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The Mn atom in the title compound, [MnCl2(C10H8N2)2(H2O)2], occupies a centre of symmetry. The pyridine rings are planar and all bond distances are normal. Bond-valence calculations show that the Mn-O bond is weaker than both the Mn-N and Mn-Cl bonds. The mol­ecules are held together in the crystal by hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005840/br6016sup1.cif
Contains datablocks global, s2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005840/br6016Isup2.hkl
Contains datablock I

CCDC reference: 165626

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.062
  • wR factor = 0.163
  • Data-to-parameter ratio = 11.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_320 Alert C Check Hybridisation of H(1O) in main residue ? PLAT_320 Alert C Check Hybridisation of H(1P) in main residue ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Part of the molecular packing of the title compound showing intermolecular hydrogen bonds creating a three-dimensional net structure. Hydrogen bonds are indicated by dashed lines.
Diaquadichloride-Bis(2,4'-Bipyridyl) Manganese(II) top
Crystal data top
[MnCl2(C10H8N2)2(H2O)2]Z = 1
Mr = 474.24F(000) = 243
Triclinic, P1Dx = 1.563 Mg m3
a = 6.8000 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6443 (8) ÅCell parameters from 3348 reflections
c = 8.9244 (9) Åθ = 5–22°
α = 84.512 (10)°µ = 0.95 mm1
β = 79.866 (9)°T = 291 K
γ = 77.834 (9)°Plate, light yellow
V = 503.87 (9) Å30.36 × 0.28 × 0.16 mm
Data collection top
Kuma KM-4 CCD
diffractometer
1790 independent reflections
Radiation source: fine-focus sealed tube1755 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
ω scansθmax = 25.1°, θmin = 3.6°
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
h = 88
Tmin = 0.727, Tmax = 0.864k = 1010
4700 measured reflectionsl = 910
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: difference Fourier map
wR(F2) = 0.163H 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 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[MnCl2(C10H8N2)2(H2O)2]γ = 77.834 (9)°
Mr = 474.24V = 503.87 (9) Å3
Triclinic, P1Z = 1
a = 6.8000 (7) ÅMo Kα radiation
b = 8.6443 (8) ŵ = 0.95 mm1
c = 8.9244 (9) ÅT = 291 K
α = 84.512 (10)°0.36 × 0.28 × 0.16 mm
β = 79.866 (9)°
Data collection top
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 = 0.864Rint = 0.069
4700 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.163H atoms treated by a mixture of independent and constrained refinement
S = 1.19Δρmax = 0.48 e Å3
1790 reflectionsΔρmin = 0.37 e Å3
163 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
Mn10.00000.00000.00000.0364 (3)
Cl10.28164 (19)0.13807 (13)0.12855 (13)0.0461 (4)
O10.2329 (6)0.1442 (5)0.1325 (5)0.0496 (9)
N10.0842 (6)0.1715 (4)0.1880 (4)0.0365 (8)
C10.1239 (8)0.1236 (5)0.3357 (5)0.0424 (11)
C20.1782 (8)0.2232 (5)0.4523 (6)0.0435 (11)
C30.1998 (7)0.3864 (5)0.4208 (5)0.0346 (9)
C40.1605 (8)0.4368 (5)0.2684 (5)0.0402 (10)
C50.1041 (8)0.3270 (5)0.1582 (5)0.0408 (11)
C60.2593 (7)0.5000 (5)0.5434 (5)0.0366 (10)
N20.2789 (6)0.4371 (5)0.6885 (4)0.0421 (9)
C70.3369 (9)0.5385 (7)0.7990 (6)0.0499 (12)
C80.3764 (8)0.7006 (6)0.7760 (6)0.0494 (13)
C90.3540 (9)0.7622 (6)0.6308 (7)0.0510 (13)
C100.2950 (8)0.6621 (6)0.5107 (6)0.0439 (11)
H1O0.333 (10)0.135 (8)0.115 (7)0.050*
H40.180 (9)0.526 (7)0.241 (6)0.050*
H100.278 (8)0.710 (6)0.414 (7)0.050*
H80.417 (8)0.756 (7)0.849 (7)0.050*
H70.347 (8)0.498 (7)0.893 (7)0.050*
H50.093 (8)0.354 (7)0.057 (7)0.050*
H90.383 (8)0.861 (7)0.604 (6)0.050*
H20.207 (8)0.181 (6)0.543 (7)0.050*
H10.111 (8)0.032 (7)0.360 (6)0.050*
H1P0.258 (9)0.210 (7)0.194 (7)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0523 (6)0.0263 (5)0.0314 (5)0.0092 (4)0.0063 (4)0.0030 (4)
Cl10.0608 (8)0.0392 (6)0.0407 (7)0.0184 (5)0.0070 (5)0.0024 (5)
O10.057 (2)0.042 (2)0.049 (2)0.0098 (18)0.0143 (19)0.0092 (16)
N10.045 (2)0.0290 (18)0.0354 (19)0.0075 (15)0.0069 (16)0.0030 (15)
C10.065 (3)0.024 (2)0.038 (2)0.009 (2)0.009 (2)0.0004 (18)
C20.064 (3)0.033 (2)0.033 (2)0.010 (2)0.010 (2)0.0037 (19)
C30.040 (2)0.031 (2)0.036 (2)0.0083 (17)0.0104 (18)0.0047 (17)
C40.054 (3)0.026 (2)0.041 (3)0.008 (2)0.007 (2)0.0034 (19)
C50.059 (3)0.033 (2)0.032 (2)0.013 (2)0.008 (2)0.0003 (18)
C60.040 (2)0.034 (2)0.037 (2)0.0062 (18)0.0081 (18)0.0030 (18)
N20.053 (2)0.039 (2)0.034 (2)0.0073 (17)0.0060 (17)0.0050 (16)
C70.059 (3)0.055 (3)0.033 (2)0.007 (2)0.004 (2)0.008 (2)
C80.054 (3)0.047 (3)0.049 (3)0.007 (2)0.003 (2)0.025 (2)
C90.064 (3)0.032 (2)0.059 (3)0.007 (2)0.013 (3)0.012 (2)
C100.059 (3)0.033 (2)0.042 (3)0.013 (2)0.009 (2)0.004 (2)
Geometric parameters (Å, º) top
Mn1—O1i2.237 (4)C3—C61.486 (6)
Mn1—O12.237 (4)C4—C51.381 (7)
Mn1—N1i2.263 (4)C4—H40.78 (6)
Mn1—N12.263 (4)C5—H50.91 (6)
Mn1—Cl12.5173 (12)C6—N21.351 (6)
Mn1—Cl1i2.5173 (12)C6—C101.382 (6)
O1—H1O0.69 (6)N2—C71.334 (6)
O1—H1P0.77 (6)C7—C81.373 (8)
N1—C51.328 (6)C7—H70.87 (6)
N1—C11.341 (6)C8—C91.348 (8)
C1—C21.365 (7)C8—H80.82 (6)
C1—H10.79 (6)C9—C101.392 (7)
C2—C31.393 (6)C9—H90.85 (6)
C2—H20.87 (6)C10—H100.92 (6)
C3—C41.386 (7)
O1i—Mn1—O1180.0C3—C2—H2123 (4)
O1i—Mn1—N1i92.16 (14)C4—C3—C2116.1 (4)
O1—Mn1—N1i87.84 (14)C4—C3—C6121.7 (4)
O1i—Mn1—N187.84 (14)C2—C3—C6122.1 (4)
O1—Mn1—N192.16 (14)C5—C4—C3119.8 (4)
N1i—Mn1—N1180.0C5—C4—H4118 (4)
O1i—Mn1—Cl194.43 (11)C3—C4—H4122 (4)
O1—Mn1—Cl185.57 (11)N1—C5—C4124.1 (4)
N1i—Mn1—Cl190.89 (10)N1—C5—H5112 (4)
N1—Mn1—Cl189.11 (10)C4—C5—H5123 (4)
O1i—Mn1—Cl1i85.57 (11)N2—C6—C10121.6 (4)
O1—Mn1—Cl1i94.43 (11)N2—C6—C3116.7 (4)
N1i—Mn1—Cl1i89.11 (10)C10—C6—C3121.7 (4)
N1—Mn1—Cl1i90.89 (10)C7—N2—C6117.0 (4)
Cl1—Mn1—Cl1i180.0N2—C7—C8124.9 (5)
Mn1—O1—H1O120 (5)N2—C7—H7117 (4)
Mn1—O1—H1P148 (4)C8—C7—H7118 (4)
H1O—O1—H1P92 (7)C9—C8—C7117.6 (5)
C5—N1—C1115.8 (4)C9—C8—H8122 (4)
C5—N1—Mn1121.8 (3)C7—C8—H8120 (4)
C1—N1—Mn1122.4 (3)C8—C9—C10120.0 (5)
N1—C1—C2124.2 (4)C8—C9—H9125 (4)
N1—C1—H1120 (4)C10—C9—H9115 (4)
C2—C1—H1116 (4)C6—C10—C9118.9 (5)
C1—C2—C3119.9 (4)C6—C10—H10124 (3)
C1—C2—H2117 (4)C9—C10—H10117 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···Cl1ii0.69 (6)2.64 (6)3.307 (4)163 (7)
O1—H1P···N2iii0.77 (6)2.12 (6)2.851 (5)159 (6)
C10—H10···Cl1iv0.92 (6)2.76 (6)3.668 (5)173 (5)
Symmetry codes: (ii) x+1, y, z; (iii) x, y, z+1; (iv) x, y1, z.

Experimental details

Crystal data
Chemical formula[MnCl2(C10H8N2)2(H2O)2]
Mr474.24
Crystal system, space groupTriclinic, 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)
V3)503.87 (9)
Z1
Radiation typeMo Kα
µ (mm1)0.95
Crystal size (mm)0.36 × 0.28 × 0.16
Data collection
DiffractometerKuma KM-4 CCD
diffractometer
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1999)
Tmin, Tmax0.727, 0.864
No. of measured, independent and
observed [I > 2σ(I)] reflections
4700, 1790, 1755
Rint0.069
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.163, 1.19
No. of reflections1790
No. of parameters163
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected bond lengths (Å) top
Mn1—O12.237 (4)Mn1—Cl12.5173 (12)
Mn1—N12.263 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···Cl1i0.69 (6)2.64 (6)3.307 (4)163 (7)
O1—H1P···N2ii0.77 (6)2.12 (6)2.851 (5)159 (6)
C10—H10···Cl1iii0.92 (6)2.76 (6)3.668 (5)173 (5)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1; (iii) x, y1, z.
 

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