(Pyridino-15-crown-5-κ5N,O,O′,O′′,O′′′)bis­(thio­cyanato-κN)manganese(II)

Li, C.; Feng, Z.; Li, D.; Wang, D.

doi:10.1107/S160053680800679X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m557

doi:10.1107/S160053680800679X

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(Pyridino-15-crown-5-κ⁵N,O,O′,O′′,O′′′)bis(thiocyanato-κN)manganese(II)

Chengjuan Li,^a Zejing Feng,^a Dacheng Li ^a ^* and Daqi Wang ^a

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: dougroup@163.com

(Received 21 November 2007; accepted 11 March 2008; online 14 March 2008)

The title complex, [Mn(NCS)₂(C₁₃H₁₉NO₄)] {systematic name: [3,6,9,12-tetraoxa-18-azabicyclo[12.3.1]octacosa-14(18),15,17-triene-κ⁵N,O,O′,O′′,O′′′]bis(thiocyanato-κN)manganese(II)}, was obtained by the reaction of MnCl₂·4H₂O and NaSCN with pyridino-15-crown-5. The Mn²⁺ center has a distorted pentagonal bipyramidal coordination geometry, coordinated by four O atoms and one N atom of the pyridino-15-crown-5 molecule, and by the N atoms of the two NCS⁻ ligands.

Related literature

For the coordination ability of pyridine crown ethers with transition metals, see: Lamb et al. (1980 ). For Mn—N(NCS) and Mn—O bond-length data, see: Wei et al. (1997 ).

Experimental

Crystal data

[Mn(NCS)₂(C₁₃H₁₉NO₄)]
M_r = 424.39
Monoclinic, P 2₁ /c
a = 15.211 (5) Å
b = 15.789 (5) Å
c = 7.868 (2) Å
β = 98.667 (4)°
V = 1868.0 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 273 (2) K
0.42 × 0.35 × 0.31 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.690, T_max = 0.756
9681 measured reflections
3294 independent reflections
2266 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.113
S = 1.04
3294 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800679X/rn2037sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800679X/rn2037Isup2.hkl

checkCIF report

Comment top

The crown ethers, especially those containing one or more pyridine units have special coordination abilities with transition metal ions (Lamb et al., 1980). To the best of our knowledge, this is the first crystal structure of the P15—C-5 complex. We report here the synthesis and structure of an Mn²⁺ complex with the P15—C-5 ligand. The title complex consists of one Mn²⁺ ion bound to one P15—C-5 and two NCS^- ligands. The Mn²⁺ ion is coordinated by four O atoms, one N atom of the P15—C-5 and two N atoms of the NCS^- ligands. The O1, O2, O3, O4, N1 atoms of the P15—C-5 crown ether are approximately co-planar and the two NCS^- ligands occupy the axial sites to form a distorted pentagonal bipyramid. Every O—Mn—O (or N) bond angle in the plane is nearly 72°, indicating that Mn²⁺ is situated at the center of the pentagon and the N,O atoms are located on the five corners. The average Mn—O [2.260 (3) Å] and Mn—N(NCS) [2.191 (3) Å] bond lengths are slightly bigger than the corresponding values in the complex [Mn(15—C-5)](SCN)₂ [average 2.232 (5)Å and 2.130 (6) Å, respectively] (Wei et al., 1997).

Related literature top

For the coordination ability of pyridine crown ether with transition metals, see: Lamb et al. (1980). For Mn—N(NCS) and Mn—O bond-length data, see: Wei et al. (1997).

Experimental top

To a solution of pyridino-15-crown-5 (0.1265 g, 0.5 mmol) in 5 ml 1,2-dichloroethane was added 5 ml of an aqueous solution of MnCl₂.4H₂O (0.394 g, 2 mmol) and NaSCN (0.80 g, 1 mmol). The mixture was stirred for 2 hrs at room temperature and then separated. Single crystals of (1) were obtained by evaporation of the substrate (m.p. 447–449 K). Analysis calculated for C₁₅H₁₉MnN₃O₄S₂: C 42.45, H 4.48, N 9.91%; found: C 42.39, H 4.38, N 10.10%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

[3,6,9,12-tetraoxa-18-azabicyclo[12.3.1]octacosa- 14 (18),15,17-triene-κ⁵N,O,O',O'',O''']bis(thiocyanato-κN)manganese(II) top

Crystal data top

[Mn(NCS)₂(C₁₃H₁₉NO₄)]	F(000) = 876
M_r = 424.39	D_x = 1.509 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.211 (5) Å	Cell parameters from 2838 reflections
b = 15.789 (5) Å	θ = 2.6–23.5°
c = 7.868 (2) Å	µ = 0.95 mm⁻¹
β = 98.667 (4)°	T = 273 K
V = 1868.0 (10) Å³	Block, colorless
Z = 4	0.42 × 0.35 × 0.31 mm

Data collection top

Bruker SMART diffractometer	3294 independent reflections
Radiation source: fine-focus sealed tube	2266 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→18
T_min = 0.690, T_max = 0.756	k = −18→18
9681 measured reflections	l = −9→8

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0368P)² + 2.3622P] where P = (F_o² + 2F_c²)/3
3294 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Mn(NCS)₂(C₁₃H₁₉NO₄)]	V = 1868.0 (10) Å³
M_r = 424.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.211 (5) Å	µ = 0.95 mm⁻¹
b = 15.789 (5) Å	T = 273 K
c = 7.868 (2) Å	0.42 × 0.35 × 0.31 mm
β = 98.667 (4)°

Data collection top

Bruker SMART diffractometer	3294 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2266 reflections with I > 2σ(I)
T_min = 0.690, T_max = 0.756	R_int = 0.035
9681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	Δρ_max = 0.63 e Å⁻³
3294 reflections	Δρ_min = −0.48 e Å⁻³
214 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
Mn1	0.74410 (4)	0.96629 (4)	0.17191 (7)	0.04475 (19)
S1	0.51780 (7)	0.82256 (8)	0.45275 (15)	0.0685 (3)
S2	0.85210 (10)	1.19638 (8)	−0.11436 (17)	0.0796 (4)
N1	0.85451 (18)	0.92824 (19)	0.3697 (4)	0.0412 (7)
N2	0.6473 (2)	0.8938 (2)	0.2869 (4)	0.0575 (7)
N3	0.8384 (2)	1.0415 (2)	0.0450 (4)	0.0566 (7)
O1	0.75950 (17)	1.06277 (16)	0.3868 (3)	0.0526 (7)
O2	0.80310 (17)	0.84282 (16)	0.0915 (3)	0.0516 (7)
O3	0.68245 (17)	0.94099 (19)	−0.1028 (3)	0.0591 (7)
O4	0.63527 (17)	1.06201 (18)	0.1082 (4)	0.0622 (8)
C1	0.7964 (3)	1.0295 (3)	0.5502 (5)	0.0608 (11)
H1A	0.7503	1.0027	0.6042	0.073*
H1B	0.8227	1.0747	0.6245	0.073*
C2	0.8661 (2)	0.9658 (2)	0.5227 (4)	0.0459 (9)
C3	0.9378 (3)	0.9460 (3)	0.6468 (5)	0.0596 (11)
H3	0.9451	0.9719	0.7542	0.072*
C4	0.9980 (3)	0.8868 (3)	0.6068 (6)	0.0661 (12)
H4	1.0468	0.8725	0.6877	0.079*
C5	0.9863 (3)	0.8492 (3)	0.4484 (5)	0.0576 (11)
H5	1.0270	0.8096	0.4201	0.069*
C6	0.9129 (2)	0.8712 (2)	0.3317 (5)	0.0440 (9)
C7	0.8949 (3)	0.8344 (3)	0.1544 (5)	0.0577 (11)
H7A	0.9296	0.8640	0.0793	0.069*
H7B	0.9116	0.7751	0.1575	0.069*
C8	0.7770 (3)	0.8223 (3)	−0.0868 (5)	0.0674 (12)
H8A	0.7808	0.7617	−0.1040	0.081*
H8B	0.8157	0.8504	−0.1564	0.081*
C9	0.6835 (3)	0.8517 (3)	−0.1365 (6)	0.0748 (14)
H9A	0.6635	0.8406	−0.2574	0.090*
H9B	0.6444	0.8222	−0.0697	0.090*
C10	0.5985 (3)	0.9822 (4)	−0.1445 (6)	0.0759 (14)
H10A	0.5533	0.9520	−0.0940	0.091*
H10B	0.5808	0.9839	−0.2682	0.091*
C11	0.6091 (3)	1.0704 (3)	−0.0733 (6)	0.0761 (14)
H11A	0.6541	1.1009	−0.1240	0.091*
H11B	0.5534	1.1012	−0.0979	0.091*
C12	0.6526 (3)	1.1394 (3)	0.2025 (6)	0.0741 (13)
H12A	0.5991	1.1736	0.1927	0.089*
H12B	0.6985	1.1716	0.1582	0.089*
C13	0.6826 (3)	1.1154 (3)	0.3863 (6)	0.0703 (13)
H13A	0.6976	1.1655	0.4559	0.084*
H13B	0.6361	1.0847	0.4319	0.084*
C14	0.5933 (3)	0.8648 (3)	0.3547 (5)	0.0575 (7)
C15	0.8454 (3)	1.1064 (3)	−0.0202 (5)	0.0566 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0393 (3)	0.0494 (4)	0.0448 (3)	0.0020 (3)	0.0038 (2)	0.0014 (3)
S1	0.0508 (6)	0.0893 (9)	0.0677 (7)	−0.0094 (6)	0.0163 (5)	0.0039 (6)
S2	0.1000 (10)	0.0599 (8)	0.0809 (9)	−0.0263 (7)	0.0198 (7)	−0.0050 (6)
N1	0.0364 (16)	0.0466 (18)	0.0405 (17)	−0.0005 (14)	0.0049 (13)	0.0040 (14)
N2	0.0462 (17)	0.0603 (18)	0.0659 (18)	−0.0026 (13)	0.0079 (13)	0.0037 (13)
N3	0.0511 (14)	0.075 (2)	0.0435 (15)	−0.0143 (15)	0.0065 (12)	−0.0042 (13)
O1	0.0518 (16)	0.0525 (16)	0.0554 (16)	0.0106 (13)	0.0145 (13)	−0.0077 (13)
O2	0.0526 (16)	0.0547 (16)	0.0474 (15)	0.0010 (13)	0.0069 (12)	−0.0103 (12)
O3	0.0454 (16)	0.076 (2)	0.0520 (16)	−0.0081 (14)	−0.0062 (12)	0.0020 (14)
O4	0.0485 (16)	0.0656 (19)	0.0708 (19)	0.0135 (14)	0.0037 (14)	0.0110 (15)
C1	0.068 (3)	0.073 (3)	0.043 (2)	−0.004 (2)	0.013 (2)	−0.008 (2)
C2	0.050 (2)	0.051 (2)	0.0370 (19)	−0.0083 (18)	0.0083 (17)	0.0059 (17)
C3	0.067 (3)	0.067 (3)	0.041 (2)	−0.024 (2)	−0.005 (2)	0.0091 (19)
C4	0.048 (2)	0.070 (3)	0.074 (3)	−0.010 (2)	−0.010 (2)	0.029 (2)
C5	0.046 (2)	0.056 (3)	0.068 (3)	0.0039 (19)	0.001 (2)	0.018 (2)
C6	0.040 (2)	0.040 (2)	0.052 (2)	−0.0001 (17)	0.0067 (17)	0.0092 (17)
C7	0.053 (3)	0.057 (3)	0.064 (3)	0.014 (2)	0.014 (2)	−0.004 (2)
C8	0.084 (3)	0.064 (3)	0.054 (3)	−0.004 (2)	0.008 (2)	−0.018 (2)
C9	0.080 (3)	0.086 (4)	0.054 (3)	−0.026 (3)	−0.004 (2)	−0.018 (2)
C10	0.047 (3)	0.116 (4)	0.059 (3)	−0.006 (3)	−0.010 (2)	0.011 (3)
C11	0.047 (3)	0.100 (4)	0.077 (3)	0.016 (3)	−0.004 (2)	0.030 (3)
C12	0.061 (3)	0.060 (3)	0.103 (4)	0.026 (2)	0.018 (3)	0.008 (3)
C13	0.068 (3)	0.061 (3)	0.086 (3)	0.018 (2)	0.027 (3)	−0.012 (2)
C14	0.0462 (17)	0.0603 (18)	0.0659 (18)	−0.0026 (13)	0.0079 (13)	0.0037 (13)
C15	0.0511 (14)	0.075 (2)	0.0435 (15)	−0.0143 (15)	0.0065 (12)	−0.0042 (13)

Geometric parameters (Å, º) top

Mn1—N2	2.168 (3)	C3—C4	1.377 (6)
Mn1—N1	2.195 (3)	C3—H3	0.9300
Mn1—N3	2.213 (3)	C4—C5	1.368 (6)
Mn1—O4	2.242 (3)	C4—H4	0.9300
Mn1—O3	2.259 (3)	C5—C6	1.380 (5)
Mn1—O1	2.262 (3)	C5—H5	0.9300
Mn1—O2	2.276 (3)	C6—C7	1.497 (5)
S1—C14	1.620 (4)	C7—H7A	0.9700
S2—C15	1.612 (5)	C7—H7B	0.9700
N1—C2	1.329 (4)	C8—C9	1.490 (6)
N1—C6	1.330 (4)	C8—H8A	0.9700
N2—C14	1.140 (5)	C8—H8B	0.9700
N3—C15	1.158 (5)	C9—H9A	0.9700
O1—C1	1.423 (5)	C9—H9B	0.9700
O1—C13	1.433 (5)	C10—C11	1.501 (7)
O2—C7	1.415 (4)	C10—H10A	0.9700
O2—C8	1.436 (5)	C10—H10B	0.9700
O3—C10	1.426 (5)	C11—H11A	0.9700
O3—C9	1.435 (5)	C11—H11B	0.9700
O4—C11	1.430 (5)	C12—C13	1.498 (6)
O4—C12	1.433 (5)	C12—H12A	0.9700
C1—C2	1.500 (5)	C12—H12B	0.9700
C1—H1A	0.9700	C13—H13A	0.9700
C1—H1B	0.9700	C13—H13B	0.9700
C2—C3	1.386 (5)

N2—Mn1—N1	93.15 (12)	C3—C4—H4	119.9
N2—Mn1—N3	177.51 (12)	C4—C5—C6	118.6 (4)
N1—Mn1—N3	89.32 (12)	C4—C5—H5	120.7
N2—Mn1—O4	85.63 (12)	C6—C5—H5	120.7
N1—Mn1—O4	143.47 (11)	N1—C6—C5	121.4 (4)
N3—Mn1—O4	92.55 (12)	N1—C6—C7	116.0 (3)
N2—Mn1—O3	95.50 (11)	C5—C6—C7	122.6 (4)
N1—Mn1—O3	142.50 (11)	O2—C7—C6	108.8 (3)
N3—Mn1—O3	82.35 (11)	O2—C7—H7A	109.9
O4—Mn1—O3	73.69 (11)	C6—C7—H7A	109.9
N2—Mn1—O1	92.52 (12)	O2—C7—H7B	109.9
N1—Mn1—O1	70.86 (10)	C6—C7—H7B	109.9
N3—Mn1—O1	88.56 (11)	H7A—C7—H7B	108.3
O4—Mn1—O1	72.72 (10)	O2—C8—C9	107.4 (3)
O3—Mn1—O1	144.69 (10)	O2—C8—H8A	110.2
N2—Mn1—O2	89.15 (11)	C9—C8—H8A	110.2
N1—Mn1—O2	70.79 (10)	O2—C8—H8B	110.2
N3—Mn1—O2	91.40 (12)	C9—C8—H8B	110.2
O4—Mn1—O2	145.52 (10)	H8A—C8—H8B	108.5
O3—Mn1—O2	72.93 (10)	O3—C9—C8	107.1 (3)
O1—Mn1—O2	141.65 (9)	O3—C9—H9A	110.3
C2—N1—C6	120.2 (3)	C8—C9—H9A	110.3
C2—N1—Mn1	120.2 (2)	O3—C9—H9B	110.3
C6—N1—Mn1	119.4 (2)	C8—C9—H9B	110.3
C14—N2—Mn1	171.8 (3)	H9A—C9—H9B	108.5
C15—N3—Mn1	141.6 (3)	O3—C10—C11	107.2 (3)
C1—O1—C13	115.3 (3)	O3—C10—H10A	110.3
C1—O1—Mn1	114.1 (2)	C11—C10—H10A	110.3
C13—O1—Mn1	113.3 (2)	O3—C10—H10B	110.3
C7—O2—C8	115.7 (3)	C11—C10—H10B	110.3
C7—O2—Mn1	113.1 (2)	H10A—C10—H10B	108.5
C8—O2—Mn1	113.7 (2)	O4—C11—C10	106.5 (4)
C10—O3—C9	116.1 (3)	O4—C11—H11A	110.4
C10—O3—Mn1	111.6 (3)	C10—C11—H11A	110.4
C9—O3—Mn1	109.6 (2)	O4—C11—H11B	110.4
C11—O4—C12	116.1 (4)	C10—C11—H11B	110.4
C11—O4—Mn1	111.8 (3)	H11A—C11—H11B	108.6
C12—O4—Mn1	112.8 (2)	O4—C12—C13	106.8 (4)
O1—C1—C2	108.0 (3)	O4—C12—H12A	110.4
O1—C1—H1A	110.1	C13—C12—H12A	110.4
C2—C1—H1A	110.1	O4—C12—H12B	110.4
O1—C1—H1B	110.1	C13—C12—H12B	110.4
C2—C1—H1B	110.1	H12A—C12—H12B	108.6
H1A—C1—H1B	108.4	O1—C13—C12	106.2 (3)
N1—C2—C3	121.4 (4)	O1—C13—H13A	110.5
N1—C2—C1	115.4 (3)	C12—C13—H13A	110.5
C3—C2—C1	123.2 (4)	O1—C13—H13B	110.5
C4—C3—C2	118.1 (4)	C12—C13—H13B	110.5
C4—C3—H3	120.9	H13A—C13—H13B	108.7
C2—C3—H3	120.9	N2—C14—S1	179.1 (4)
C5—C4—C3	120.3 (4)	N3—C15—S2	178.3 (4)
C5—C4—H4	119.9

Experimental details

Crystal data
Chemical formula	[Mn(NCS)₂(C₁₃H₁₉NO₄)]
M_r	424.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	15.211 (5), 15.789 (5), 7.868 (2)
β (°)	98.667 (4)
V (Å³)	1868.0 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.42 × 0.35 × 0.31

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.690, 0.756
No. of measured, independent and observed [I > 2σ(I)] reflections	9681, 3294, 2266
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.04
No. of reflections	3294
No. of parameters	214
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.48

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge the support of the National Natural Science Foundation of China, the Natural Science Foundation of Liaocheng University and Liaocheng University.

References

Lamb, J. D., Izatt, R. M., Swain, C. S. & Christensen, J. J. (1980). J. Am. Chem. Soc. 102, 475–479. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wei, Y. H., Dai, Y. & Huang, B. B. (1997). Chem. J. Chin. Univ. 18, 193–195. CAS Google Scholar