Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108018039/sk3226sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108018039/sk3226Isup2.hkl |
CCDC reference: 700008
Caution: Perchlorate salts of metal complexes are potentially explosive. Only small quantities of the compound should be prepared and handled with care! Bis-N,N'-pyridinyl methylenehydrazine (1 mmol) was prepared as described previously (El-Rayyes & Katrib, 1983). A methanolic solution of bis-N,N'-pyridinyl methylenehydrazine (0.2 mmol, 0.04 g) was added dropwise to a stirred solution of iron(II) perchlorate hydrate (0.2 mmol, 0.05 g) and potassium thiocyanate (0.3 mmol, 0.03 g) in MeOH/EtOH/MeCN (15 ml, 1:1:1 v/v). The solution was stirred under N2 for 1 h at room temperature and then filtered. Uniform reddish–orange prisms were collected after 1 week and dried in air. Spectroscopic analysis: IR: (ν, cm-1, KBr): 496 (m, υMN), 687 (m, SCN-), 810 (m, SCN-), 1012 (m, υMeOH), 1310 (s, υOH), 1427 (s, δC═N), 2070 (s, SCN-), 3274 (m, b, OHstretching).
Density functional theory calculations were performed using the B3LYP function (Lee et al. 1988; Becke, 1993) as implemented in SPARTAN 06 (Wavefunction, 2007) with the 6-31G** basis set.
H atoms were constrained to ideal geometry using an appropriate riding model, with C—H = 0.95–0.98 Å and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(Caryl), 1.5Ueq(Cmethyl) or 1.5Ueq(O). [Please check added text]
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005) and CrystalMaker (Palmer, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Fe(SCN)2(C12H10N4)(CH4O)2] | F(000) = 460 |
Mr = 446.33 | Dx = 1.449 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3168 reflections |
a = 7.6903 (4) Å | θ = 2.5–25.4° |
b = 12.8591 (7) Å | µ = 0.96 mm−1 |
c = 10.8707 (6) Å | T = 153 K |
β = 107.941 (1)° | Prism, orange |
V = 1022.73 (10) Å3 | 0.09 × 0.08 × 0.04 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2549 independent reflections |
Radiation source: fine-focus sealed tube | 1950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ω scans | θmax = 28.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.871, Tmax = 0.962 | k = −17→17 |
14356 measured reflections | l = −14→14 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0407P)2 + 0.3402P] where P = (Fo2 + 2Fc2)/3 |
2549 reflections | (Δ/σ)max = 0.001 |
126 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Fe(SCN)2(C12H10N4)(CH4O)2] | V = 1022.73 (10) Å3 |
Mr = 446.33 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6903 (4) Å | µ = 0.96 mm−1 |
b = 12.8591 (7) Å | T = 153 K |
c = 10.8707 (6) Å | 0.09 × 0.08 × 0.04 mm |
β = 107.941 (1)° |
Bruker SMART CCD area-detector diffractometer | 2549 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1950 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 0.962 | Rint = 0.054 |
14356 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.38 e Å−3 |
2549 reflections | Δρmin = −0.28 e Å−3 |
126 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 | ||
Fe1 | 0.5000 | 0.0000 | 0.5000 | 0.01727 (12) | |
S1 | 0.78749 (7) | 0.26381 (4) | 0.30208 (5) | 0.02902 (15) | |
N1B | 0.6090 (2) | 0.10991 (14) | 0.39959 (16) | 0.0257 (4) | |
C2B | 0.6815 (3) | 0.17423 (16) | 0.35895 (19) | 0.0212 (4) | |
C1A | 0.3227 (4) | 0.2164 (2) | 0.5436 (3) | 0.0552 (8) | |
H1A1 | 0.2826 | 0.2554 | 0.6074 | 0.083* | |
H1A2 | 0.2155 | 0.1929 | 0.4738 | 0.083* | |
H1A3 | 0.3981 | 0.2613 | 0.5077 | 0.083* | |
O1A | 0.42808 (19) | 0.12770 (11) | 0.60489 (14) | 0.0280 (3) | |
H1A | 0.5228 | 0.1480 | 0.6620 | 0.042* | |
N1 | −0.4234 (2) | −0.01217 (14) | 0.05369 (17) | 0.0290 (4) | |
C1 | −0.2850 (3) | 0.04268 (17) | 0.0538 (2) | 0.0244 (4) | |
H1 | −0.2954 | 0.0926 | −0.0125 | 0.029* | |
C2 | −0.1103 (3) | 0.02909 (16) | 0.15562 (19) | 0.0211 (4) | |
C3 | 0.0467 (3) | 0.07343 (17) | 0.1409 (2) | 0.0277 (5) | |
H3 | 0.0409 | 0.1125 | 0.0656 | 0.033* | |
C4 | 0.2112 (3) | 0.06022 (17) | 0.2369 (2) | 0.0265 (5) | |
H4 | 0.3177 | 0.0898 | 0.2244 | 0.032* | |
N5 | 0.2286 (2) | 0.00802 (12) | 0.34638 (15) | 0.0201 (3) | |
C6 | 0.0760 (3) | −0.03521 (16) | 0.3593 (2) | 0.0226 (4) | |
H6 | 0.0855 | −0.0734 | 0.4358 | 0.027* | |
C7 | −0.0935 (3) | −0.02724 (16) | 0.2677 (2) | 0.0234 (4) | |
H7 | −0.1971 | −0.0598 | 0.2811 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01201 (19) | 0.0192 (2) | 0.0188 (2) | −0.00087 (15) | 0.00216 (14) | 0.00115 (16) |
S1 | 0.0286 (3) | 0.0248 (3) | 0.0358 (3) | −0.0040 (2) | 0.0130 (2) | 0.0053 (2) |
N1B | 0.0179 (8) | 0.0312 (10) | 0.0241 (9) | −0.0020 (7) | 0.0009 (7) | 0.0054 (7) |
C2B | 0.0151 (9) | 0.0242 (10) | 0.0210 (10) | 0.0030 (8) | 0.0007 (8) | 0.0013 (8) |
C1A | 0.0484 (16) | 0.0399 (15) | 0.0639 (19) | 0.0210 (13) | −0.0023 (14) | −0.0160 (14) |
O1A | 0.0236 (8) | 0.0273 (8) | 0.0306 (8) | 0.0015 (6) | 0.0046 (6) | −0.0065 (6) |
N1 | 0.0160 (8) | 0.0396 (11) | 0.0247 (9) | −0.0032 (8) | −0.0036 (7) | 0.0064 (8) |
C1 | 0.0165 (9) | 0.0304 (11) | 0.0235 (11) | −0.0011 (8) | 0.0019 (8) | 0.0041 (9) |
C2 | 0.0150 (9) | 0.0252 (10) | 0.0201 (10) | 0.0000 (7) | 0.0010 (8) | −0.0023 (8) |
C3 | 0.0203 (10) | 0.0359 (12) | 0.0219 (10) | −0.0042 (9) | −0.0006 (8) | 0.0062 (9) |
C4 | 0.0167 (10) | 0.0350 (12) | 0.0256 (11) | −0.0070 (8) | 0.0030 (8) | 0.0041 (9) |
N5 | 0.0144 (7) | 0.0243 (9) | 0.0197 (8) | 0.0001 (7) | 0.0026 (6) | −0.0002 (7) |
C6 | 0.0168 (9) | 0.0281 (10) | 0.0229 (10) | −0.0003 (8) | 0.0058 (8) | 0.0026 (8) |
C7 | 0.0147 (9) | 0.0307 (11) | 0.0247 (10) | −0.0019 (8) | 0.0058 (8) | 0.0004 (8) |
Fe1—N1Bi | 2.1105 (17) | N1—N1ii | 1.415 (3) |
Fe1—N1B | 2.1105 (17) | C1—C2 | 1.464 (3) |
Fe1—O1Ai | 2.1659 (14) | C1—H1 | 0.9500 |
Fe1—N5 | 2.2381 (15) | C2—C3 | 1.388 (3) |
Fe1—N5i | 2.2381 (15) | C2—C7 | 1.389 (3) |
S1—C2B | 1.638 (2) | C3—C4 | 1.380 (3) |
N1B—C2B | 1.159 (3) | C3—H3 | 0.9500 |
C1A—O1A | 1.438 (3) | C4—N5 | 1.337 (3) |
C1A—H1A1 | 0.9800 | C4—H4 | 0.9500 |
C1A—H1A2 | 0.9800 | N5—C6 | 1.344 (2) |
C1A—H1A3 | 0.9800 | C6—C7 | 1.378 (3) |
O1A—H1A | 0.8400 | C6—H6 | 0.9500 |
N1—C1 | 1.276 (3) | C7—H7 | 0.9500 |
N1Bi—Fe1—N1B | 180.0 | N1—C1—H1 | 119.8 |
N1Bi—Fe1—O1Ai | 88.34 (7) | C2—C1—H1 | 119.8 |
N1B—Fe1—O1Ai | 91.66 (6) | C3—C2—C7 | 117.75 (18) |
N1Bi—Fe1—N5 | 89.38 (6) | C3—C2—C1 | 119.48 (18) |
N1B—Fe1—N5 | 90.62 (6) | C7—C2—C1 | 122.77 (18) |
O1Ai—Fe1—N5 | 88.44 (6) | C4—C3—C2 | 119.33 (19) |
N1Bi—Fe1—N5i | 90.62 (6) | C4—C3—H3 | 120.3 |
N1B—Fe1—N5i | 89.38 (6) | C2—C3—H3 | 120.3 |
O1Ai—Fe1—N5i | 91.56 (5) | N5—C4—C3 | 123.49 (18) |
N5—Fe1—N5i | 180.0 | N5—C4—H4 | 118.3 |
C2B—N1B—Fe1 | 171.79 (16) | C3—C4—H4 | 118.3 |
N1B—C2B—S1 | 178.93 (18) | C4—N5—C6 | 116.69 (17) |
O1A—C1A—H1A1 | 109.5 | C4—N5—Fe1 | 120.14 (13) |
O1A—C1A—H1A2 | 109.5 | C6—N5—Fe1 | 123.14 (13) |
H1A1—C1A—H1A2 | 109.5 | N5—C6—C7 | 123.75 (19) |
O1A—C1A—H1A3 | 109.5 | N5—C6—H6 | 118.1 |
H1A1—C1A—H1A3 | 109.5 | C7—C6—H6 | 118.1 |
H1A2—C1A—H1A3 | 109.5 | C6—C7—C2 | 118.96 (18) |
C1A—O1A—H1A | 109.5 | C6—C7—H7 | 120.5 |
C1—N1—N1ii | 111.2 (2) | C2—C7—H7 | 120.5 |
N1—C1—C2 | 120.36 (19) | ||
N1ii—N1—C1—C2 | −179.1 (2) | O1Ai—Fe1—N5—C4 | −83.17 (16) |
N1—C1—C2—C3 | 167.2 (2) | N1Bi—Fe1—N5—C6 | 10.50 (16) |
N1—C1—C2—C7 | −12.5 (3) | N1B—Fe1—N5—C6 | −169.50 (16) |
C7—C2—C3—C4 | −0.1 (3) | O1Ai—Fe1—N5—C6 | 98.85 (16) |
C1—C2—C3—C4 | −179.8 (2) | C4—N5—C6—C7 | −0.8 (3) |
C2—C3—C4—N5 | −1.3 (3) | Fe1—N5—C6—C7 | 177.23 (15) |
C3—C4—N5—C6 | 1.8 (3) | N5—C6—C7—C2 | −0.5 (3) |
C3—C4—N5—Fe1 | −176.34 (17) | C3—C2—C7—C6 | 1.0 (3) |
N1Bi—Fe1—N5—C4 | −171.53 (16) | C1—C2—C7—C6 | −179.3 (2) |
N1B—Fe1—N5—C4 | 8.47 (16) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···S1iii | 0.84 | 2.42 | 3.2451 (15) | 169 |
C4—H4···N1B | 0.95 | 2.47 | 3.092 (3) | 123 |
C6—H6···N1Bi | 0.95 | 2.52 | 3.123 (3) | 121 |
O1A—H1A···N5i | 0.84 | 2.79 | 3.072 (3) | 102 |
C1A—H1A2···N5 | 0.98 | 2.77 | 3.368 (3) | 120 |
C1A—H1A3···N1B | 0.98 | 3.00 | 3.361 (3) | 103 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(SCN)2(C12H10N4)(CH4O)2] |
Mr | 446.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 7.6903 (4), 12.8591 (7), 10.8707 (6) |
β (°) | 107.941 (1) |
V (Å3) | 1022.73 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.09 × 0.08 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.871, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14356, 2549, 1950 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.084, 1.00 |
No. of reflections | 2549 |
No. of parameters | 126 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.28 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2005) and CrystalMaker (Palmer, 2008).
Fe1—N1B | 2.1105 (17) | Fe1—N5 | 2.2381 (15) |
Fe1—O1Ai | 2.1659 (14) | N1—N1ii | 1.415 (3) |
N1Bi—Fe1—O1Ai | 88.34 (7) | O1Ai—Fe1—N5 | 88.44 (6) |
N1B—Fe1—O1Ai | 91.66 (6) | N1Bi—Fe1—N5i | 90.62 (6) |
N1Bi—Fe1—N5 | 89.38 (6) | O1Ai—Fe1—N5i | 91.56 (5) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x−1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···S1iii | 0.84 | 2.42 | 3.2451 (15) | 169.1 |
C4—H4···N1B | 0.95 | 2.47 | 3.092 (3) | 123.4 |
C6—H6···N1Bi | 0.95 | 2.52 | 3.123 (3) | 121.4 |
O1A—H1A···N5i | 0.84 | 2.79 | 3.072 (3) | 101.5 |
C1A—H1A2···N5 | 0.98 | 2.77 | 3.368 (3) | 120.0 |
C1A—H1A3···N1B | 0.98 | 3.00 | 3.361 (3) | 103.4 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) x, −y+1/2, z+1/2. |
Great interest is currently devoted to exploring the versatility of coordination and hydrogen bonds with the aim of obtaining rational control over the creation of molecular framework materials (Delgado-Friedrichs et al., 2007; Champness, 2006; Öhrström & Larsson, 2005). In this context, the monodentate rigid rod-like ligand 1,4-bis(4-pyridyl)methylene hydrazine has frequently been used, giving rise to one- and two-dimensional frameworks (Diskin-Posner et al., 2002; Shi et al., 2002; Patra & Goldberg, 2003; Kennedy et al., 2005; Granifo et al., 2006; Zhang et al., 2006; Zhou et al., 2006; Dong et al., 2000; Shen, 2003). 1,4-Bis(4-pyridyl)methylene hydrazine and similar ligands have limited influence over network topology since in most complexes the ligand occupies only two metal coordination sites, offering a weak influence over the rest of the metal coordination environment. However, further support of the molecular architecture may be acquired through hydrogen bonds. We reported recently on two different hydrogen-bonding motifs observed in compounds of this ligand, depending on the counterions (Ghazzali et al., 2007), and we present here the structure of the title compound, (I), and show how conformational differences have a large impact on the final supramolecular arrangement in the crystal structure.
A perspective displacement ellipsoid drawing of (I) with the atomic numbering scheme is shown in Fig. 1. Selected bond distances and angles are summarized in Table 1. The FeII centre exhibits a nearly ideal high-spin octahedral geometry with two trans N-isothiocyanate anions [maximum SCN- deviation from linearity 1.082 (2)°], two O atoms of two methanol molecules and the repeating 1,4-bis(4-pyridyl)methylene hydrazine ligands propagating in a perfect linear pattern, giving a one-dimensional chain topology with an Fe···Fe distance of 15.866 (7) Å. The N1—N1ii single bond lies on a crystallographic centre of symmetry exhibiting a perfect antiperiplanar conformation (see Table 1 for symmetry code). As a result, the two pyridinyl rings are parallel, with an interplanar distance of 0.417 (2) Å and a dihedral angle of 12.389 (1)° with the mean plane of the –CH═N—N═ CH– symmetrical spacer.
There are a fair number of isostructural FeII and MnII coordination polymers in the literature (see, for example, Abu-Youssef et al., 2008) and although the structure presented here is topologically similar to that of [MnII(1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene)(NCS)2(CH3OH)2] (Shen, 2003), exhibiting a similar chain architecture with a slightly longer M···M distance of 16.036 (2) Å, the two compounds are not isostructural.
In the present FeII case, the chains are interconnected with O—H···S hydrogen bonds between MeOH and SCN- groups, supporting the molecular arrays with a C(6) chain pattern at the first-level graph-set, as defined by Bernstein et al. (1995) and Grell et al. (1999) (Table 2). The supramolecular architecture can be described as a two-dimensional (8.4 × 8.4 Å) square grid based on hydrogen bonds (Fig. 2), combined with the one-dimensional coordination polymer, giving a three-dimensional net with pcu topology (O'Keeffe et al., 2008), the most common of the six-connected three-dimensional nets. The complete structure can then be described as two interpenetrating networks (Fig. 3). In contrast, [MnII(1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene)(NCS)2(CH3OH)2] (Shen, 2003) contains O—H···N hydrogen bonds to the diaza unit, giving a (4,4) grid consolidating a sheet structure.
The striking difference between the Fe and Mn structures may be traced to the different orientations of the MeOH ligand. In the FeII compound the O—H bond is nearly parallell to the Fe—N(pyridine) bond (dihedral angle 12.15°) and the methyl group has a weak intramolecular hydrogen bond to the thiocyanate N atom (Table 2), and there is possibly also an interaction between O—H and the pyridine (O···N = 3.072 Å, H···N = 2.792 Å and O—H···N = 101.49°). In the MnII compound, the O—H bond is parallel to the Mn—NCS link and no corresponding weak interactions can be detected. Probably the slightly longer metal–ligand bond distances in the MnII compound (average Mn—L = 2.23 Å versus average Fe—L = 2.17 Å) mean that the ligands are too far from each other to interact, giving rise to another conformation, and thus the resulting supramolecular arrangement in the crystal structure of the FeII compound is determined by the ligand–MeOH interactions.
Further evidence for this argument comes from quantum mechanical DFT calculations. The bridging ligand was replaced by pyridine molecules and two single-point calculations were carried out for each compound to probe the effects of the different MeOH orientations. The results show that, while changing the conformation of MeOH in the MnII compound is only slightly unfavourable from an energetic point of view (31 kJ mol-1), the energy of the FeII compound is strongly dependent on the orientation of the MeOH ligand: a 90° rotation around the Fe—O bond to give a similar conformation to the MnII compound gives an energy increase of 141 kJ mol-1. In the latter case, this corresponds to the loss of up to six hydrogen-bond interactions between the methanol and the other ligands (Table 2). Summing over six weak interactions with average bond energies of 16.7 kJ mol-1 (Jeffrey, 1997) yields 100 kJ mol-1 which can be considered an upper-limit estimate. Thus, the calculated value is of a reasonable magnitude, although probably exaggerated.
In conclusion, these results suggest that seemingly minor conformational changes may have a large effect on the overall topology of the network.