{N,N′-Bis[1-(2-pyrid­yl)ethyl­idene]propane-1,2-diamine-κ⁴N,N′,N′′,N′′′}bis­(thio­cyanato-κN)manganese(II)

In the title compound, [Mn(NCS)₂(C₁₇H₂₀N₄)], the Mn^II atom is six-coordinated by the N,N′,N′′,N′′′-tetra­dentate Schiff base ligand and by two trans-N atoms from two thio­cyanate anions, forming a distorted octa­hedral geometry. The dihedral angle between the aromatic rings of the Schiff base is 9.5 (3)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.077
• wR factor = 0.224
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C18

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 Perc.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.02
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N5
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C19
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         10
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         17
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         37

Alert level G
PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large.       0.10
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        300 Deg.
PLAT793_ALERT_4_G The Model has Chirality at C8      (Verify) ....          S

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   0 ALERT type 5 Informative message, check

---

S1. Comment

Metal complexes with Schiff bases have been known since 1840 but only one complex derived from 1,2-bis(2'-pyridylmethyleneamino)propane has been reported (Ouyang et al., 2002). In this paper, the title new manganese(II) complex is reported.

In the title complex, Fig. 1, the Mn^II atom is six-coordinated by four N atoms of the Schiff base ligand 1,2-bis(2'-pyridylmethyleneamino)propane, and by two N atoms from two thiocyanate ligands, forming a distorted octahedral geometry. The coordinate bond lengths (Table 1) are comparable with those observed in other similar manganese(II) complexes with Schiff bases (Louloudi et al., 1999; Sra et al., 2000; Karmakar et al., 2005; Deoghoria et al., 2005).

Related literature

For another complex containing 1,2-bis(2'-pyridylmethyleneamino)propane, see: Ouyang et al. (2002). For related manganese(II) complexes with Schiff bases, see: Louloudi et al. (1999); Sra et al. (2000); Karmakar et al. (2005); Deoghoria et al. (2005). For the synthesis of the Schiff base, see: Gourbatsis et al. (1990).

S2. Experimental

The Schiff base ligand 1,2-bis(2'-pyridylmethyleneamino)propane was synthesized according to the literature method (Gourbatsis et al., 1990). To a stirred methanol solution of the Schiff base ligand (1.0 mmol, 0.280 g) was added a methanol solution of manganese acetate (1.0 mmol, 0.245 g) and ammonium thiocyanate (1.0 mmol, 0.076 g). The mixture was boiled under reflux for 2 h, then cooled to room temperature. Brown blocks of (I) were formed after slow evaporation of the solution in air for a few days.

S3. Refinement

Hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93–0.97 Å, and with U_iso(H) set at 1.2U_eq(C) and 1.5U_eq(C_methyl).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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

Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 30% probability level.

{N,N'-Bis[1-(2-pyridyl)ethylidene]propane-1,2-diamine- κ⁴N,N',N'',N'''}bis(thiocyanato- κN)manganese(II)

Crystal data

[Mn(NCS)2(C17H20N4)]	Z = 2
Mr = 451.47	F(000) = 466
Triclinic, P1	Dx = 1.403 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.647 (3) Å	Cell parameters from 1307 reflections
b = 9.135 (2) Å	θ = 2.3–24.5°
c = 14.608 (3) Å	µ = 0.83 mm^−1
α = 84.701 (3)°	T = 298 K
β = 79.407 (3)°	Block, brown
γ = 70.509 (3)°	0.33 × 0.30 × 0.30 mm
V = 1068.6 (5) Å^3

Data collection

Bruker SMART CCD diffractometer	4608 independent reflections
Radiation source: fine-focus sealed tube	2211 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scan	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.771, Tmax = 0.789	k = −11→11
11100 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.224	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.1044P)^2] where P = (Fo^2 + 2Fc^2)/3
4608 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	1.02210 (10)	0.54382 (9)	0.27241 (5)	0.0601 (3)
N1	1.2061 (6)	0.6565 (5)	0.3134 (3)	0.0644 (12)
N2	1.0220 (6)	0.7580 (5)	0.1819 (3)	0.0673 (12)
N3	0.8157 (6)	0.5912 (5)	0.1875 (3)	0.0701 (13)
N4	0.9013 (5)	0.3471 (5)	0.3008 (3)	0.0665 (12)
N5	0.8737 (7)	0.6394 (7)	0.3994 (4)	0.0906 (17)
N6	1.2282 (6)	0.3744 (6)	0.1940 (4)	0.0772 (15)
S1	0.6757 (2)	0.8093 (2)	0.54416 (16)	0.1097 (7)
S2	1.4735 (2)	0.1575 (2)	0.08162 (12)	0.0855 (5)
C1	1.2937 (8)	0.6060 (8)	0.3826 (5)	0.089 (2)
H1	1.2883	0.5148	0.4151	0.107*
C2	1.3917 (9)	0.6811 (8)	0.4088 (5)	0.096 (2)
H2	1.4508	0.6422	0.4578	0.116*
C3	1.3997 (8)	0.8144 (8)	0.3608 (5)	0.088 (2)
H3	1.4654	0.8677	0.3765	0.106*
C4	1.3109 (7)	0.8693 (6)	0.2897 (5)	0.0750 (17)
H4	1.3155	0.9601	0.2565	0.090*
C5	1.2135 (6)	0.7880 (6)	0.2674 (4)	0.0574 (13)
C6	1.1124 (7)	0.8394 (7)	0.1905 (4)	0.0631 (14)
C7	1.1270 (9)	0.9785 (7)	0.1307 (5)	0.095 (2)
H7A	1.2372	0.9548	0.0956	0.142*
H7B	1.1054	1.0646	0.1696	0.142*
H7C	1.0477	1.0050	0.0888	0.142*
C8	0.9234 (8)	0.7889 (8)	0.1062 (4)	0.087 (2)
H8	0.8913	0.8996	0.0880	0.104*
C9	1.0322 (10)	0.6917 (9)	0.0230 (5)	0.106 (2)
H9A	1.1312	0.7198	0.0042	0.159*
H9B	0.9712	0.7114	−0.0281	0.159*
H9C	1.0619	0.5833	0.0409	0.159*
C10	0.7743 (8)	0.7434 (8)	0.1372 (5)	0.098 (2)
H10A	0.7250	0.7379	0.0837	0.118*
H10B	0.6935	0.8213	0.1779	0.118*
C11	0.7315 (7)	0.4988 (6)	0.1900 (4)	0.0617 (14)
C12	0.5892 (7)	0.5241 (7)	0.1393 (5)	0.0843 (19)
H12A	0.5809	0.6123	0.0970	0.126*
H12B	0.4880	0.5428	0.1833	0.126*
H12C	0.6072	0.4335	0.1050	0.126*
C13	0.7763 (6)	0.3606 (6)	0.2541 (4)	0.0613 (14)
C14	0.6956 (7)	0.2485 (8)	0.2671 (5)	0.0826 (18)
H14	0.6105	0.2573	0.2340	0.099*
C15	0.7432 (8)	0.1242 (8)	0.3297 (5)	0.094 (2)
H15	0.6899	0.0495	0.3389	0.112*
C16	0.8672 (9)	0.1124 (8)	0.3771 (5)	0.094 (2)
H16	0.9006	0.0303	0.4195	0.112*
C17	0.9429 (8)	0.2251 (7)	0.3610 (4)	0.0808 (18)
H17	1.0283	0.2165	0.3937	0.097*
C18	0.7938 (7)	0.7096 (6)	0.4577 (4)	0.0589 (14)
C19	1.3320 (7)	0.2828 (7)	0.1471 (4)	0.0631 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0670 (6)	0.0649 (6)	0.0607 (5)	−0.0367 (5)	−0.0173 (4)	0.0090 (4)
N1	0.082 (3)	0.060 (3)	0.064 (3)	−0.036 (2)	−0.024 (2)	0.011 (2)
N2	0.078 (3)	0.075 (3)	0.066 (3)	−0.041 (3)	−0.030 (2)	0.012 (2)
N3	0.075 (3)	0.072 (3)	0.077 (3)	−0.039 (3)	−0.026 (3)	0.017 (3)
N4	0.063 (3)	0.077 (3)	0.071 (3)	−0.036 (2)	−0.018 (2)	0.009 (3)
N5	0.089 (4)	0.110 (5)	0.082 (4)	−0.051 (4)	−0.001 (3)	−0.006 (3)
N6	0.079 (4)	0.077 (4)	0.086 (4)	−0.040 (3)	−0.016 (3)	0.003 (3)
S1	0.0955 (14)	0.1071 (16)	0.1234 (16)	−0.0214 (12)	−0.0135 (12)	−0.0410 (13)
S2	0.0850 (12)	0.0822 (12)	0.0928 (12)	−0.0285 (10)	−0.0153 (9)	−0.0139 (9)
C1	0.116 (5)	0.088 (5)	0.091 (5)	−0.060 (4)	−0.049 (4)	0.026 (4)
C2	0.114 (5)	0.099 (5)	0.102 (5)	−0.051 (5)	−0.063 (4)	0.019 (4)
C3	0.096 (5)	0.078 (5)	0.115 (5)	−0.047 (4)	−0.047 (4)	0.001 (4)
C4	0.080 (4)	0.052 (3)	0.103 (5)	−0.029 (3)	−0.030 (4)	0.003 (3)
C5	0.055 (3)	0.060 (3)	0.062 (3)	−0.025 (3)	−0.010 (3)	−0.006 (3)
C6	0.065 (3)	0.067 (4)	0.064 (3)	−0.030 (3)	−0.015 (3)	0.008 (3)
C7	0.121 (6)	0.080 (5)	0.103 (5)	−0.061 (4)	−0.037 (4)	0.039 (4)
C8	0.113 (5)	0.080 (5)	0.085 (4)	−0.049 (4)	−0.042 (4)	0.027 (4)
C9	0.143 (7)	0.102 (6)	0.083 (5)	−0.051 (5)	−0.026 (5)	0.003 (4)
C10	0.108 (5)	0.110 (6)	0.110 (5)	−0.070 (5)	−0.060 (4)	0.042 (4)
C11	0.057 (3)	0.059 (3)	0.075 (4)	−0.026 (3)	−0.011 (3)	−0.005 (3)
C12	0.065 (4)	0.088 (5)	0.112 (5)	−0.032 (3)	−0.037 (4)	0.006 (4)
C13	0.056 (3)	0.064 (4)	0.069 (3)	−0.032 (3)	0.002 (3)	−0.004 (3)
C14	0.067 (4)	0.086 (5)	0.113 (5)	−0.046 (4)	−0.021 (4)	0.000 (4)
C15	0.094 (5)	0.090 (5)	0.113 (6)	−0.059 (4)	−0.015 (4)	0.022 (4)
C16	0.099 (5)	0.089 (5)	0.106 (5)	−0.054 (4)	−0.022 (4)	0.034 (4)
C17	0.087 (4)	0.086 (5)	0.088 (4)	−0.047 (4)	−0.034 (4)	0.022 (4)
C18	0.057 (4)	0.052 (4)	0.075 (4)	−0.026 (3)	−0.022 (3)	0.013 (3)
C19	0.063 (4)	0.061 (4)	0.075 (4)	−0.030 (3)	−0.024 (3)	0.013 (3)

Geometric parameters (Å, º)

Mn1—N5	2.127 (6)	C5—C6	1.495 (7)
Mn1—N6	2.149 (6)	C6—C7	1.501 (8)
Mn1—N2	2.258 (5)	C7—H7A	0.9600
Mn1—N3	2.260 (4)	C7—H7B	0.9600
Mn1—N4	2.334 (4)	C7—H7C	0.9600
Mn1—N1	2.346 (4)	C8—C10	1.465 (8)
N1—C1	1.331 (7)	C8—C9	1.540 (9)
N1—C5	1.336 (6)	C8—H8	0.9800
N2—C6	1.274 (6)	C9—H9A	0.9600
N2—C8	1.470 (7)	C9—H9B	0.9600
N3—C11	1.281 (6)	C9—H9C	0.9600
N3—C10	1.476 (7)	C10—H10A	0.9700
N4—C17	1.345 (7)	C10—H10B	0.9700
N4—C13	1.348 (6)	C11—C13	1.486 (8)
N5—C18	1.097 (7)	C11—C12	1.493 (7)
N6—C19	1.164 (7)	C12—H12A	0.9600
S1—C18	1.608 (7)	C12—H12B	0.9600
S2—C19	1.600 (7)	C12—H12C	0.9600
C1—C2	1.376 (8)	C13—C14	1.402 (7)
C1—H1	0.9300	C14—C15	1.389 (8)
C2—C3	1.364 (9)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.351 (8)
C3—C4	1.364 (8)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.376 (8)
C4—C5	1.389 (7)	C16—H16	0.9300
C4—H4	0.9300	C17—H17	0.9300
N5—Mn1—N6	152.6 (2)	H7A—C7—H7B	109.5
N5—Mn1—N2	102.5 (2)	C6—C7—H7C	109.5
N6—Mn1—N2	99.53 (18)	H7A—C7—H7C	109.5
N5—Mn1—N3	98.1 (2)	H7B—C7—H7C	109.5
N6—Mn1—N3	103.71 (18)	C10—C8—N2	109.6 (5)
N2—Mn1—N3	73.15 (16)	C10—C8—C9	109.9 (6)
N5—Mn1—N4	86.78 (19)	N2—C8—C9	107.8 (5)
N6—Mn1—N4	85.41 (17)	C10—C8—H8	109.8
N2—Mn1—N4	142.80 (16)	N2—C8—H8	109.8
N3—Mn1—N4	69.88 (16)	C9—C8—H8	109.8
N5—Mn1—N1	82.92 (18)	C8—C9—H9A	109.5
N6—Mn1—N1	89.82 (17)	C8—C9—H9B	109.5
N2—Mn1—N1	69.50 (15)	H9A—C9—H9B	109.5
N3—Mn1—N1	141.88 (17)	C8—C9—H9C	109.5
N4—Mn1—N1	147.69 (16)	H9A—C9—H9C	109.5
C1—N1—C5	117.9 (5)	H9B—C9—H9C	109.5
C1—N1—Mn1	125.2 (4)	C8—C10—N3	110.8 (5)
C5—N1—Mn1	116.7 (3)	C8—C10—H10A	109.5
C6—N2—C8	121.8 (5)	N3—C10—H10A	109.5
C6—N2—Mn1	122.4 (4)	C8—C10—H10B	109.5
C8—N2—Mn1	115.5 (3)	N3—C10—H10B	109.5
C11—N3—C10	122.6 (5)	H10A—C10—H10B	108.1
C11—N3—Mn1	122.1 (4)	N3—C11—C13	115.4 (5)
C10—N3—Mn1	114.9 (3)	N3—C11—C12	125.6 (5)
C17—N4—C13	117.9 (5)	C13—C11—C12	118.9 (5)
C17—N4—Mn1	125.7 (4)	C11—C12—H12A	109.5
C13—N4—Mn1	116.3 (3)	C11—C12—H12B	109.5
C18—N5—Mn1	169.2 (6)	H12A—C12—H12B	109.5
C19—N6—Mn1	174.9 (5)	C11—C12—H12C	109.5
N1—C1—C2	123.6 (6)	H12A—C12—H12C	109.5
N1—C1—H1	118.2	H12B—C12—H12C	109.5
C2—C1—H1	118.2	N4—C13—C14	120.4 (5)
C3—C2—C1	118.0 (6)	N4—C13—C11	116.3 (5)
C3—C2—H2	121.0	C14—C13—C11	123.3 (5)
C1—C2—H2	121.0	C15—C14—C13	119.7 (6)
C2—C3—C4	119.7 (6)	C15—C14—H14	120.2
C2—C3—H3	120.1	C13—C14—H14	120.2
C4—C3—H3	120.1	C16—C15—C14	119.6 (6)
C3—C4—C5	119.2 (6)	C16—C15—H15	120.2
C3—C4—H4	120.4	C14—C15—H15	120.2
C5—C4—H4	120.4	C15—C16—C17	118.2 (6)
N1—C5—C4	121.6 (5)	C15—C16—H16	120.9
N1—C5—C6	115.6 (4)	C17—C16—H16	120.9
C4—C5—C6	122.8 (5)	N4—C17—C16	124.2 (6)
N2—C6—C5	115.6 (5)	N4—C17—H17	117.9
N2—C6—C7	126.2 (5)	C16—C17—H17	117.9
C5—C6—C7	118.2 (5)	N5—C18—S1	178.7 (6)
C6—C7—H7A	109.5	N6—C19—S2	179.4 (6)
C6—C7—H7B	109.5