Diazido-bis[(1-methyl-1H-benzimidazol-2-yl)methanol-κN,O]manganese(II).

The title complex, [Mn(N(3))(2)(C(9)H(10)N(2)O)(2)], possesses crystallographically imposed twofold symmetry. The Mn(II) atom is coordinated by four N atoms and two O atoms in a distorted octa-hedral geometry. The crystal packing is stabilized by strong inter-molecular O-H⋯N hydrogen bonds.

Related literature

For the synthesis of the ligand, see: van Albada et al. (1995 ▶) and literature cited therein. For the metal(II) complexes of a similar N-heterocycle, see: Zeng et al. (2006 ▶); Zhou et al. (2007 ▶); Alagna et al. (1984 ▶); Hamilton et al. (1979 ▶).

Experimental

Crystal data

[Mn(N3)2(C9H10N2O)2]

M = 463.38

Monoclinic,

a = 15.466 (3) Å

b = 7.5438 (16) Å

c = 18.095 (4) Å

β = 109.989 (4)°

V = 1984.0 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.71 mm−1

T = 173 K

0.33 × 0.22 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan SADABS (Sheldrick, 1996 ▶) T min = 0.801, T max = 0.933

4125 measured reflections

1741 independent reflections

1345 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.116

S = 1.02

1741 reflections

142 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002126/si2238sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002126/si2238Isup2.hkl

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

[Mn(N3)2(C9H10N2O)2]	F(000) = 956
Mr = 463.38	Dx = 1.551 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1818 reflections
a = 15.466 (3) Å	θ = 2.4–26.7°
b = 7.5438 (16) Å	µ = 0.71 mm−1
c = 18.095 (4) Å	T = 173 K
β = 109.989 (4)°	Block, colorless
V = 1984.0 (7) Å3	0.33 × 0.22 × 0.10 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	1741 independent reflections
Radiation source: fine-focus sealed tube	1345 reflections with I > 2σ(I)
graphite	Rint = 0.029
phi and ω scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −16→18
Tmin = 0.801, Tmax = 0.933	k = −8→8
4125 measured reflections	l = −15→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0608P)2 + 4.1072P] where P = (Fo2 + 2Fc2)/3
1741 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.In Checkcif report, the following ALERTS were generatedPLAT230_ALERT_2_C Hirshfeld Test Diff for N3 – N4.. 5.98 su Author response: It is due to electron shift or resonance (N=N–N or N–N=N) bond lengths appear shorter than expected, see: Albada et al. (1995).

	x	y	z	Uiso*/Ueq
O1	0.12170 (15)	0.1356 (3)	0.26588 (12)	0.0324 (5)
H1	0.1264	0.0343	0.2875	0.049*
Mn1	0.0000	0.32504 (9)	0.2500	0.0247 (2)
N1	−0.00030 (17)	0.2562 (3)	0.13315 (13)	0.0228 (6)
N2	0.07803 (16)	0.1833 (3)	0.05480 (14)	0.0226 (5)
N3	0.1101 (2)	0.5198 (4)	0.28397 (17)	0.0405 (7)
N4	0.11891 (18)	0.6678 (4)	0.30523 (15)	0.0324 (7)
N5	0.1360 (3)	0.8099 (4)	0.3311 (2)	0.0545 (9)
C1	0.1524 (2)	0.1270 (5)	0.20037 (18)	0.0316 (8)
H1A	0.1698	0.0038	0.1928	0.038*
H1B	0.2070	0.2037	0.2096	0.038*
C2	0.0761 (2)	0.1879 (4)	0.12911 (17)	0.0226 (6)
C3	−0.05362 (19)	0.2995 (4)	0.05571 (17)	0.0208 (6)
C4	−0.1407 (2)	0.3733 (4)	0.02570 (18)	0.0257 (7)
H4A	−0.1745	0.4034	0.0590	0.031*
C5	−0.1764 (2)	0.4013 (4)	−0.05442 (18)	0.0307 (7)
H5A	−0.2359	0.4520	−0.0767	0.037*
C6	−0.1269 (2)	0.3569 (4)	−0.10337 (18)	0.0331 (8)
H6A	−0.1538	0.3782	−0.1583	0.040*
C7	−0.0403 (2)	0.2830 (4)	−0.07448 (18)	0.0289 (7)
H7B	−0.0068	0.2526	−0.1080	0.035*
C8	−0.0045 (2)	0.2554 (4)	0.00618 (17)	0.0230 (6)
C9	0.1533 (2)	0.1183 (5)	0.03086 (19)	0.0309 (7)
H9A	0.1617	−0.0089	0.0419	0.046*
H9B	0.2100	0.1814	0.0602	0.046*
H9C	0.1387	0.1388	−0.0256	0.046*

	U11	U22	U33	U12	U13	U23
O1	0.0388 (13)	0.0343 (13)	0.0242 (11)	0.0082 (10)	0.0111 (10)	0.0071 (9)
Mn1	0.0313 (4)	0.0266 (4)	0.0185 (3)	0.000	0.0116 (3)	0.000
N1	0.0244 (13)	0.0266 (14)	0.0183 (12)	0.0014 (11)	0.0087 (10)	−0.0004 (10)
N2	0.0221 (13)	0.0260 (13)	0.0238 (12)	0.0008 (10)	0.0129 (10)	−0.0026 (10)
N3	0.0522 (19)	0.0308 (18)	0.0451 (18)	−0.0144 (14)	0.0254 (15)	−0.0073 (14)
N4	0.0325 (15)	0.043 (2)	0.0243 (14)	−0.0057 (14)	0.0135 (12)	0.0027 (13)
N5	0.081 (3)	0.0340 (19)	0.048 (2)	−0.0135 (18)	0.0225 (19)	−0.0063 (16)
C1	0.0296 (17)	0.0375 (19)	0.0296 (17)	0.0092 (14)	0.0125 (14)	0.0043 (14)
C2	0.0248 (16)	0.0230 (16)	0.0214 (14)	−0.0001 (13)	0.0096 (12)	−0.0014 (12)
C3	0.0216 (15)	0.0198 (15)	0.0221 (14)	−0.0029 (12)	0.0088 (12)	0.0016 (11)
C4	0.0231 (16)	0.0266 (17)	0.0295 (16)	−0.0012 (13)	0.0117 (13)	−0.0016 (13)
C5	0.0238 (16)	0.0314 (18)	0.0314 (17)	0.0006 (14)	0.0023 (14)	0.0036 (14)
C6	0.0376 (19)	0.036 (2)	0.0205 (15)	−0.0087 (15)	0.0031 (14)	0.0024 (13)
C7	0.0333 (18)	0.0334 (19)	0.0235 (15)	−0.0070 (14)	0.0140 (14)	−0.0023 (13)
C8	0.0233 (15)	0.0240 (15)	0.0237 (15)	−0.0033 (12)	0.0106 (12)	−0.0022 (12)
C9	0.0273 (17)	0.0376 (19)	0.0330 (17)	0.0039 (14)	0.0170 (14)	−0.0043 (14)

O1—C1	1.421 (4)	C1—H1A	0.9900
O1—Mn1	2.302 (2)	C1—H1B	0.9900
O1—H1	0.8500	C3—C4	1.385 (4)
Mn1—N3	2.172 (3)	C3—C8	1.399 (4)
Mn1—N3i	2.172 (3)	C4—C5	1.380 (4)
Mn1—N1	2.176 (2)	C4—H4A	0.9500
Mn1—N1i	2.176 (2)	C5—C6	1.395 (5)
Mn1—O1i	2.302 (2)	C5—H5A	0.9500
N1—C2	1.314 (4)	C6—C7	1.379 (5)
N1—C3	1.400 (4)	C6—H6A	0.9500
N2—C2	1.355 (4)	C7—C8	1.388 (4)
N2—C8	1.389 (4)	C7—H7B	0.9500
N2—C9	1.459 (4)	C9—H9A	0.9800
N3—N4	1.174 (4)	C9—H9B	0.9800
N4—N5	1.163 (4)	C9—H9C	0.9800
C1—C2	1.492 (4)
C1—O1—Mn1	114.60 (17)	C2—C1—H1B	110.0
C1—O1—H1	110.0	H1A—C1—H1B	108.4
Mn1—O1—H1	123.6	N1—C2—N2	113.0 (3)
N3—Mn1—N3i	94.89 (17)	N1—C2—C1	122.2 (3)
N3—Mn1—N1	100.23 (10)	N2—C2—C1	124.8 (3)
N3i—Mn1—N1	98.36 (10)	C4—C3—C8	120.8 (3)
N3—Mn1—N1i	98.36 (10)	C4—C3—N1	130.3 (3)
N3i—Mn1—N1i	100.23 (10)	C8—C3—N1	108.8 (3)
N1—Mn1—N1i	152.37 (14)	C5—C4—C3	117.4 (3)
N3—Mn1—O1i	169.59 (9)	C5—C4—H4A	121.3
N3i—Mn1—O1i	81.74 (10)	C3—C4—H4A	121.3
N1—Mn1—O1i	90.02 (9)	C4—C5—C6	121.4 (3)
N1i—Mn1—O1i	72.72 (8)	C4—C5—H5A	119.3
N3—Mn1—O1	81.74 (10)	C6—C5—H5A	119.3
N3i—Mn1—O1	169.59 (9)	C7—C6—C5	122.0 (3)
N1—Mn1—O1	72.72 (8)	C7—C6—H6A	119.0
N1i—Mn1—O1	90.02 (9)	C5—C6—H6A	119.0
O1i—Mn1—O1	103.23 (12)	C6—C7—C8	116.5 (3)
C2—N1—C3	105.6 (2)	C6—C7—H7B	121.8
C2—N1—Mn1	116.39 (19)	C8—C7—H7B	121.8
C3—N1—Mn1	136.2 (2)	C7—C8—N2	132.4 (3)
C2—N2—C8	106.9 (2)	C7—C8—C3	121.9 (3)
C2—N2—C9	126.4 (3)	N2—C8—C3	105.7 (2)
C8—N2—C9	126.6 (2)	N2—C9—H9A	109.5
N4—N3—Mn1	136.7 (3)	N2—C9—H9B	109.5
N5—N4—N3	173.4 (4)	H9A—C9—H9B	109.5
O1—C1—C2	108.4 (2)	N2—C9—H9C	109.5
O1—C1—H1A	110.0	H9A—C9—H9C	109.5
C2—C1—H1A	110.0	H9B—C9—H9C	109.5
O1—C1—H1B	110.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N5ii	0.85	1.85	2.701 (4)	178

Table 1

Selected bond lengths (Å)

O1—Mn1	2.302 (2)
Mn1—N3	2.172 (3)
Mn1—N1	2.176 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N5ii	0.85	1.85	2.701 (4)	178

Symmetry code: (ii) .