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This study characterizes the supra­molecular synthons that dominate the inter­molecular organization of the title compounds, namely dichloridobis(dipyrido[f,h]quinoxaline-6,7-dicarbonitrile)zinc(II), [ZnCl2(C16H6N6)2], (I), and tetrachlorido(dipyrido[f,h]quinoxaline-6,7-dicarbonitrile)tin(IV), [SnCl4(C16H6N6)], (II), in their respective crystal structures. Mol­ecules of (I) are located on 2b axes of rotational symmetry. Their crystal packing is stabilized mostly by π–π stacking and dipole–dipole attractions between the organic ligand fragments of inversion-related neighbouring species, as well as by weak inter­molecular C—H...N hydrogen bonds. On the other hand, Cl...π and N...π inter­actions seem to direct the crystal packing in (II), which is unusual in the sense that its aromatic fragments are not involved in π–π stacking. Mol­ecules of (II) are located on mb planes of mirror symmetry. This study confirms the diverse structural chemistry of this organic ligand, which can be involved in a wide range of supra­molecular inter­actions. These include effective coordination to various metal ions via the phenathroline N-atom sites, π–π stacking and π...halogen contacts through its extended π-system, and hydrogen bonding and N...π inter­actions through its nitrile groups. The competing natures of the latter make it difficult to predict a priori the preferred supra­molecular motif that may form in a given structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010800303X/ln3086sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010800303X/ln3086Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010800303X/ln3086IIsup3.hkl
Contains datablock II

CCDC references: 682795; 682796

Comment top

The phenathroline-based 6,7-dicyanodipyridoquinoxaline (DICNQ) ligand has an extended π electron system and multiple N-sites, which make it an attractive reagent in diverse applications. It has been widely used as a multidentate coordination ligand in the synthesis of various transition metal complexes (Liu et al., 2001; Xu et al., 2002; Stephenson & Hardie, 2006). It has also been employed as an efficient antenna chromophore in the design of photonic and biochemical sensors (van der Tol et al., 1998; Arounaguiri & Maiya, 1999; Ambroize & Maiya, 2000). The redox chemistry of RuI complexes of DICNQ has been investigated too (Kulkarni et al., 2004). We were also interested in exploring the supramolecular reactivity of DICNQ, by evaluating the preferred modes of its intermolecular organization as a free ligand or in the form of its various complexes with metal ions. To this end, we synthesized DICNQ by a literature procedure (van der Tol et al., 1998; Arounaguiri & Maiya, 1999), determined its crystal structure, and characterized its remarkable ππ stacking as a dominant intermolecular interaction in the solid phase (Kozlov et al., 2008). Here, we report the crystal structures of the 2:1 complex of DICNQ with zinc(II) dichloride, (I), and the 1:1 complex of DICNQ with tin(IV) tetrachloride, (II), with an emphasis on their supramolecular self-organization and descriptions of the interaction synthons that operate therein.

Representations of (I) and (II) are shown in Fig. 1. In (I), molecules of the complex are located on axes of twofold rotation and the two DICNQ ligands bound to the ZnII ion are symmetry equivalent. In (II), the complex resides on a mirror plane, which is perpendicular to the plane of the ligand. The DICNQ framework is aromatic, and it is quite planar in the two structures. For the 18-membered delocalized system (excluding the two –CN substituents), the deviations of the individual atoms from their mean plane does not exceed ±0.06 Å (r.m.s. 0.03 Å) in (I) and 0.05 Å (r.m.s. 0.03 Å) in (II). In both structures, the cyano groups deviate to a minor extent from the mean plane of the corresponding aromatic fragment.

The overall topology of complex (I) is dictated by the preferred tetrahedral coordination environment of the ZnII ion with respect to the four ligating species, with the Cl- anions occupying two vertices of the tetrahedron. Along the other two directions, the ZnII is coordinated in a chelating manner by the phenanthroline side of two rotation-related DICNQ ligands. If the N sites of the coordinated phenanthroline moieties are counted as separate ligands, the coordination environment around the ZnII ion can be described alternatively as a distorted octahedron. No metal coordination by the cyano sites is observed.

It appears that the intermolecular organization in the condensed solid phase of the species thus formed cannot be optimized solely by ππ stacking as in the crystal structure of the free flat DICNQ ligand (Kozlov et al., 2008). Instead, in (I), three different types of specific interactions (in addition to common dispersion) operate in concert. Fig. 2(a) illustrates the ππ stacking and dipole–dipole interactions beween DICNQ fragments related to one another by centres of inversion. Thus, significant overlap occurs between the quinoxaline moieties related by the symmetry operator (3/4 - x, 1/2 - y, 1 - z) (in the centre of Fig. 2a). The relatively short interplanar distance between the corresponding fragments (C8/C9/N17/C19–C22) is 3.29 (1) Å, which is indicative of a strong ππ interaction. In addition, dipolar attractions operate between the cyano groups of DICNQ residues inter-related by inversion at (1/2 - x, -y, 1/2 - z). The distance between the antiparallel pairs of CN dipoles of the two molecules is 3.123 (4) Å, which reflects a rather strong interaction. Preliminary density functional theory calculations (Software and reference?) confirm the attractive nature of the ππ and dipole–dipole interactions. The third component of the supramolecular interaction in this structure is shown in Fig. 2(b). It involves weak CH···N(cyano) hydrogen bonds (Table 1). Every molecule of complex (I) associates via eight such hydrogen bonds to four neighbouring species, yielding an extended supramolecular network that propagates through the crystal structure. The unit cell shown in Fig. 3 partly illustrates the combination of the above-described interaction synthons in the crystal structure of (I). It also shows that the Cl- ligands of one complex are oriented perpendicular to the π system of adjacent moieties, suggesting the presence of Cl···π interactions as well. The observed distance of the Cl- anions from the plane of the corresponding DICNQ ring is 3.640 (5) Å, which is, however, considerably longer than expected for a Cl-···π interaction [Rosokha et al., 2004; see also structure (II) below]. As the ππ stacking and dipole–dipole interactions operate in directions perpendicular to the two DICNQ rings, while the hydrogen bonds operate in different directions parallel to these rings, the entire supramolecular assembly exhibits a three-dimensional connectivity scheme. Structure (I) is nearly isomorphous with the structure of the cobalt dibromide analogue (Stephenson & Hardie, 2006).

The tin tetracholoride complex, (II), is characterized by a distorted octahedral geometry, with the two N atoms of the phenanthroline fragment occupying two adjacent coordination sites of the metal ion (Fig. 1b). Somewhat surprisingly, the supramolecular organization of (II) lacks the ππ stacking interactions between aromatic ligands which are often observed in the crystal structures of various metal ions with phenanthroline-type ligands (e.g. Bergman et al., 2002; Gut et al., 2002; Gupta et al., 2004; Rubin-Preminger et al., 2008). This may be mainly due to strong attractions between the electron-rich Cl- ligand and the electron-deficient areas of the π electron system in DICNQ. These interactions are illustrated in Fig. 4. They are reflected well in the rather short contact distances, Cl4···C13(1/2 + x, y, -1/2 - z) = 3.254 (3) Å and Cl2···C14(1/2 - x, 1/2 + y, 1/2 + z) = 3.346 (4) Å, indicative of arrays of significant Cl···π interactions that extend in two dimensions, which is consistent with earlier reports (Rosokha et al., 2004). Furthermore, atom Cl4 is located 3.147 (10) Å above the plane of the proxime quinoxaline ring [atoms C10/N12/C13 at (1/2 + x, y, -1/2 - z) and at (1/2 + x, 1/2 - y, -1/2 - z)]. Thus, every molecule of the complex is involved in eight such Cl···π contacts through its Cl sites (`donating' electrons) and its π system (`accepting' electrons). Fig. 4 also shows that N···π interactions provide additional enthalpic stabilization to the observed structure along one direction of the two-dimensional supramolecular array. They involve the C—N groups of one species that interact with the π system of the two pyrido rings of adjacent species. Thus, the observed C9···N15(1/2 + x, y, -1/2 - z) distance is 3.163 (4) Å, and this N atom is located 3.010 (8) Å above the plane of the corresponding aromatic ring (N5/C6–C9/C11). Each molecule of the complex associates in four such interactions through its pair of cyano groups and the two pyrido rings. The CN bond is not perpendicular to the aromatic ring it overlaps, the approach angle being 46.20 (7) instead of 90°. Similar CN···π interactions were observed earlier in the structure of the octahedral [Ni(DICNQ)3]Br2 complex (Stephenson & Hardie, 2006). The above-described array of intermolecular interactions gives rise to two-dimensional supramolecular motifs. Another observation related to the presence of the N···π interactions is the slight inward bending of the cyano groups in (II) compared with the structure of the free DICNQ ligand (Kozlov et al., 2008). The intramolecular N15···N15(x, 1/2 - y, z) distance is 3.615 (5) Å in (II) compared with 3.999 (6) Å in the structure of the free ligand.

In summary, the supramolecular organization in (II) is stabilized mainly by the somewhat less common Cl···π and N···π interactions in two dimensions, but not by ππ stacking forces like those observed in the structure of DICNQ (Kozlov et al., 2008) and many other complexes of phenanthroline-type ligands (Bergman et al., 2002; Gut et al., 2002; Gupta et al., 2004; Rubin-Preminger et al., 2008).

This study demonstrates the diverse supramolecular reactivity of the DICNQ ligand. The competing natures of the secondary interactions, which involve the extended π system and the nitrile groups, make it difficult to predict a priori the preferred supramolecular organization in a given structure.

Related literature top

For related literature, see: Ambroise & Maiya (2000); Arounaguiri & Maiya (1999); Bergman et al. (2002); Gupta et al. (2004); Gut et al. (2002); Kozlov et al. (2008); Kulkarni et al. (2004); Liu et al. (2001); Rosokha et al. (2004); Rubin-Preminger, Kozlov & Goldberg (2008); Stephenson & Hardie (2006); Tol et al. (1998); Xu et al. (2002).

Experimental top

DICNQ was synthesized by previously reported procedures (Arounaguiri & Maiya, 1999; van der Tol et al., 1998) and crystallized from ethanol by slow evaporation. For the synthesis of the zinc complex, (I), DICNQ (17.2 mg, 0.06 mmol) was dissolved in hot acetonitrile (15 ml). This solution was then mixed with a solution of zinc dichloride (2.9 mg, 0.02 mmol) in boiling acetonitrile (2.5 ml). Slow evaporation of the resulting mixture yielded plate–needle-shaped yellow crystals of (I) after three weeks. For the synthesis of the tin complex, (II), DICNQ (22.8 mg, 0.08 mmol) was dissolved in a hot methanol–ethyl acetate mixture (10 ml, 1:3 v/v). This solution was then mixed with a solution of tin dichloride dihydrate (12.8 mg, 0.06 mmol) in methanol (2.5 ml) under boiling/reflux conditions. Brown needle-shaped crystals of (I) appeared after one month of slow evaporation of the solvent under ambient conditions. It appears that during the preparative process of (II), the SnII species was oxidized to an SnIV moiety, leading to the SnCl4–DICNQ product.

Refinement top

H atoms bound to C atoms were located in calculated positions and constrained to ride on their parent atoms, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C). The residual electron-density map of (I) contains a single peak of 1.82 e Å-3, about 2.2 Å from N24, which could not be accounted for. It may be due to a systematic error in the intensity data set (e.g. an unnoticed diffraction from ice in the low-temperature experiment).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structures of the title compounds, showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level at ca 110 K, and H atoms are shown as small spheres of arbitrary radii. (a) Compound (I), which is located on the twofold rotation axis at (1, y, 3/4) passing through the ZnII ion; only atoms of the asymmetric unit are labelled. (b) Compound (II). Atoms of the asymmetric unit are labelled. The entire molecule of the complex is located on a plane of mirror symmetry (x, 1/4, z), which passes through the SnIV ion and perpendicular to the plane of the DICNQ ligand.
[Figure 2] Fig. 2. (a) The ππ stacking and dipole–dipole interaction modes in (I). The DICNQ fragment labelled (1) is at the symmetry position (x, y, z), that labelled (2) is at (1 - x, -y, 1 - z) and that labelled (3) is at (3/2 - x, 1/2 - y, 1 - z). The predominantly dipole–dipole interactions are indicated by dotted lines, while the ππ stacking is indicated by the double arrow. (b) The intermolecular hydrogen-bonding scheme (dotted lines) in (I). The DICNQ fragment labelled (1) is at the symmetry position (x, y, z), that labelled (2) is at (2 - x, -y, 1 - z) and that labelled (3) is at (1/2 - x, 1/2 - y, 1 - z). Zn and Cl atoms are denoted by small spheres. H atoms have been omitted for clarity. Primed atom N23' is at symmetry position (2) and doubly primed atom N24'' is at symmetry position (3).
[Figure 3] Fig. 3. The unit-cell contents in (I), showing some of the supramolecular interactions. The DICNQ fragment labelled (1) is at the symmetry position (x, y, z), that labelled (2) is at (1 - x, 1 - y, 1 - z), that labelled (3) is at (x - 1/2, y + 1/2, z) and that labelled (4) is at (3/2 - x, 1/2 - y, 1 - z). The weak hydrogen bond from primed atom C6' at (x - 1/2, y + 1/2, z) to doubly primed atom N23'' at (3/2 - x, 1/2 - y, 1 - z) and its inversion-related counterpart are marked by dotted lines. The ππ stacking interactions between overlapping DICNQ fragments are indicated by arrows. Zn and Cl atoms are denoted by small spheres. H atoms have been omitted for clarity.
[Figure 4] Fig. 4. The intermolecular interaction scheme in (II). The Cl···π interactions and interactions between neighbouring species are indicated by dotted lines. The N···π interactions are indicated by dashed arrows. Sn atoms are denoted by small spheres. H atoms have been omitted. Primed atoms are at the symmetry position (1/2 + x, y, -1/2 - z) and doubly primed atoms are the (1/2 - x, 1/2 + y, 1/2 - z).
[Figure 5] Fig. 5. The crystal packing of (II). The Cl···π and N···π interactions are indicated by dotted lines. Sn atoms are denoted by small spheres. H atoms have been omitted.
(I) dichloridobis(dipyrido[f,h]quinoxaline-6,7-dicarbonitrile)zinc(II) top
Crystal data top
[ZnCl2(C32H12N12)]F(000) = 1408
Mr = 700.81Dx = 1.597 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 8.3051 (2) ÅCell parameters from 2759 reflections
b = 12.6449 (3) Åθ = 1.4–27.9°
c = 28.0176 (12) ŵ = 1.07 mm1
β = 97.766 (2)°T = 110 K
V = 2915.34 (16) Å3Plate, yellow
Z = 40.40 × 0.20 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer
3433 independent reflections
Radiation source: fine-focus sealed tube2501 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 12.8 pixels mm-1θmax = 27.8°, θmin = 3.0°
1 deg. ϕ and ω scansh = 108
Absorption correction: multi-scan
(Blessing, 1995)
k = 169
Tmin = 0.673, Tmax = 0.856l = 3636
9284 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)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0799P)2 + 10.2582P]
where P = (Fo2 + 2Fc2)/3
3433 reflections(Δ/σ)max < 0.001
213 parametersΔρmax = 1.82 e Å3
0 restraintsΔρmin = 0.52 e Å3
Crystal data top
[ZnCl2(C32H12N12)]V = 2915.34 (16) Å3
Mr = 700.81Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.3051 (2) ŵ = 1.07 mm1
b = 12.6449 (3) ÅT = 110 K
c = 28.0176 (12) Å0.40 × 0.20 × 0.15 mm
β = 97.766 (2)°
Data collection top
Nonius KappaCCD
diffractometer
3433 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
2501 reflections with I > 2σ(I)
Tmin = 0.673, Tmax = 0.856Rint = 0.035
9284 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.173H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0799P)2 + 10.2582P]
where P = (Fo2 + 2Fc2)/3
3433 reflectionsΔρmax = 1.82 e Å3
213 parametersΔρmin = 0.52 e Å3
Special details top

Experimental. One hemisphere of data was collected

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
xyzUiso*/Ueq
Zn11.00000.46608 (5)0.75000.0273 (2)
Cl20.87310 (11)0.59024 (9)0.79770 (4)0.0360 (3)
N31.0649 (4)0.3338 (3)0.70149 (12)0.0268 (7)
C41.2074 (4)0.2864 (3)0.70188 (14)0.0300 (9)
H41.29200.30270.72710.036*
C51.2389 (5)0.2136 (3)0.66688 (15)0.0317 (9)
H51.34320.18190.66840.038*
C61.1187 (5)0.1880 (3)0.63033 (16)0.0335 (9)
H61.13830.13960.60580.040*
C70.9653 (5)0.2354 (3)0.63000 (14)0.0299 (9)
C80.8298 (5)0.2111 (3)0.59291 (15)0.0339 (9)
C90.6769 (5)0.2603 (3)0.59410 (15)0.0340 (9)
C100.6554 (4)0.3359 (3)0.63142 (15)0.0300 (9)
C110.5073 (4)0.3884 (4)0.63364 (15)0.0338 (10)
H110.41560.37450.61040.041*
C120.4975 (4)0.4596 (3)0.66968 (15)0.0327 (9)
H120.39780.49460.67220.039*
C130.6349 (4)0.4807 (3)0.70287 (15)0.0294 (9)
H130.62630.53080.72760.035*
N140.7781 (3)0.4333 (3)0.70127 (12)0.0269 (7)
C150.9437 (4)0.3079 (3)0.66576 (13)0.0251 (8)
C160.7877 (4)0.3607 (3)0.66633 (14)0.0260 (8)
N170.8560 (5)0.1431 (3)0.55784 (13)0.0388 (9)
N180.5518 (4)0.2406 (3)0.55932 (13)0.0389 (9)
C190.7290 (6)0.1242 (4)0.52388 (17)0.0459 (12)
C200.5779 (6)0.1740 (4)0.52503 (16)0.0445 (12)
C210.7511 (7)0.0558 (4)0.48534 (17)0.0515 (14)
C220.4514 (7)0.1522 (5)0.48621 (17)0.0523 (14)
N230.7675 (8)0.0001 (5)0.4531 (2)0.0831 (18)
N240.3496 (7)0.1364 (5)0.4546 (2)0.0856 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0162 (3)0.0314 (4)0.0328 (4)0.0000.0029 (2)0.000
Cl20.0223 (5)0.0362 (6)0.0489 (7)0.0017 (4)0.0020 (4)0.0110 (5)
N30.0225 (15)0.0271 (17)0.0288 (17)0.0007 (13)0.0030 (12)0.0029 (14)
C40.0211 (18)0.035 (2)0.032 (2)0.0011 (15)0.0029 (15)0.0040 (18)
C50.028 (2)0.029 (2)0.038 (2)0.0034 (16)0.0024 (16)0.0018 (18)
C60.040 (2)0.026 (2)0.035 (2)0.0009 (17)0.0040 (17)0.0005 (18)
C70.031 (2)0.029 (2)0.028 (2)0.0022 (16)0.0002 (16)0.0046 (17)
C80.039 (2)0.032 (2)0.030 (2)0.0062 (18)0.0009 (17)0.0000 (18)
C90.034 (2)0.034 (2)0.031 (2)0.0109 (18)0.0047 (16)0.0066 (18)
C100.0240 (18)0.032 (2)0.032 (2)0.0083 (16)0.0032 (15)0.0028 (17)
C110.0202 (18)0.043 (3)0.035 (2)0.0073 (17)0.0071 (15)0.007 (2)
C120.0171 (17)0.040 (2)0.041 (2)0.0007 (16)0.0008 (15)0.011 (2)
C130.0222 (18)0.033 (2)0.033 (2)0.0003 (15)0.0014 (15)0.0072 (17)
N140.0169 (14)0.0322 (18)0.0306 (18)0.0001 (13)0.0007 (12)0.0042 (15)
C150.0251 (18)0.0235 (19)0.026 (2)0.0025 (15)0.0010 (14)0.0041 (16)
C160.0228 (17)0.027 (2)0.0267 (19)0.0043 (15)0.0016 (14)0.0073 (17)
N170.047 (2)0.035 (2)0.033 (2)0.0100 (17)0.0010 (16)0.0016 (17)
N180.0366 (19)0.045 (2)0.031 (2)0.0127 (17)0.0074 (15)0.0033 (17)
C190.059 (3)0.040 (3)0.036 (3)0.014 (2)0.002 (2)0.006 (2)
C200.049 (3)0.049 (3)0.031 (2)0.020 (2)0.0092 (19)0.002 (2)
C210.081 (4)0.046 (3)0.025 (2)0.026 (3)0.000 (2)0.010 (2)
C220.063 (3)0.059 (3)0.031 (2)0.030 (3)0.010 (2)0.002 (2)
N230.117 (5)0.075 (4)0.058 (3)0.027 (4)0.014 (3)0.006 (3)
N240.081 (4)0.109 (5)0.062 (3)0.036 (4)0.011 (3)0.013 (3)
Geometric parameters (Å, º) top
Zn1—N142.180 (3)C10—C161.405 (5)
Zn1—N32.265 (3)C10—C111.406 (6)
Zn1—Cl22.3962 (11)C11—C121.363 (6)
N3—C41.326 (5)C11—H110.9500
N3—C151.361 (5)C12—C131.397 (5)
C4—C51.395 (6)C12—H120.9500
C4—H40.9500C13—N141.337 (5)
C5—C61.369 (6)C13—H130.9500
C5—H50.9500N14—C161.353 (5)
C6—C71.406 (6)C15—C161.459 (5)
C6—H60.9500N17—C191.343 (6)
C7—C151.388 (6)N18—C201.318 (6)
C7—C81.458 (6)C19—C201.408 (8)
C8—N171.346 (6)C19—C211.414 (7)
C8—C91.418 (6)C20—C221.434 (6)
C9—N181.349 (5)C21—N231.171 (8)
C9—C101.445 (6)C22—N241.156 (7)
N14i—Zn1—N14158.10 (18)C16—C10—C9119.3 (4)
N14—Zn1—N374.56 (12)C11—C10—C9122.6 (4)
N14—Zn1—N3i89.19 (12)C12—C11—C10119.0 (3)
N3—Zn1—N3i84.85 (17)C12—C11—H11120.5
N14—Zn1—Cl294.32 (9)C10—C11—H11120.5
N3—Zn1—Cl2167.54 (8)C11—C12—C13119.6 (4)
N14—Zn1—Cl2i99.99 (9)C11—C12—H12120.2
N3—Zn1—Cl2i89.47 (9)C13—C12—H12120.2
Cl2—Zn1—Cl2i98.14 (6)N14—C13—C12122.9 (4)
C4—N3—C15117.9 (3)N14—C13—H13118.6
C4—N3—Zn1127.9 (3)C12—C13—H13118.6
C15—N3—Zn1114.0 (2)C13—N14—C16117.9 (3)
N3—C4—C5123.0 (4)C13—N14—Zn1125.1 (3)
N3—C4—H4118.5C16—N14—Zn1117.0 (2)
C5—C4—H4118.5N3—C15—C7122.4 (3)
C6—C5—C4119.7 (4)N3—C15—C16116.9 (3)
C6—C5—H5120.2C7—C15—C16120.8 (3)
C4—C5—H5120.2N14—C16—C10122.6 (3)
C5—C6—C7118.2 (4)N14—C16—C15117.2 (3)
C5—C6—H6120.9C10—C16—C15120.2 (4)
C7—C6—H6120.9C19—N17—C8116.2 (4)
C15—C7—C6118.8 (4)C20—N18—C9117.3 (4)
C15—C7—C8119.4 (4)N17—C19—C20121.4 (5)
C6—C7—C8121.8 (4)N17—C19—C21118.6 (5)
N17—C8—C9122.1 (4)C20—C19—C21119.9 (4)
N17—C8—C7118.0 (4)N18—C20—C19122.5 (4)
C9—C8—C7119.9 (4)N18—C20—C22120.0 (5)
N18—C9—C8120.5 (4)C19—C20—C22117.4 (5)
N18—C9—C10119.1 (4)N23—C21—C19179.1 (7)
C8—C9—C10120.4 (4)N24—C22—C20178.8 (6)
C16—C10—C11118.1 (4)
N14i—Zn1—N3—C415.5 (3)N18—C9—C10—C16176.8 (4)
N14—Zn1—N3—C4179.4 (4)C8—C9—C10—C160.5 (6)
N3i—Zn1—N3—C490.1 (3)N18—C9—C10—C111.4 (6)
Cl2—Zn1—N3—C4153.3 (3)C8—C9—C10—C11178.7 (4)
Cl2i—Zn1—N3—C478.8 (3)C16—C10—C11—C121.0 (6)
N14i—Zn1—N3—C15170.1 (3)C9—C10—C11—C12179.2 (4)
N14—Zn1—N3—C155.0 (3)C10—C11—C12—C131.5 (6)
N3i—Zn1—N3—C1595.5 (3)C16—N14—C13—C121.2 (6)
Cl2—Zn1—N3—C1532.3 (6)Zn1—N14—C13—C12177.6 (3)
Cl2i—Zn1—N3—C1595.6 (3)C11—C12—C13—N140.4 (6)
N14i—Zn1—N14—C13133.8 (3)C4—N3—C15—C70.8 (6)
N3i—Zn1—N14—C1392.4 (3)Zn1—N3—C15—C7174.2 (3)
N3—Zn1—N14—C13177.2 (3)C4—N3—C15—C16179.6 (3)
Cl2—Zn1—N14—C132.9 (3)Zn1—N3—C15—C165.4 (4)
Cl2i—Zn1—N14—C1396.1 (3)C6—C7—C15—N30.9 (6)
N14i—Zn1—N14—C1647.3 (3)C8—C7—C15—N3179.8 (4)
N3i—Zn1—N14—C1688.8 (3)C6—C7—C15—C16178.8 (4)
N3—Zn1—N14—C163.9 (3)C8—C7—C15—C160.6 (6)
Cl2—Zn1—N14—C16178.2 (3)C13—N14—C16—C101.8 (6)
Cl2i—Zn1—N14—C1682.7 (3)Zn1—N14—C16—C10177.2 (3)
C15—N3—C4—C51.5 (6)C13—N14—C16—C15178.6 (3)
Zn1—N3—C4—C5172.7 (3)Zn1—N14—C16—C152.5 (4)
N3—C4—C5—C60.5 (6)C11—C10—C16—N140.7 (6)
C4—C5—C6—C71.1 (6)C9—C10—C16—N14177.6 (4)
C5—C6—C7—C151.8 (6)C11—C10—C16—C15179.6 (4)
C5—C6—C7—C8178.8 (4)C9—C10—C16—C152.1 (6)
C19—N17—C8—C90.0 (6)N3—C15—C16—N142.1 (5)
C19—N17—C8—C7178.9 (4)C7—C15—C16—N14177.5 (3)
C15—C7—C8—N17177.9 (4)N3—C15—C16—C10178.2 (3)
C6—C7—C8—N171.5 (6)C7—C15—C16—C102.2 (6)
C15—C7—C8—C91.0 (6)C8—N17—C19—C200.6 (7)
C6—C7—C8—C9179.7 (4)C8—N17—C19—C21178.1 (4)
C20—N18—C9—C80.5 (6)C9—N18—C20—C190.1 (7)
C20—N18—C9—C10177.7 (4)C9—N18—C20—C22178.1 (4)
N17—C8—C9—N180.5 (6)N17—C19—C20—N180.7 (7)
C7—C8—C9—N18178.3 (4)C21—C19—C20—N18178.1 (4)
N17—C8—C9—C10177.7 (4)N17—C19—C20—C22177.5 (4)
C7—C8—C9—C101.1 (6)C21—C19—C20—C220.1 (7)
Symmetry code: (i) x+2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N23ii0.952.613.549 (8)171
C11—H11···N24iii0.952.663.608 (6)172
Symmetry codes: (ii) x+2, y, z+1; (iii) x+1/2, y+1/2, z+1.
(II) tetrachlorido(dipyrido[f,h]quinoxaline-6,7-dicarbonitrile)tin(IV) top
Crystal data top
[SnCl4(C16H6N6)]Dx = 1.910 Mg m3
Mr = 542.77Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 2487 reflections
a = 14.8630 (4) Åθ = 2.5–27.9°
b = 12.8457 (3) ŵ = 1.93 mm1
c = 9.8852 (2) ÅT = 110 K
V = 1887.34 (8) Å3Needle, brown
Z = 40.55 × 0.15 × 0.06 mm
F(000) = 1048
Data collection top
Nonius KappaCCD
diffractometer
2292 independent reflections
Radiation source: fine-focus sealed tube1822 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
Detector resolution: 12.8 pixels mm-1θmax = 27.9°, θmin = 2.5°
1 deg. ϕ scansh = 190
Absorption correction: multi-scan
(Blessing, 1995)
k = 015
Tmin = 0.492, Tmax = 0.915l = 012
14219 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0419P)2 + 1.6487P]
where P = (Fo2 + 2Fc2)/3
2292 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
[SnCl4(C16H6N6)]V = 1887.34 (8) Å3
Mr = 542.77Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 14.8630 (4) ŵ = 1.93 mm1
b = 12.8457 (3) ÅT = 110 K
c = 9.8852 (2) Å0.55 × 0.15 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
2292 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
1822 reflections with I > 2σ(I)
Tmin = 0.492, Tmax = 0.915Rint = 0.055
14219 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.04Δρmax = 0.53 e Å3
2292 reflectionsΔρmin = 0.78 e Å3
127 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
xyzUiso*/Ueq
Sn10.45953 (2)0.25000.17411 (3)0.03787 (13)
Cl20.54487 (7)0.39021 (8)0.25853 (10)0.0538 (3)
Cl30.35726 (9)0.25000.36490 (12)0.0467 (3)
Cl40.53914 (8)0.25000.03944 (12)0.0424 (3)
N50.35850 (18)0.1448 (2)0.0769 (3)0.0351 (6)
C60.3634 (3)0.0404 (3)0.0708 (3)0.0413 (8)
H60.41590.00650.10310.050*
C70.2938 (3)0.0191 (3)0.0186 (4)0.0444 (9)
H70.29930.09270.01400.053*
C80.2174 (2)0.0284 (3)0.0261 (3)0.0399 (8)
H80.16870.01200.05960.048*
C90.2111 (2)0.1379 (3)0.0224 (3)0.0333 (7)
C100.1330 (2)0.1950 (3)0.0685 (3)0.0339 (7)
C110.2841 (2)0.1933 (3)0.0293 (3)0.0342 (7)
N120.06107 (19)0.1398 (2)0.1106 (3)0.0387 (7)
C130.0094 (2)0.1958 (3)0.1474 (3)0.0374 (7)
C140.0903 (3)0.1424 (3)0.1920 (3)0.0429 (8)
N150.1568 (2)0.1093 (3)0.2295 (3)0.0535 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0388 (2)0.0459 (2)0.02890 (18)0.0000.00373 (14)0.000
Cl20.0563 (6)0.0621 (6)0.0431 (5)0.0125 (5)0.0116 (4)0.0052 (4)
Cl30.0546 (8)0.0520 (7)0.0334 (6)0.0000.0042 (5)0.000
Cl40.0369 (7)0.0582 (8)0.0320 (6)0.0000.0009 (5)0.000
N50.0349 (15)0.0405 (16)0.0299 (13)0.0000 (12)0.0005 (11)0.0026 (12)
C60.045 (2)0.0399 (19)0.0394 (18)0.0053 (15)0.0009 (16)0.0058 (15)
C70.051 (2)0.0359 (18)0.046 (2)0.0009 (16)0.0048 (18)0.0037 (16)
C80.043 (2)0.0391 (18)0.0374 (18)0.0066 (15)0.0041 (15)0.0013 (15)
C90.0345 (18)0.0387 (17)0.0268 (15)0.0024 (14)0.0046 (13)0.0015 (13)
C100.0314 (17)0.0448 (18)0.0255 (15)0.0045 (14)0.0038 (13)0.0026 (13)
C110.0377 (19)0.0375 (18)0.0275 (15)0.0018 (14)0.0045 (14)0.0027 (13)
N120.0370 (16)0.0471 (16)0.0321 (14)0.0034 (13)0.0017 (12)0.0000 (13)
C130.0322 (17)0.0498 (19)0.0302 (16)0.0039 (15)0.0001 (14)0.0007 (14)
C140.044 (2)0.051 (2)0.0338 (18)0.0040 (17)0.0017 (16)0.0045 (16)
N150.048 (2)0.067 (2)0.0454 (18)0.0081 (17)0.0077 (16)0.0058 (16)
Geometric parameters (Å, º) top
Sn1—N52.237 (3)C8—H80.9500
Sn1—Cl22.3556 (10)C9—C111.395 (5)
Sn1—Cl42.4200 (12)C9—C101.446 (5)
Sn1—Cl32.4223 (13)C10—N121.349 (4)
N5—C61.344 (4)C10—C10i1.414 (7)
N5—C111.353 (4)C11—C11i1.457 (6)
C6—C71.386 (5)N12—C131.322 (4)
C6—H60.9500C13—C13i1.391 (7)
C7—C81.362 (5)C13—C141.452 (5)
C7—H70.9500C14—N151.138 (5)
C8—C91.410 (5)
N5—Sn1—N5i74.33 (14)C7—C8—C9119.6 (3)
N5—Sn1—Cl2i92.96 (8)C7—C8—H8120.2
N5—Sn1—Cl2167.29 (8)C9—C8—H8120.2
Cl2i—Sn1—Cl299.74 (5)C11—C9—C8117.8 (3)
N5—Sn1—Cl487.33 (7)C11—C9—C10118.8 (3)
Cl2—Sn1—Cl492.62 (3)C8—C9—C10123.4 (3)
N5—Sn1—Cl385.03 (7)N12—C10—C10i121.69 (19)
Cl2—Sn1—Cl393.56 (3)N12—C10—C9117.9 (3)
Cl4—Sn1—Cl3170.40 (4)C10i—C10—C9120.46 (18)
C6—N5—C11119.2 (3)N5—C11—C9121.9 (3)
C6—N5—Sn1125.9 (2)N5—C11—C11i117.43 (18)
C11—N5—Sn1114.8 (2)C9—C11—C11i120.66 (19)
N5—C6—C7121.8 (3)C13—N12—C10115.3 (3)
N5—C6—H6119.1N12—C13—C13i123.0 (2)
C7—C6—H6119.1N12—C13—C14118.8 (3)
C8—C7—C6119.7 (4)C13i—C13—C14118.2 (2)
C8—C7—H7120.2N15—C14—C13173.8 (4)
C6—C7—H7120.2
N5i—Sn1—N5—C6175.3 (2)C13—N12—C10—C10i2.0 (3)
Cl2i—Sn1—N5—C65.2 (3)C13—N12—C10—C9177.8 (3)
Cl2—Sn1—N5—C6177.4 (2)C11—C9—C10—N12176.1 (3)
Cl4—Sn1—N5—C687.3 (3)C8—C9—C10—N123.5 (5)
Cl3—Sn1—N5—C698.5 (3)C11—C9—C10—C10i3.8 (3)
N5i—Sn1—N5—C119.4 (2)C8—C9—C10—C10i176.7 (2)
Cl2i—Sn1—N5—C11170.2 (2)C6—N5—C11—C91.8 (4)
Cl2—Sn1—N5—C117.3 (5)Sn1—N5—C11—C9173.8 (2)
Cl4—Sn1—N5—C1197.4 (2)C6—N5—C11—C11i175.9 (2)
Cl3—Sn1—N5—C1176.8 (2)Sn1—N5—C11—C11i8.4 (2)
C11—N5—C6—C70.8 (5)C8—C9—C11—N51.0 (4)
Sn1—N5—C6—C7174.4 (2)C10—C9—C11—N5178.6 (3)
N5—C6—C7—C81.1 (5)C8—C9—C11—C11i176.6 (2)
C6—C7—C8—C91.8 (5)C10—C9—C11—C11i3.8 (3)
C7—C8—C9—C110.8 (5)C10—N12—C13—C13i2.0 (3)
C7—C8—C9—C10179.6 (3)C10—N12—C13—C14179.0 (3)
Symmetry code: (i) x, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[ZnCl2(C32H12N12)][SnCl4(C16H6N6)]
Mr700.81542.77
Crystal system, space groupMonoclinic, C2/cOrthorhombic, Pnma
Temperature (K)110110
a, b, c (Å)8.3051 (2), 12.6449 (3), 28.0176 (12)14.8630 (4), 12.8457 (3), 9.8852 (2)
α, β, γ (°)90, 97.766 (2), 9090, 90, 90
V3)2915.34 (16)1887.34 (8)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.071.93
Crystal size (mm)0.40 × 0.20 × 0.150.55 × 0.15 × 0.06
Data collection
DiffractometerNonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Multi-scan
(Blessing, 1995)
Tmin, Tmax0.673, 0.8560.492, 0.915
No. of measured, independent and
observed [I > 2σ(I)] reflections
9284, 3433, 2501 14219, 2292, 1822
Rint0.0350.055
(sin θ/λ)max1)0.6570.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.173, 1.07 0.038, 0.089, 1.04
No. of reflections34332292
No. of parameters213127
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0799P)2 + 10.2582P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0419P)2 + 1.6487P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.82, 0.520.53, 0.78

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N23i0.952.613.549 (8)171
C11—H11···N24ii0.952.663.608 (6)172
Symmetry codes: (i) x+2, y, z+1; (ii) x+1/2, y+1/2, z+1.
 

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