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In the title mol­ecular compound, [Mn(C6H7N2S)2(CH4O)2], the Mn atom is octa­hedrally coordinated by two N atoms and two S atoms from two 4,6-dimethyl-2-pyrimidine­thiol­ate anions and two O atoms from two methanol mol­ecules. The mol­ecule lies on a twofold rotation axis. The methanol mol­ecule engages in hydrogen bonding with the N atom of an adjacent mol­ecule to form a chain that runs along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042833/ng2320sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042833/ng2320Isup2.hkl
Contains datablock I

CCDC reference: 663570

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.031
  • wR factor = 0.071
  • Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - S1 .. 7.66 su
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 1.99 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Over past decades considerable attention has been paid to the synthesis and characterization of metal complexes of heterocyclic thiones due to their aesthetically interesting structures (Zhao et al., 2001), their luminescence properties (Tzeng et al., 1999), medicinal applications (Das & Seth, 1997) and their potential relevance to active sites in metalloenzymes (Halcrow & Christou, 1994). Among the heterocyclic thiols, pyrimidinethiols, are some of the most versatile sulfur donor ligands as they can act as monodentate, chelating and bridging ligands to yield complexes with variable nuclearity and a wide range of structural geometries (Rodríguez et al., 2003). A lot of mononuclear pyrimidine-2-thiolate complexes of Hg, Sb, Mo (Cotton & Ilsley, 1981; Hadjikakou et al., 2005), oligomeric complexes of Cu, Ag, Au (Han et al., 2004; Zhang et al., 2003) and polmeric structures of Zn(II), Cd(II), Ni(II) (Eichhöfer & Buth, 2005; Lang et al., 2003) have been reported. However, the chemistry of manganese derivatives of this type of ligands, remains undeveloped. The synthesis and structural characterization of only a few manganese complexes such as trans-{dichlorotetraquis-[2(lH)-pyridinethione]}manganese(II) (Constable et al., 1991) and [Mn(dmpymt)2phen] [phen is 1,10-phenanthroline; Castro et al., 1995] were described. We report here the crystal structure of the title complex Mn(dmpymt)2(MeOH)2 (I).

An X-ray analysis revealed that complex (I) crystallizes in the monclinic space group C2/c and the asymmetric unit contains one-half of the discrete molecule Mn(dmpymt)2(MeOH)2. In the structure of (I), the Mn atom is coordinated by two S atoms and two N atoms to form a distorted octahedral geometry (Figure 1). The environment around the manganese center is [MnN4S2], with the sulfur atoms mutually trans. Each dmpymt ligand coordinates to one Mn atom in an N,S-bidentate fashion, forming a heteroatomic four-membered chelate ring. The chelate bite angle S(1)—Mn(1)—N(2) [64.42 (4)°] is comparable to those found in Mn(phen)(dmpymt)2 [64.6 (2)° and 64.3 (2)°; Castro et al., 1995]. The S(1)—Mn(1)—S(1i), O(1)—Mn(1)—N(2i) and O(1i)-Mn(1)—N(2) [i = -x, y, -z + 3/2] bond angles are 165.47 (3)°, 161.78 (6)° and 161.78 (6)°, respectively. The Mn—S bond distance of 2.6165 (8) Å is longer than the corresponding ones found in Mn(phen)(dmpymt)2 [2.593 (3) Å; Castro et al., 1995], [MnLCl(MeOH)] [2.559 (3) Å; L is 2-[2-(2pyridil)ethylamino]ethanethiolate; Mikuriya et al., 1991], but shorter than that observed in trans-{dichlorotetraquis-[2(lH)-pyridinethione]}manganese(II) [2.84 (1) Å and 2.656 (1) Å; Constable et al., 1991]. The Mn—N bond length [2.2706 (17) Å] of this title complex is slightly longer than that observed in Mn(phen)(dmpymt)2 [2.258 (2) Å; Castro et al., 1995]. The Mn—O bond distance [2.1951 (16) Å] is shorter than that reported in MnL(CH3OH) [2.277 (3) Å; L is N-(2-hydroxybenzoyl)-N'-(2-hydroxybenzylidene)propane-1,2-diamnine; Costes et al., 2004]. The Mn—N bond distance is 2.2706 (17) Å, which is shorter than that in observed [Mn(acac)2phen] [2.307 (5) Å; acac is 2,4-pentanedionato; Stephens, 1977].

In the crystal of (I), the OH group of each MeOH molecule interacts with atom N(1) in an adjacent molecule to afford pairwise intermolecular C—H···N contacts, thereby forming chains of molecules running along c axis (Figure 2 and Table 2).

Related literature top

For the chemistry, properties, and medicinal and biological relevance of metal thiolates, see Das & Seth (1997); Halcrow & Christou (1994); Tzeng et al. (1999); Zhao et al. (2001). For structural studies of metal thiolates, see Castro et al. (1995); Constable et al. (1991); Costes et al. (2004); Cotton & Ilsley (1981); Eichhöfer & Buth (2005); Hadjikakou et al. (2005); Han et al. (2004); Lang et al. (2003); MacGillvray et al. (2000); Mikuriya et al. (1991); Rodríguez et al. (2003); Stephens (1977); Zhang et al. (2003).

Experimental top

A solution of dmpymtH (0.2861 g, 20 mmol) in MeOH (5 ml) was added to MnAc.2H2O (0.2455 g, 10 mmol) in MeOH (10 ml). A yellow precipitate was observed to form within an hour. The mixture was stirred at room temperature for ten hours and then filtered. The resulting solid was redissolved in MeOH and CH2Cl2 (V: V = 1: 1) and filtered again. Diethyl ether was layered onto the filtrate to form yellow crystals of compound (I) in several days, which was collected by filtration, washed by Et2O, and dried in vacuo. Yield 0.353 g, 89% (based on Mn). Analysis found: C 42.47, H 5.22, N 14.19%; calculated for C14H22N4O2S2Mn: C 42.31, H 5.58, N 14.10%.

Refinement top

The H atom of the MeOH group was located in a Fourier map, and the O—H distance was fixed at 0.800 (16) Å. All other hydrogen atoms were placed in geometrically idealized positions (C—H = 0.98 Å for methyl groups, and C—H = 0.95 Å for ring CH groups) and constrained to ride on their parent atoms with Uiso(H) = 1.5Ueq for methyl group and Uiso(H) = 1.2Ueq for ring CH groups.

Structure description top

Over past decades considerable attention has been paid to the synthesis and characterization of metal complexes of heterocyclic thiones due to their aesthetically interesting structures (Zhao et al., 2001), their luminescence properties (Tzeng et al., 1999), medicinal applications (Das & Seth, 1997) and their potential relevance to active sites in metalloenzymes (Halcrow & Christou, 1994). Among the heterocyclic thiols, pyrimidinethiols, are some of the most versatile sulfur donor ligands as they can act as monodentate, chelating and bridging ligands to yield complexes with variable nuclearity and a wide range of structural geometries (Rodríguez et al., 2003). A lot of mononuclear pyrimidine-2-thiolate complexes of Hg, Sb, Mo (Cotton & Ilsley, 1981; Hadjikakou et al., 2005), oligomeric complexes of Cu, Ag, Au (Han et al., 2004; Zhang et al., 2003) and polmeric structures of Zn(II), Cd(II), Ni(II) (Eichhöfer & Buth, 2005; Lang et al., 2003) have been reported. However, the chemistry of manganese derivatives of this type of ligands, remains undeveloped. The synthesis and structural characterization of only a few manganese complexes such as trans-{dichlorotetraquis-[2(lH)-pyridinethione]}manganese(II) (Constable et al., 1991) and [Mn(dmpymt)2phen] [phen is 1,10-phenanthroline; Castro et al., 1995] were described. We report here the crystal structure of the title complex Mn(dmpymt)2(MeOH)2 (I).

An X-ray analysis revealed that complex (I) crystallizes in the monclinic space group C2/c and the asymmetric unit contains one-half of the discrete molecule Mn(dmpymt)2(MeOH)2. In the structure of (I), the Mn atom is coordinated by two S atoms and two N atoms to form a distorted octahedral geometry (Figure 1). The environment around the manganese center is [MnN4S2], with the sulfur atoms mutually trans. Each dmpymt ligand coordinates to one Mn atom in an N,S-bidentate fashion, forming a heteroatomic four-membered chelate ring. The chelate bite angle S(1)—Mn(1)—N(2) [64.42 (4)°] is comparable to those found in Mn(phen)(dmpymt)2 [64.6 (2)° and 64.3 (2)°; Castro et al., 1995]. The S(1)—Mn(1)—S(1i), O(1)—Mn(1)—N(2i) and O(1i)-Mn(1)—N(2) [i = -x, y, -z + 3/2] bond angles are 165.47 (3)°, 161.78 (6)° and 161.78 (6)°, respectively. The Mn—S bond distance of 2.6165 (8) Å is longer than the corresponding ones found in Mn(phen)(dmpymt)2 [2.593 (3) Å; Castro et al., 1995], [MnLCl(MeOH)] [2.559 (3) Å; L is 2-[2-(2pyridil)ethylamino]ethanethiolate; Mikuriya et al., 1991], but shorter than that observed in trans-{dichlorotetraquis-[2(lH)-pyridinethione]}manganese(II) [2.84 (1) Å and 2.656 (1) Å; Constable et al., 1991]. The Mn—N bond length [2.2706 (17) Å] of this title complex is slightly longer than that observed in Mn(phen)(dmpymt)2 [2.258 (2) Å; Castro et al., 1995]. The Mn—O bond distance [2.1951 (16) Å] is shorter than that reported in MnL(CH3OH) [2.277 (3) Å; L is N-(2-hydroxybenzoyl)-N'-(2-hydroxybenzylidene)propane-1,2-diamnine; Costes et al., 2004]. The Mn—N bond distance is 2.2706 (17) Å, which is shorter than that in observed [Mn(acac)2phen] [2.307 (5) Å; acac is 2,4-pentanedionato; Stephens, 1977].

In the crystal of (I), the OH group of each MeOH molecule interacts with atom N(1) in an adjacent molecule to afford pairwise intermolecular C—H···N contacts, thereby forming chains of molecules running along c axis (Figure 2 and Table 2).

For the chemistry, properties, and medicinal and biological relevance of metal thiolates, see Das & Seth (1997); Halcrow & Christou (1994); Tzeng et al. (1999); Zhao et al. (2001). For structural studies of metal thiolates, see Castro et al. (1995); Constable et al. (1991); Costes et al. (2004); Cotton & Ilsley (1981); Eichhöfer & Buth (2005); Hadjikakou et al. (2005); Han et al. (2004); Lang et al. (2003); MacGillvray et al. (2000); Mikuriya et al. (1991); Rodríguez et al. (2003); Stephens (1977); Zhang et al. (2003).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-labling scheme. Displacement elipsoids are drawn at the 30% probability level and H atoms are drawn as spheres of arbitrary radii. [Symmetry code:(i) -x, y, -z + 3/2.]
[Figure 2] Fig. 2. A packing diagram for (I) viewed down the c axis. Dashed lines represent the O—H···N hydrogen bonding interaction.
Bis(4,6-dimethyl-2-pyrimidinethiolato-κ2N,S)-βis(methanol-κO)manganese(II) top
Crystal data top
[Mn(C6H7N2S)2(CH4O)2]F(000) = 828
Mr = 397.44Dx = 1.466 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3136 reflections
a = 15.150 (3) Åθ = 3.2–25.4°
b = 8.6713 (17) ŵ = 0.98 mm1
c = 13.890 (3) ÅT = 153 K
β = 99.31 (3)°Block, yellow
V = 1800.7 (6) Å30.35 × 0.25 × 0.20 mm
Z = 4
Data collection top
Rigaku Mercury
diffractometer
1656 independent reflections
Radiation source: fine-focus sealed tube1565 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 25.3°, θmin = 3.2°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 1818
Tmin = 0.726, Tmax = 0.828k = 108
8481 measured reflectionsl = 1616
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0278P)2 + 3.1898P]
where P = (Fo2 + 2Fc2)/3
1656 reflections(Δ/σ)max = 0.001
112 parametersΔρmax = 0.28 e Å3
1 restraintΔρmin = 0.25 e Å3
Crystal data top
[Mn(C6H7N2S)2(CH4O)2]V = 1800.7 (6) Å3
Mr = 397.44Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.150 (3) ŵ = 0.98 mm1
b = 8.6713 (17) ÅT = 153 K
c = 13.890 (3) Å0.35 × 0.25 × 0.20 mm
β = 99.31 (3)°
Data collection top
Rigaku Mercury
diffractometer
1656 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
1565 reflections with I > 2σ(I)
Tmin = 0.726, Tmax = 0.828Rint = 0.026
8481 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.28 e Å3
1656 reflectionsΔρmin = 0.25 e Å3
112 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
Mn10.00000.03331 (5)0.75000.01898 (14)
S10.10027 (3)0.07146 (6)0.61515 (4)0.02198 (15)
O10.08155 (9)0.14465 (17)0.66532 (10)0.0228 (3)
H10.0602 (16)0.181 (3)0.6212 (15)0.037 (8)*
N10.00580 (11)0.25958 (19)0.48392 (12)0.0204 (4)
N20.05222 (11)0.20439 (19)0.63054 (11)0.0190 (4)
C10.01101 (13)0.1891 (2)0.57136 (14)0.0184 (4)
C20.07078 (16)0.4251 (3)0.35684 (16)0.0302 (5)
H2A0.01240.46830.34970.045*
H2B0.11550.50770.35030.045*
H2C0.08830.34740.30610.045*
C30.06489 (14)0.3517 (2)0.45536 (14)0.0229 (5)
C40.12950 (14)0.3754 (3)0.51330 (15)0.0256 (5)
H40.17800.44370.49330.031*
C50.12206 (13)0.2972 (2)0.60133 (14)0.0220 (4)
C60.19153 (14)0.3138 (3)0.66618 (16)0.0290 (5)
H6A0.24580.25840.63750.043*
H6B0.20550.42330.67290.043*
H6C0.16870.27070.73060.043*
C70.17601 (15)0.1366 (3)0.63694 (17)0.0381 (6)
H7A0.20170.07350.68390.057*
H7B0.20130.24080.63540.057*
H7C0.19000.09020.57200.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0182 (2)0.0232 (2)0.0156 (2)0.0000.00279 (16)0.000
S10.0182 (3)0.0266 (3)0.0213 (3)0.0034 (2)0.0036 (2)0.0024 (2)
O10.0206 (8)0.0267 (8)0.0212 (8)0.0014 (6)0.0044 (6)0.0027 (6)
N10.0233 (9)0.0183 (8)0.0193 (8)0.0012 (7)0.0023 (7)0.0008 (7)
N20.0180 (8)0.0201 (9)0.0187 (8)0.0007 (7)0.0020 (7)0.0010 (7)
C10.0194 (10)0.0166 (10)0.0183 (9)0.0028 (8)0.0009 (8)0.0028 (8)
C20.0402 (14)0.0260 (12)0.0227 (11)0.0035 (10)0.0003 (10)0.0044 (9)
C30.0298 (11)0.0175 (10)0.0193 (10)0.0016 (9)0.0019 (8)0.0012 (8)
C40.0264 (11)0.0249 (11)0.0237 (11)0.0071 (9)0.0018 (9)0.0010 (9)
C50.0207 (10)0.0233 (11)0.0207 (10)0.0003 (8)0.0002 (8)0.0053 (8)
C60.0222 (11)0.0376 (13)0.0267 (11)0.0058 (10)0.0029 (9)0.0044 (10)
C70.0207 (12)0.0606 (17)0.0329 (13)0.0064 (11)0.0041 (10)0.0050 (12)
Geometric parameters (Å, º) top
Mn1—O12.1957 (15)C2—H2A0.9800
Mn1—O1i2.1957 (15)C2—H2B0.9800
Mn1—N2i2.2706 (17)C2—H2C0.9800
Mn1—N22.2706 (17)C3—C41.379 (3)
Mn1—S12.6165 (8)C4—C51.386 (3)
Mn1—S1i2.6165 (8)C4—H40.9500
S1—C11.724 (2)C5—C61.499 (3)
O1—C71.423 (3)C6—H6A0.9800
O1—H10.800 (16)C6—H6B0.9800
N1—C31.343 (3)C6—H6C0.9800
N1—C11.351 (3)C7—H7A0.9800
N2—C51.339 (3)C7—H7B0.9800
N2—C11.366 (3)C7—H7C0.9800
C2—C31.499 (3)
O1—Mn1—O1i90.69 (8)C3—C2—H2B109.5
O1—Mn1—N2i161.81 (6)H2A—C2—H2B109.5
O1i—Mn1—N2i88.19 (6)C3—C2—H2C109.5
O1—Mn1—N288.19 (6)H2A—C2—H2C109.5
O1i—Mn1—N2161.81 (6)H2B—C2—H2C109.5
N2i—Mn1—N298.41 (9)N1—C3—C4121.55 (19)
O1—Mn1—S192.69 (4)N1—C3—C2116.69 (19)
O1i—Mn1—S197.51 (4)C4—C3—C2121.8 (2)
N2i—Mn1—S1105.46 (4)C3—C4—C5118.54 (19)
N2—Mn1—S164.42 (4)C3—C4—H4120.7
O1—Mn1—S1i97.51 (4)C5—C4—H4120.7
O1i—Mn1—S1i92.69 (4)N2—C5—C4120.56 (19)
N2i—Mn1—S1i64.42 (4)N2—C5—C6118.22 (18)
N2—Mn1—S1i105.46 (4)C4—C5—C6121.22 (19)
S1—Mn1—S1i165.47 (3)C5—C6—H6A109.5
C1—S1—Mn179.29 (7)C5—C6—H6B109.5
C7—O1—Mn1124.58 (14)H6A—C6—H6B109.5
C7—O1—H1108.6 (18)C5—C6—H6C109.5
Mn1—O1—H1115.0 (19)H6A—C6—H6C109.5
C3—N1—C1117.55 (17)H6B—C6—H6C109.5
C5—N2—C1118.22 (17)O1—C7—H7A109.5
C5—N2—Mn1141.17 (14)O1—C7—H7B109.5
C1—N2—Mn1100.41 (12)H7A—C7—H7B109.5
N1—C1—N2123.54 (18)O1—C7—H7C109.5
N1—C1—S1120.88 (15)H7A—C7—H7C109.5
N2—C1—S1115.58 (14)H7B—C7—H7C109.5
C3—C2—H2A109.5
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1ii0.80 (2)1.92 (2)2.716 (2)178 (3)
Symmetry code: (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Mn(C6H7N2S)2(CH4O)2]
Mr397.44
Crystal system, space groupMonoclinic, C2/c
Temperature (K)153
a, b, c (Å)15.150 (3), 8.6713 (17), 13.890 (3)
β (°) 99.31 (3)
V3)1800.7 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.98
Crystal size (mm)0.35 × 0.25 × 0.20
Data collection
DiffractometerRigaku Mercury
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.726, 0.828
No. of measured, independent and
observed [I > 2σ(I)] reflections
8481, 1656, 1565
Rint0.026
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.071, 1.09
No. of reflections1656
No. of parameters112
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.28, 0.25

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.800 (16)1.916 (17)2.716 (2)178 (3)
Symmetry code: (i) x, y, z+1.
 

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