Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614025650/wq3078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025650/wq3078Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025650/wq3078IIsup3.hkl |
CCDC references: 1035508; 1035507
Hydrogen-bond-based organic–inorganic hybrid materials have gained widespread interest because of their structural, magnetic, optical and electrical properties (Weng et al., 2011; Pardo et al., 2011; Sanchez et al., 2014). The use of hydrogen-bonding interactions with metal salts to control the crystal structure of the product has also recently received attention (Felloni et al., 2004; Boldog et al., 2009; Al-Ktaifani & Rukiah, 2012). Many research groups have contributed to this area, utilizing supramolecular synthons, such as charge-assisted N—H···Cl hydrogen bonds, to form organic–inorganic hybrid crystalline solids containing organic cations and anionic metal complexes (Podesta & Orpen, 2005; Kumar et al., 2006; Deifel & Cahill, 2009; Vitorica-Yrezabal et al., 2011). In these assemblies, the cations are usually protonated nitrogen bases with peripheral functional groups, such as bipyridinium groups, and the anionic metal complexes generally refer to the primary coordination sphere of metal ions containing halogens. Typical bond acceptors are, for example, [MCl4]2- and [MCl6]2-. Deliberate efforts have been made to construct intriguing supramolecular assemblies using metal–halide-based hydrogen bonds formed between organic molecules containing protonated ring N atoms (either aromatic or alicyclic) and inorganic perhalometallate salts (MX4; M = transition metal, X = halogen, mainly Cl) (Zordan et al., 2005; Rademeyer et al., 2011).
In this context, we reported recently the synthesis and molecular structure characterization of the complex salts (C18H16N5)[CuCl4]Cl, (C18H16N5)2[MCl4]·4H2O (M = Pd or Pt; Enríquez et al., 2012), (C12H16N3O)2[PdCl4]3 and (C12H16N3O)[PtCl4]Cl (Campos-Gaxiola, Almaral Sánchez et al., 2013; Campos-Gaxiola, Báez-Castro et al., 2013).
In the present article, the synthesis of 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridocobaltate(II), (I), and 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridozincate(II), (II), is presented, together with their structural characterization by single-crystal X-ray diffraction analysis.
The chemicals and solvents used in this work were of analytical grade, commercially available and used without further purification. FT–IR spectra were recorded as KBr pellets in the range 4000–400 cm-1 on a Bruker Alpha Tensor 27 spectrophotometer. Thermogravimetric analyses (TGA) were performed under nitrogen (50 ml min-1) in the temperature range 303–1073 K (283 K min-1 [Should this be 10 K min-1?]) using a TA SDT Q600 apparatus.
For the synthesis of (I), a mixture of cobalt(II) chloride (0.23 g) and 4-[(E)-2-(pyridin-2-yl)vinyl]pyridine (0.30 g) (1:1 molar ratio) was dissolved in an aqueous solution of hydrochloric acid [Volume? Concentration or pH?]. The mixture was stirred for 1 h and then kept at room temperature. After two weeks, green crystals of (I) had formed (yield 53%). IR (KBr, ν, cm-1): 3242–3102 (+N—Hpy), 3055–2933 (C—Hpy + ═C—Hvinyl), 1616 (C═N), 1535–1458 (C═Cvinyl + C═Cpy). TGA analysis, calculated for 2HCl: 18.9%, found: 17.9% (368–629 K); calculated for C7H7N: 27.9%, found: 27.3% (629–742 K); calculated for C5H5N: 20.3%, found: 20.7% (742–1004 K).
For the synthesis of (II), a mixture of zinc(II) chloride (0.22 g) and 4-[(E)-2-(pyridin-2-yl)vinyl]pyridine (0.30 g) (1:1 molar ratio) was dissolved in an aqueous solution of hydrochloric acid [Volume? Concentration or pH?]. The mixture was stirred for 30 min and then kept at room temperature. After three weeks, amber crystals of (II) had formed (yield 60%). IR (KBr, cm-1): 3242–3104 (+N—Hpy), 3056–2934 (C—py + ═C—Hvinyl), 1615 (C═N), 1535–1457 (C═Cvinyl + C═Cpy). TGA analysis, calculated for 2HCl: 18.6%, found: 17.0% (306–607 K); calculated for C7H7N: 26.6%, found: 27.5% (607–723 K); calculated for C5H5N+2HCl: 38.6%, found: 36.7% (723–925 K).
C-bound H atoms were positioned geometrically and constrained using the riding-model approximation, with vinyl and aryl C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C). N-bound H atoms were located in difference Fourier maps. Their distances were fixed at N—H = 0.840 (1) Å (pyridinium), with Uiso(H) = 1.5Ueq(N), and the coordinates were refined with this restraint.
X-ray crystallographic study of (I) and (II) reveals that both structures crystallize in a monoclinic crystal system with the space group P21/c. The compounds are isostructural. Each asymmetric unit contains one [MCl4]2- dianion and one 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium dication (Fig. 1). The [CoCl4]2- anions in (I) and the [ZnCl4]2- anions in (II) have distorted tetrahedral coordination environments, with Co—Cl bond lengths in the range 2.2519 (6)–2.2953 (6) Å and Cl—Co—Cl bond angles in the range 107.01 (2)–111.65 (2)° in (I) (Table 2). For (II), the Zn—Cl bond lengths are in the range 2.2470 (7)–2.3024 (6) Å and the Cl—Zn—Cl bond angles vary from 107.37 (2) to 111.80 (2)° (Table 3). Regarding the organic cations in the two crystal structures, the pyridinium rings attached to the central vinylene fragment adopt an anti conformation, as indicated by the central C3—C6—C7—C8 torsion angles of 177.48 (17) and 177.4 (2)° in (I) and (II), respectively. The planes of the pyridine rings in each ligand are inclined to one another, by 17.18 (10)° in (I) and 17.02 (11)° in (II).
In the crystal structures of (I) and (II), the [MCl4]2- anions operate as linking building blocks between the dipyridinium cations to give, in the first instance, one-dimensional chains along b (Fig. 2a). Within these chains, the [MCl4]2- and dipyridinium ions are connected through strong intermolecular N+—H···Cl- hydrogen-bonding interactions, with N1···Cl3 and N2···Cl4 separations of 3.109 (2) and 3.145 (2) Å, respectively, for (I), and 3.111 (2) and 3..149 (3) Å, respectively, for (II). These distances are similar to previously reported values (Brammer et al., 2001; Valdés-Martínez et al., 2007). Adjacent one-dimensional chains are further interconnected through a C—H···Cl- contact [C6···Cl2 = 3.659 (2) Å in (I) and 3.660 (3) Å in (II)] and two crystallographically independent π–π interactions involving inversion-related pyridinium rings [for (I): Cg···Cgi = 3.465 (1) Å, interplanar distance = 3.285 Å; Cg'···Cg'ii = 4.376 (2) Å, interplanar distance = 3.409 Å; for (II): Cg···Cgi = 3.466 (1) Å, interplanar distance = 3.285 Å; Cg'···Cg'ii = 4.389 (2) Å, interplanar distance = 3.418 Å; Cg and Cg' are the centroids of the N1/C1–C5 ring [If they refer to the same ring, can just Cg be used for both and the primed one omitted, as in the next paragraph?]; symmetry codes: (i) -x, -y + 1, -z; (ii) -x, -y + 2, -z] to form double chains running parallel to the b axis (Figs. 2b and 3a).
In the remaining directions of the crystal structure, these double chains are interconnected through additional C—H···Cl- [C4···Cl4 = 3.502 (2) and 3.509 (3) Å; C5···Cl1 = 3.691 (2) and 3.702 (3) Å; C11···Cl1 = 3.533 (2) and 3.540 (2) Å for (I) and (II), respectively] and π–π contacts [for (I): Cg···Cgi = 4.728 (2) Å, interplanar distance = 3.274 Å; for (II): Cg···Cgi = 4.732 (2) Å, interplanar distance = 3.289 Å; Cg is the centroid of the N1/C1–C5 ring; symmetry code: (i) -x + 1, -y + 2, -z] to form an overall three-dimensional supramolecular network structure (Fig. 3b).
In the C—H···Cl contacts, both C—H groups of the vinylene and the pyridinium groups are involved (meta position). All hydrogen-bonding distances summarized in Tables 4 and 5 are within the range found for pyridinium perhalometallates (Brammer et al., 2001; Valdés-Martínez et al., 2007).
The IR spectra for (I) and (II) are in good agreement with the results of the X-ray structural analyses and are shown in Fig. 4. They show characteristic absorption bands resulting from: (i) the skeletal vibrations of the vinyl group and the aromatic rings in the 1535–1458 cm-1 region; (ii) the stretching vibration of the C═Nimino functions at 1616 and 1615 cm-1, respectively, and (iii) the pyridinium+ N—H stretching vibrations in the range 3242–3104 cm-1. The vibration bands in the region of 1000 and 500 cm-1 are attributed to out-of-plane bending modes for C—H, C—C and C—N (Paciorek et al., 2013; Al-Otaibi & Al-Wabli, 2015).
To examine the thermal stability of (I) and (II), thermogravimetric analyses (TGA) were performed under an N2 atmosphere for crystalline samples with a heating rate of 283 K min-1 [Should this be 10 K min-1?] from ambient temperature up to 1073 K. The TGA curve of (I) reveals three main regions of weight loss (see Fig. 5). The first initiates at 368 K with completeness at 629 K, and corresponds to the elimination of two HCl molecules. The observed weight loss of 17.9% is close to the calculated value (18.9%). The second step, in the temperature range 629–742 K, corresponds to the loss of one vinylpyridine (C7H7N) equivalent. The observed weight loss of 27.3% is in good agreement with the calculated value of 27.9%. Finally, a third step (found 20.7%; theoretical 20.3%), in the range 742–1004 K, is attributed to the loss of one equivalent of pyridine (C5H5N). As shown in Fig. 4, the TGA curve of (II) also reveals three main weight loss steps. The first, starting at 306 K with completeness at 607 K, corresponds to the elimination of two HCl molecules (found 17.0%; theoretical 18.6%). The second step, in the range 607–723 K, corresponds to the loss of one vinylpyridine (C7H7N) equivalent (found 27.5%; theoretical 26.6%). However, in the third step (found 36.7%; theoretical 38.0%), in the range 723–925 K, there is a larger weight loss that might correspond to the loss of one pyridine and two additional equivalents of HCl.
The analysis of the crystal structures described herein has shown that the dipyridinium cation is a suitable ionic tecton for the crystal engineering of higher-dimensional networks when combined with perhalometallates. This is because the pyridinium and vinylene groups can form charge-assisted N+—H···Cl- and C—H···Cl- hydrogen bonds, as well as π–π contacts, to stabilize the supramolecular networks.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus NT (Bruker 2001); data reduction: SAINT-Plus NT (Bruker 2001); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
(C12H12N2)[CoCl4] | F(000) = 772 |
Mr = 384.97 | Dx = 1.713 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6971 (11) Å | Cell parameters from 5346 reflections |
b = 12.4656 (18) Å | θ = 2.6–28.3° |
c = 15.915 (2) Å | µ = 1.85 mm−1 |
β = 102.171 (2)° | T = 100 K |
V = 1492.7 (4) Å3 | Block, blue |
Z = 4 | 0.50 × 0.44 × 0.41 mm |
Bruker SMART CCD area-detector diffractometer | 2632 independent reflections |
Radiation source: fine-focus sealed tube | 2617 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.46, Tmax = 0.52 | k = −14→14 |
11172 measured reflections | l = −18→18 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0104P)2 + 1.9738P] where P = (Fo2 + 2Fc2)/3 |
2632 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 0.29 e Å−3 |
2 restraints | Δρmin = −0.29 e Å−3 |
(C12H12N2)[CoCl4] | V = 1492.7 (4) Å3 |
Mr = 384.97 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6971 (11) Å | µ = 1.85 mm−1 |
b = 12.4656 (18) Å | T = 100 K |
c = 15.915 (2) Å | 0.50 × 0.44 × 0.41 mm |
β = 102.171 (2)° |
Bruker SMART CCD area-detector diffractometer | 2632 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2617 reflections with I > 2σ(I) |
Tmin = 0.46, Tmax = 0.52 | Rint = 0.022 |
11172 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 2 restraints |
wR(F2) = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.29 e Å−3 |
2632 reflections | Δρmin = −0.29 e Å−3 |
178 parameters |
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 | ||
Co1 | 0.31255 (3) | 0.30215 (2) | 0.264095 (16) | 0.01246 (8) | |
Cl1 | 0.43900 (6) | 0.22524 (4) | 0.39020 (3) | 0.01845 (11) | |
Cl2 | 0.05993 (6) | 0.21481 (4) | 0.19900 (3) | 0.01601 (11) | |
Cl3 | 0.51384 (6) | 0.29302 (4) | 0.17648 (3) | 0.01642 (11) | |
Cl4 | 0.23596 (7) | 0.47555 (4) | 0.28215 (3) | 0.02002 (12) | |
N1 | 0.3614 (2) | 1.07680 (14) | 0.09541 (11) | 0.0183 (4) | |
H1' | 0.413 (3) | 1.1358 (10) | 0.1076 (15) | 0.027* | |
N2 | −0.0683 (2) | 0.55033 (13) | 0.12896 (10) | 0.0137 (3) | |
H2' | −0.001 (2) | 0.5576 (18) | 0.1775 (6) | 0.021* | |
C1 | 0.3301 (3) | 1.01655 (16) | 0.16037 (13) | 0.0184 (4) | |
H1 | 0.3723 | 1.0390 | 0.2181 | 0.022* | |
C2 | 0.2374 (3) | 0.92271 (16) | 0.14346 (13) | 0.0163 (4) | |
H2 | 0.2154 | 0.8797 | 0.1894 | 0.020* | |
C3 | 0.1751 (2) | 0.89039 (15) | 0.05831 (12) | 0.0135 (4) | |
C4 | 0.2114 (3) | 0.95548 (16) | −0.00735 (13) | 0.0165 (4) | |
H4 | 0.1714 | 0.9351 | −0.0657 | 0.020* | |
C5 | 0.3052 (3) | 1.04911 (16) | 0.01272 (13) | 0.0185 (4) | |
H5 | 0.3300 | 1.0939 | −0.0316 | 0.022* | |
C6 | 0.0710 (3) | 0.79290 (15) | 0.03567 (12) | 0.0143 (4) | |
H6 | 0.0193 | 0.7815 | −0.0233 | 0.017* | |
C7 | 0.0430 (3) | 0.71857 (15) | 0.09150 (12) | 0.0141 (4) | |
H7 | 0.0981 | 0.7277 | 0.1504 | 0.017* | |
C8 | −0.0677 (2) | 0.62398 (15) | 0.06720 (12) | 0.0127 (4) | |
C9 | −0.1728 (3) | 0.60398 (15) | −0.01367 (12) | 0.0142 (4) | |
H9 | −0.1746 | 0.6535 | −0.0592 | 0.017* | |
C10 | −0.2743 (3) | 0.51220 (16) | −0.02762 (12) | 0.0155 (4) | |
H10 | −0.3463 | 0.4988 | −0.0829 | 0.019* | |
C11 | −0.2724 (3) | 0.43905 (16) | 0.03836 (12) | 0.0156 (4) | |
H11 | −0.3436 | 0.3761 | 0.0292 | 0.019* | |
C12 | −0.1654 (3) | 0.45980 (15) | 0.11695 (12) | 0.0150 (4) | |
H12 | −0.1598 | 0.4104 | 0.1629 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01372 (14) | 0.01341 (14) | 0.00992 (14) | −0.00001 (10) | 0.00177 (10) | 0.00069 (10) |
Cl1 | 0.0156 (2) | 0.0226 (3) | 0.0160 (2) | −0.00006 (19) | 0.00055 (18) | 0.00790 (19) |
Cl2 | 0.0156 (2) | 0.0188 (2) | 0.0128 (2) | −0.00303 (18) | 0.00119 (18) | 0.00045 (18) |
Cl3 | 0.0174 (2) | 0.0188 (2) | 0.0142 (2) | −0.00533 (18) | 0.00578 (18) | −0.00266 (18) |
Cl4 | 0.0223 (3) | 0.0174 (2) | 0.0171 (2) | 0.0057 (2) | −0.00304 (19) | −0.00318 (19) |
N1 | 0.0140 (9) | 0.0132 (8) | 0.0276 (10) | −0.0008 (7) | 0.0041 (7) | −0.0027 (7) |
N2 | 0.0135 (8) | 0.0176 (8) | 0.0097 (8) | −0.0003 (7) | 0.0016 (6) | 0.0002 (7) |
C1 | 0.0172 (10) | 0.0183 (10) | 0.0184 (10) | 0.0034 (8) | 0.0011 (8) | −0.0026 (8) |
C2 | 0.0172 (10) | 0.0158 (10) | 0.0151 (10) | 0.0021 (8) | 0.0015 (8) | −0.0001 (8) |
C3 | 0.0102 (9) | 0.0140 (10) | 0.0156 (9) | 0.0034 (7) | 0.0014 (7) | 0.0002 (7) |
C4 | 0.0157 (10) | 0.0185 (10) | 0.0151 (10) | 0.0021 (8) | 0.0026 (8) | 0.0010 (8) |
C5 | 0.0162 (11) | 0.0181 (10) | 0.0219 (11) | 0.0016 (8) | 0.0052 (8) | 0.0037 (8) |
C6 | 0.0139 (10) | 0.0161 (10) | 0.0119 (9) | 0.0007 (8) | 0.0004 (8) | −0.0018 (7) |
C7 | 0.0144 (10) | 0.0164 (10) | 0.0113 (9) | 0.0017 (8) | 0.0027 (7) | −0.0019 (8) |
C8 | 0.0108 (9) | 0.0154 (9) | 0.0130 (9) | 0.0033 (7) | 0.0051 (7) | 0.0003 (7) |
C9 | 0.0143 (10) | 0.0161 (10) | 0.0125 (9) | 0.0030 (8) | 0.0034 (7) | 0.0016 (7) |
C10 | 0.0130 (10) | 0.0190 (10) | 0.0143 (10) | 0.0017 (8) | 0.0025 (8) | −0.0039 (8) |
C11 | 0.0127 (10) | 0.0151 (10) | 0.0204 (10) | −0.0010 (8) | 0.0067 (8) | −0.0029 (8) |
C12 | 0.0162 (10) | 0.0142 (9) | 0.0162 (10) | 0.0000 (8) | 0.0071 (8) | 0.0025 (8) |
Co1—Cl1 | 2.2519 (6) | C4—C5 | 1.374 (3) |
Co1—Cl4 | 2.2745 (6) | C4—H4 | 0.9500 |
Co1—Cl2 | 2.2782 (6) | C5—H5 | 0.9500 |
Co1—Cl3 | 2.2953 (6) | C6—C7 | 1.332 (3) |
N1—C1 | 1.340 (3) | C6—H6 | 0.9500 |
N1—C5 | 1.341 (3) | C7—C8 | 1.458 (3) |
N1—H1' | 0.8400 (11) | C7—H7 | 0.9500 |
N2—C12 | 1.345 (3) | C8—C9 | 1.391 (3) |
N2—C8 | 1.346 (2) | C9—C10 | 1.377 (3) |
N2—H2' | 0.8400 (10) | C9—H9 | 0.9500 |
C1—C2 | 1.367 (3) | C10—C11 | 1.388 (3) |
C1—H1 | 0.9500 | C10—H10 | 0.9500 |
C2—C3 | 1.398 (3) | C11—C12 | 1.369 (3) |
C2—H2 | 0.9500 | C11—H11 | 0.9500 |
C3—C4 | 1.397 (3) | C12—H12 | 0.9500 |
C3—C6 | 1.458 (3) | ||
Cl1—Co1—Cl4 | 111.52 (2) | N1—C5—C4 | 119.45 (19) |
Cl1—Co1—Cl2 | 111.65 (2) | N1—C5—H5 | 120.3 |
Cl4—Co1—Cl2 | 107.01 (2) | C4—C5—H5 | 120.3 |
Cl1—Co1—Cl3 | 107.46 (2) | C7—C6—C3 | 124.92 (18) |
Cl4—Co1—Cl3 | 110.49 (2) | C7—C6—H6 | 117.5 |
Cl2—Co1—Cl3 | 108.71 (2) | C3—C6—H6 | 117.5 |
C1—N1—C5 | 122.65 (18) | C6—C7—C8 | 123.57 (18) |
C1—N1—H1' | 117.8 (17) | C6—C7—H7 | 118.2 |
C5—N1—H1' | 119.5 (17) | C8—C7—H7 | 118.2 |
C12—N2—C8 | 123.80 (17) | N2—C8—C9 | 117.55 (17) |
C12—N2—H2' | 116.0 (16) | N2—C8—C7 | 116.74 (17) |
C8—N2—H2' | 120.1 (16) | C9—C8—C7 | 125.71 (17) |
N1—C1—C2 | 119.93 (19) | C10—C9—C8 | 119.86 (18) |
N1—C1—H1 | 120.0 | C10—C9—H9 | 120.1 |
C2—C1—H1 | 120.0 | C8—C9—H9 | 120.1 |
C1—C2—C3 | 119.70 (19) | C9—C10—C11 | 120.57 (18) |
C1—C2—H2 | 120.1 | C9—C10—H10 | 119.7 |
C3—C2—H2 | 120.1 | C11—C10—H10 | 119.7 |
C4—C3—C2 | 118.41 (18) | C12—C11—C10 | 118.37 (18) |
C4—C3—C6 | 119.04 (17) | C12—C11—H11 | 120.8 |
C2—C3—C6 | 122.54 (18) | C10—C11—H11 | 120.8 |
C5—C4—C3 | 119.85 (19) | N2—C12—C11 | 119.83 (18) |
C5—C4—H4 | 120.1 | N2—C12—H12 | 120.1 |
C3—C4—H4 | 120.1 | C11—C12—H12 | 120.1 |
C5—N1—C1—C2 | 0.0 (3) | C12—N2—C8—C9 | −0.6 (3) |
N1—C1—C2—C3 | −0.3 (3) | C12—N2—C8—C7 | 178.96 (17) |
C1—C2—C3—C4 | 0.5 (3) | C6—C7—C8—N2 | 173.12 (18) |
C1—C2—C3—C6 | −178.18 (18) | C6—C7—C8—C9 | −7.4 (3) |
C2—C3—C4—C5 | −0.5 (3) | N2—C8—C9—C10 | 0.9 (3) |
C6—C3—C4—C5 | 178.25 (17) | C7—C8—C9—C10 | −178.58 (18) |
C1—N1—C5—C4 | 0.1 (3) | C8—C9—C10—C11 | −0.2 (3) |
C3—C4—C5—N1 | 0.2 (3) | C9—C10—C11—C12 | −0.9 (3) |
C4—C3—C6—C7 | 172.60 (19) | C8—N2—C12—C11 | −0.5 (3) |
C2—C3—C6—C7 | −8.7 (3) | C10—C11—C12—N2 | 1.3 (3) |
C3—C6—C7—C8 | 177.48 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2′···Cl4 | 0.84 | 2.42 | 3.145 (2) | 145 |
N1—H1′···Cl3i | 0.84 | 2.30 | 3.109 (2) | 162 |
C4—H4···Cl4ii | 0.95 | 2.80 | 3.502 (2) | 131 |
C5—H5···Cl1ii | 0.95 | 2.79 | 3.691 (2) | 159 |
C6—H6···Cl2iii | 0.95 | 2.73 | 3.659 (2) | 165 |
C11—H11···Cl1iv | 0.95 | 2.78 | 3.533 (2) | 137 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x−1, −y+1/2, z−1/2. |
(C12H12N2)[ZnCl4] | F(000) = 784 |
Mr = 391.41 | Dx = 1.737 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7074 (7) Å | Cell parameters from 9787 reflections |
b = 12.4680 (11) Å | θ = 2.6–28.3° |
c = 15.9344 (14) Å | µ = 2.34 mm−1 |
β = 102.173 (1)° | T = 100 K |
V = 1496.8 (2) Å3 | Block, brown |
Z = 4 | 0.49 × 0.43 × 0.42 mm |
Bruker SMART CCD area-detector diffractometer | 2549 independent reflections |
Radiation source: fine-focus sealed tube | 2442 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→9 |
Tmin = 0.39, Tmax = 0.44 | k = −14→14 |
7110 measured reflections | l = −18→16 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0279P)2 + 1.2017P] where P = (Fo2 + 2Fc2)/3 |
2549 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.43 e Å−3 |
2 restraints | Δρmin = −0.48 e Å−3 |
(C12H12N2)[ZnCl4] | V = 1496.8 (2) Å3 |
Mr = 391.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7074 (7) Å | µ = 2.34 mm−1 |
b = 12.4680 (11) Å | T = 100 K |
c = 15.9344 (14) Å | 0.49 × 0.43 × 0.42 mm |
β = 102.173 (1)° |
Bruker SMART CCD area-detector diffractometer | 2549 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2442 reflections with I > 2σ(I) |
Tmin = 0.39, Tmax = 0.44 | Rint = 0.025 |
7110 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 2 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.43 e Å−3 |
2549 reflections | Δρmin = −0.48 e Å−3 |
178 parameters |
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 | ||
Zn1 | 0.31141 (4) | 0.30176 (2) | 0.264259 (17) | 0.01287 (10) | |
Cl1 | 0.43838 (8) | 0.22471 (5) | 0.38967 (4) | 0.01838 (14) | |
Cl2 | 0.05976 (8) | 0.21417 (4) | 0.19880 (4) | 0.01610 (14) | |
Cl3 | 0.51252 (8) | 0.29376 (4) | 0.17615 (4) | 0.01638 (14) | |
Cl4 | 0.23619 (8) | 0.47508 (4) | 0.28222 (4) | 0.02006 (15) | |
N1 | 0.3613 (3) | 1.07702 (16) | 0.09563 (14) | 0.0184 (5) | |
H1' | 0.418 (3) | 1.1344 (12) | 0.1089 (18) | 0.028* | |
N2 | −0.0678 (3) | 0.55020 (15) | 0.12901 (12) | 0.0138 (4) | |
H2' | −0.003 (3) | 0.560 (2) | 0.1778 (7) | 0.021* | |
C1 | 0.3306 (3) | 1.01641 (19) | 0.16039 (17) | 0.0191 (5) | |
H1 | 0.3730 | 1.0387 | 0.2181 | 0.023* | |
C2 | 0.2386 (3) | 0.92263 (18) | 0.14344 (16) | 0.0165 (5) | |
H2 | 0.2172 | 0.8794 | 0.1893 | 0.020* | |
C3 | 0.1758 (3) | 0.89017 (18) | 0.05846 (15) | 0.0136 (5) | |
C4 | 0.2121 (3) | 0.95564 (18) | −0.00707 (16) | 0.0164 (5) | |
H4 | 0.1726 | 0.9352 | −0.0654 | 0.020* | |
C5 | 0.3047 (3) | 1.04935 (19) | 0.01292 (16) | 0.0183 (5) | |
H5 | 0.3287 | 1.0943 | −0.0314 | 0.022* | |
C6 | 0.0716 (3) | 0.79282 (17) | 0.03569 (16) | 0.0150 (5) | |
H6 | 0.0197 | 0.7815 | −0.0232 | 0.018* | |
C7 | 0.0438 (3) | 0.71859 (18) | 0.09158 (15) | 0.0141 (5) | |
H7 | 0.0991 | 0.7275 | 0.1503 | 0.017* | |
C8 | −0.0675 (3) | 0.62423 (18) | 0.06699 (15) | 0.0134 (5) | |
C9 | −0.1719 (3) | 0.60408 (18) | −0.01343 (15) | 0.0142 (5) | |
H9 | −0.1733 | 0.6536 | −0.0589 | 0.017* | |
C10 | −0.2742 (3) | 0.51214 (19) | −0.02776 (16) | 0.0159 (5) | |
H10 | −0.3460 | 0.4988 | −0.0830 | 0.019* | |
C11 | −0.2725 (3) | 0.43912 (18) | 0.03841 (16) | 0.0164 (5) | |
H11 | −0.3437 | 0.3763 | 0.0294 | 0.020* | |
C12 | −0.1657 (3) | 0.46004 (18) | 0.11672 (15) | 0.0155 (5) | |
H12 | −0.1607 | 0.4107 | 0.1626 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01101 (17) | 0.01667 (15) | 0.01050 (17) | −0.00008 (10) | 0.00128 (13) | 0.00070 (10) |
Cl1 | 0.0132 (3) | 0.0250 (3) | 0.0159 (3) | 0.0000 (2) | 0.0005 (3) | 0.0075 (2) |
Cl2 | 0.0128 (3) | 0.0219 (3) | 0.0129 (3) | −0.0033 (2) | 0.0010 (3) | 0.0005 (2) |
Cl3 | 0.0146 (3) | 0.0213 (3) | 0.0141 (3) | −0.0053 (2) | 0.0050 (3) | −0.0023 (2) |
Cl4 | 0.0194 (3) | 0.0201 (3) | 0.0176 (3) | 0.0056 (2) | −0.0030 (3) | −0.0031 (2) |
N1 | 0.0118 (11) | 0.0164 (10) | 0.0266 (13) | −0.0010 (8) | 0.0032 (10) | −0.0028 (9) |
N2 | 0.0108 (11) | 0.0209 (10) | 0.0090 (10) | 0.0002 (8) | 0.0002 (9) | 0.0001 (8) |
C1 | 0.0141 (13) | 0.0231 (12) | 0.0187 (14) | 0.0032 (10) | 0.0001 (11) | −0.0029 (10) |
C2 | 0.0145 (13) | 0.0193 (12) | 0.0147 (13) | 0.0037 (10) | 0.0008 (11) | 0.0014 (9) |
C3 | 0.0074 (12) | 0.0176 (11) | 0.0151 (13) | 0.0044 (9) | 0.0007 (10) | 0.0009 (9) |
C4 | 0.0120 (12) | 0.0214 (12) | 0.0149 (13) | 0.0019 (10) | 0.0008 (11) | −0.0001 (10) |
C5 | 0.0133 (13) | 0.0219 (12) | 0.0199 (14) | 0.0025 (10) | 0.0040 (11) | 0.0033 (10) |
C6 | 0.0116 (12) | 0.0203 (12) | 0.0121 (13) | 0.0006 (9) | 0.0000 (11) | −0.0018 (9) |
C7 | 0.0116 (12) | 0.0204 (11) | 0.0096 (12) | 0.0012 (9) | 0.0009 (10) | −0.0013 (9) |
C8 | 0.0084 (12) | 0.0195 (11) | 0.0135 (13) | 0.0033 (9) | 0.0050 (10) | 0.0002 (9) |
C9 | 0.0105 (12) | 0.0194 (11) | 0.0129 (13) | 0.0024 (9) | 0.0028 (11) | 0.0018 (9) |
C10 | 0.0091 (12) | 0.0225 (12) | 0.0154 (13) | 0.0015 (10) | 0.0011 (10) | −0.0044 (10) |
C11 | 0.0123 (12) | 0.0186 (11) | 0.0196 (14) | −0.0011 (9) | 0.0062 (11) | −0.0022 (10) |
C12 | 0.0127 (13) | 0.0189 (11) | 0.0168 (14) | 0.0000 (10) | 0.0078 (11) | 0.0033 (9) |
Zn1—Cl1 | 2.2470 (7) | C4—C5 | 1.371 (3) |
Zn1—Cl4 | 2.2710 (6) | C4—H4 | 0.9500 |
Zn1—Cl2 | 2.2780 (7) | C5—H5 | 0.9500 |
Zn1—Cl3 | 2.3024 (6) | C6—C7 | 1.333 (3) |
N1—C1 | 1.340 (3) | C6—H6 | 0.9500 |
N1—C5 | 1.343 (3) | C7—C8 | 1.460 (3) |
N1—H1' | 0.8400 (11) | C7—H7 | 0.9500 |
N2—C12 | 1.345 (3) | C8—C9 | 1.385 (3) |
N2—C8 | 1.353 (3) | C9—C10 | 1.383 (3) |
N2—H2' | 0.8400 (10) | C9—H9 | 0.9500 |
C1—C2 | 1.365 (3) | C10—C11 | 1.391 (3) |
C1—H1 | 0.9500 | C10—H10 | 0.9500 |
C2—C3 | 1.398 (3) | C11—C12 | 1.367 (4) |
C2—H2 | 0.9500 | C11—H11 | 0.9500 |
C3—C4 | 1.399 (3) | C12—H12 | 0.9500 |
C3—C6 | 1.459 (3) | ||
Cl1—Zn1—Cl4 | 111.69 (2) | N1—C5—C4 | 119.5 (2) |
Cl1—Zn1—Cl2 | 111.80 (2) | N1—C5—H5 | 120.3 |
Cl4—Zn1—Cl2 | 107.37 (2) | C4—C5—H5 | 120.3 |
Cl1—Zn1—Cl3 | 107.50 (2) | C7—C6—C3 | 124.7 (2) |
Cl4—Zn1—Cl3 | 109.92 (2) | C7—C6—H6 | 117.6 |
Cl2—Zn1—Cl3 | 108.52 (2) | C3—C6—H6 | 117.6 |
C1—N1—C5 | 122.5 (2) | C6—C7—C8 | 123.2 (2) |
C1—N1—H1' | 117 (2) | C6—C7—H7 | 118.4 |
C5—N1—H1' | 121 (2) | C8—C7—H7 | 118.4 |
C12—N2—C8 | 123.4 (2) | N2—C8—C9 | 117.5 (2) |
C12—N2—H2' | 117.4 (19) | N2—C8—C7 | 116.4 (2) |
C8—N2—H2' | 119.1 (19) | C9—C8—C7 | 126.1 (2) |
N1—C1—C2 | 120.0 (2) | C10—C9—C8 | 120.2 (2) |
N1—C1—H1 | 120.0 | C10—C9—H9 | 119.9 |
C2—C1—H1 | 120.0 | C8—C9—H9 | 119.9 |
C1—C2—C3 | 119.9 (2) | C9—C10—C11 | 120.2 (2) |
C1—C2—H2 | 120.0 | C9—C10—H10 | 119.9 |
C3—C2—H2 | 120.0 | C11—C10—H10 | 119.9 |
C4—C3—C2 | 118.1 (2) | C12—C11—C10 | 118.3 (2) |
C4—C3—C6 | 119.1 (2) | C12—C11—H11 | 120.8 |
C2—C3—C6 | 122.8 (2) | C10—C11—H11 | 120.8 |
C5—C4—C3 | 120.0 (2) | N2—C12—C11 | 120.2 (2) |
C5—C4—H4 | 120.0 | N2—C12—H12 | 119.9 |
C3—C4—H4 | 120.0 | C11—C12—H12 | 119.9 |
C5—N1—C1—C2 | −0.1 (3) | C12—N2—C8—C9 | −1.1 (3) |
N1—C1—C2—C3 | −0.2 (3) | C12—N2—C8—C7 | 178.8 (2) |
C1—C2—C3—C4 | 0.7 (3) | C6—C7—C8—N2 | 173.0 (2) |
C1—C2—C3—C6 | −177.9 (2) | C6—C7—C8—C9 | −7.0 (4) |
C2—C3—C4—C5 | −0.9 (3) | N2—C8—C9—C10 | 1.2 (3) |
C6—C3—C4—C5 | 177.8 (2) | C7—C8—C9—C10 | −178.7 (2) |
C1—N1—C5—C4 | −0.1 (3) | C8—C9—C10—C11 | −0.2 (3) |
C3—C4—C5—N1 | 0.6 (3) | C9—C10—C11—C12 | −1.0 (3) |
C4—C3—C6—C7 | 172.7 (2) | C8—N2—C12—C11 | −0.1 (3) |
C2—C3—C6—C7 | −8.7 (4) | C10—C11—C12—N2 | 1.1 (3) |
C3—C6—C7—C8 | 177.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2′···Cl4 | 0.84 | 2.45 | 3.149 (2) | 142 |
N1—H1′···Cl3i | 0.84 | 2.30 | 3.111 (2) | 162 |
C4—H4···Cl4ii | 0.95 | 2.81 | 3.509 (3) | 131 |
C5—H5···Cl1ii | 0.95 | 2.80 | 3.702 (3) | 159 |
C6—H6···Cl2iii | 0.95 | 2.74 | 3.660 (3) | 165 |
C11—H11···Cl1iv | 0.95 | 2.79 | 3.540 (2) | 136 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x−1, −y+1/2, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C12H12N2)[CoCl4] | (C12H12N2)[ZnCl4] |
Mr | 384.97 | 391.41 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.6971 (11), 12.4656 (18), 15.915 (2) | 7.7074 (7), 12.4680 (11), 15.9344 (14) |
β (°) | 102.171 (2) | 102.173 (1) |
V (Å3) | 1492.7 (4) | 1496.8 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.85 | 2.34 |
Crystal size (mm) | 0.50 × 0.44 × 0.41 | 0.49 × 0.43 × 0.42 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.46, 0.52 | 0.39, 0.44 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11172, 2632, 2617 | 7110, 2549, 2442 |
Rint | 0.022 | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.049, 1.08 | 0.026, 0.064, 1.09 |
No. of reflections | 2632 | 2549 |
No. of parameters | 178 | 178 |
No. of restraints | 2 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.29 | 0.43, −0.48 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus NT (Bruker 2001), SHELXTL-NT (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
Co1—Cl1 | 2.2519 (6) | Co1—Cl2 | 2.2782 (6) |
Co1—Cl4 | 2.2745 (6) | Co1—Cl3 | 2.2953 (6) |
Cl1—Co1—Cl4 | 111.52 (2) | Cl1—Co1—Cl3 | 107.46 (2) |
Cl1—Co1—Cl2 | 111.65 (2) | Cl4—Co1—Cl3 | 110.49 (2) |
Cl4—Co1—Cl2 | 107.01 (2) | Cl2—Co1—Cl3 | 108.71 (2) |
Zn1—Cl1 | 2.2470 (7) | Zn1—Cl2 | 2.2780 (7) |
Zn1—Cl4 | 2.2710 (6) | Zn1—Cl3 | 2.3024 (6) |
Cl1—Zn1—Cl4 | 111.69 (2) | Cl1—Zn1—Cl3 | 107.50 (2) |
Cl1—Zn1—Cl2 | 111.80 (2) | Cl4—Zn1—Cl3 | 109.92 (2) |
Cl4—Zn1—Cl2 | 107.37 (2) | Cl2—Zn1—Cl3 | 108.52 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2'···Cl4 | 0.84 | 2.42 | 3.145 (2) | 145 |
N1—H1'···Cl3i | 0.84 | 2.30 | 3.109 (2) | 162 |
C4—H4···Cl4ii | 0.95 | 2.80 | 3.502 (2) | 131 |
C5—H5···Cl1ii | 0.95 | 2.79 | 3.691 (2) | 159 |
C6—H6···Cl2iii | 0.95 | 2.73 | 3.659 (2) | 165 |
C11—H11···Cl1iv | 0.95 | 2.78 | 3.533 (2) | 137 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x−1, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2'···Cl4 | 0.84 | 2.45 | 3.149 (2) | 142 |
N1—H1'···Cl3i | 0.84 | 2.30 | 3.111 (2) | 162 |
C4—H4···Cl4ii | 0.95 | 2.81 | 3.509 (3) | 131 |
C5—H5···Cl1ii | 0.95 | 2.80 | 3.702 (3) | 159 |
C6—H6···Cl2iii | 0.95 | 2.74 | 3.660 (3) | 165 |
C11—H11···Cl1iv | 0.95 | 2.79 | 3.540 (2) | 136 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x−1, −y+1/2, z−1/2. |