Bis(azido-κN)bis-[6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine-κ(2)N(1),N(6)]manganese(II).

In the title complex, [Mn(N(3))(2)(C(8)H(8)N(6))(2)], the complete molecule is generated by the application of twofold symmetry, and is in a distorted octa-hedral environment, coordinated by four N atoms of two bidentate 6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine ligands and two N atoms from two azide anions. The two chelated 6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine ligands form a dihedral angle 74.75 (5)°. The mononuclear mol-ecules are alternatively linked into layers parallel to the ac plane via N-H⋯N hydrogen bonds. Adjacent layers are connected into a three-dimensional supra-molecular framework by futher N-H⋯N hydrogen-bonding inter-actions.

Related literature

For background to pyridyl-substituted diamino­triazine and azide ligands, see: Duong et al. (2011 ▶); He et al. (2004 ▶); Carranza et al. (2008 ▶). For an isotypic ZnII structure, see: Zhao et al. (2009 ▶).

Experimental

Crystal data

[Mn(N3)2(C8H8N6)2]

M = 515.41

Monoclinic,

a = 18.330 (3) Å

b = 14.412 (3) Å

c = 9.1915 (17) Å

β = 115.044 (2)°

V = 2199.8 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.65 mm−1

T = 293 K

0.17 × 0.11 × 0.10 mm

Data collection

Bruker APEXII 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.924, T max = 0.947

7095 measured reflections

2600 independent reflections

1562 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.106

S = 1.01

2600 reflections

159 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201046X/pv2519sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201046X/pv2519Isup2.hkl

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

[Mn(N3)2(C8H8N6)2]	F(000) = 1052
Mr = 515.41	Dx = 1.556 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1457 reflections
a = 18.330 (3) Å	θ = 2.5–21.6°
b = 14.412 (3) Å	µ = 0.65 mm−1
c = 9.1915 (17) Å	T = 293 K
β = 115.044 (2)°	Block, pink
V = 2199.8 (7) Å3	0.17 × 0.11 × 0.10 mm
Z = 4

Bruker APEXII 1K CCD area-detector diffractometer	2600 independent reflections
Radiation source: fine-focus sealed tube	1562 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
phi and ω scans	θmax = 28.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −21→24
Tmin = 0.924, Tmax = 0.947	k = −19→17
7095 measured reflections	l = −11→11

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) = 0.106	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0378P)2] where P = (Fo2 + 2Fc2)/3
2600 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.38 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	0.5000	0.26907 (4)	0.2500	0.0319 (2)
N1	0.41792 (13)	0.16367 (15)	0.2907 (3)	0.0378 (6)
N2	0.27367 (13)	0.16204 (14)	−0.1202 (2)	0.0341 (6)
N3	0.32528 (13)	0.25285 (15)	−0.2755 (2)	0.0352 (6)
N4	0.39898 (13)	0.23967 (15)	0.0092 (2)	0.0319 (5)
N5	0.44191 (14)	0.33368 (17)	−0.1419 (3)	0.0506 (7)
H5A	0.4366	0.3567	−0.2322	0.061*
H5B	0.4825	0.3490	−0.0548	0.061*
N6	0.20573 (14)	0.17337 (17)	−0.3926 (3)	0.0517 (8)
H6A	0.2000	0.1938	−0.4847	0.062*
H6B	0.1697	0.1376	−0.3858	0.062*
N7	0.56500 (14)	0.37854 (17)	0.1881 (3)	0.0400 (6)
N8	0.58818 (14)	0.44325 (19)	0.2785 (3)	0.0420 (6)
N9	0.61109 (17)	0.50489 (19)	0.3684 (3)	0.0631 (9)
C1	0.4266 (2)	0.1298 (2)	0.4336 (4)	0.0555 (9)
H1A	0.4746	0.1416	0.5230	0.067*
C2	0.3687 (2)	0.0789 (2)	0.4542 (4)	0.0595 (10)
H2A	0.3773	0.0572	0.5555	0.071*
C3	0.29800 (19)	0.0605 (2)	0.3237 (4)	0.0478 (8)
H3A	0.2576	0.0263	0.3350	0.057*
C4	0.28749 (17)	0.09327 (18)	0.1750 (3)	0.0385 (7)
H4A	0.2403	0.0807	0.0843	0.046*
C5	0.34803 (16)	0.14502 (18)	0.1631 (3)	0.0306 (6)
C6	0.33940 (16)	0.18485 (17)	0.0066 (3)	0.0291 (6)
C7	0.26999 (16)	0.19689 (19)	−0.2612 (3)	0.0341 (7)
C8	0.38731 (16)	0.27449 (19)	−0.1370 (3)	0.0329 (6)

	U11	U22	U33	U12	U13	U23
Mn1	0.0284 (3)	0.0374 (4)	0.0248 (3)	0.000	0.0064 (2)	0.000
N1	0.0369 (14)	0.0401 (15)	0.0285 (13)	−0.0048 (11)	0.0062 (11)	0.0062 (10)
N2	0.0321 (13)	0.0406 (14)	0.0254 (12)	−0.0039 (11)	0.0081 (10)	0.0001 (10)
N3	0.0322 (13)	0.0442 (15)	0.0243 (12)	−0.0066 (11)	0.0073 (10)	−0.0001 (10)
N4	0.0304 (13)	0.0382 (14)	0.0243 (11)	−0.0043 (11)	0.0087 (10)	0.0007 (10)
N5	0.0422 (16)	0.076 (2)	0.0260 (13)	−0.0219 (14)	0.0071 (11)	0.0089 (12)
N6	0.0431 (16)	0.076 (2)	0.0263 (13)	−0.0227 (14)	0.0057 (12)	0.0010 (12)
N7	0.0357 (15)	0.0461 (16)	0.0370 (14)	−0.0042 (12)	0.0142 (12)	−0.0013 (12)
N8	0.0308 (14)	0.0508 (17)	0.0409 (15)	−0.0008 (13)	0.0119 (12)	0.0098 (13)
N9	0.069 (2)	0.0530 (19)	0.0545 (18)	−0.0183 (15)	0.0141 (16)	−0.0114 (14)
C1	0.053 (2)	0.063 (2)	0.0345 (18)	−0.0142 (17)	0.0040 (15)	0.0131 (15)
C2	0.070 (2)	0.064 (2)	0.0374 (18)	−0.0201 (19)	0.0166 (17)	0.0160 (16)
C3	0.054 (2)	0.0431 (19)	0.052 (2)	−0.0071 (16)	0.0276 (17)	0.0071 (15)
C4	0.0367 (18)	0.0364 (17)	0.0383 (16)	−0.0056 (13)	0.0118 (14)	−0.0016 (13)
C5	0.0336 (16)	0.0296 (15)	0.0284 (14)	−0.0004 (12)	0.0127 (12)	0.0009 (12)
C6	0.0303 (15)	0.0286 (15)	0.0273 (14)	0.0015 (12)	0.0111 (12)	−0.0009 (11)
C7	0.0287 (16)	0.0393 (17)	0.0286 (15)	0.0007 (13)	0.0067 (12)	−0.0020 (12)
C8	0.0298 (15)	0.0406 (17)	0.0264 (14)	−0.0005 (13)	0.0100 (12)	0.0007 (12)

Mn1—N7i	2.192 (2)	N5—H5B	0.8600
Mn1—N7	2.192 (2)	N6—C7	1.325 (3)
Mn1—N4	2.244 (2)	N6—H6A	0.8600
Mn1—N4i	2.244 (2)	N6—H6B	0.8600
Mn1—N1	2.277 (2)	N7—N8	1.201 (3)
Mn1—N1i	2.277 (2)	N8—N9	1.164 (3)
N1—C1	1.346 (3)	C1—C2	1.368 (4)
N1—C5	1.348 (3)	C1—H1A	0.9300
N2—C6	1.315 (3)	C2—C3	1.369 (4)
N2—C7	1.365 (3)	C2—H2A	0.9300
N3—C8	1.336 (3)	C3—C4	1.380 (4)
N3—C7	1.345 (3)	C3—H3A	0.9300
N4—C6	1.340 (3)	C4—C5	1.379 (4)
N4—C8	1.364 (3)	C4—H4A	0.9300
N5—C8	1.330 (3)	C5—C6	1.493 (3)
N5—H5A	0.8600
N7i—Mn1—N7	87.95 (13)	H6A—N6—H6B	120.0
N7i—Mn1—N4	94.56 (8)	N8—N7—Mn1	116.8 (2)
N7—Mn1—N4	101.08 (8)	N9—N8—N7	178.8 (3)
N7i—Mn1—N4i	101.08 (8)	N1—C1—C2	123.4 (3)
N7—Mn1—N4i	94.56 (8)	N1—C1—H1A	118.3
N4—Mn1—N4i	158.23 (11)	C2—C1—H1A	118.3
N7i—Mn1—N1	88.17 (9)	C1—C2—C3	119.0 (3)
N7—Mn1—N1	172.72 (8)	C1—C2—H2A	120.5
N4—Mn1—N1	73.10 (8)	C3—C2—H2A	120.5
N4i—Mn1—N1	92.23 (8)	C2—C3—C4	119.0 (3)
N7i—Mn1—N1i	172.72 (8)	C2—C3—H3A	120.5
N7—Mn1—N1i	88.17 (9)	C4—C3—H3A	120.5
N4—Mn1—N1i	92.23 (8)	C5—C4—C3	119.0 (3)
N4i—Mn1—N1i	73.10 (8)	C5—C4—H4A	120.5
N1—Mn1—N1i	96.33 (12)	C3—C4—H4A	120.5
C1—N1—C5	117.0 (2)	N1—C5—C4	122.6 (2)
C1—N1—Mn1	126.03 (19)	N1—C5—C6	115.8 (2)
C5—N1—Mn1	116.15 (17)	C4—C5—C6	121.6 (2)
C6—N2—C7	114.1 (2)	N2—C6—N4	126.7 (2)
C8—N3—C7	114.8 (2)	N2—C6—C5	116.2 (2)
C6—N4—C8	114.4 (2)	N4—C6—C5	117.1 (2)
C6—N4—Mn1	117.05 (16)	N6—C7—N3	118.7 (3)
C8—N4—Mn1	128.46 (18)	N6—C7—N2	116.0 (3)
C8—N5—H5A	120.0	N3—C7—N2	125.3 (2)
C8—N5—H5B	120.0	N5—C8—N3	117.8 (2)
H5A—N5—H5B	120.0	N5—C8—N4	117.6 (2)
C7—N6—H6A	120.0	N3—C8—N4	124.6 (3)
C7—N6—H6B	120.0
N7i—Mn1—N1—C1	−81.4 (3)	C1—N1—C5—C4	−0.4 (4)
N4—Mn1—N1—C1	−176.8 (3)	Mn1—N1—C5—C4	−170.5 (2)
N4i—Mn1—N1—C1	19.6 (3)	C1—N1—C5—C6	178.9 (3)
N1i—Mn1—N1—C1	92.8 (3)	Mn1—N1—C5—C6	8.9 (3)
N7i—Mn1—N1—C5	87.6 (2)	C3—C4—C5—N1	1.2 (4)
N4—Mn1—N1—C5	−7.71 (19)	C3—C4—C5—C6	−178.2 (3)
N4i—Mn1—N1—C5	−171.4 (2)	C7—N2—C6—N4	2.4 (4)
N1i—Mn1—N1—C5	−98.1 (2)	C7—N2—C6—C5	−177.4 (2)
N7i—Mn1—N4—C6	−81.2 (2)	C8—N4—C6—N2	0.7 (4)
N7—Mn1—N4—C6	−170.01 (19)	Mn1—N4—C6—N2	177.3 (2)
N4i—Mn1—N4—C6	54.83 (18)	C8—N4—C6—C5	−179.5 (2)
N1—Mn1—N4—C6	5.48 (18)	Mn1—N4—C6—C5	−2.9 (3)
N1i—Mn1—N4—C6	101.42 (19)	N1—C5—C6—N2	175.8 (2)
N7i—Mn1—N4—C8	94.8 (2)	C4—C5—C6—N2	−4.9 (4)
N7—Mn1—N4—C8	6.0 (2)	N1—C5—C6—N4	−4.1 (4)
N4i—Mn1—N4—C8	−129.1 (2)	C4—C5—C6—N4	175.3 (2)
N1—Mn1—N4—C8	−178.5 (2)	C8—N3—C7—N6	178.8 (3)
N1i—Mn1—N4—C8	−82.5 (2)	C8—N3—C7—N2	−0.5 (4)
N7i—Mn1—N7—N8	43.16 (18)	C6—N2—C7—N6	178.2 (2)
N4—Mn1—N7—N8	137.4 (2)	C6—N2—C7—N3	−2.6 (4)
N4i—Mn1—N7—N8	−57.8 (2)	C7—N3—C8—N5	−176.4 (3)
N1i—Mn1—N7—N8	−130.7 (2)	C7—N3—C8—N4	4.1 (4)
C5—N1—C1—C2	−0.3 (5)	C6—N4—C8—N5	176.3 (2)
Mn1—N1—C1—C2	168.6 (3)	Mn1—N4—C8—N5	0.1 (4)
N1—C1—C2—C3	0.3 (6)	C6—N4—C8—N3	−4.2 (4)
C1—C2—C3—C4	0.4 (5)	Mn1—N4—C8—N3	179.68 (19)
C2—C3—C4—C5	−1.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···N7	0.86	2.14	2.986 (3)	166
N5—H5A···N9ii	0.86	2.32	2.996 (4)	136
N6—H6A···N3iii	0.86	2.19	3.048 (3)	175
N6—H6B···N7iv	0.86	2.30	3.063 (3)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5B⋯N7	0.86	2.14	2.986 (3)	166
N5—H5A⋯N9i	0.86	2.32	2.996 (4)	136
N6—H6A⋯N3ii	0.86	2.19	3.048 (3)	175
N6—H6B⋯N7iii	0.86	2.30	3.063 (3)	148

Symmetry codes: (i) ; (ii) ; (iii) .