise loosely bonded cyclic ligands such as crown ethers (Nurtaeva & Holt, 2002; Doxsee et al., 1994; Junk et al., 2001), calyxarenes (Beer et al., 1995) or nidoboranes (Greenwood et al., 1971; Allmann et al., 1976), and also the tetranitratozincate(II) anion (Bellito et al., 1976; Chekhlov et al., 2007). Knowing that the eight-coordinated compound [Cu(dpp)₂(NO₃)₂] (dpp = 4,7-diphenyl-1,10-phenanthroline, C₂₄H₁₆N₂) has serendipitously been prepared (Moreno et al., 2006), we decided to test the preparation of the zinc(II) analogue using for that purpose hydrothermal synthetic approaches which have been used systematically in our research group (Paz & Klinowski, 2003; Paz & Klinowski, 2004; Paz & Klinowski, 2007; Paz et al., 2005).

The title compound comprises a twofold axial symmetric Zn²⁺ coordination compound containing two dpp ligands and two nitrato ions (see Scheme). The asymmetric unit comprises half of the complex, in which the metal centre and the O2, N3, N4 and O4 atoms of the nitrato ligands are located in special positions along the rotation axis (Figure 1). The coordination environment around the metal centre can be envisaged as a highly distorted octahedron, where the dpp ligands occupy the equatorial positions and the nitrato ligands are in apical positions. While the Zn—N distances are 2.0843 (12) and 2.1309 (12) Å, the Zn—O ones are instead 2.4926 (15) and 2.6673 (15) Å. The latter values correspond to long Zn—O distances, but nevertheless they are considerably shorter than the Cu—O analogues observed in the isostructural Cu²⁺ compound (Moreno et al., 2006). This feature, in addition to the existence of a common twofold axis with the [Zn(dpp)₂]²⁺ fragment, is a clear indication that the nitrate is effectively interacting with the metallic centre. The octahedral cis and trans angles are highly deviated from the ideal value. Considering the centre of gravity (C_g) of the O—N—O chelating moieties as the points where angles are measured, the cis angles range from ca 76.1 (N2—Zn1···C_g) to 104.89 (4)° (N2—Zn1—N1ⁱ; symmetry code (i): -x, y, 0.5 - z). Conversely, the trans angles can be as small as 152.24 (7)° (N2—Zn1—N2ⁱ). The average planes of the peripheral phenyl moieties of dpp form angles of ca 43.4 and 49.6° with the average plane of the phenanthroline fragment.

The crystal structure is rich in weak supramolecular interactions such as π–π stacking, C—H···π (Babu, 2003) and C—H···O. Due to the complexity of the network created by these intermolecular interactions they have been omitted from Figure 2 (crystal packing) for simplicity. Weak π-π stacking interactions occur between pairs of symmetry-equivalent peripheral phenyl substituents, with distances between the centroids (C_t) of ca 3.80 and 4.18 Å. C—H/π interactions occur between five H atoms and neighbouring aromatic rings, with 〈(C—H···C_t) larger than ca 147° and d_H···C_t in the ca 2.80–3.45 Å range. C—H···O hydrogen bonding interactions occur between four H-atoms and neighbouring O-atoms from the nitrato groups: 〈(DHA) larger than ca 140° and internuclear D···A distances in the ca 3.29–3.50 Å range.

Related literature top

For an isotypic compound containing copper(II), see: Moreno et al. (2006). For eight-coordinated zinc(II) compounds with crown ethers, see: Nurtaeva & Holt (2002); Doxsee et al. (1994); Junk et al. (2001). For an eight-coordinated zinc(II) compound with a calyxarene, see: Beer et al. (1995). For eight-coordinated zinc(II) compounds containing nidoboranes, see: Greenwood et al. (1971); Allmann et al. (1976). For compounds containing the tetranitratozincate(II) anion, see: Bellito et al. (1976); Chekhlov et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002). For geometrical aspects of C—H···p contacts, see: Babu (2003). For background research from our group focused on the use of hydrothermal synthesis to prepare metastable hybrid compounds, see: Paz & Klinowski (2003, 2004, 2007); Paz et al. (2005).

Experimental top

Starting chemicals were purchased from commercial sources and were used as received without any further purification. The title compound was prepared in a Teflon-lined reaction vessel under static hydrothermal conditions in an oven preheated at 160 °C. The total reaction time was of 2 days. The reactive mixture was prepared by using a Zn(NO₃)₂.6H₂O: dpp (4,7-diphenyl-1,10-phenanthroline) molar ratio of about 2: 1. After reacting, a large amount of brown-red crystals could be directly isolated from the contents of the reaction vessel.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Schematic representation of the molecular unit of the title compound. All non-hydrogen atoms are represented as displacement ellipsoids drawn at the 50% probability level and hydrogen atoms as small spheres with arbitrary radius. Labels are provided for all non-hydrogen atoms composing the asymmetric unit. Symmetry transformation used to generate equivalent atoms is (i) = (-x, y, 0.5 - z).

Fig. 2. Crystal packing of the title compound viewed in perspective along the [001] direction of the unit cell. Supramolecular interactions (see main text) have been omitted for clarity purposes.

trans-Bis(4,7-diphenyl-1,10-phenanthroline- κ²N,N')bis(nitrato-κ²O,O')zinc(II) top

Crystal data top

[Zn(NO₃)₂(C₂₄H₁₆N₂)₂]	F(000) = 1760
M_r = 854.17	D_x = 1.509 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9894 reflections
a = 20.5074 (4) Å	θ = 3.0–30.2°
b = 17.4116 (3) Å	µ = 0.72 mm⁻¹
c = 12.7089 (3) Å	T = 180 K
β = 124.035 (1)°	Prism, colourless
V = 3760.56 (13) Å³	0.40 × 0.28 × 0.15 mm
Z = 4

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	4283 independent reflections
Radiation source: fine-focus sealed tube	3824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and φ scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −26→26
T_min = 0.762, T_max = 0.900	k = −22→20
36092 measured reflections	l = −16→16

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0361P)² + 3.6556P] where P = (F_o² + 2F_c²)/3
4283 reflections	(Δ/σ)_max = 0.001
278 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Zn(NO₃)₂(C₂₄H₁₆N₂)₂]	V = 3760.56 (13) Å³
M_r = 854.17	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.5074 (4) Å	µ = 0.72 mm⁻¹
b = 17.4116 (3) Å	T = 180 K
c = 12.7089 (3) Å	0.40 × 0.28 × 0.15 mm
β = 124.035 (1)°

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	4283 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	3824 reflections with I > 2σ(I)
T_min = 0.762, T_max = 0.900	R_int = 0.030
36092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.06	Δρ_max = 0.29 e Å⁻³
4283 reflections	Δρ_min = −0.41 e Å⁻³
278 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
Zn1	0.0000	0.406835 (14)	0.2500	0.02344 (8)
N1	0.10982 (7)	0.42246 (7)	0.27115 (11)	0.0191 (2)
N2	0.07903 (7)	0.37812 (7)	0.44046 (11)	0.0205 (2)
C1	0.06298 (8)	0.36151 (8)	0.52558 (15)	0.0239 (3)
H1	0.0096	0.3623	0.4996	0.029*
C2	0.12052 (9)	0.34307 (8)	0.65081 (14)	0.0236 (3)
H2	0.1063	0.3345	0.7093	0.028*
C3	0.19831 (8)	0.33704 (8)	0.69094 (13)	0.0190 (3)
C4	0.21717 (8)	0.35236 (8)	0.60058 (13)	0.0175 (3)
C5	0.15537 (8)	0.37498 (8)	0.47776 (13)	0.0173 (3)
C6	0.25883 (8)	0.31729 (8)	0.82531 (13)	0.0205 (3)
C7	0.26247 (9)	0.35967 (9)	0.92152 (15)	0.0269 (3)
H7	0.2273	0.4014	0.9005	0.032*
C8	0.31732 (10)	0.34113 (10)	1.04812 (15)	0.0316 (4)
H8	0.3204	0.3709	1.1134	0.038*
C9	0.36722 (9)	0.27957 (10)	1.07902 (14)	0.0295 (3)
H9	0.4045	0.2669	1.1656	0.035*
C10	0.36317 (9)	0.23612 (9)	0.98444 (15)	0.0269 (3)
H10	0.3968	0.1930	1.0061	0.032*
C11	0.30981 (8)	0.25548 (9)	0.85766 (14)	0.0233 (3)
H11	0.3081	0.2264	0.7929	0.028*
C12	0.29576 (8)	0.35127 (8)	0.63016 (13)	0.0194 (3)
H12	0.3378	0.3344	0.7117	0.023*
C13	0.31121 (8)	0.37373 (8)	0.54435 (13)	0.0199 (3)
H13	0.3641	0.3735	0.5679	0.024*
C14	0.24988 (8)	0.39783 (8)	0.41882 (13)	0.0174 (3)
C15	0.17192 (8)	0.39831 (7)	0.38575 (13)	0.0173 (3)
C16	0.26372 (8)	0.42396 (8)	0.32660 (13)	0.0180 (3)
C17	0.19943 (8)	0.45022 (8)	0.21198 (13)	0.0212 (3)
H17	0.2066	0.4695	0.1492	0.025*
C18	0.12428 (8)	0.44864 (8)	0.18798 (13)	0.0218 (3)
H18	0.0814	0.4671	0.1085	0.026*
C19	0.34289 (8)	0.42377 (8)	0.34930 (13)	0.0200 (3)
C20	0.39130 (9)	0.35907 (9)	0.39623 (14)	0.0248 (3)
H20	0.3747	0.3145	0.4182	0.030*
C21	0.46359 (9)	0.35970 (10)	0.41090 (15)	0.0317 (4)
H21	0.4963	0.3155	0.4429	0.038*
C22	0.48832 (9)	0.42424 (11)	0.37928 (16)	0.0337 (4)
H22	0.5378	0.4242	0.3893	0.040*
C23	0.44103 (10)	0.48887 (10)	0.33299 (16)	0.0323 (4)
H23	0.4580	0.5333	0.3115	0.039*
C24	0.36867 (9)	0.48850 (9)	0.31812 (14)	0.0260 (3)
H24	0.3363	0.5329	0.2863	0.031*
N3	0.0000	0.22985 (10)	0.2500	0.0302 (4)
O1	0.04653 (7)	0.26663 (8)	0.23472 (13)	0.0460 (3)
O2	0.0000	0.15898 (9)	0.2500	0.0450 (5)
N4	0.0000	0.57342 (10)	0.2500	0.0246 (4)
O3	−0.02609 (8)	0.53615 (8)	0.14987 (13)	0.0462 (3)
O4	0.0000	0.64379 (9)	0.2500	0.0333 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01213 (12)	0.03237 (15)	0.02007 (13)	0.000	0.00548 (10)	0.000
N1	0.0154 (5)	0.0210 (6)	0.0167 (6)	−0.0005 (4)	0.0065 (5)	0.0001 (4)
N2	0.0158 (5)	0.0210 (6)	0.0245 (6)	0.0004 (4)	0.0112 (5)	0.0015 (5)
C1	0.0180 (7)	0.0255 (7)	0.0323 (8)	0.0018 (5)	0.0166 (6)	0.0045 (6)
C2	0.0257 (7)	0.0235 (7)	0.0294 (8)	0.0018 (6)	0.0203 (7)	0.0041 (6)
C3	0.0216 (7)	0.0164 (6)	0.0209 (7)	−0.0008 (5)	0.0131 (6)	−0.0004 (5)
C4	0.0172 (6)	0.0177 (6)	0.0182 (6)	−0.0007 (5)	0.0104 (5)	−0.0018 (5)
C5	0.0149 (6)	0.0170 (6)	0.0193 (6)	−0.0009 (5)	0.0092 (5)	−0.0015 (5)
C6	0.0215 (7)	0.0235 (7)	0.0201 (7)	−0.0034 (5)	0.0140 (6)	0.0012 (5)
C7	0.0327 (8)	0.0280 (8)	0.0268 (8)	−0.0003 (6)	0.0208 (7)	−0.0004 (6)
C8	0.0410 (9)	0.0375 (9)	0.0227 (8)	−0.0079 (7)	0.0218 (7)	−0.0054 (6)
C9	0.0281 (8)	0.0394 (9)	0.0190 (7)	−0.0069 (7)	0.0120 (6)	0.0045 (6)
C10	0.0241 (7)	0.0301 (8)	0.0264 (8)	0.0008 (6)	0.0140 (6)	0.0061 (6)
C11	0.0248 (7)	0.0250 (7)	0.0223 (7)	−0.0009 (6)	0.0144 (6)	0.0007 (6)
C12	0.0148 (6)	0.0247 (7)	0.0154 (6)	0.0015 (5)	0.0064 (5)	0.0003 (5)
C13	0.0137 (6)	0.0263 (7)	0.0187 (7)	0.0011 (5)	0.0084 (6)	−0.0003 (5)
C14	0.0165 (6)	0.0187 (6)	0.0165 (6)	−0.0005 (5)	0.0089 (5)	−0.0016 (5)
C15	0.0159 (6)	0.0166 (6)	0.0171 (6)	−0.0009 (5)	0.0079 (5)	−0.0015 (5)
C16	0.0193 (7)	0.0168 (6)	0.0188 (6)	−0.0007 (5)	0.0112 (6)	−0.0014 (5)
C17	0.0234 (7)	0.0221 (7)	0.0188 (7)	−0.0001 (5)	0.0123 (6)	0.0022 (5)
C18	0.0203 (7)	0.0225 (7)	0.0163 (6)	0.0007 (5)	0.0064 (6)	0.0021 (5)
C19	0.0199 (7)	0.0252 (7)	0.0168 (6)	−0.0003 (5)	0.0115 (6)	−0.0013 (5)
C20	0.0268 (8)	0.0258 (7)	0.0259 (7)	0.0030 (6)	0.0174 (6)	0.0010 (6)
C21	0.0269 (8)	0.0404 (9)	0.0306 (8)	0.0102 (7)	0.0179 (7)	0.0019 (7)
C22	0.0219 (8)	0.0546 (11)	0.0298 (8)	−0.0020 (7)	0.0178 (7)	−0.0050 (7)
C23	0.0311 (9)	0.0404 (9)	0.0322 (8)	−0.0079 (7)	0.0219 (7)	−0.0007 (7)
C24	0.0271 (8)	0.0274 (8)	0.0265 (8)	0.0000 (6)	0.0169 (7)	0.0026 (6)
N3	0.0194 (9)	0.0234 (9)	0.0284 (10)	0.000	0.0016 (8)	0.000
O1	0.0320 (7)	0.0442 (8)	0.0517 (8)	−0.0079 (6)	0.0172 (6)	0.0062 (6)
O2	0.0322 (9)	0.0204 (8)	0.0539 (11)	0.000	0.0066 (8)	0.000
N4	0.0198 (8)	0.0247 (9)	0.0339 (10)	0.000	0.0178 (8)	0.000
O3	0.0391 (7)	0.0525 (8)	0.0517 (8)	−0.0126 (6)	0.0283 (7)	−0.0281 (7)
O4	0.0374 (9)	0.0207 (8)	0.0483 (10)	0.000	0.0278 (8)	0.000

Geometric parameters (Å, º) top

Zn1—N2ⁱ	2.0843 (12)	C10—H10	0.9500
Zn1—N2	2.0843 (12)	C11—H11	0.9500
Zn1—N1	2.1309 (12)	C12—C13	1.352 (2)
Zn1—N1ⁱ	2.1309 (12)	C12—H12	0.9500
Zn1—O3ⁱ	2.4926 (15)	C13—C14	1.4343 (19)
Zn1—O3	2.4926 (15)	C13—H13	0.9500
Zn1—O1ⁱ	2.6673 (15)	C14—C15	1.4073 (19)
Zn1—O1	2.6673 (15)	C14—C16	1.4261 (19)
N1—C18	1.3282 (18)	C16—C17	1.3854 (19)
N1—C15	1.3578 (17)	C16—C19	1.4814 (19)
N2—C1	1.3270 (19)	C17—C18	1.394 (2)
N2—C5	1.3594 (17)	C17—H17	0.9500
C1—C2	1.388 (2)	C18—H18	0.9500
C1—H1	0.9500	C19—C24	1.393 (2)
C2—C3	1.3803 (19)	C19—C20	1.396 (2)
C2—H2	0.9500	C20—C21	1.387 (2)
C3—C4	1.4271 (19)	C20—H20	0.9500
C3—C6	1.4840 (19)	C21—C22	1.382 (3)
C4—C5	1.4083 (19)	C21—H21	0.9500
C4—C12	1.4356 (18)	C22—C23	1.383 (3)
C5—C15	1.4464 (19)	C22—H22	0.9500
C6—C11	1.392 (2)	C23—C24	1.387 (2)
C6—C7	1.394 (2)	C23—H23	0.9500
C7—C8	1.390 (2)	C24—H24	0.9500
C7—H7	0.9500	N3—O2	1.234 (2)
C8—C9	1.379 (2)	N3—O1	1.2513 (16)
C8—H8	0.9500	N3—O1ⁱ	1.2513 (16)
C9—C10	1.383 (2)	N4—O4	1.225 (2)
C9—H9	0.9500	N4—O3	1.2508 (15)
C10—C11	1.390 (2)	N4—O3ⁱ	1.2508 (15)

N2ⁱ—Zn1—N2	152.24 (7)	C7—C8—H8	120.0
N2ⁱ—Zn1—N1	104.89 (4)	C8—C9—C10	120.26 (14)
N2—Zn1—N1	78.71 (4)	C8—C9—H9	119.9
N2ⁱ—Zn1—N1ⁱ	78.71 (4)	C10—C9—H9	119.9
N2—Zn1—N1ⁱ	104.89 (4)	C9—C10—C11	120.00 (15)
N1—Zn1—N1ⁱ	165.33 (6)	C9—C10—H10	120.0
N2ⁱ—Zn1—O3ⁱ	127.93 (4)	C11—C10—H10	120.0
N2—Zn1—O3ⁱ	79.55 (4)	C10—C11—C6	120.23 (14)
N1—Zn1—O3ⁱ	84.87 (4)	C10—C11—H11	119.9
N1ⁱ—Zn1—O3ⁱ	81.88 (4)	C6—C11—H11	119.9
N2ⁱ—Zn1—O3	79.55 (4)	C13—C12—C4	121.36 (12)
N2—Zn1—O3	127.93 (4)	C13—C12—H12	119.3
N1—Zn1—O3	81.88 (4)	C4—C12—H12	119.3
N1ⁱ—Zn1—O3	84.87 (4)	C12—C13—C14	121.75 (12)
O3ⁱ—Zn1—O3	50.81 (6)	C12—C13—H13	119.1
N2ⁱ—Zn1—O1ⁱ	77.74 (5)	C14—C13—H13	119.1
N2—Zn1—O1ⁱ	76.89 (4)	C15—C14—C16	117.91 (12)
N1—Zn1—O1ⁱ	120.24 (4)	C15—C14—C13	118.44 (12)
N1ⁱ—Zn1—O1ⁱ	74.34 (4)	C16—C14—C13	123.61 (12)
O3ⁱ—Zn1—O1ⁱ	140.61 (4)	N1—C15—C14	123.29 (12)
O3—Zn1—O1ⁱ	151.71 (4)	N1—C15—C5	116.78 (12)
N2ⁱ—Zn1—O1	76.89 (4)	C14—C15—C5	119.89 (12)
N2—Zn1—O1	77.74 (5)	C17—C16—C14	117.34 (12)
N1—Zn1—O1	74.34 (4)	C17—C16—C19	119.99 (12)
N1ⁱ—Zn1—O1	120.24 (4)	C14—C16—C19	122.67 (12)
O3ⁱ—Zn1—O1	151.71 (4)	C16—C17—C18	120.58 (13)
O3—Zn1—O1	140.61 (4)	C16—C17—H17	119.7
O1ⁱ—Zn1—O1	47.53 (6)	C18—C17—H17	119.7
C18—N1—C15	117.83 (12)	N1—C18—C17	123.00 (13)
C18—N1—Zn1	129.38 (9)	N1—C18—H18	118.5
C15—N1—Zn1	112.73 (9)	C17—C18—H18	118.5
C1—N2—C5	118.01 (12)	C24—C19—C20	118.83 (13)
C1—N2—Zn1	127.78 (10)	C24—C19—C16	119.45 (13)
C5—N2—Zn1	114.19 (9)	C20—C19—C16	121.66 (13)
N2—C1—C2	123.07 (13)	C21—C20—C19	120.15 (14)
N2—C1—H1	118.5	C21—C20—H20	119.9
C2—C1—H1	118.5	C19—C20—H20	119.9
C3—C2—C1	120.41 (13)	C22—C21—C20	120.40 (15)
C3—C2—H2	119.8	C22—C21—H21	119.8
C1—C2—H2	119.8	C20—C21—H21	119.8
C2—C3—C4	117.79 (13)	C21—C22—C23	120.07 (15)
C2—C3—C6	119.47 (12)	C21—C22—H22	120.0
C4—C3—C6	122.72 (12)	C23—C22—H22	120.0
C5—C4—C3	117.58 (12)	C22—C23—C24	119.74 (15)
C5—C4—C12	118.42 (12)	C22—C23—H23	120.1
C3—C4—C12	123.85 (12)	C24—C23—H23	120.1
N2—C5—C4	122.97 (12)	C23—C24—C19	120.81 (15)
N2—C5—C15	116.89 (12)	C23—C24—H24	119.6
C4—C5—C15	120.12 (12)	C19—C24—H24	119.6
C11—C6—C7	119.16 (13)	O2—N3—O1	120.79 (10)
C11—C6—C3	121.67 (13)	O2—N3—O1ⁱ	120.79 (10)
C7—C6—C3	119.11 (13)	O1—N3—O1ⁱ	118.4 (2)
C8—C7—C6	120.25 (15)	N3—O1—Zn1	97.02 (11)
C8—C7—H7	119.9	O4—N4—O3	121.25 (10)
C6—C7—H7	119.9	O4—N4—O3ⁱ	121.25 (10)
C9—C8—C7	120.07 (15)	O3—N4—O3ⁱ	117.5 (2)
C9—C8—H8	120.0	N4—O3—Zn1	95.84 (11)

N2ⁱ—Zn1—N1—C18	32.48 (13)	C5—C4—C12—C13	2.2 (2)
N2—Zn1—N1—C18	−175.80 (13)	C3—C4—C12—C13	−173.24 (13)
N1ⁱ—Zn1—N1—C18	−70.00 (12)	C4—C12—C13—C14	−1.6 (2)
O3ⁱ—Zn1—N1—C18	−95.46 (12)	C12—C13—C14—C15	0.4 (2)
O3—Zn1—N1—C18	−44.37 (12)	C12—C13—C14—C16	178.20 (13)
O1ⁱ—Zn1—N1—C18	116.78 (12)	C18—N1—C15—C14	−1.7 (2)
O1—Zn1—N1—C18	103.92 (13)	Zn1—N1—C15—C14	175.54 (10)
N2ⁱ—Zn1—N1—C15	−144.42 (9)	C18—N1—C15—C5	175.91 (12)
N2—Zn1—N1—C15	7.31 (9)	Zn1—N1—C15—C5	−6.80 (15)
N1ⁱ—Zn1—N1—C15	113.11 (9)	C16—C14—C15—N1	−0.2 (2)
O3ⁱ—Zn1—N1—C15	87.65 (9)	C13—C14—C15—N1	177.73 (12)
O3—Zn1—N1—C15	138.74 (10)	C16—C14—C15—C5	−177.75 (12)
O1ⁱ—Zn1—N1—C15	−60.11 (10)	C13—C14—C15—C5	0.14 (19)
O1—Zn1—N1—C15	−72.97 (9)	N2—C5—C15—N1	1.08 (18)
N2ⁱ—Zn1—N2—C1	−84.68 (12)	C4—C5—C15—N1	−177.28 (12)
N1—Zn1—N2—C1	174.74 (13)	N2—C5—C15—C14	178.82 (12)
N1ⁱ—Zn1—N2—C1	9.35 (14)	C4—C5—C15—C14	0.46 (19)
O3ⁱ—Zn1—N2—C1	87.95 (13)	C15—C14—C16—C17	1.90 (19)
O3—Zn1—N2—C1	104.51 (13)	C13—C14—C16—C17	−175.87 (13)
O1ⁱ—Zn1—N2—C1	−60.25 (12)	C15—C14—C16—C19	−178.05 (12)
O1—Zn1—N2—C1	−109.04 (13)	C13—C14—C16—C19	4.2 (2)
N2ⁱ—Zn1—N2—C5	93.76 (9)	C14—C16—C17—C18	−1.8 (2)
N1—Zn1—N2—C5	−6.81 (9)	C19—C16—C17—C18	178.14 (13)
N1ⁱ—Zn1—N2—C5	−172.20 (9)	C15—N1—C18—C17	1.9 (2)
O3ⁱ—Zn1—N2—C5	−93.60 (10)	Zn1—N1—C18—C17	−174.87 (10)
O3—Zn1—N2—C5	−77.04 (11)	C16—C17—C18—N1	−0.1 (2)
O1ⁱ—Zn1—N2—C5	118.20 (10)	C17—C16—C19—C24	46.16 (19)
O1—Zn1—N2—C5	69.41 (10)	C14—C16—C19—C24	−133.88 (14)
C5—N2—C1—C2	1.6 (2)	C17—C16—C19—C20	−131.04 (15)
Zn1—N2—C1—C2	−179.98 (11)	C14—C16—C19—C20	48.91 (19)
N2—C1—C2—C3	−3.7 (2)	C24—C19—C20—C21	−0.2 (2)
C1—C2—C3—C4	1.6 (2)	C16—C19—C20—C21	177.05 (13)
C1—C2—C3—C6	179.98 (13)	C19—C20—C21—C22	0.0 (2)
C2—C3—C4—C5	2.00 (19)	C20—C21—C22—C23	0.2 (3)
C6—C3—C4—C5	−176.28 (12)	C21—C22—C23—C24	−0.2 (3)
C2—C3—C4—C12	177.44 (13)	C22—C23—C24—C19	0.0 (2)
C6—C3—C4—C12	−0.8 (2)	C20—C19—C24—C23	0.2 (2)
C1—N2—C5—C4	2.3 (2)	C16—C19—C24—C23	−177.13 (14)
Zn1—N2—C5—C4	−176.27 (10)	O2—N3—O1—Zn1	180.0
C1—N2—C5—C15	−175.98 (12)	O1ⁱ—N3—O1—Zn1	0.0
Zn1—N2—C5—C15	5.42 (15)	N2ⁱ—Zn1—O1—N3	−85.27 (7)
C3—C4—C5—N2	−4.1 (2)	N2—Zn1—O1—N3	83.35 (8)
C12—C4—C5—N2	−179.82 (12)	N1—Zn1—O1—N3	164.89 (8)
C3—C4—C5—C15	174.13 (12)	N1ⁱ—Zn1—O1—N3	−16.89 (9)
C12—C4—C5—C15	−1.56 (19)	O3ⁱ—Zn1—O1—N3	120.67 (8)
C2—C3—C6—C11	125.56 (15)	O3—Zn1—O1—N3	−140.03 (7)
C4—C3—C6—C11	−56.18 (19)	O1ⁱ—Zn1—O1—N3	0.0
C2—C3—C6—C7	−51.64 (19)	O4—N4—O3—Zn1	180.0
C4—C3—C6—C7	126.62 (15)	O3ⁱ—N4—O3—Zn1	0.0
C11—C6—C7—C8	1.1 (2)	N2ⁱ—Zn1—O3—N4	163.13 (7)
C3—C6—C7—C8	178.40 (13)	N2—Zn1—O3—N4	−21.21 (9)
C6—C7—C8—C9	−1.5 (2)	N1—Zn1—O3—N4	−89.99 (7)
C7—C8—C9—C10	0.2 (2)	N1ⁱ—Zn1—O3—N4	83.70 (7)
C8—C9—C10—C11	1.4 (2)	O3ⁱ—Zn1—O3—N4	0.0
C9—C10—C11—C6	−1.8 (2)	O1ⁱ—Zn1—O3—N4	126.09 (8)
C7—C6—C11—C10	0.5 (2)	O1—Zn1—O3—N4	−142.88 (6)
C3—C6—C11—C10	−176.71 (13)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(NO₃)₂(C₂₄H₁₆N₂)₂]
M_r	854.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	180
a, b, c (Å)	20.5074 (4), 17.4116 (3), 12.7089 (3)
β (°)	124.035 (1)
V (Å³)	3760.56 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.40 × 0.28 × 0.15

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.762, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	36092, 4283, 3824
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.06
No. of reflections	4283
No. of parameters	278
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.41

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Footnotes

‡Present address: REQUIMTE/Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal.

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support, for the post-doctoral research grants Nos. SFRH/BPD/63736/2009 (to JAF), SFRH/BPD/26097/2005 (to FYL), SFRH/BPD/34895/2007 (to LCS), and for specific funding toward the purchase of the diffractometer.

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