Tetra­kis(1-allyl-1H-imidazole-κN3)bis­(thio­cyanato-κN)manganese(II)

Zhao, J.; Jin, Y.-L.

doi:10.1107/S1600536811051282

Tetrakis(1-allyl-1H-imidazole-κN³)bis(thiocyanato-κN)manganese(II)

The structure of the title compound, [Mn(NCS)₂(C₆H₈N₂)₄], consists of isolated molecules of [Mn(NCS)₂(Aim)₄] (Aim = 1-allylimidazole), which contain a compressed octahedral MnN₆ chromophore (site symmetry $\overline1$ ). The NCS⁻ anions are trans and four N atoms from the Aim ligands define the equatorial plane. The mean Mn—N(Aim) and Mn—N(NCS) distances are 2.270 and 2.229 Å, respectively. Weak C—H

N interactions contribute to the crystal packing stability.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811051282/hg5141sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811051282/hg5141Isup2.hkl Contains datablock I
	Chemdraw file https://doi.org/10.1107/S1600536811051282/hg5141Isup3.cdx Supplementary material

CCDC reference: 861672

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.009 Å
R factor = 0.059
wR factor = 0.162
Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT234_ALERT_4_C Large Hirshfeld Difference C1     --  C2      ..       0.16 Ang.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0092 Ang
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A    ..  N4      ..       2.88 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5B    ..  N4      ..       2.82 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12A   ..  N5      ..       2.72 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

   2 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
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

The molecular structure of (I) is shown in Fig. 1. The Mn atom displays an octahedral coordination geometry, with six N atoms from two thiocyanate anions and four 1-allylimidazole ligands. The equatorial plane of the complex is formed by four Mn—N(1-allylimadazole) bonds with lengths of 2.269 (3) and 2.271 (3) Å, and the axial positions are occupied by two N-bonded NCS groups [Mn—N(NCS) = 2.229 (4) Å]. These values agree well with those observed in [Mn(NCS)₂(1-ethylimidazole)₄] (Liu et al., 2008). The values of the bond angles around manganese are close to those expected for a regular octahedral geometry, the N—Mn—N angles range from 88.32 (13) to 91.68 (13) °, and the thiocyanate ligands are almost linear. Weak C—H···N interactions contribute to the crystal packing stability.

In the corresponding manganese compound [Mn(NCS)₂(1-ethylimidazole)₄] (Liu, et al., 2008), the Mn^II ions have a distorted octahedral environment.

Related literature top

In the corresponding manganese compound [Mn(NCS)₂(1-ethylimidazole)₄] (Liu, et al., 2008), the Mn^II ions have a distorted octahedral environment.

Experimental top

The title compound was prepared by the reaction of 1-allylimidazole (1.21 g, 20 mmol) with MnCl₂.4H₂O(0.99 g, 5 mmol) and potassium thiocyanate (0.98 g, 10 mmol) by means of hydrothermal synthesis in stainless-steel reactor with Teflon liner at 383 K for 24 h. Analysis, calculated for C₂₆H₃₂MnN₁₀S₂: C 51.73, H 5.34, N 23.20%; found: C 51.97, H 5.29, N 23.01%. Single crystals suitable for X-ray measurements were obtained by recrystallization from methanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing of (I), viewed down the b axis.

Tetrakis(1-allyl-1H-imidazole-κN³)bis(thiocyanato- κN)manganese(II) top

Crystal data top

[Mn(NCS)₂(C₆H₈N₂)₄]	F(000) = 1260
M_r = 603.70	D_x = 1.297 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 24.564 (5) Å	θ = 9–12°
b = 7.2200 (14) Å	µ = 0.60 mm⁻¹
c = 21.287 (4) Å	T = 293 K
β = 125.04 (3)°	Block, colorless
V = 3091.0 (15) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2814 independent reflections
Radiation source: fine-focus sealed tube	1750 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
thin–slice ω scans	θ_max = 25.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = 0→29
T_min = 0.890, T_max = 0.943	k = 0→8
2885 measured reflections	l = −25→20

Refinement top

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
2814 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Mn(NCS)₂(C₆H₈N₂)₄]	V = 3091.0 (15) Å³
M_r = 603.70	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.564 (5) Å	µ = 0.60 mm⁻¹
b = 7.2200 (14) Å	T = 293 K
c = 21.287 (4) Å	0.20 × 0.10 × 0.10 mm
β = 125.04 (3)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2814 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1750 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.943	R_int = 0.033
2885 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.01	Δρ_max = 0.31 e Å⁻³
2814 reflections	Δρ_min = −0.34 e Å⁻³
178 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

	x	y	z	U_iso*/U_eq
Mn	0.2500	0.7500	0.0000	0.0393 (3)
S	0.38490 (7)	1.1290 (2)	0.23301 (7)	0.0754 (5)
N1	0.20466 (18)	0.4508 (6)	0.1457 (2)	0.0542 (10)
N2	0.21204 (16)	0.6197 (5)	0.06496 (19)	0.0447 (9)
N3	0.41287 (16)	0.3410 (5)	0.0976 (2)	0.0457 (9)
N4	0.34393 (16)	0.5759 (5)	0.06687 (19)	0.0448 (9)
N5	0.29713 (18)	0.9709 (5)	0.0893 (2)	0.0543 (10)
C1	0.1320 (3)	0.1161 (10)	0.1924 (4)	0.116 (3)
H1A	0.1358	0.1802	0.2327	0.139*
H1B	0.1016	0.0196	0.1686	0.139*
C2	0.1692 (3)	0.1613 (9)	0.1695 (3)	0.0911 (19)
H2A	0.1640	0.0938	0.1291	0.109*
C3	0.2181 (3)	0.3078 (8)	0.2018 (3)	0.0725 (16)
H3A	0.2616	0.2548	0.2227	0.087*
H3B	0.2191	0.3649	0.2437	0.087*
C4	0.1559 (2)	0.5784 (7)	0.1165 (3)	0.0570 (13)
H4A	0.1250	0.5921	0.1281	0.068*
C5	0.1607 (2)	0.6819 (7)	0.0675 (3)	0.0540 (12)
H5B	0.1332	0.7812	0.0394	0.065*
C6	0.2375 (2)	0.4801 (7)	0.1133 (3)	0.0533 (12)
H6A	0.2736	0.4103	0.1238	0.064*
C7	0.4849 (3)	0.2836 (9)	0.0313 (3)	0.0841 (18)
H7A	0.4652	0.3981	0.0257	0.101*
H7B	0.5106	0.2656	0.0126	0.101*
C8	0.4765 (2)	0.1509 (8)	0.0647 (3)	0.0626 (14)
H8A	0.4972	0.0392	0.0689	0.075*
C9	0.4373 (2)	0.1569 (7)	0.0974 (3)	0.0577 (13)
H9A	0.3996	0.0740	0.0683	0.069*
H9B	0.4647	0.1113	0.1497	0.069*
C10	0.4487 (2)	0.4823 (7)	0.1465 (3)	0.0584 (13)
H10A	0.4939	0.4811	0.1855	0.070*
C11	0.4066 (2)	0.6240 (7)	0.1280 (3)	0.0556 (12)
H11A	0.4182	0.7378	0.1530	0.067*
C12	0.3500 (2)	0.4037 (7)	0.0506 (2)	0.0470 (11)
H12A	0.3150	0.3340	0.0114	0.056*
C13	0.3337 (2)	1.0360 (6)	0.1494 (3)	0.0467 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0374 (5)	0.0426 (5)	0.0373 (5)	0.0014 (5)	0.0210 (4)	0.0017 (5)
S	0.0671 (9)	0.1062 (13)	0.0473 (8)	−0.0215 (8)	0.0295 (7)	−0.0212 (8)
N1	0.048 (2)	0.070 (3)	0.047 (2)	−0.002 (2)	0.0289 (19)	0.012 (2)
N2	0.047 (2)	0.049 (2)	0.042 (2)	0.0012 (18)	0.0277 (17)	0.0060 (19)
N3	0.0365 (19)	0.052 (2)	0.047 (2)	0.0070 (18)	0.0229 (17)	0.0047 (19)
N4	0.040 (2)	0.050 (2)	0.041 (2)	0.0055 (18)	0.0210 (17)	0.0058 (18)
N5	0.056 (2)	0.052 (2)	0.053 (2)	−0.010 (2)	0.030 (2)	−0.011 (2)
C1	0.107 (5)	0.108 (6)	0.130 (6)	−0.023 (5)	0.067 (5)	0.032 (5)
C2	0.116 (5)	0.065 (4)	0.073 (4)	−0.007 (4)	0.043 (4)	0.011 (3)
C3	0.069 (3)	0.081 (4)	0.064 (3)	−0.003 (3)	0.036 (3)	0.023 (3)
C4	0.055 (3)	0.072 (3)	0.056 (3)	−0.001 (3)	0.039 (2)	0.002 (3)
C5	0.059 (3)	0.052 (3)	0.056 (3)	0.004 (2)	0.036 (3)	0.003 (2)
C6	0.049 (3)	0.060 (3)	0.051 (3)	0.007 (2)	0.029 (2)	0.010 (3)
C7	0.093 (4)	0.094 (5)	0.094 (4)	0.008 (4)	0.070 (4)	0.001 (4)
C8	0.057 (3)	0.062 (3)	0.073 (3)	0.008 (3)	0.040 (3)	−0.007 (3)
C9	0.051 (3)	0.052 (3)	0.067 (3)	0.009 (2)	0.032 (3)	0.007 (3)
C10	0.041 (3)	0.070 (4)	0.052 (3)	0.005 (3)	0.020 (2)	−0.006 (3)
C11	0.049 (3)	0.056 (3)	0.054 (3)	−0.001 (2)	0.025 (2)	−0.010 (3)
C12	0.039 (2)	0.055 (3)	0.044 (2)	0.002 (2)	0.022 (2)	0.002 (2)
C13	0.046 (3)	0.048 (3)	0.054 (3)	0.003 (2)	0.033 (2)	0.003 (2)

Geometric parameters (Å, º) top

Mn—N5ⁱ	2.229 (4)	C1—H1B	0.9300
Mn—N5	2.229 (4)	C2—C3	1.444 (7)
Mn—N2	2.269 (3)	C2—H2A	0.9300
Mn—N2ⁱ	2.269 (3)	C3—H3A	0.9700
Mn—N4ⁱ	2.271 (3)	C3—H3B	0.9700
Mn—N4	2.271 (3)	C4—C5	1.342 (6)
S—C13	1.621 (5)	C4—H4A	0.9300
N1—C6	1.345 (5)	C5—H5B	0.9300
N1—C4	1.346 (6)	C6—H6A	0.9300
N1—C3	1.465 (6)	C7—C8	1.279 (7)
N2—C6	1.315 (5)	C7—H7A	0.9300
N2—C5	1.368 (5)	C7—H7B	0.9300
N3—C12	1.348 (5)	C8—C9	1.477 (6)
N3—C10	1.358 (6)	C8—H8A	0.9300
N3—C9	1.460 (6)	C9—H9A	0.9700
N4—C12	1.322 (5)	C9—H9B	0.9700
N4—C11	1.373 (5)	C10—C11	1.342 (6)
N5—C13	1.160 (5)	C10—H10A	0.9300
C1—C2	1.301 (8)	C11—H11A	0.9300
C1—H1A	0.9300	C12—H12A	0.9300

N5ⁱ—Mn—N5	180.0 (2)	N1—C3—H3A	109.0
N5ⁱ—Mn—N2	91.68 (13)	C2—C3—H3B	109.0
N5—Mn—N2	88.32 (13)	N1—C3—H3B	109.0
N5ⁱ—Mn—N2ⁱ	88.32 (13)	H3A—C3—H3B	107.8
N5—Mn—N2ⁱ	91.68 (13)	C5—C4—N1	106.8 (4)
N2—Mn—N2ⁱ	180.00 (19)	C5—C4—H4A	126.6
N5ⁱ—Mn—N4ⁱ	91.04 (14)	N1—C4—H4A	126.6
N5—Mn—N4ⁱ	88.96 (14)	C4—C5—N2	110.0 (4)
N2—Mn—N4ⁱ	89.22 (12)	C4—C5—H5B	125.0
N2ⁱ—Mn—N4ⁱ	90.78 (12)	N2—C5—H5B	125.0
N5ⁱ—Mn—N4	88.96 (14)	N2—C6—N1	111.5 (4)
N5—Mn—N4	91.04 (14)	N2—C6—H6A	124.2
N2—Mn—N4	90.78 (12)	N1—C6—H6A	124.2
N2ⁱ—Mn—N4	89.22 (12)	C8—C7—H7A	120.0
N4ⁱ—Mn—N4	180.0	C8—C7—H7B	120.0
C6—N1—C4	106.9 (4)	H7A—C7—H7B	120.0
C6—N1—C3	127.5 (4)	C7—C8—C9	126.7 (5)
C4—N1—C3	125.6 (4)	C7—C8—H8A	116.7
C6—N2—C5	104.8 (4)	C9—C8—H8A	116.7
C6—N2—Mn	128.2 (3)	N3—C9—C8	114.1 (4)
C5—N2—Mn	126.8 (3)	N3—C9—H9A	108.7
C12—N3—C10	106.2 (4)	C8—C9—H9A	108.7
C12—N3—C9	127.0 (4)	N3—C9—H9B	108.7
C10—N3—C9	126.9 (4)	C8—C9—H9B	108.7
C12—N4—C11	104.6 (4)	H9A—C9—H9B	107.6
C12—N4—Mn	125.7 (3)	C11—C10—N3	107.3 (4)
C11—N4—Mn	129.6 (3)	C11—C10—H10A	126.4
C13—N5—Mn	157.6 (4)	N3—C10—H10A	126.4
C2—C1—H1A	120.0	C10—C11—N4	109.9 (4)
C2—C1—H1B	120.0	C10—C11—H11A	125.0
H1A—C1—H1B	120.0	N4—C11—H11A	125.0
C1—C2—C3	125.2 (7)	N4—C12—N3	112.0 (4)
C1—C2—H2A	117.4	N4—C12—H12A	124.0
C3—C2—H2A	117.4	N3—C12—H12A	124.0
C2—C3—N1	113.1 (4)	N5—C13—S	179.4 (5)
C2—C3—H3A	109.0

N5ⁱ—Mn—N2—C6	81.3 (4)	C4—N1—C3—C2	72.8 (7)
N5—Mn—N2—C6	−98.7 (4)	C6—N1—C4—C5	−0.2 (5)
N4ⁱ—Mn—N2—C6	172.3 (4)	C3—N1—C4—C5	−179.9 (4)
N4—Mn—N2—C6	−7.7 (4)	N1—C4—C5—N2	0.5 (6)
N5ⁱ—Mn—N2—C5	−105.3 (4)	C6—N2—C5—C4	−0.5 (5)
N5—Mn—N2—C5	74.7 (4)	Mn—N2—C5—C4	−175.1 (3)
N4ⁱ—Mn—N2—C5	−14.3 (4)	C5—N2—C6—N1	0.3 (5)
N4—Mn—N2—C5	165.7 (4)	Mn—N2—C6—N1	174.8 (3)
N5ⁱ—Mn—N4—C12	−8.1 (3)	C4—N1—C6—N2	−0.1 (5)
N5—Mn—N4—C12	171.9 (3)	C3—N1—C6—N2	179.6 (4)
N2—Mn—N4—C12	83.6 (3)	C12—N3—C9—C8	105.3 (5)
N2ⁱ—Mn—N4—C12	−96.4 (3)	C10—N3—C9—C8	−76.3 (6)
N5ⁱ—Mn—N4—C11	167.3 (4)	C7—C8—C9—N3	−7.1 (8)
N5—Mn—N4—C11	−12.7 (4)	C12—N3—C10—C11	0.5 (5)
N2—Mn—N4—C11	−101.0 (4)	C9—N3—C10—C11	−178.2 (4)
N2ⁱ—Mn—N4—C11	79.0 (4)	N3—C10—C11—N4	−0.7 (6)
N2—Mn—N5—C13	67.0 (9)	C12—N4—C11—C10	0.7 (5)
N2ⁱ—Mn—N5—C13	−113.0 (9)	Mn—N4—C11—C10	−175.4 (3)
N4ⁱ—Mn—N5—C13	156.3 (9)	C11—N4—C12—N3	−0.4 (5)
N4—Mn—N5—C13	−23.7 (9)	Mn—N4—C12—N3	175.9 (3)
C1—C2—C3—N1	−120.3 (7)	C10—N3—C12—N4	−0.1 (5)
C6—N1—C3—C2	−106.9 (6)	C9—N3—C12—N4	178.6 (4)

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N3	0.93	2.54	2.857 (9)	101
C6—H6A···N4	0.93	2.88	3.355 (8)	113
C5—H5B···N4ⁱ	0.93	2.82	3.298 (7)	113
C12—H12A···N5ⁱ	0.93	2.72	3.224 (6)	115

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	[Mn(NCS)₂(C₆H₈N₂)₄]
M_r	603.70
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	24.564 (5), 7.2200 (14), 21.287 (4)
β (°)	125.04 (3)
V (Å³)	3091.0 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.890, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	2885, 2814, 1750
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.162, 1.01
No. of reflections	2814
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.34

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N3	0.93	2.537	2.857 (9)	100.57
C6—H6A···N4	0.93	2.878	3.355 (8)	113.26
C5—H5B···N4ⁱ	0.93	2.821	3.298 (7)	113.07
C12—H12A···N5ⁱ	0.93	2.718	3.224 (6)	115.03

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Tetra­kis(1-allyl-1H-imidazole-κN3)bis­(thio­cyanato-κN)manganese(II)

Supporting information

Key indicators

checkCIF/PLATON results

Tetrakis(1-allyl-1H-imidazole-κN³)bis(thiocyanato-κN)manganese(II)