Crystal structure of bis­(4-acetyl­pyridine-κN)bis­(ethanol-κO)bis­(thio­cyanato-κN)manganese(II)

In the crystal structure of the title compound, [Mn(NCS)₂(C₇H₇NO)₂(C₂H₅OH)₂], the Mn^II atom is coordin­ated by two N-bonded thio­cyanate anions, two 4-acetyl­pyridine ligands, and two ethanol mol­ecules within a slightly distorted octa­hedron. The asymmetric unit consits of one manganese cation, located on a centre of inversion, one thio­cyanate anion, one 4-acetyl­pyridine ligand and one ethanol mol­ecule in general positions. The discrete complexes are connected by inter­molecular O—H...O hydrogen bonds between the alcohol OH group and the carbonyl O atom into chains parallel to [011].

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.088
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

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Alert level C
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         C1 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         44 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C1      ..        7.4 su
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         21 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Synthesis and crystallization

MnSO₄·H₂O was purchased from Merck; 4-acetyl­pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂·3H₂O and 9.88 g (58.44 mmol) MnSO₄·H₂O in 400 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and the solvent evaporated using a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 42.8 mg (0.25 mmol) Mn(NCS)₂ and 55.1 µl (0.50 mmol) 4-acetyl­pyridine in 1.5 ml ethanol at room temperature. After several days, suitable crystals of the title compound were obtained.

S2. Refinement

The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methyl­ene and C—H = 0.98 Å for methyl H atoms. The O-bound H atom was located in a difference map. Its bond length was set to a value of 0.84 Å and it was refined with U_iso(H) = 1.5U_eq(O) using a riding model.

Related literature

For a similar structure with thiocyanato anions in terminal coordination to a manganese(II) atom, see: Li et al. (2007).

Structure description

For a similar structure with thiocyanato anions in terminal coordination to a manganese(II) atom, see: Li et al. (2007).

Synthesis and crystallization

MnSO₄·H₂O was purchased from Merck; 4-acetyl­pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂·3H₂O and 9.88 g (58.44 mmol) MnSO₄·H₂O in 400 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and the solvent evaporated using a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 42.8 mg (0.25 mmol) Mn(NCS)₂ and 55.1 µl (0.50 mmol) 4-acetyl­pyridine in 1.5 ml ethanol at room temperature. After several days, suitable crystals of the title compound were obtained.

Refinement details

The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methyl­ene and C—H = 0.98 Å for methyl H atoms. The O-bound H atom was located in a difference map. Its bond length was set to a value of 0.84 Å and it was refined with U_iso(H) = 1.5U_eq(O) using a riding model.

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The coordination environment of the Mn^II atom in the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 2, -y + 1, -z + 1.]
	Fig. 2. Crystal structure of the title compound in a view along [010]. Hydrogen bonds are indicated by dashed lines.

Bis(ethanol-κO)bis[1-(pyridin-4-yl)ethan-1-one-κN]bis(thiocyanato-κN)manganese(II)

Crystal data

[Mn(NCS)2(C7H7NO)2(C2H6O)2]	Z = 1
Mr = 505.51	F(000) = 263
Triclinic, P1	Dx = 1.380 Mg m^−3
a = 6.9547 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7733 (9) Å	Cell parameters from 6535 reflections
c = 10.1859 (9) Å	θ = 2.4–27.0°
α = 117.449 (10)°	µ = 0.75 mm^−1
β = 94.978 (11)°	T = 200 K
γ = 93.379 (11)°	Block, colorless
V = 608.23 (11) Å^3	0.04 × 0.03 × 0.02 mm

Data collection

Stoe IPDS-1 diffractometer	2163 reflections with I > 2σ(I)
phi scans	Rint = 0.039
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	θmax = 27.0°, θmin = 2.4°
Tmin = 0.966, Tmax = 0.977	h = −8→8
6535 measured reflections	k = −12→12
2583 independent reflections	l = −13→13

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0565P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.088	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.26 e Å^−3
2583 reflections	Δρmin = −0.35 e Å^−3
144 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.069 (8)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	1.0000	0.5000	0.5000	0.02081 (14)
N1	0.9402 (2)	0.42929 (18)	0.66517 (15)	0.0300 (3)
C1	0.8976 (2)	0.35987 (19)	0.72660 (17)	0.0245 (3)
S1	0.83508 (10)	0.25963 (7)	0.80913 (7)	0.05345 (19)
N11	0.8542 (2)	0.25989 (15)	0.30663 (15)	0.0250 (3)
C11	0.8030 (3)	0.1414 (2)	0.33223 (19)	0.0339 (4)
H11	0.8081	0.1609	0.4329	0.041*
C12	0.7431 (3)	−0.0080 (2)	0.22080 (19)	0.0338 (4)
H12	0.7099	−0.0886	0.2451	0.041*
C13	0.7325 (2)	−0.03842 (18)	0.07316 (17)	0.0241 (3)
C14	0.7813 (3)	0.0837 (2)	0.04487 (18)	0.0276 (4)
H14	0.7738	0.0676	−0.0549	0.033*
C15	0.8413 (3)	0.2296 (2)	0.16300 (18)	0.0278 (4)
H15	0.8749	0.3123	0.1417	0.033*
C16	0.6741 (3)	−0.19848 (19)	−0.05499 (18)	0.0285 (4)
C17	0.6365 (3)	−0.3314 (2)	−0.0243 (2)	0.0417 (5)
H17A	0.6077	−0.4275	−0.1188	0.063*
H17B	0.5254	−0.3158	0.0322	0.063*
H17C	0.7515	−0.3384	0.0341	0.063*
O11	0.6621 (2)	−0.21465 (16)	−0.18155 (14)	0.0409 (3)
C21	0.6624 (4)	0.8271 (3)	0.4935 (3)	0.0549 (6)
H21A	0.5856	0.8597	0.4296	0.082*
H21B	0.6313	0.8831	0.5958	0.082*
H21C	0.8010	0.8504	0.4921	0.082*
C22	0.6154 (3)	0.6558 (2)	0.4366 (2)	0.0367 (4)
H22A	0.4748	0.6326	0.4363	0.044*
H22B	0.6445	0.5999	0.3325	0.044*
O21	0.72349 (18)	0.60072 (14)	0.52571 (12)	0.0291 (3)
H1O1	0.6854	0.6446	0.6101	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0266 (2)	0.01896 (19)	0.01844 (18)	0.00180 (12)	0.00503 (13)	0.00984 (14)
N1	0.0409 (9)	0.0290 (7)	0.0236 (7)	0.0005 (6)	0.0079 (6)	0.0150 (6)
C1	0.0280 (8)	0.0232 (7)	0.0217 (7)	0.0021 (6)	0.0039 (6)	0.0099 (6)
S1	0.0678 (4)	0.0535 (4)	0.0652 (4)	0.0037 (3)	0.0157 (3)	0.0489 (3)
N11	0.0295 (7)	0.0219 (7)	0.0220 (6)	0.0014 (5)	0.0027 (5)	0.0091 (6)
C11	0.0525 (12)	0.0266 (8)	0.0206 (7)	−0.0014 (8)	0.0051 (7)	0.0099 (7)
C12	0.0539 (12)	0.0225 (8)	0.0245 (8)	−0.0016 (8)	0.0056 (8)	0.0111 (7)
C13	0.0237 (8)	0.0241 (7)	0.0219 (7)	0.0041 (6)	0.0051 (6)	0.0080 (6)
C14	0.0323 (9)	0.0305 (8)	0.0194 (7)	0.0012 (7)	0.0039 (6)	0.0114 (7)
C15	0.0338 (9)	0.0267 (8)	0.0240 (7)	−0.0015 (7)	0.0026 (7)	0.0136 (7)
C16	0.0273 (8)	0.0258 (8)	0.0254 (8)	0.0060 (7)	0.0056 (7)	0.0053 (7)
C17	0.0550 (13)	0.0229 (9)	0.0374 (10)	−0.0008 (8)	0.0026 (9)	0.0069 (8)
O11	0.0527 (8)	0.0372 (7)	0.0221 (6)	0.0057 (6)	0.0073 (6)	0.0043 (5)
C21	0.0604 (15)	0.0522 (13)	0.0762 (16)	0.0160 (11)	0.0178 (13)	0.0477 (13)
C22	0.0325 (9)	0.0459 (11)	0.0341 (9)	0.0083 (8)	0.0003 (7)	0.0210 (9)
O21	0.0336 (6)	0.0315 (6)	0.0238 (5)	0.0115 (5)	0.0080 (5)	0.0128 (5)

Geometric parameters (Å, º)

Mn1—N1^i	2.1543 (15)	C14—C15	1.385 (2)
Mn1—N1	2.1543 (15)	C14—H14	0.9500
Mn1—O21^i	2.1928 (12)	C15—H15	0.9500
Mn1—O21	2.1929 (12)	C16—O11	1.219 (2)
Mn1—N11^i	2.3508 (14)	C16—C17	1.484 (3)
Mn1—N11	2.3508 (14)	C17—H17A	0.9800
N1—C1	1.157 (2)	C17—H17B	0.9800
C1—S1	1.6211 (18)	C17—H17C	0.9800
N11—C11	1.334 (2)	C21—C22	1.502 (3)
N11—C15	1.346 (2)	C21—H21A	0.9800
C11—C12	1.383 (2)	C21—H21B	0.9800
C11—H11	0.9500	C21—H21C	0.9800
C12—C13	1.386 (2)	C22—O21	1.435 (2)
C12—H12	0.9500	C22—H22A	0.9900
C13—C14	1.381 (3)	C22—H22B	0.9900
C13—C16	1.505 (2)	O21—H1O1	0.8400
N1^i—Mn1—N1	180.0	C13—C14—H14	120.2
N1^i—Mn1—O21^i	88.59 (5)	C15—C14—H14	120.2
N1—Mn1—O21^i	91.41 (5)	N11—C15—C14	123.05 (16)
N1^i—Mn1—O21	91.41 (5)	N11—C15—H15	118.5
N1—Mn1—O21	88.59 (5)	C14—C15—H15	118.5
O21^i—Mn1—O21	180.0	O11—C16—C17	122.10 (16)
N1^i—Mn1—N11^i	91.13 (5)	O11—C16—C13	118.40 (17)
N1—Mn1—N11^i	88.87 (5)	C17—C16—C13	119.49 (16)
O21^i—Mn1—N11^i	92.35 (5)	C16—C17—H17A	109.5
O21—Mn1—N11^i	87.65 (5)	C16—C17—H17B	109.5
N1^i—Mn1—N11	88.87 (5)	H17A—C17—H17B	109.5
N1—Mn1—N11	91.13 (5)	C16—C17—H17C	109.5
O21^i—Mn1—N11	87.65 (5)	H17A—C17—H17C	109.5
O21—Mn1—N11	92.35 (5)	H17B—C17—H17C	109.5
N11^i—Mn1—N11	180.0	C22—C21—H21A	109.5
C1—N1—Mn1	164.93 (13)	C22—C21—H21B	109.5
N1—C1—S1	178.67 (16)	H21A—C21—H21B	109.5
C11—N11—C15	116.73 (14)	C22—C21—H21C	109.5
C11—N11—Mn1	121.49 (11)	H21A—C21—H21C	109.5
C15—N11—Mn1	121.25 (11)	H21B—C21—H21C	109.5
N11—C11—C12	123.87 (16)	O21—C22—C21	112.19 (18)
N11—C11—H11	118.1	O21—C22—H22A	109.2
C12—C11—H11	118.1	C21—C22—H22A	109.2
C11—C12—C13	118.96 (17)	O21—C22—H22B	109.2
C11—C12—H12	120.5	C21—C22—H22B	109.2
C13—C12—H12	120.5	H22A—C22—H22B	107.9
C14—C13—C12	117.87 (15)	C22—O21—Mn1	130.79 (11)
C14—C13—C16	119.69 (15)	C22—O21—H1O1	105.5
C12—C13—C16	122.44 (16)	Mn1—O21—H1O1	120.2
C13—C14—C15	119.50 (15)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H1O1···O11^ii	0.84	1.95	2.7714 (17)	164

Symmetry code: (ii) x, y+1, z+1.