Azido{4,4'-dibromo-2,2'-[ethane-1,2-diyl-bis(nitrilo-methanylylidene)]diphenol-ato-κO,N,N',O'}manganese(III).

In the title compound, [Mn(C(16)H(12)Br(2)N(2)O(2))(N(3))], the Mn(III) ion is chelated by a tetra-dentate Schiff base ligand and coordinated by the N atom of an azide ligand in a distorted square-pyramidal arrangement. It forms phenolate-bridged out-of-plane dimers with Mn⋯O(phenolate) distances of 2.667 (2) Å between pairs of inversion-related mol-ecules. In the crystal, there are offset inter-complex face-to-face π-π inter-actions [centroid-centroid distances = 3.598 (2) Å] involving one of the benzene rings of the ligands.

Related literature

For related structures, see: Mikuriya et al. (1992 ▶); Li et al. (1997 ▶); Lu et al. (2006 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

[Mn(n class="CellLine">C16H12Br2N2O2)(N3)]

M = 1042.13

Monoclinic,

a = 8.7068 (17) Å

b = 15.269 (3) Å

c = 13.684 (3) Å

β = 107.47 (3)°

V = 1735.4 (6) Å3

Z = 2

Mo Kα radiation

μ = 5.39 mm−1

T = 153 K

0.20 × 0.17 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.352, T max = 0.583

7747 measured reflections

3961 independent reflections

3093 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.074

S = 1.04

3961 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.82 e Å−3

Δρmin = −0.90 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and maXus (Mackay et al., 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: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004594/pk2299sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004594/pk2299Isup2.hkl

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

[Mn(C16H12Br2N2O2)(N3)]	F(000) = 1016
Mr = 1042.13	Dx = 1.994 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 19417 reflections
a = 8.7068 (17) Å	θ = 3.4–27.5°
b = 15.269 (3) Å	µ = 5.39 mm−1
c = 13.684 (3) Å	T = 153 K
β = 107.47 (3)°	Block, black
V = 1735.4 (6) Å3	0.20 × 0.17 × 0.10 mm
Z = 2

Nonius KappaCCD diffractometer	3961 independent reflections
Radiation source: fine-focus sealed tube	3093 reflections with I > 2σ(I)
graphite	Rint = 0.015
ω scans	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −11→11
Tmin = 0.352, Tmax = 0.583	k = −19→19
7747 measured reflections	l = −17→17

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0376P)2 + 0.8161P] where P = (Fo2 + 2Fc2)/3
3961 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.82 e Å−3
0 restraints	Δρmin = −0.90 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	0.85052 (5)	0.50918 (2)	0.38001 (3)	0.02912 (10)
Br1	1.11255 (4)	0.95137 (2)	0.37896 (3)	0.05433 (11)
Br2	0.43251 (4)	0.106181 (19)	0.44904 (2)	0.04785 (10)
C1	0.9787 (3)	0.67065 (17)	0.46365 (19)	0.0282 (5)
C2	0.9438 (3)	0.74469 (17)	0.5129 (2)	0.0323 (6)
H2	0.8919	0.7381	0.5627	0.039*
C3	0.9851 (3)	0.82750 (18)	0.4890 (2)	0.0358 (6)
H3	0.9580	0.8764	0.5208	0.043*
C4	1.0675 (3)	0.83713 (17)	0.4168 (2)	0.0336 (6)
C5	1.1113 (3)	0.76578 (18)	0.3710 (2)	0.0321 (6)
H5	1.1715	0.7732	0.3258	0.039*
C6	1.0655 (3)	0.68135 (17)	0.39187 (19)	0.0279 (5)
C7	1.1100 (3)	0.60754 (17)	0.33963 (19)	0.0307 (5)
H7	1.1928	0.6147	0.3104	0.037*
C8	1.0902 (4)	0.45714 (18)	0.2823 (2)	0.0403 (7)
H8A	1.1603	0.4191	0.3333	0.048*
H8B	1.1476	0.4763	0.2354	0.048*
C9	0.9380 (4)	0.4093 (2)	0.2250 (2)	0.0446 (7)
H9A	0.8813	0.4411	0.1634	0.054*
H9B	0.9636	0.3512	0.2056	0.054*
C10	0.7619 (3)	0.33187 (17)	0.30160 (19)	0.0314 (5)
H10	0.7730	0.2845	0.2615	0.038*
C11	0.6617 (3)	0.32053 (16)	0.36746 (19)	0.0274 (5)
C12	0.6028 (3)	0.23581 (17)	0.37468 (19)	0.0309 (5)
H12	0.6289	0.1898	0.3380	0.037*
C13	0.5066 (3)	0.22139 (16)	0.4361 (2)	0.0316 (6)
C14	0.4649 (3)	0.28895 (18)	0.4908 (2)	0.0348 (6)
H14	0.3986	0.2780	0.5315	0.042*
C15	0.5215 (3)	0.37191 (18)	0.4848 (2)	0.0344 (6)
H15	0.4912	0.4173	0.5204	0.041*
C16	0.6248 (3)	0.38931 (16)	0.4256 (2)	0.0285 (5)
N1	1.0407 (3)	0.53307 (14)	0.33190 (16)	0.0304 (5)
N2	0.8372 (3)	0.40293 (14)	0.29446 (16)	0.0314 (5)
N3	0.7109 (3)	0.60055 (17)	0.2717 (2)	0.0449 (6)
N4	0.5810 (3)	0.62722 (17)	0.26329 (18)	0.0412 (6)
N5	0.4533 (4)	0.6552 (3)	0.2518 (3)	0.0747 (10)
O1	0.9342 (2)	0.59151 (11)	0.48779 (14)	0.0333 (4)
O2	0.6852 (2)	0.46910 (12)	0.42930 (15)	0.0362 (4)

	U11	U22	U33	U12	U13	U23
Mn1	0.0366 (2)	0.02311 (19)	0.0337 (2)	−0.00517 (16)	0.01976 (18)	−0.00327 (16)
Br1	0.0655 (2)	0.02778 (16)	0.0791 (3)	−0.00838 (14)	0.03595 (19)	0.00547 (15)
Br2	0.0672 (2)	0.02952 (16)	0.05173 (19)	−0.01626 (14)	0.02536 (16)	−0.00135 (13)
C1	0.0296 (12)	0.0273 (13)	0.0273 (12)	−0.0038 (10)	0.0079 (11)	0.0013 (10)
C2	0.0329 (13)	0.0305 (13)	0.0362 (14)	−0.0032 (11)	0.0147 (12)	−0.0028 (11)
C3	0.0336 (14)	0.0287 (14)	0.0472 (16)	−0.0010 (11)	0.0154 (13)	−0.0036 (12)
C4	0.0332 (14)	0.0243 (12)	0.0417 (15)	−0.0062 (11)	0.0090 (12)	0.0028 (11)
C5	0.0304 (13)	0.0330 (14)	0.0331 (14)	−0.0066 (11)	0.0096 (11)	0.0033 (11)
C6	0.0284 (12)	0.0273 (13)	0.0285 (13)	−0.0026 (10)	0.0092 (11)	0.0025 (10)
C7	0.0322 (13)	0.0331 (14)	0.0293 (13)	−0.0012 (11)	0.0129 (11)	0.0040 (11)
C8	0.0549 (18)	0.0305 (14)	0.0490 (17)	0.0016 (13)	0.0359 (15)	−0.0012 (12)
C9	0.070 (2)	0.0367 (16)	0.0416 (16)	−0.0095 (14)	0.0383 (16)	−0.0092 (13)
C10	0.0389 (14)	0.0269 (13)	0.0282 (13)	0.0003 (11)	0.0101 (11)	−0.0034 (10)
C11	0.0288 (12)	0.0250 (13)	0.0282 (13)	−0.0032 (10)	0.0080 (11)	−0.0008 (10)
C12	0.0363 (14)	0.0244 (13)	0.0305 (13)	−0.0038 (11)	0.0076 (11)	−0.0027 (10)
C13	0.0355 (14)	0.0239 (13)	0.0327 (13)	−0.0065 (10)	0.0061 (12)	0.0009 (10)
C14	0.0326 (14)	0.0335 (14)	0.0417 (15)	−0.0060 (11)	0.0162 (13)	−0.0004 (12)
C15	0.0349 (14)	0.0295 (14)	0.0438 (16)	−0.0020 (11)	0.0194 (13)	−0.0047 (12)
C16	0.0290 (12)	0.0219 (12)	0.0357 (14)	−0.0037 (10)	0.0112 (11)	−0.0011 (10)
N1	0.0386 (12)	0.0272 (11)	0.0309 (11)	−0.0008 (9)	0.0189 (10)	0.0017 (9)
N2	0.0432 (12)	0.0282 (11)	0.0283 (11)	−0.0045 (10)	0.0190 (10)	−0.0033 (9)
N3	0.0442 (15)	0.0419 (15)	0.0490 (15)	−0.0026 (12)	0.0146 (12)	0.0109 (12)
N4	0.0473 (15)	0.0413 (14)	0.0349 (13)	−0.0036 (12)	0.0121 (12)	0.0038 (11)
N5	0.061 (2)	0.105 (3)	0.060 (2)	0.028 (2)	0.0223 (17)	0.0147 (19)
O1	0.0480 (11)	0.0255 (9)	0.0327 (9)	−0.0090 (8)	0.0215 (9)	−0.0016 (7)
O2	0.0427 (11)	0.0239 (9)	0.0514 (12)	−0.0061 (8)	0.0283 (10)	−0.0083 (8)

Mn1—O2	1.8669 (18)	C8—C9	1.511 (4)
Mn1—O1	1.9083 (19)	C8—H8A	0.9700
Mn1—N2	1.984 (2)	C8—H8B	0.9700
Mn1—N1	1.991 (2)	C9—N2	1.478 (3)
Mn1—N3	2.130 (3)	C9—H9A	0.9700
Br1—C4	1.894 (3)	C9—H9B	0.9700
Br2—C13	1.900 (2)	C10—N2	1.286 (3)
C1—O1	1.340 (3)	C10—C11	1.441 (3)
C1—C2	1.396 (4)	C10—H10	0.9300
C1—C6	1.418 (3)	C11—C12	1.406 (3)
C2—C3	1.381 (4)	C11—C16	1.411 (3)
C2—H2	0.9300	C12—C13	1.371 (4)
C3—C4	1.392 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.385 (4)
C4—C5	1.367 (4)	C14—C15	1.371 (4)
C5—C6	1.404 (4)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.405 (4)
C6—C7	1.448 (4)	C15—H15	0.9300
C7—N1	1.277 (3)	C16—O2	1.322 (3)
C7—H7	0.9300	N3—N4	1.175 (3)
C8—N1	1.472 (3)	N4—N5	1.157 (4)
O2—Mn1—O1	95.38 (8)	N2—C9—C8	107.2 (2)
O2—Mn1—N2	91.73 (8)	N2—C9—H9A	110.3
O1—Mn1—N2	159.40 (9)	C8—C9—H9A	110.3
O2—Mn1—N1	171.04 (9)	N2—C9—H9B	110.3
O1—Mn1—N1	88.41 (9)	C8—C9—H9B	110.3
N2—Mn1—N1	82.06 (9)	H9A—C9—H9B	108.5
O2—Mn1—N3	97.19 (10)	N2—C10—C11	124.5 (2)
O1—Mn1—N3	96.43 (10)	N2—C10—H10	117.7
N2—Mn1—N3	101.83 (10)	C11—C10—H10	117.7
N1—Mn1—N3	90.43 (9)	C12—C11—C16	119.7 (2)
O1—C1—C2	119.4 (2)	C12—C11—C10	117.2 (2)
O1—C1—C6	121.9 (2)	C16—C11—C10	123.1 (2)
C2—C1—C6	118.7 (2)	C13—C12—C11	119.6 (2)
C3—C2—C1	121.2 (2)	C13—C12—H12	120.2
C3—C2—H2	119.4	C11—C12—H12	120.2
C1—C2—H2	119.4	C12—C13—C14	121.3 (2)
C2—C3—C4	119.4 (3)	C12—C13—Br2	119.5 (2)
C2—C3—H3	120.3	C14—C13—Br2	119.22 (19)
C4—C3—H3	120.3	C15—C14—C13	119.9 (2)
C5—C4—C3	121.0 (2)	C15—C14—H14	120.0
C5—C4—Br1	119.94 (19)	C13—C14—H14	120.0
C3—C4—Br1	119.0 (2)	C14—C15—C16	120.9 (2)
C4—C5—C6	120.2 (2)	C14—C15—H15	119.6
C4—C5—H5	119.9	C16—C15—H15	119.6
C6—C5—H5	119.9	O2—C16—C15	117.9 (2)
C5—C6—C1	119.3 (2)	O2—C16—C11	123.6 (2)
C5—C6—C7	118.7 (2)	C15—C16—C11	118.5 (2)
C1—C6—C7	122.0 (2)	C7—N1—C8	122.9 (2)
N1—C7—C6	123.0 (2)	C7—N1—Mn1	123.72 (18)
N1—C7—H7	118.5	C8—N1—Mn1	113.33 (16)
C6—C7—H7	118.5	C10—N2—C9	121.2 (2)
N1—C8—C9	106.7 (2)	C10—N2—Mn1	125.88 (17)
N1—C8—H8A	110.4	C9—N2—Mn1	112.66 (17)
C9—C8—H8A	110.4	N4—N3—Mn1	128.8 (2)
N1—C8—H8B	110.4	N5—N4—N3	177.5 (3)
C9—C8—H8B	110.4	C1—O1—Mn1	118.36 (16)
H8A—C8—H8B	108.6	C16—O2—Mn1	128.97 (16)
O1—C1—C2—C3	−178.9 (3)	O1—Mn1—N1—C7	−33.1 (2)
C6—C1—C2—C3	3.3 (4)	N2—Mn1—N1—C7	165.2 (2)
C1—C2—C3—C4	−2.1 (4)	N3—Mn1—N1—C7	63.3 (2)
C2—C3—C4—C5	−1.4 (4)	O2—Mn1—N1—C8	34.1 (7)
C2—C3—C4—Br1	176.4 (2)	O1—Mn1—N1—C8	149.32 (19)
C3—C4—C5—C6	3.6 (4)	N2—Mn1—N1—C8	−12.37 (19)
Br1—C4—C5—C6	−174.3 (2)	N3—Mn1—N1—C8	−114.3 (2)
C4—C5—C6—C1	−2.3 (4)	C11—C10—N2—C9	179.9 (3)
C4—C5—C6—C7	178.2 (2)	C11—C10—N2—Mn1	6.0 (4)
O1—C1—C6—C5	−178.9 (2)	C8—C9—N2—C10	−137.6 (3)
C2—C1—C6—C5	−1.2 (4)	C8—C9—N2—Mn1	37.1 (3)
O1—C1—C6—C7	0.6 (4)	O2—Mn1—N2—C10	−13.6 (2)
C2—C1—C6—C7	178.3 (2)	O1—Mn1—N2—C10	96.7 (3)
C5—C6—C7—N1	−161.0 (3)	N1—Mn1—N2—C10	159.9 (2)
C1—C6—C7—N1	19.5 (4)	N3—Mn1—N2—C10	−111.3 (2)
N1—C8—C9—N2	−45.4 (3)	O2—Mn1—N2—C9	172.0 (2)
N2—C10—C11—C12	−173.0 (3)	O1—Mn1—N2—C9	−77.7 (3)
N2—C10—C11—C16	5.3 (4)	N1—Mn1—N2—C9	−14.4 (2)
C16—C11—C12—C13	1.7 (4)	N3—Mn1—N2—C9	74.3 (2)
C10—C11—C12—C13	−179.9 (2)	O2—Mn1—N3—N4	12.9 (3)
C11—C12—C13—C14	0.5 (4)	O1—Mn1—N3—N4	−83.4 (3)
C11—C12—C13—Br2	−178.1 (2)	N2—Mn1—N3—N4	106.2 (3)
C12—C13—C14—C15	−0.7 (4)	N1—Mn1—N3—N4	−171.8 (3)
Br2—C13—C14—C15	178.0 (2)	Mn1—N3—N4—N5	−177 (100)
C13—C14—C15—C16	−1.5 (4)	C2—C1—O1—Mn1	139.8 (2)
C14—C15—C16—O2	−174.8 (3)	C6—C1—O1—Mn1	−42.5 (3)
C14—C15—C16—C11	3.7 (4)	O2—Mn1—O1—C1	−138.02 (18)
C12—C11—C16—O2	174.7 (2)	N2—Mn1—O1—C1	112.3 (3)
C10—C11—C16—O2	−3.6 (4)	N1—Mn1—O1—C1	50.12 (18)
C12—C11—C16—C15	−3.8 (4)	N3—Mn1—O1—C1	−40.14 (19)
C10—C11—C16—C15	177.9 (2)	C15—C16—O2—Mn1	168.3 (2)
C6—C7—N1—C8	−177.5 (2)	C11—C16—O2—Mn1	−10.2 (4)
C6—C7—N1—Mn1	5.1 (4)	O1—Mn1—O2—C16	−144.9 (2)
C9—C8—N1—C7	−142.4 (3)	N2—Mn1—O2—C16	15.7 (2)
C9—C8—N1—Mn1	35.2 (3)	N1—Mn1—O2—C16	−30.2 (7)
O2—Mn1—N1—C7	−148.3 (5)	N3—Mn1—O2—C16	117.9 (2)