{4,6-Bis[(E)-1-methyl-2-(pyridin-2-yl-methyl-idene)hydrazinyl]pyrimidine-κN,N',N''}dichloridomanganese(II).

In the title compound, [MnCl(2)(C(18)H(18)N(8))], the geometry around the Mn(II) centre is distorted square-pyramidal. In the crystal structure, mol-ecules pack via weak C-H⋯N and C-H⋯Cl inter-actions.

Related literature

For the synthesis of the ligand, see: Schmitt et al. (2003 ▶). For the coordination chemistry of similar ligand types, see: Stadler et al. (2005 ▶, 2006 ▶). For coordination chemistry of similar complexes that contain Mn—N bonds, see: Romain et al. (2011 ▶). For a related structure containing copper(II) ions, see: Marzec et al. (2011 ▶).

Experimental

Crystal data

[MnCl2(C18H18N8)]

M = 472.24

Triclinic,

a = 8.8355 (12) Å

b = 10.0972 (14) Å

c = 12.1466 (17) Å

α = 72.571 (3)°

β = 77.694 (3)°

γ = 75.700 (3)°

V = 990.4 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.96 mm−1

T = 123 K

0.15 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Blessing, 1995 ▶) T min = 0.891, T max = 0.926

13578 measured reflections

4889 independent reflections

4095 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.088

S = 1.04

4889 reflections

264 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2011 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811043352/su2330sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043352/su2330Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811043352/su2330Isup3.mol

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[MnCl2(C18H18N8)]	Z = 2
Mr = 472.24	F(000) = 482
Triclinic, P1	Dx = 1.583 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8355 (12) Å	Cell parameters from 209 reflections
b = 10.0972 (14) Å	θ = 1.8–28.4°
c = 12.1466 (17) Å	µ = 0.96 mm−1
α = 72.571 (3)°	T = 123 K
β = 77.694 (3)°	Block, orange
γ = 75.700 (3)°	0.15 × 0.10 × 0.08 mm
V = 990.4 (2) Å3

Bruker SMART CCD diffractometer	4889 independent reflections
Radiation source: fine-focus sealed tube	4095 reflections with I > 2σ(I)
graphite	Rint = 0.029
ω and φ scans	θmax = 28.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −11→11
Tmin = 0.891, Tmax = 0.926	k = −13→13
13578 measured reflections	l = −16→16

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0408P)2 + 0.5107P] where P = (Fo2 + 2Fc2)/3
4889 reflections	(Δ/σ)max = 0.001
264 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn1	0.67993 (3)	0.16794 (3)	0.82771 (3)	0.01792 (9)
Cl3	0.79147 (6)	0.23004 (5)	0.96172 (5)	0.02639 (12)
Cl6	0.83681 (6)	0.18893 (6)	0.64375 (4)	0.02952 (13)
N1	0.01708 (19)	0.67410 (17)	0.66222 (14)	0.0208 (3)
N2	0.14098 (19)	0.69997 (17)	0.69778 (15)	0.0212 (3)
N3	−0.3287 (2)	0.85135 (18)	0.53910 (16)	0.0256 (4)
N4	0.37974 (19)	0.59915 (17)	0.76727 (15)	0.0213 (3)
N5	0.47733 (18)	0.34990 (17)	0.80430 (14)	0.0191 (3)
N6	0.32711 (18)	0.19442 (17)	0.79741 (15)	0.0201 (3)
N7	0.45792 (18)	0.09592 (16)	0.82524 (14)	0.0183 (3)
N8	0.72286 (18)	−0.07073 (17)	0.88859 (14)	0.0193 (3)
C1	−0.2119 (2)	0.7419 (2)	0.57423 (17)	0.0213 (4)
C2	−0.4426 (2)	0.8238 (2)	0.49708 (19)	0.0282 (5)
H2	−0.5268	0.8997	0.4731	0.034*
C3	−0.4455 (3)	0.6926 (2)	0.48639 (19)	0.0291 (5)
H3	−0.5288	0.6789	0.4553	0.035*
C4	−0.3236 (3)	0.5808 (2)	0.52218 (19)	0.0294 (5)
H4	−0.3217	0.4888	0.5160	0.035*
C5	−0.2060 (2)	0.6057 (2)	0.56669 (18)	0.0257 (4)
H5	−0.1215	0.5309	0.5921	0.031*
C6	−0.0873 (2)	0.7771 (2)	0.61700 (17)	0.0219 (4)
H6	−0.0844	0.8724	0.6113	0.026*
C7	0.1690 (2)	0.8430 (2)	0.6747 (2)	0.0269 (4)
H7A	0.0817	0.8981	0.7172	0.040*
H7B	0.1756	0.8885	0.5908	0.040*
H7C	0.2683	0.8385	0.7006	0.040*
C8	0.2476 (2)	0.5803 (2)	0.74022 (16)	0.0192 (4)
C9	0.2191 (2)	0.4463 (2)	0.75266 (17)	0.0202 (4)
H9	0.1217	0.4339	0.7398	0.024*
C10	0.3397 (2)	0.3324 (2)	0.78463 (16)	0.0178 (4)
C11	0.4861 (2)	0.4824 (2)	0.79677 (18)	0.0218 (4)
H11	0.5805	0.4943	0.8149	0.026*
C12	0.1896 (2)	0.1539 (2)	0.7783 (2)	0.0257 (4)
H12A	0.1624	0.0739	0.8428	0.039*
H12B	0.2136	0.1263	0.7047	0.039*
H12C	0.1001	0.2341	0.7744	0.039*
C13	0.4659 (2)	−0.0363 (2)	0.83818 (17)	0.0211 (4)
H13	0.3820	−0.0705	0.8253	0.025*
C14	0.6114 (2)	−0.1315 (2)	0.87384 (16)	0.0189 (4)
C15	0.6297 (2)	−0.2762 (2)	0.89248 (18)	0.0236 (4)
H15	0.5485	−0.3155	0.8816	0.028*
C16	0.7687 (2)	−0.3630 (2)	0.92733 (18)	0.0252 (4)
H16	0.7850	−0.4627	0.9400	0.030*
C17	0.8830 (2)	−0.3016 (2)	0.94323 (18)	0.0243 (4)
H17	0.9791	−0.3585	0.9675	0.029*
C18	0.8557 (2)	−0.1558 (2)	0.92326 (17)	0.0217 (4)
H18	0.9348	−0.1145	0.9347	0.026*

	U11	U22	U33	U12	U13	U23
Mn1	0.01333 (14)	0.01712 (15)	0.02342 (16)	−0.00139 (10)	−0.00637 (11)	−0.00423 (11)
Cl3	0.0216 (2)	0.0294 (3)	0.0326 (3)	−0.00431 (19)	−0.0116 (2)	−0.0098 (2)
Cl6	0.0247 (3)	0.0315 (3)	0.0265 (3)	−0.0013 (2)	−0.0011 (2)	−0.0043 (2)
N1	0.0168 (8)	0.0219 (8)	0.0227 (8)	−0.0002 (6)	−0.0064 (6)	−0.0049 (7)
N2	0.0178 (8)	0.0173 (8)	0.0283 (9)	0.0002 (6)	−0.0094 (7)	−0.0047 (7)
N3	0.0191 (8)	0.0237 (9)	0.0309 (9)	0.0026 (7)	−0.0094 (7)	−0.0042 (7)
N4	0.0189 (8)	0.0192 (8)	0.0273 (9)	−0.0003 (6)	−0.0082 (7)	−0.0075 (7)
N5	0.0149 (7)	0.0200 (8)	0.0234 (8)	−0.0008 (6)	−0.0065 (6)	−0.0068 (6)
N6	0.0130 (7)	0.0175 (8)	0.0294 (9)	−0.0005 (6)	−0.0083 (6)	−0.0041 (7)
N7	0.0135 (7)	0.0185 (8)	0.0211 (8)	0.0012 (6)	−0.0057 (6)	−0.0039 (6)
N8	0.0175 (8)	0.0189 (8)	0.0213 (8)	−0.0021 (6)	−0.0062 (6)	−0.0038 (6)
C1	0.0180 (9)	0.0223 (9)	0.0205 (9)	0.0003 (7)	−0.0052 (7)	−0.0030 (8)
C2	0.0185 (10)	0.0324 (11)	0.0302 (11)	−0.0001 (8)	−0.0087 (8)	−0.0036 (9)
C3	0.0233 (10)	0.0387 (12)	0.0266 (11)	−0.0096 (9)	−0.0074 (8)	−0.0050 (9)
C4	0.0326 (12)	0.0275 (11)	0.0287 (11)	−0.0073 (9)	−0.0070 (9)	−0.0055 (9)
C5	0.0245 (10)	0.0232 (10)	0.0265 (10)	0.0001 (8)	−0.0075 (8)	−0.0034 (8)
C6	0.0199 (9)	0.0190 (9)	0.0244 (10)	0.0000 (7)	−0.0051 (8)	−0.0039 (8)
C7	0.0236 (10)	0.0183 (9)	0.0391 (12)	−0.0005 (8)	−0.0115 (9)	−0.0061 (9)
C8	0.0170 (9)	0.0216 (9)	0.0174 (9)	−0.0001 (7)	−0.0034 (7)	−0.0052 (7)
C9	0.0143 (9)	0.0209 (9)	0.0247 (10)	0.0001 (7)	−0.0073 (7)	−0.0048 (8)
C10	0.0153 (8)	0.0193 (9)	0.0191 (9)	−0.0020 (7)	−0.0034 (7)	−0.0060 (7)
C11	0.0175 (9)	0.0225 (10)	0.0275 (10)	−0.0017 (7)	−0.0082 (8)	−0.0079 (8)
C12	0.0159 (9)	0.0231 (10)	0.0401 (12)	−0.0034 (7)	−0.0101 (8)	−0.0075 (9)
C13	0.0176 (9)	0.0210 (9)	0.0254 (10)	−0.0031 (7)	−0.0071 (8)	−0.0048 (8)
C14	0.0164 (9)	0.0189 (9)	0.0202 (9)	−0.0023 (7)	−0.0041 (7)	−0.0036 (7)
C15	0.0225 (10)	0.0205 (9)	0.0293 (11)	−0.0035 (8)	−0.0082 (8)	−0.0064 (8)
C16	0.0282 (10)	0.0168 (9)	0.0291 (11)	0.0008 (8)	−0.0076 (9)	−0.0055 (8)
C17	0.0209 (10)	0.0245 (10)	0.0242 (10)	0.0039 (8)	−0.0087 (8)	−0.0044 (8)
C18	0.0176 (9)	0.0236 (10)	0.0238 (10)	−0.0025 (7)	−0.0072 (8)	−0.0045 (8)

Mn1—N5	2.2227 (16)	C3—H3	0.9500
Mn1—N8	2.2580 (16)	C4—C5	1.373 (3)
Mn1—N7	2.2628 (16)	C4—H4	0.9500
Mn1—Cl6	2.3453 (7)	C5—H5	0.9500
Mn1—Cl3	2.3695 (6)	C6—H6	0.9500
N1—C6	1.279 (2)	C7—H7A	0.9800
N1—N2	1.365 (2)	C7—H7B	0.9800
N2—C8	1.373 (2)	C7—H7C	0.9800
N2—C7	1.459 (3)	C8—C9	1.396 (3)
N3—C2	1.339 (3)	C9—C10	1.382 (2)
N3—C1	1.345 (2)	C9—H9	0.9500
N4—C11	1.320 (2)	C11—H11	0.9500
N4—C8	1.348 (2)	C12—H12A	0.9800
N5—C11	1.334 (2)	C12—H12B	0.9800
N5—C10	1.350 (2)	C12—H12C	0.9800
N6—N7	1.355 (2)	C13—C14	1.463 (3)
N6—C10	1.385 (2)	C13—H13	0.9500
N6—C12	1.457 (2)	C14—C15	1.384 (3)
N7—C13	1.282 (2)	C15—C16	1.387 (3)
N8—C18	1.338 (2)	C15—H15	0.9500
N8—C14	1.348 (2)	C16—C17	1.380 (3)
C1—C5	1.394 (3)	C16—H16	0.9500
C1—C6	1.468 (3)	C17—C18	1.385 (3)
C2—C3	1.376 (3)	C17—H17	0.9500
C2—H2	0.9500	C18—H18	0.9500
C3—C4	1.389 (3)
N5—Mn1—N8	138.73 (6)	N1—C6—H6	121.4
N5—Mn1—N7	69.14 (6)	C1—C6—H6	121.4
N8—Mn1—N7	71.34 (6)	N2—C7—H7A	109.5
N5—Mn1—Cl6	105.58 (5)	N2—C7—H7B	109.5
N8—Mn1—Cl6	98.09 (4)	H7A—C7—H7B	109.5
N7—Mn1—Cl6	109.23 (4)	N2—C7—H7C	109.5
N5—Mn1—Cl3	98.11 (4)	H7A—C7—H7C	109.5
N8—Mn1—Cl3	103.08 (4)	H7B—C7—H7C	109.5
N7—Mn1—Cl3	137.70 (4)	N4—C8—N2	117.01 (17)
Cl6—Mn1—Cl3	113.06 (2)	N4—C8—C9	122.41 (17)
C6—N1—N2	120.08 (17)	N2—C8—C9	120.58 (17)
N1—N2—C8	114.05 (15)	C10—C9—C8	116.66 (17)
N1—N2—C7	121.98 (15)	C10—C9—H9	121.7
C8—N2—C7	123.26 (16)	C8—C9—H9	121.7
C2—N3—C1	116.94 (18)	N5—C10—C9	121.65 (17)
C11—N4—C8	115.07 (17)	N5—C10—N6	116.17 (16)
C11—N5—C10	115.84 (16)	C9—C10—N6	122.17 (17)
C11—N5—Mn1	123.94 (12)	N4—C11—N5	128.05 (18)
C10—N5—Mn1	119.88 (12)	N4—C11—H11	116.0
N7—N6—C10	114.64 (15)	N5—C11—H11	116.0
N7—N6—C12	120.81 (15)	N6—C12—H12A	109.5
C10—N6—C12	124.50 (15)	N6—C12—H12B	109.5
C13—N7—N6	122.20 (16)	H12A—C12—H12B	109.5
C13—N7—Mn1	118.24 (12)	N6—C12—H12C	109.5
N6—N7—Mn1	119.14 (12)	H12A—C12—H12C	109.5
C18—N8—C14	117.69 (16)	H12B—C12—H12C	109.5
C18—N8—Mn1	125.94 (13)	N7—C13—C14	116.34 (17)
C14—N8—Mn1	115.79 (12)	N7—C13—H13	121.8
N3—C1—C5	122.57 (18)	C14—C13—H13	121.8
N3—C1—C6	115.26 (17)	N8—C14—C15	122.81 (17)
C5—C1—C6	122.13 (17)	N8—C14—C13	116.59 (16)
N3—C2—C3	124.18 (19)	C15—C14—C13	120.59 (17)
N3—C2—H2	117.9	C14—C15—C16	118.86 (18)
C3—C2—H2	117.9	C14—C15—H15	120.6
C2—C3—C4	118.28 (19)	C16—C15—H15	120.6
C2—C3—H3	120.9	C17—C16—C15	118.62 (18)
C4—C3—H3	120.9	C17—C16—H16	120.7
C5—C4—C3	118.8 (2)	C15—C16—H16	120.7
C5—C4—H4	120.6	C16—C17—C18	119.14 (18)
C3—C4—H4	120.6	C16—C17—H17	120.4
C4—C5—C1	119.22 (19)	C18—C17—H17	120.4
C4—C5—H5	120.4	N8—C18—C17	122.87 (18)
C1—C5—H5	120.4	N8—C18—H18	118.6
N1—C6—C1	117.14 (18)	C17—C18—H18	118.6
C6—N1—N2—C8	−177.44 (18)	N3—C1—C6—N1	173.05 (18)
C6—N1—N2—C7	−6.8 (3)	C5—C1—C6—N1	−9.2 (3)
N8—Mn1—N5—C11	160.34 (14)	C11—N4—C8—N2	−173.62 (17)
N7—Mn1—N5—C11	177.93 (17)	C11—N4—C8—C9	5.6 (3)
Cl6—Mn1—N5—C11	−77.03 (16)	N1—N2—C8—N4	174.36 (16)
Cl3—Mn1—N5—C11	39.75 (16)	C7—N2—C8—N4	3.8 (3)
N8—Mn1—N5—C10	−26.59 (19)	N1—N2—C8—C9	−4.8 (3)
N7—Mn1—N5—C10	−9.01 (13)	C7—N2—C8—C9	−175.38 (19)
Cl6—Mn1—N5—C10	96.04 (14)	N4—C8—C9—C10	−5.5 (3)
Cl3—Mn1—N5—C10	−147.19 (14)	N2—C8—C9—C10	173.61 (17)
C10—N6—N7—C13	−178.82 (18)	C11—N5—C10—C9	3.3 (3)
C12—N6—N7—C13	−1.4 (3)	Mn1—N5—C10—C9	−170.32 (14)
C10—N6—N7—Mn1	−6.4 (2)	C11—N5—C10—N6	−177.21 (17)
C12—N6—N7—Mn1	171.03 (14)	Mn1—N5—C10—N6	9.2 (2)
N5—Mn1—N7—C13	−179.21 (16)	C8—C9—C10—N5	0.8 (3)
N8—Mn1—N7—C13	−11.35 (14)	C8—C9—C10—N6	−178.64 (17)
Cl6—Mn1—N7—C13	80.91 (15)	N7—N6—C10—N5	−1.6 (2)
Cl3—Mn1—N7—C13	−100.42 (15)	C12—N6—C10—N5	−178.96 (18)
N5—Mn1—N7—N6	8.07 (13)	N7—N6—C10—C9	177.86 (17)
N8—Mn1—N7—N6	175.93 (15)	C12—N6—C10—C9	0.5 (3)
Cl6—Mn1—N7—N6	−91.81 (13)	C8—N4—C11—N5	−0.9 (3)
Cl3—Mn1—N7—N6	86.86 (14)	C10—N5—C11—N4	−3.4 (3)
N5—Mn1—N8—C18	−161.13 (14)	Mn1—N5—C11—N4	169.90 (16)
N7—Mn1—N8—C18	−178.46 (17)	N6—N7—C13—C14	−177.09 (16)
Cl6—Mn1—N8—C18	73.90 (16)	Mn1—N7—C13—C14	10.4 (2)
Cl3—Mn1—N8—C18	−42.16 (16)	C18—N8—C14—C15	−0.3 (3)
N5—Mn1—N8—C14	27.89 (18)	Mn1—N8—C14—C15	171.45 (15)
N7—Mn1—N8—C14	10.56 (13)	C18—N8—C14—C13	178.80 (17)
Cl6—Mn1—N8—C14	−97.09 (13)	Mn1—N8—C14—C13	−9.4 (2)
Cl3—Mn1—N8—C14	146.86 (13)	N7—C13—C14—N8	−0.5 (3)
C2—N3—C1—C5	0.8 (3)	N7—C13—C14—C15	178.61 (19)
C2—N3—C1—C6	178.55 (18)	N8—C14—C15—C16	−0.3 (3)
C1—N3—C2—C3	−1.0 (3)	C13—C14—C15—C16	−179.37 (19)
N3—C2—C3—C4	0.6 (3)	C14—C15—C16—C17	0.6 (3)
C2—C3—C4—C5	0.1 (3)	C15—C16—C17—C18	−0.4 (3)
C3—C4—C5—C1	−0.2 (3)	C14—N8—C18—C17	0.6 (3)
N3—C1—C5—C4	−0.2 (3)	Mn1—N8—C18—C17	−170.26 (15)
C6—C1—C5—C4	−177.8 (2)	C16—C17—C18—N8	−0.2 (3)
N2—N1—C6—C1	176.38 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N3i	0.95	2.50	3.358 (3)	151
C18—H18···Cl3ii	0.95	2.80	3.508 (2)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N3i	0.95	2.50	3.358 (3)	151
C18—H18⋯Cl3ii	0.95	2.80	3.508 (2)	133

Symmetry codes: (i) ; (ii) .