Crystal structure of bis­[4-(di­methyl­amino)­pyridine-κN¹]bis­(methanol-κO)bis­(thio­cyanato-κN)manganese(II)

The whole mol­ecule of the title compound, [Mn(NCS)₂(CH₃OH)₂(C₅H₆N₂)₂], is generated by inversion symmetry. The Mn^II ion, which is located on an inversion center, is coordinated by two 4-(di­methyl­amino)­pyridine ligands, two methanol ligands and two terminally N-bonded thio­cyanate anions, forming a slightly distorted octa­hedron. In the crystal, mol­ecules are linked by O—H...S hydrogen bonds, forming chains extending along the a-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.100
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.969 Note
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         65 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4 Note

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.01100 Degree
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C1      ..        5.7 su
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C17 Check
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         28 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
   6 ALERT level G = General information/check it is not something unexpected

   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
   4 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 and 4-(di­methyl­amino)­pyridine and Ba(NCS)₂.3 H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂.3 H₂O and 9.88 g (58.44 mmol) MnSO₄.H₂O in 300 mL H₂O at room temperature for three hours. The white precipitate of BaSO₄ was filtered of and the solvent removed with 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 (0.18 mmol) 30.8 mg Mn(NCS)₂ and (0.3 mmol) 36.7 mg 4-(di­methyl­amino)­pyridine in 1.0 mL methanol at room temperature. After a few days colorless plate shaped crystals of the title compound were obtained.

S2. Refinement

The C—H H atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) = 1.2 U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic and and C—H = 0.98 Å for methyl H atoms. The O—H H atom was located in a difference map, its bond length set to ideal values of 0.85 Å and refined with U_iso(H) = 1.5 U_eq(O)using a riding model.

Related literature

For the structure of another discrete complex with 4-(dimethylamino)pyridine and thiocyanate ligands, see: Chen et al. (2007). For general background to this work, see: Näther et al. (2013).

Structure description

For the structure of another discrete complex with 4-(dimethylamino)pyridine and thiocyanate ligands, see: Chen et al. (2007). For general background to this work, see: Näther et al. (2013).

Synthesis and crystallization

MnSO₄.H₂O was purchased from Merck and 4-(di­methyl­amino)­pyridine and Ba(NCS)₂.3 H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂.3 H₂O and 9.88 g (58.44 mmol) MnSO₄.H₂O in 300 mL H₂O at room temperature for three hours. The white precipitate of BaSO₄ was filtered of and the solvent removed with 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 (0.18 mmol) 30.8 mg Mn(NCS)₂ and (0.3 mmol) 36.7 mg 4-(di­methyl­amino)­pyridine in 1.0 mL methanol at room temperature. After a few days colorless plate shaped crystals of the title compound were obtained.

Refinement details

The C—H H atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) = 1.2 U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic and and C—H = 0.98 Å for methyl H atoms. The O—H H atom was located in a difference map, its bond length set to ideal values of 0.85 Å and refined with U_iso(H) = 1.5 U_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. Structure of the title complex with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: i = -x+1,-y,-z+1.
	Fig. 2. Crystal structure of the title compound viewed perpendicular to the crystallographic a,c plane.

Bis[4-(dimethylamino)pyridine-κN¹]bis(methanol-κO)bis(thiocyanato-κN)manganese(II)

Crystal data

[Mn(NCS)2(CH4O)2(C5H6N2)2]	Z = 1
Mr = 479.52	F(000) = 251
Triclinic, P1	Dx = 1.362 Mg m^−3
a = 7.0771 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1586 (8) Å	Cell parameters from 4585 reflections
c = 10.6491 (10) Å	θ = 2.6–27.0°
α = 76.381 (11)°	µ = 0.77 mm^−1
β = 81.672 (11)°	T = 180 K
γ = 79.809 (11)°	Plate, colorless
V = 584.72 (10) Å^3	0.16 × 0.10 × 0.04 mm

Data collection

Stoe IPDS-1 diffractometer	1885 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
phi scans	θmax = 27.0°, θmin = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −9→9
Tmin = 0.903, Tmax = 0.959	k = −10→10
4585 measured reflections	l = −13→13
2459 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0598P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2459 reflections	Δρmax = 0.30 e Å^−3
133 parameters	Δρmin = −0.59 e Å^−3

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	0.5000	0.0000	0.5000	0.02111 (15)
N1	0.6294 (3)	0.0926 (3)	0.63997 (19)	0.0312 (5)
C1	0.7395 (3)	0.1199 (3)	0.7004 (2)	0.0236 (5)
S1	0.89299 (9)	0.15954 (10)	0.78630 (6)	0.0394 (2)
O31	0.2205 (2)	0.1737 (2)	0.53900 (16)	0.0339 (4)
H1O	0.1462	0.1444	0.6079	0.051*
C31	0.0945 (4)	0.2643 (4)	0.4439 (3)	0.0486 (7)
H31A	−0.0136	0.3337	0.4847	0.073*
H31B	0.0448	0.1828	0.4074	0.073*
H31C	0.1659	0.3386	0.3743	0.073*
N11	0.5945 (3)	0.2090 (2)	0.33954 (17)	0.0222 (4)
N12	0.7263 (3)	0.6192 (2)	0.03652 (18)	0.0274 (4)
C11	0.5795 (3)	0.3682 (3)	0.3576 (2)	0.0264 (5)
H11	0.5369	0.3866	0.4427	0.032*
C12	0.6210 (3)	0.5063 (3)	0.2624 (2)	0.0252 (5)
H12	0.6057	0.6157	0.2825	0.030*
C13	0.6867 (3)	0.4861 (3)	0.1345 (2)	0.0210 (4)
C14	0.7077 (3)	0.3182 (3)	0.1162 (2)	0.0230 (4)
H14	0.7554	0.2942	0.0334	0.028*
C15	0.6594 (3)	0.1895 (3)	0.2177 (2)	0.0235 (5)
H15	0.6727	0.0783	0.2011	0.028*
C16	0.6858 (4)	0.7919 (3)	0.0569 (3)	0.0353 (6)
H16A	0.7210	0.8713	−0.0243	0.053*
H16B	0.7612	0.8015	0.1244	0.053*
H16C	0.5479	0.8196	0.0844	0.053*
C17	0.7938 (3)	0.5957 (3)	−0.0944 (2)	0.0309 (5)
H17A	0.8140	0.7059	−0.1514	0.046*
H17B	0.6972	0.5482	−0.1267	0.046*
H17C	0.9158	0.5171	−0.0934	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0216 (2)	0.0237 (3)	0.0185 (2)	−0.00575 (18)	0.00127 (17)	−0.00564 (18)
N1	0.0330 (10)	0.0364 (12)	0.0282 (10)	−0.0112 (9)	−0.0016 (8)	−0.0117 (9)
C1	0.0254 (11)	0.0242 (11)	0.0201 (10)	−0.0035 (8)	0.0040 (8)	−0.0067 (9)
S1	0.0261 (3)	0.0703 (5)	0.0288 (3)	−0.0110 (3)	0.0005 (2)	−0.0240 (3)
O31	0.0250 (8)	0.0444 (11)	0.0258 (8)	0.0030 (7)	0.0033 (6)	−0.0046 (8)
C31	0.0373 (15)	0.062 (2)	0.0343 (14)	0.0113 (13)	−0.0022 (11)	−0.0017 (13)
N11	0.0272 (9)	0.0210 (9)	0.0188 (9)	−0.0037 (7)	0.0014 (7)	−0.0070 (7)
N12	0.0300 (10)	0.0241 (10)	0.0248 (10)	−0.0039 (8)	0.0015 (8)	−0.0017 (8)
C11	0.0325 (12)	0.0263 (12)	0.0210 (11)	−0.0043 (9)	0.0028 (8)	−0.0100 (9)
C12	0.0306 (11)	0.0201 (11)	0.0267 (11)	−0.0032 (9)	−0.0011 (9)	−0.0100 (9)
C13	0.0143 (9)	0.0245 (11)	0.0238 (10)	−0.0031 (8)	−0.0019 (7)	−0.0040 (9)
C14	0.0205 (10)	0.0270 (11)	0.0210 (10)	−0.0009 (8)	0.0022 (8)	−0.0090 (9)
C15	0.0222 (10)	0.0242 (11)	0.0258 (11)	−0.0021 (8)	0.0013 (8)	−0.0119 (9)
C16	0.0405 (14)	0.0234 (12)	0.0399 (14)	−0.0064 (10)	−0.0011 (11)	−0.0034 (11)
C17	0.0274 (11)	0.0402 (14)	0.0217 (11)	−0.0070 (10)	−0.0001 (9)	0.0001 (10)

Geometric parameters (Å, º)

Mn1—N1^i	2.192 (2)	N12—C16	1.448 (3)
Mn1—N1	2.192 (2)	N12—C17	1.452 (3)
Mn1—N11	2.2302 (17)	C11—C12	1.370 (3)
Mn1—N11^i	2.2302 (17)	C11—H11	0.9500
Mn1—O31	2.2676 (17)	C12—C13	1.412 (3)
Mn1—O31^i	2.2676 (17)	C12—H12	0.9500
N1—C1	1.160 (3)	C13—C14	1.408 (3)
C1—S1	1.634 (2)	C14—C15	1.368 (3)
O31—C31	1.429 (3)	C14—H14	0.9500
O31—H1O	0.8500	C15—H15	0.9500
C31—H31A	0.9800	C16—H16A	0.9800
C31—H31B	0.9800	C16—H16B	0.9800
C31—H31C	0.9800	C16—H16C	0.9800
N11—C11	1.341 (3)	C17—H17A	0.9800
N11—C15	1.349 (3)	C17—H17B	0.9800
N12—C13	1.355 (3)	C17—H17C	0.9800
N1^i—Mn1—N1	180.0	C13—N12—C17	121.3 (2)
N1^i—Mn1—N11	89.19 (7)	C16—N12—C17	117.81 (19)
N1—Mn1—N11	90.81 (7)	N11—C11—C12	124.8 (2)
N1^i—Mn1—N11^i	90.81 (7)	N11—C11—H11	117.6
N1—Mn1—N11^i	89.19 (7)	C12—C11—H11	117.6
N11—Mn1—N11^i	180.0	C11—C12—C13	120.0 (2)
N1^i—Mn1—O31	90.50 (7)	C11—C12—H12	120.0
N1—Mn1—O31	89.50 (7)	C13—C12—H12	120.0
N11—Mn1—O31	89.07 (6)	N12—C13—C14	122.6 (2)
N11^i—Mn1—O31	90.93 (6)	N12—C13—C12	122.2 (2)
N1^i—Mn1—O31^i	89.50 (7)	C14—C13—C12	115.22 (19)
N1—Mn1—O31^i	90.50 (7)	C15—C14—C13	120.1 (2)
N11—Mn1—O31^i	90.93 (6)	C15—C14—H14	120.0
N11^i—Mn1—O31^i	89.07 (6)	C13—C14—H14	120.0
O31—Mn1—O31^i	180.0	N11—C15—C14	124.7 (2)
C1—N1—Mn1	162.79 (19)	N11—C15—H15	117.6
N1—C1—S1	179.4 (2)	C14—C15—H15	117.6
C31—O31—Mn1	125.44 (16)	N12—C16—H16A	109.5
C31—O31—H1O	105.1	N12—C16—H16B	109.5
Mn1—O31—H1O	119.1	H16A—C16—H16B	109.5
O31—C31—H31A	109.5	N12—C16—H16C	109.5
O31—C31—H31B	109.5	H16A—C16—H16C	109.5
H31A—C31—H31B	109.5	H16B—C16—H16C	109.5
O31—C31—H31C	109.5	N12—C17—H17A	109.5
H31A—C31—H31C	109.5	N12—C17—H17B	109.5
H31B—C31—H31C	109.5	H17A—C17—H17B	109.5
C11—N11—C15	115.11 (18)	N12—C17—H17C	109.5
C11—N11—Mn1	120.90 (14)	H17A—C17—H17C	109.5
C15—N11—Mn1	123.89 (15)	H17B—C17—H17C	109.5
C13—N12—C16	120.6 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H1O···S1^ii	0.85	2.42	3.2409 (18)	161

Symmetry code: (ii) x−1, y, z.