Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005840/br6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005840/br6016Isup2.hkl |
CCDC reference: 165626
A solution of 4.3 mmol of manganese(II) chloride in 20 ml water was added to a solution of 12.8 mmol of 2,4'-bipyridyl in 10 ml water containing a few drops of 95% EtOH. The mixture was heated at 353 K for 15 min and allowed to cool (Czakis-Sulikowska & Kałużna, 1999). After several days, a fine crystalline compound was obtained. The product was dissolved in the equivolume mixture of water and 95% EtOH, and the solution was kept at 277 K. After one month, plate-shaped crystals had grown.
Data collection: CrysAlis CCD (UNIL IC & Kuma, 2000); cell refinement: CrysAlis RED (UNIL IC & Kuma, 2000); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[MnCl2(C10H8N2)2(H2O)2] | Z = 1 |
Mr = 474.24 | F(000) = 243 |
Triclinic, P1 | Dx = 1.563 Mg m−3 |
a = 6.8000 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.6443 (8) Å | Cell parameters from 3348 reflections |
c = 8.9244 (9) Å | θ = 5–22° |
α = 84.512 (10)° | µ = 0.95 mm−1 |
β = 79.866 (9)° | T = 291 K |
γ = 77.834 (9)° | Plate, light yellow |
V = 503.87 (9) Å3 | 0.36 × 0.28 × 0.16 mm |
Kuma KM-4 CCD diffractometer | 1790 independent reflections |
Radiation source: fine-focus sealed tube | 1755 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ω scans | θmax = 25.1°, θmin = 3.6° |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | h = −8→8 |
Tmin = 0.727, Tmax = 0.864 | k = −10→10 |
4700 measured reflections | l = −9→10 |
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)] = 0.062 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0493P)2 + 1.3653P] where P = (Fo2 + 2Fc2)/3 |
1790 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[MnCl2(C10H8N2)2(H2O)2] | γ = 77.834 (9)° |
Mr = 474.24 | V = 503.87 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8000 (7) Å | Mo Kα radiation |
b = 8.6443 (8) Å | µ = 0.95 mm−1 |
c = 8.9244 (9) Å | T = 291 K |
α = 84.512 (10)° | 0.36 × 0.28 × 0.16 mm |
β = 79.866 (9)° |
Kuma KM-4 CCD diffractometer | 1790 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | 1755 reflections with I > 2σ(I) |
Tmin = 0.727, Tmax = 0.864 | Rint = 0.069 |
4700 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | Δρmax = 0.48 e Å−3 |
1790 reflections | Δρmin = −0.37 e Å−3 |
163 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 | ||
Mn1 | 0.0000 | 0.0000 | 0.0000 | 0.0364 (3) | |
Cl1 | 0.28164 (19) | 0.13807 (13) | −0.12855 (13) | 0.0461 (4) | |
O1 | 0.2329 (6) | −0.1442 (5) | 0.1325 (5) | 0.0496 (9) | |
N1 | 0.0842 (6) | −0.1715 (4) | −0.1880 (4) | 0.0365 (8) | |
C1 | 0.1239 (8) | −0.1236 (5) | −0.3357 (5) | 0.0424 (11) | |
C2 | 0.1782 (8) | −0.2232 (5) | −0.4523 (6) | 0.0435 (11) | |
C3 | 0.1998 (7) | −0.3864 (5) | −0.4208 (5) | 0.0346 (9) | |
C4 | 0.1605 (8) | −0.4368 (5) | −0.2684 (5) | 0.0402 (10) | |
C5 | 0.1041 (8) | −0.3270 (5) | −0.1582 (5) | 0.0408 (11) | |
C6 | 0.2593 (7) | −0.5000 (5) | −0.5434 (5) | 0.0366 (10) | |
N2 | 0.2789 (6) | −0.4371 (5) | −0.6885 (4) | 0.0421 (9) | |
C7 | 0.3369 (9) | −0.5385 (7) | −0.7990 (6) | 0.0499 (12) | |
C8 | 0.3764 (8) | −0.7006 (6) | −0.7760 (6) | 0.0494 (13) | |
C9 | 0.3540 (9) | −0.7622 (6) | −0.6308 (7) | 0.0510 (13) | |
C10 | 0.2950 (8) | −0.6621 (6) | −0.5107 (6) | 0.0439 (11) | |
H1O | 0.333 (10) | −0.135 (8) | 0.115 (7) | 0.050* | |
H4 | 0.180 (9) | −0.526 (7) | −0.241 (6) | 0.050* | |
H10 | 0.278 (8) | −0.710 (6) | −0.414 (7) | 0.050* | |
H8 | 0.417 (8) | −0.756 (7) | −0.849 (7) | 0.050* | |
H7 | 0.347 (8) | −0.498 (7) | −0.893 (7) | 0.050* | |
H5 | 0.093 (8) | −0.354 (7) | −0.057 (7) | 0.050* | |
H9 | 0.383 (8) | −0.861 (7) | −0.604 (6) | 0.050* | |
H2 | 0.207 (8) | −0.181 (6) | −0.543 (7) | 0.050* | |
H1 | 0.111 (8) | −0.032 (7) | −0.360 (6) | 0.050* | |
H1P | 0.258 (9) | −0.210 (7) | 0.194 (7) | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0523 (6) | 0.0263 (5) | 0.0314 (5) | −0.0092 (4) | −0.0063 (4) | −0.0030 (4) |
Cl1 | 0.0608 (8) | 0.0392 (6) | 0.0407 (7) | −0.0184 (5) | −0.0070 (5) | 0.0024 (5) |
O1 | 0.057 (2) | 0.042 (2) | 0.049 (2) | −0.0098 (18) | −0.0143 (19) | 0.0092 (16) |
N1 | 0.045 (2) | 0.0290 (18) | 0.0354 (19) | −0.0075 (15) | −0.0069 (16) | −0.0030 (15) |
C1 | 0.065 (3) | 0.024 (2) | 0.038 (2) | −0.009 (2) | −0.009 (2) | 0.0004 (18) |
C2 | 0.064 (3) | 0.033 (2) | 0.033 (2) | −0.010 (2) | −0.010 (2) | 0.0037 (19) |
C3 | 0.040 (2) | 0.031 (2) | 0.036 (2) | −0.0083 (17) | −0.0104 (18) | −0.0047 (17) |
C4 | 0.054 (3) | 0.026 (2) | 0.041 (3) | −0.008 (2) | −0.007 (2) | −0.0034 (19) |
C5 | 0.059 (3) | 0.033 (2) | 0.032 (2) | −0.013 (2) | −0.008 (2) | −0.0003 (18) |
C6 | 0.040 (2) | 0.034 (2) | 0.037 (2) | −0.0062 (18) | −0.0081 (18) | −0.0030 (18) |
N2 | 0.053 (2) | 0.039 (2) | 0.034 (2) | −0.0073 (17) | −0.0060 (17) | −0.0050 (16) |
C7 | 0.059 (3) | 0.055 (3) | 0.033 (2) | −0.007 (2) | −0.004 (2) | −0.008 (2) |
C8 | 0.054 (3) | 0.047 (3) | 0.049 (3) | −0.007 (2) | −0.003 (2) | −0.025 (2) |
C9 | 0.064 (3) | 0.032 (2) | 0.059 (3) | −0.007 (2) | −0.013 (3) | −0.012 (2) |
C10 | 0.059 (3) | 0.033 (2) | 0.042 (3) | −0.013 (2) | −0.009 (2) | −0.004 (2) |
Mn1—O1i | 2.237 (4) | C3—C6 | 1.486 (6) |
Mn1—O1 | 2.237 (4) | C4—C5 | 1.381 (7) |
Mn1—N1i | 2.263 (4) | C4—H4 | 0.78 (6) |
Mn1—N1 | 2.263 (4) | C5—H5 | 0.91 (6) |
Mn1—Cl1 | 2.5173 (12) | C6—N2 | 1.351 (6) |
Mn1—Cl1i | 2.5173 (12) | C6—C10 | 1.382 (6) |
O1—H1O | 0.69 (6) | N2—C7 | 1.334 (6) |
O1—H1P | 0.77 (6) | C7—C8 | 1.373 (8) |
N1—C5 | 1.328 (6) | C7—H7 | 0.87 (6) |
N1—C1 | 1.341 (6) | C8—C9 | 1.348 (8) |
C1—C2 | 1.365 (7) | C8—H8 | 0.82 (6) |
C1—H1 | 0.79 (6) | C9—C10 | 1.392 (7) |
C2—C3 | 1.393 (6) | C9—H9 | 0.85 (6) |
C2—H2 | 0.87 (6) | C10—H10 | 0.92 (6) |
C3—C4 | 1.386 (7) | ||
O1i—Mn1—O1 | 180.0 | C3—C2—H2 | 123 (4) |
O1i—Mn1—N1i | 92.16 (14) | C4—C3—C2 | 116.1 (4) |
O1—Mn1—N1i | 87.84 (14) | C4—C3—C6 | 121.7 (4) |
O1i—Mn1—N1 | 87.84 (14) | C2—C3—C6 | 122.1 (4) |
O1—Mn1—N1 | 92.16 (14) | C5—C4—C3 | 119.8 (4) |
N1i—Mn1—N1 | 180.0 | C5—C4—H4 | 118 (4) |
O1i—Mn1—Cl1 | 94.43 (11) | C3—C4—H4 | 122 (4) |
O1—Mn1—Cl1 | 85.57 (11) | N1—C5—C4 | 124.1 (4) |
N1i—Mn1—Cl1 | 90.89 (10) | N1—C5—H5 | 112 (4) |
N1—Mn1—Cl1 | 89.11 (10) | C4—C5—H5 | 123 (4) |
O1i—Mn1—Cl1i | 85.57 (11) | N2—C6—C10 | 121.6 (4) |
O1—Mn1—Cl1i | 94.43 (11) | N2—C6—C3 | 116.7 (4) |
N1i—Mn1—Cl1i | 89.11 (10) | C10—C6—C3 | 121.7 (4) |
N1—Mn1—Cl1i | 90.89 (10) | C7—N2—C6 | 117.0 (4) |
Cl1—Mn1—Cl1i | 180.0 | N2—C7—C8 | 124.9 (5) |
Mn1—O1—H1O | 120 (5) | N2—C7—H7 | 117 (4) |
Mn1—O1—H1P | 148 (4) | C8—C7—H7 | 118 (4) |
H1O—O1—H1P | 92 (7) | C9—C8—C7 | 117.6 (5) |
C5—N1—C1 | 115.8 (4) | C9—C8—H8 | 122 (4) |
C5—N1—Mn1 | 121.8 (3) | C7—C8—H8 | 120 (4) |
C1—N1—Mn1 | 122.4 (3) | C8—C9—C10 | 120.0 (5) |
N1—C1—C2 | 124.2 (4) | C8—C9—H9 | 125 (4) |
N1—C1—H1 | 120 (4) | C10—C9—H9 | 115 (4) |
C2—C1—H1 | 116 (4) | C6—C10—C9 | 118.9 (5) |
C1—C2—C3 | 119.9 (4) | C6—C10—H10 | 124 (3) |
C1—C2—H2 | 117 (4) | C9—C10—H10 | 117 (3) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···Cl1ii | 0.69 (6) | 2.64 (6) | 3.307 (4) | 163 (7) |
O1—H1P···N2iii | 0.77 (6) | 2.12 (6) | 2.851 (5) | 159 (6) |
C10—H10···Cl1iv | 0.92 (6) | 2.76 (6) | 3.668 (5) | 173 (5) |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x, y, z+1; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [MnCl2(C10H8N2)2(H2O)2] |
Mr | 474.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 6.8000 (7), 8.6443 (8), 8.9244 (9) |
α, β, γ (°) | 84.512 (10), 79.866 (9), 77.834 (9) |
V (Å3) | 503.87 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.36 × 0.28 × 0.16 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.727, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4700, 1790, 1755 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.163, 1.19 |
No. of reflections | 1790 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.37 |
Computer programs: CrysAlis CCD (UNIL IC & Kuma, 2000), CrysAlis RED (UNIL IC & Kuma, 2000), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1990) and ORTEP-3 (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···Cl1i | 0.69 (6) | 2.64 (6) | 3.307 (4) | 163 (7) |
O1—H1P···N2ii | 0.77 (6) | 2.12 (6) | 2.851 (5) | 159 (6) |
C10—H10···Cl1iii | 0.92 (6) | 2.76 (6) | 3.668 (5) | 173 (5) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z+1; (iii) x, y−1, z. |
This work forms part of a continuing study of 2,4'-bipyridyl complexes with copper(II) and manganese(II) salts (Bartczak et al., 1998; Kruszynski et al., 2001). Although coordination compounds of these salts with 2,2'-bipyridyl and 4,4'-bipyridyl have been extensively investigated, there are only a small number of reports describing structures of 2,4'-bipyridyl complexes. The structure determination of the title compound, (I), was thus undertaken.
All interatomic distances in (I) are normal. The molecular geometry of (I) (Fig. 1) is similar to diaquadi(acetato-O)bis(2,4'-bipyridyl)manganese(II) (Bartczak et al., 1998). The Mn atom occupies a centre of symmetry and adopts almost ideal square-bipyramidal (4 + 2) coordination. It has been stated that the bond length to bond valence correlation represents a measure of the strength of a bond that is independent of the atomic size (Brown, 1994). The application of this correlation allows us to compare the relative importance of Mn—N, Mn—O and Mn—Cl bonds for different molecules and to check the valence-sum rule for coordinated atoms (Sieroń & Bukowska-Strzyżewska, 1999). The valence sum rule states that the sum of the valences of the bonds formed by an atom is equal to the valence (formal oxidation state) of the atom. The bond valences were computed as νij = exp[(Rij-dij)/0.37] (Brown, 1992, 1997), where Rij is the bond-valence parameter (in the formal sense Rij is the single-bond length between i and j atoms) (Sieroń & Bukowska-Strzyżewska, 1999). The RMn—O, RMn—N and RMn—Cl were taken as 1.790, 1.87 and 2.13 (O'Keeffe & Brese 1991), respectively. The computed bond valences of the manganese are νMn—O = 0.30, νMn—N = 0.35 and νMn—Cl = 0.35 v.u. (valence units), thus the computed valence of the Mn1 atom is 2.00 v.u., which consist with formal oxidation state of manganese. According to bond valences it can be stated that Mn—O bond is distinctly weaker than other manganese bonds, which can be explained by weak O1—H1O···Cl1 and C10—H10···Cl1 hydrogen bonds (for details see Table 2). All least-squares planes of the manganese polyhedra are exactly planar by symmetry. The dihedral angle between least-squares planes calculated through Mn1/O1/Cl1 and Mn1/O1/N1 is 88.84 (11)°, between Mn1/O1/N1 and Mn1/Cl1/N1 is 85.59 (9)° and between Mn1/O1/Cl11 and Mn1/Cl1/N1 is 87.76 (9)°. The pyridine rings are planar within 3 s.u.'s and are inclined at 4.97 (5)° to each other within each 2,4'-bipyridyl group. The pyridyl ring attached to manganese forms dihedral angles of 89.52 (14), 48.69 (14) and 45.80 (12)° with the least-squares planes calculated through Mn1/O1/Cl1, Mn1/O1/N1 and Mn1/Cl1/N1, recpectively. The decrease in the H—O—H angle, which has a value of 92 (7)°, and the diffusion of the electron density of the H atoms in the water molecule seen in the difference Fourier map is imposed by the O—H···Cli and O—H···Nii hydrogen bonds [the Cl···O···N angle is 89.83 (13)°] [symmetry codes: (i) -x + 1, -y, -z; (ii) x, y, z + 1]. The crystals of title compound are held together by strong O—H···N, and weak O—H···Cl and C—H···Cl hydrogen bonds (Desiraju & Steiner, 1999), resulting in a three-dimensional infinite framework (Fig. 2 and Table 2).