Dibromido(2,4,6-tri-2-pyridyl-1,3,5-triazine-κN,N,N)manganese(II).

The Mn(II) ion in the title complex, [MnBr(2)(C(18)H(12)N(6))], is five-coordinated in a distorted square-pyramidal geometry by three N atoms of the tridentate 2,4,6-tri-2-pyridyl-1,3,5-triazine (tptz) ligand and two bromide anions. In the crystal, the pyridyl rings coordinated to the Mn atom are inclined slightly to their carrier triazine ring [dihedral angles = 8.0 (3) and 7.5 (3)°], whereas the uncoordinated pyridyl ring is located approximately parallel to the triazine ring [dihedral angle = 3.7 (3)°]. The complexes are stacked in columns along the a axis and linked by inter-molecular C-H⋯Br hydrogen bonds, forming chains. In the column, inter-molecular π-π inter-actions between the six-membered rings are present, the shortest centroid-centroid distance being 3.750 (4) Å.

Related literature

For the crystal structure of the related compound [MnBr2(tptz)(H2O)]·H2O, see: Ha (2011 ▶).

Experimental

Crystal data

[MnBr2(C18H12N6)]

M = 527.10

Triclinic,

a = 8.7095 (19) Å

b = 10.498 (2) Å

c = 11.213 (3) Å

α = 110.094 (4)°

β = 98.471 (4)°

γ = 91.820 (5)°

V = 948.5 (4) Å3

Z = 2

Mo Kα radiation

μ = 4.92 mm−1

T = 200 K

0.27 × 0.17 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.695, T max = 1.000

6897 measured reflections

4548 independent reflections

3124 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.114

S = 1.14

4548 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.90 e Å−3

Δρmin = −1.00 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811045211/zq2132sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045211/zq2132Isup2.hkl

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

[MnBr2(C18H12N6)]	Z = 2
Mr = 527.10	F(000) = 514
Triclinic, P1	Dx = 1.846 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7095 (19) Å	Cell parameters from 2967 reflections
b = 10.498 (2) Å	θ = 2.3–28.3°
c = 11.213 (3) Å	µ = 4.92 mm−1
α = 110.094 (4)°	T = 200 K
β = 98.471 (4)°	Block, orange
γ = 91.820 (5)°	0.27 × 0.17 × 0.09 mm
V = 948.5 (4) Å3

Bruker SMART 1000 CCD diffractometer	4548 independent reflections
Radiation source: fine-focus sealed tube	3124 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→6
Tmin = 0.695, Tmax = 1.000	k = −12→14
6897 measured reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0037P)2 + 4.4503P] where P = (Fo2 + 2Fc2)/3
4548 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.90 e Å−3
0 restraints	Δρmin = −1.00 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	0.60194 (9)	1.09912 (9)	0.35103 (8)	0.0302 (2)
Br1	0.69262 (7)	1.19838 (8)	0.19802 (6)	0.04687 (19)
Br2	0.77379 (7)	1.18883 (7)	0.56522 (6)	0.04513 (19)
N1	0.3893 (5)	0.9697 (4)	0.2464 (4)	0.0269 (9)
N2	0.2650 (5)	0.7593 (4)	0.0981 (4)	0.0285 (10)
N3	0.1203 (5)	0.9522 (5)	0.1701 (4)	0.0302 (10)
N4	0.6578 (5)	0.8741 (5)	0.2753 (4)	0.0302 (10)
N5	−0.0035 (5)	0.6182 (5)	−0.0683 (5)	0.0377 (11)
N6	0.3875 (5)	1.2202 (5)	0.4059 (4)	0.0314 (10)
C1	0.3892 (5)	0.8368 (6)	0.1774 (5)	0.0254 (11)
C2	0.5412 (6)	0.7819 (6)	0.1970 (5)	0.0296 (12)
C3	0.5601 (6)	0.6439 (6)	0.1409 (5)	0.0352 (13)
H3	0.4751	0.5824	0.0868	0.042*
C4	0.7049 (7)	0.5973 (7)	0.1651 (6)	0.0430 (15)
H4	0.7213	0.5039	0.1274	0.052*
C5	0.8253 (7)	0.6917 (7)	0.2461 (6)	0.0435 (15)
H5	0.9256	0.6635	0.2654	0.052*
C6	0.7969 (6)	0.8277 (6)	0.2984 (6)	0.0369 (14)
H6	0.8801	0.8910	0.3533	0.044*
C7	0.1345 (6)	0.8229 (5)	0.0923 (5)	0.0263 (11)
C8	−0.0098 (6)	0.7492 (6)	0.0026 (5)	0.0291 (11)
C9	−0.1432 (6)	0.8194 (6)	−0.0015 (6)	0.0358 (13)
H9	−0.1421	0.9126	0.0505	0.043*
C10	−0.2769 (6)	0.7486 (7)	−0.0842 (6)	0.0419 (15)
H10	−0.3699	0.7926	−0.0902	0.050*
C11	−0.2733 (7)	0.6134 (7)	−0.1577 (6)	0.0412 (15)
H11	−0.3630	0.5629	−0.2156	0.049*
C12	−0.1355 (7)	0.5530 (7)	−0.1450 (6)	0.0465 (16)
H12	−0.1350	0.4591	−0.1940	0.056*
C13	0.2490 (6)	1.0202 (5)	0.2444 (5)	0.0275 (11)
C14	0.2470 (6)	1.1606 (6)	0.3374 (5)	0.0313 (12)
C15	0.1094 (7)	1.2227 (6)	0.3520 (6)	0.0456 (16)
H15	0.0128	1.1771	0.3020	0.055*
C16	0.1168 (8)	1.3530 (7)	0.4413 (8)	0.060 (2)
H16	0.0247	1.3986	0.4536	0.071*
C17	0.2589 (8)	1.4160 (7)	0.5124 (7)	0.0547 (19)
H17	0.2661	1.5054	0.5744	0.066*
C18	0.3904 (7)	1.3475 (6)	0.4924 (6)	0.0387 (14)
H18	0.4878	1.3919	0.5417	0.046*

	U11	U22	U33	U12	U13	U23
Mn1	0.0218 (4)	0.0322 (5)	0.0322 (4)	−0.0010 (3)	−0.0009 (3)	0.0085 (4)
Br1	0.0296 (3)	0.0690 (5)	0.0512 (4)	0.0037 (3)	0.0040 (3)	0.0339 (4)
Br2	0.0370 (3)	0.0562 (4)	0.0340 (3)	−0.0057 (3)	−0.0062 (2)	0.0114 (3)
N1	0.020 (2)	0.024 (2)	0.030 (2)	−0.0003 (17)	0.0017 (17)	0.0040 (18)
N2	0.025 (2)	0.030 (3)	0.029 (2)	0.0073 (18)	0.0027 (18)	0.0082 (19)
N3	0.020 (2)	0.027 (3)	0.042 (3)	0.0041 (18)	−0.0024 (19)	0.013 (2)
N4	0.0149 (19)	0.037 (3)	0.032 (2)	0.0013 (18)	−0.0042 (17)	0.008 (2)
N5	0.027 (2)	0.036 (3)	0.043 (3)	0.001 (2)	−0.005 (2)	0.009 (2)
N6	0.019 (2)	0.031 (3)	0.038 (3)	0.0010 (18)	0.0027 (18)	0.006 (2)
C1	0.008 (2)	0.041 (3)	0.024 (2)	0.0005 (19)	0.0005 (17)	0.008 (2)
C2	0.026 (3)	0.029 (3)	0.028 (3)	0.000 (2)	0.004 (2)	0.003 (2)
C3	0.030 (3)	0.033 (3)	0.036 (3)	0.002 (2)	0.002 (2)	0.006 (2)
C4	0.038 (3)	0.039 (4)	0.048 (4)	0.017 (3)	0.005 (3)	0.010 (3)
C5	0.028 (3)	0.044 (4)	0.052 (4)	0.011 (3)	−0.003 (3)	0.012 (3)
C6	0.020 (3)	0.045 (4)	0.040 (3)	0.004 (2)	0.000 (2)	0.009 (3)
C7	0.022 (2)	0.026 (3)	0.029 (3)	0.001 (2)	0.000 (2)	0.009 (2)
C8	0.027 (3)	0.030 (3)	0.030 (3)	−0.001 (2)	0.001 (2)	0.012 (2)
C9	0.028 (3)	0.037 (3)	0.043 (3)	0.006 (2)	0.000 (2)	0.017 (3)
C10	0.023 (3)	0.058 (4)	0.046 (4)	0.002 (3)	−0.004 (2)	0.023 (3)
C11	0.027 (3)	0.051 (4)	0.039 (3)	−0.010 (3)	−0.008 (2)	0.012 (3)
C12	0.040 (4)	0.034 (4)	0.053 (4)	−0.006 (3)	0.002 (3)	0.003 (3)
C13	0.018 (2)	0.028 (3)	0.036 (3)	0.003 (2)	0.000 (2)	0.012 (2)
C14	0.029 (3)	0.029 (3)	0.036 (3)	0.004 (2)	0.007 (2)	0.010 (2)
C15	0.022 (3)	0.040 (4)	0.063 (4)	0.005 (2)	0.002 (3)	0.006 (3)
C16	0.044 (4)	0.030 (4)	0.087 (6)	0.011 (3)	0.013 (4)	−0.004 (4)
C17	0.049 (4)	0.036 (4)	0.065 (5)	0.001 (3)	0.013 (3)	−0.001 (3)
C18	0.034 (3)	0.030 (3)	0.045 (3)	−0.004 (2)	0.005 (3)	0.005 (3)

Mn1—N1	2.181 (4)	C4—H4	0.9500
Mn1—N4	2.314 (5)	C5—C6	1.390 (8)
Mn1—N6	2.331 (4)	C5—H5	0.9500
Mn1—Br2	2.4884 (11)	C6—H6	0.9500
Mn1—Br1	2.4957 (11)	C7—C8	1.490 (7)
N1—C1	1.343 (7)	C8—C9	1.399 (8)
N1—C13	1.348 (6)	C9—C10	1.387 (8)
N2—C1	1.337 (6)	C9—H9	0.9500
N2—C7	1.341 (6)	C10—C11	1.378 (9)
N3—C13	1.314 (6)	C10—H10	0.9500
N3—C7	1.359 (7)	C11—C12	1.386 (9)
N4—C6	1.343 (7)	C11—H11	0.9500
N4—C2	1.353 (6)	C12—H12	0.9500
N5—C12	1.335 (7)	C13—C14	1.486 (7)
N5—C8	1.338 (7)	C14—C15	1.387 (8)
N6—C14	1.350 (7)	C15—C16	1.383 (9)
N6—C18	1.352 (7)	C15—H15	0.9500
C1—C2	1.477 (7)	C16—C17	1.379 (9)
C2—C3	1.393 (8)	C16—H16	0.9500
C3—C4	1.390 (8)	C17—C18	1.377 (9)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.393 (8)	C18—H18	0.9500
N1—Mn1—N4	70.43 (15)	N4—C6—H6	118.3
N1—Mn1—N6	71.07 (16)	C5—C6—H6	118.3
N4—Mn1—N6	137.87 (15)	N2—C7—N3	123.9 (4)
N1—Mn1—Br2	143.00 (12)	N2—C7—C8	120.3 (5)
N4—Mn1—Br2	102.02 (11)	N3—C7—C8	115.6 (4)
N6—Mn1—Br2	98.41 (11)	N5—C8—C9	124.0 (5)
N1—Mn1—Br1	105.80 (12)	N5—C8—C7	117.3 (5)
N4—Mn1—Br1	104.49 (12)	C9—C8—C7	118.6 (5)
N6—Mn1—Br1	101.81 (12)	C10—C9—C8	117.8 (6)
Br2—Mn1—Br1	111.10 (4)	C10—C9—H9	121.1
C1—N1—C13	115.7 (4)	C8—C9—H9	121.1
C1—N1—Mn1	122.8 (3)	C11—C10—C9	119.1 (6)
C13—N1—Mn1	121.5 (3)	C11—C10—H10	120.4
C1—N2—C7	115.2 (4)	C9—C10—H10	120.4
C13—N3—C7	115.9 (4)	C10—C11—C12	118.5 (5)
C6—N4—C2	117.2 (5)	C10—C11—H11	120.8
C6—N4—Mn1	125.8 (4)	C12—C11—H11	120.8
C2—N4—Mn1	116.9 (3)	N5—C12—C11	124.2 (6)
C12—N5—C8	116.3 (5)	N5—C12—H12	117.9
C14—N6—C18	116.7 (5)	C11—C12—H12	117.9
C14—N6—Mn1	116.3 (4)	N3—C13—N1	124.1 (5)
C18—N6—Mn1	126.7 (4)	N3—C13—C14	120.9 (5)
N2—C1—N1	124.3 (4)	N1—C13—C14	114.9 (4)
N2—C1—C2	122.1 (5)	N6—C14—C15	123.6 (5)
N1—C1—C2	113.6 (4)	N6—C14—C13	114.9 (5)
N4—C2—C3	123.0 (5)	C15—C14—C13	121.5 (5)
N4—C2—C1	115.3 (5)	C16—C15—C14	118.1 (6)
C3—C2—C1	121.7 (5)	C16—C15—H15	120.9
C4—C3—C2	119.2 (5)	C14—C15—H15	120.9
C4—C3—H3	120.4	C17—C16—C15	119.3 (6)
C2—C3—H3	120.4	C17—C16—H16	120.3
C3—C4—C5	118.0 (6)	C15—C16—H16	120.3
C3—C4—H4	121.0	C18—C17—C16	119.1 (6)
C5—C4—H4	121.0	C18—C17—H17	120.5
C6—C5—C4	119.2 (5)	C16—C17—H17	120.5
C6—C5—H5	120.4	N6—C18—C17	123.2 (5)
C4—C5—H5	120.4	N6—C18—H18	118.4
N4—C6—C5	123.3 (5)	C17—C18—H18	118.4
N4—Mn1—N1—C1	−9.0 (4)	C3—C4—C5—C6	−0.5 (10)
N6—Mn1—N1—C1	−171.5 (4)	C2—N4—C6—C5	0.1 (9)
Br2—Mn1—N1—C1	−93.0 (4)	Mn1—N4—C6—C5	−177.4 (5)
Br1—Mn1—N1—C1	91.1 (4)	C4—C5—C6—N4	0.2 (10)
N4—Mn1—N1—C13	172.9 (4)	C1—N2—C7—N3	−7.0 (8)
N6—Mn1—N1—C13	10.3 (4)	C1—N2—C7—C8	177.1 (5)
Br2—Mn1—N1—C13	88.9 (4)	C13—N3—C7—N2	7.4 (8)
Br1—Mn1—N1—C13	−87.0 (4)	C13—N3—C7—C8	−176.5 (5)
N1—Mn1—N4—C6	−176.0 (5)	C12—N5—C8—C9	−1.3 (9)
N6—Mn1—N4—C6	−151.0 (4)	C12—N5—C8—C7	178.0 (5)
Br2—Mn1—N4—C6	−33.8 (5)	N2—C7—C8—N5	1.4 (8)
Br1—Mn1—N4—C6	82.0 (5)	N3—C7—C8—N5	−174.9 (5)
N1—Mn1—N4—C2	6.5 (4)	N2—C7—C8—C9	−179.4 (5)
N6—Mn1—N4—C2	31.5 (5)	N3—C7—C8—C9	4.3 (7)
Br2—Mn1—N4—C2	148.8 (4)	N5—C8—C9—C10	0.1 (9)
Br1—Mn1—N4—C2	−95.4 (4)	C7—C8—C9—C10	−179.1 (5)
N1—Mn1—N6—C14	−8.0 (4)	C8—C9—C10—C11	0.2 (9)
N4—Mn1—N6—C14	−32.9 (5)	C9—C10—C11—C12	0.6 (9)
Br2—Mn1—N6—C14	−151.4 (4)	C8—N5—C12—C11	2.2 (10)
Br1—Mn1—N6—C14	94.9 (4)	C10—C11—C12—N5	−1.9 (10)
N1—Mn1—N6—C18	177.2 (5)	C7—N3—C13—N1	0.3 (8)
N4—Mn1—N6—C18	152.3 (4)	C7—N3—C13—C14	−177.6 (5)
Br2—Mn1—N6—C18	33.8 (5)	C1—N1—C13—N3	−7.6 (8)
Br1—Mn1—N6—C18	−79.9 (5)	Mn1—N1—C13—N3	170.7 (4)
C7—N2—C1—N1	−1.2 (7)	C1—N1—C13—C14	170.5 (5)
C7—N2—C1—C2	178.8 (5)	Mn1—N1—C13—C14	−11.2 (6)
C13—N1—C1—N2	8.0 (7)	C18—N6—C14—C15	−0.2 (9)
Mn1—N1—C1—N2	−170.2 (4)	Mn1—N6—C14—C15	−175.6 (5)
C13—N1—C1—C2	−171.9 (5)	C18—N6—C14—C13	−179.4 (5)
Mn1—N1—C1—C2	9.8 (6)	Mn1—N6—C14—C13	5.3 (6)
C6—N4—C2—C3	0.0 (8)	N3—C13—C14—N6	−178.6 (5)
Mn1—N4—C2—C3	177.7 (4)	N1—C13—C14—N6	3.2 (7)
C6—N4—C2—C1	178.3 (5)	N3—C13—C14—C15	2.2 (9)
Mn1—N4—C2—C1	−4.1 (6)	N1—C13—C14—C15	−175.9 (6)
N2—C1—C2—N4	176.9 (5)	N6—C14—C15—C16	0.2 (10)
N1—C1—C2—N4	−3.1 (7)	C13—C14—C15—C16	179.3 (6)
N2—C1—C2—C3	−4.8 (8)	C14—C15—C16—C17	−0.2 (11)
N1—C1—C2—C3	175.1 (5)	C15—C16—C17—C18	0.1 (12)
N4—C2—C3—C4	−0.4 (9)	C14—N6—C18—C17	0.2 (9)
C1—C2—C3—C4	−178.5 (5)	Mn1—N6—C18—C17	175.0 (5)
C2—C3—C4—C5	0.6 (9)	C16—C17—C18—N6	−0.2 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Br1i	0.95	2.91	3.782 (6)	153.
C15—H15···Br1ii	0.95	2.91	3.744 (6)	148.

Mn1—N1	2.181 (4)
Mn1—N4	2.314 (5)
Mn1—N6	2.331 (4)
Mn1—Br2	2.4884 (11)
Mn1—Br1	2.4957 (11)

N1—Mn1—N4	70.43 (15)
N1—Mn1—N6	71.07 (16)
Br2—Mn1—Br1	111.10 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Br1i	0.95	2.91	3.782 (6)	153
C15—H15⋯Br1ii	0.95	2.91	3.744 (6)	148

Symmetry codes: (i) ; (ii) .