Dimeric (2-cyano-phenolato-κO){2,2'-[ethyl-enebis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III) monohydrate.

The molecules of the title compound, [Mn(C(7)H(4)NO)(C(16)H(14)N(2)O(2))]·H(2)O, form dimers in the solid state across a crystallographic inversion center. The bridging Mn(2)O(2) group is built of phen-oxy groups, and is asymmetric, with an Mn-O distances of 1.9002 (13) and 2.6236 (14) Å. A substantial cavity between the two Mn atoms [Mn⋯Mn = 3.5082 (4) Å] is produced by the formation of the dimer. In the crystal, an extended network of O-H⋯O hydrogen-bonding inter-actions stabil-izes the structure.

Related literature

For related structures, see: Mirkhani et al. (2006 ▶); Oyaizu et al. (2000 ▶); Zhang et al. (2009 ▶). For applications of MnII complexes in catalysis, see: Ourari et al. (2006 ▶, 2008 ▶); Srinivasan et al. (1986 ▶); Salomao et al. (2007 ▶); Moutet & Ourari (1997 ▶). For the synthesis, see: Trivedi et al. (1992 ▶).

Experimental

Crystal data

[Mn(C7H4NO)(C16H12N2O2)]·H2O

M = 457.36

Monoclinic,

a = 12.8693 (3) Å

b = 14.2487 (3) Å

c = 11.6357 (3) Å

β = 104.297 (1)°

V = 2067.57 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.67 mm−1

T = 293 K

0.08 × 0.06 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

8907 measured reflections

4732 independent reflections

3574 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 1.05

4601 reflections

288 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026584/om2428sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026584/om2428Isup2.hkl

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

[Mn(C7H4NO)(C16H14N2O2)]·H2O	F(000) = 944
Mr = 457.36	Dx = 1.469 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3574 reflections
a = 12.8693 (3) Å	θ = 1.0–27.5°
b = 14.2487 (3) Å	µ = 0.67 mm−1
c = 11.6357 (3) Å	T = 293 K
β = 104.297 (1)°	Prism, brown
V = 2067.57 (8) Å3	0.08 × 0.06 × 0.04 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3574 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
graphite	θmax = 27.5°, θmin = 3.1°
Detector resolution: 8.192 pixels mm-1	h = −16→16
ω scans	k = −18→18
8907 measured reflections	l = −15→15
4732 independent reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.4975P] where P = (Fo2 + 2Fc2)/3
4601 reflections	(Δ/σ)max = 0.003
288 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.99092 (2)	0.43893 (2)	0.62805 (2)	0.02983 (10)
O1	0.90494 (10)	0.43871 (10)	0.46974 (11)	0.0357 (3)
O2	1.08666 (10)	0.34558 (9)	0.60129 (11)	0.0350 (3)
O3	0.89791 (11)	0.35388 (11)	0.70612 (13)	0.0448 (4)
N1	0.91679 (14)	0.55496 (11)	0.66080 (14)	0.0354 (4)
N2	1.08619 (13)	0.46912 (11)	0.78489 (13)	0.0339 (3)
N3	0.7505 (2)	0.48210 (18)	0.8743 (2)	0.0767 (7)
C1	0.79945 (15)	0.45831 (14)	0.44352 (17)	0.0337 (4)
C2	0.73190 (17)	0.41319 (16)	0.34833 (19)	0.0435 (5)
H2	0.7596	0.3694	0.3046	0.052*
C3	0.62331 (18)	0.43313 (17)	0.3182 (2)	0.0525 (6)
H3	0.5786	0.4019	0.2547	0.063*
C4	0.58015 (18)	0.49842 (19)	0.3805 (2)	0.0568 (6)
H4	0.5068	0.5102	0.3599	0.068*
C5	0.64539 (18)	0.54566 (17)	0.4724 (2)	0.0483 (5)
H5	0.6166	0.5916	0.5122	0.058*
C6	0.75579 (16)	0.52575 (14)	0.50774 (18)	0.0373 (4)
C7	0.82058 (17)	0.57678 (15)	0.60655 (18)	0.0397 (5)
H7	0.7904	0.6294	0.6329	0.048*
C8	0.97976 (19)	0.60968 (15)	0.76127 (19)	0.0445 (5)
H8A	0.9330	0.6482	0.7954	0.053*
H8B	1.0302	0.6502	0.7356	0.053*
C9	1.03842 (19)	0.53916 (16)	0.85072 (18)	0.0426 (5)
H9A	1.0941	0.5700	0.9103	0.051*
H9B	0.9891	0.5089	0.8900	0.051*
C10	1.17722 (17)	0.43171 (15)	0.83253 (17)	0.0387 (4)
H10	1.2138	0.4538	0.9067	0.046*
C11	1.22743 (15)	0.35839 (14)	0.78078 (17)	0.0362 (4)
C12	1.32795 (17)	0.32527 (17)	0.84575 (19)	0.0465 (5)
H12	1.3599	0.3530	0.9182	0.056*
C13	1.38001 (18)	0.25341 (17)	0.8053 (2)	0.0488 (5)
H13	1.4465	0.2327	0.8492	0.059*
C14	1.33099 (18)	0.21203 (16)	0.6970 (2)	0.0460 (5)
H14	1.3648	0.1623	0.6692	0.055*
C15	1.23384 (17)	0.24326 (14)	0.63047 (19)	0.0405 (5)
H15	1.2033	0.2148	0.5581	0.049*
C16	1.17987 (15)	0.31754 (13)	0.66996 (16)	0.0328 (4)
C17	0.80118 (16)	0.31955 (14)	0.66939 (17)	0.0365 (4)
C18	0.7748 (2)	0.25034 (16)	0.5805 (2)	0.0474 (5)
H18	0.8274	0.2283	0.5451	0.057*
C19	0.6724 (2)	0.21485 (19)	0.5453 (2)	0.0584 (6)
H19	0.6570	0.1695	0.4860	0.070*
C20	0.5921 (2)	0.2451 (2)	0.5959 (2)	0.0607 (7)
H20	0.5235	0.2200	0.5715	0.073*
C21	0.61415 (18)	0.31221 (18)	0.6821 (2)	0.0517 (6)
H21	0.5603	0.3329	0.7166	0.062*
C22	0.71671 (17)	0.34976 (15)	0.71865 (18)	0.0404 (5)
C23	0.7380 (2)	0.42338 (17)	0.8061 (2)	0.0514 (6)
O1W	0.9967 (2)	0.18475 (15)	0.44789 (18)	0.0744 (6)
H2W	0.962 (3)	0.185 (3)	0.366 (3)	0.110 (13)*
H1W	1.004 (4)	0.244 (3)	0.461 (4)	0.125 (16)*

	U11	U22	U33	U12	U13	U23
Mn1	0.03033 (16)	0.03349 (17)	0.02616 (15)	0.00335 (11)	0.00787 (11)	−0.00182 (11)
O1	0.0314 (7)	0.0465 (8)	0.0293 (6)	0.0064 (6)	0.0079 (5)	−0.0036 (6)
O2	0.0332 (7)	0.0383 (7)	0.0326 (7)	0.0049 (6)	0.0061 (5)	−0.0033 (5)
O3	0.0369 (7)	0.0539 (9)	0.0434 (8)	−0.0077 (7)	0.0098 (6)	0.0072 (7)
N1	0.0408 (9)	0.0361 (9)	0.0321 (8)	0.0045 (7)	0.0142 (7)	−0.0014 (7)
N2	0.0382 (9)	0.0366 (8)	0.0276 (8)	−0.0009 (7)	0.0095 (6)	−0.0017 (6)
N3	0.110 (2)	0.0640 (15)	0.0607 (14)	0.0043 (14)	0.0301 (14)	−0.0113 (12)
C1	0.0298 (9)	0.0394 (10)	0.0326 (9)	0.0020 (8)	0.0091 (7)	0.0074 (8)
C2	0.0399 (11)	0.0444 (11)	0.0442 (12)	0.0010 (9)	0.0069 (9)	−0.0002 (9)
C3	0.0380 (12)	0.0519 (14)	0.0613 (14)	−0.0043 (10)	0.0004 (10)	0.0004 (11)
C4	0.0311 (11)	0.0618 (15)	0.0754 (17)	0.0032 (11)	0.0092 (11)	0.0041 (13)
C5	0.0368 (11)	0.0511 (13)	0.0599 (14)	0.0107 (9)	0.0176 (10)	0.0056 (11)
C6	0.0353 (10)	0.0387 (10)	0.0403 (10)	0.0041 (8)	0.0136 (8)	0.0076 (8)
C7	0.0429 (11)	0.0402 (11)	0.0406 (11)	0.0090 (9)	0.0194 (9)	0.0016 (9)
C8	0.0521 (13)	0.0398 (11)	0.0413 (11)	0.0067 (10)	0.0107 (9)	−0.0108 (9)
C9	0.0515 (12)	0.0445 (11)	0.0325 (10)	0.0013 (9)	0.0120 (9)	−0.0093 (8)
C10	0.0403 (11)	0.0452 (11)	0.0273 (9)	−0.0031 (9)	0.0022 (8)	−0.0021 (8)
C11	0.0341 (10)	0.0403 (10)	0.0336 (10)	0.0007 (8)	0.0074 (8)	0.0046 (8)
C12	0.0400 (11)	0.0555 (13)	0.0399 (11)	0.0009 (10)	0.0022 (9)	0.0040 (10)
C13	0.0331 (11)	0.0582 (14)	0.0526 (13)	0.0081 (10)	0.0058 (9)	0.0122 (11)
C14	0.0373 (11)	0.0460 (12)	0.0578 (13)	0.0090 (9)	0.0180 (10)	0.0080 (10)
C15	0.0379 (11)	0.0413 (11)	0.0435 (11)	0.0037 (9)	0.0122 (9)	0.0005 (9)
C16	0.0299 (9)	0.0347 (10)	0.0351 (9)	0.0001 (7)	0.0106 (7)	0.0053 (8)
C17	0.0385 (10)	0.0373 (10)	0.0343 (10)	−0.0023 (8)	0.0099 (8)	0.0085 (8)
C18	0.0549 (14)	0.0459 (12)	0.0447 (12)	−0.0022 (10)	0.0188 (10)	−0.0012 (10)
C19	0.0704 (17)	0.0579 (15)	0.0442 (13)	−0.0176 (13)	0.0089 (12)	−0.0077 (11)
C20	0.0450 (14)	0.0773 (18)	0.0549 (14)	−0.0177 (12)	0.0029 (11)	0.0073 (13)
C21	0.0392 (12)	0.0618 (15)	0.0560 (14)	0.0011 (11)	0.0150 (10)	0.0109 (11)
C22	0.0429 (11)	0.0412 (11)	0.0393 (10)	0.0008 (9)	0.0144 (9)	0.0056 (9)
C23	0.0620 (15)	0.0505 (13)	0.0463 (13)	0.0017 (11)	0.0223 (11)	0.0034 (11)
O1W	0.1058 (17)	0.0567 (12)	0.0507 (11)	0.0004 (11)	0.0002 (11)	−0.0084 (9)

Mn1—O2	1.8903 (13)	C8—H8B	0.9700
Mn1—O1	1.9002 (13)	C9—H9A	0.9700
Mn1—N2	1.9782 (16)	C9—H9B	0.9700
Mn1—N1	1.9921 (16)	C10—C11	1.436 (3)
Mn1—O3	2.0649 (14)	C10—H10	0.9300
Mn1—O1i	2.6236 (14)	C11—C12	1.409 (3)
O1—C1	1.345 (2)	C11—C16	1.409 (3)
O2—C16	1.328 (2)	C12—C13	1.369 (3)
O3—C17	1.307 (2)	C12—H12	0.9300
N1—C7	1.282 (3)	C13—C14	1.394 (3)
N1—C8	1.471 (3)	C13—H13	0.9300
N2—C10	1.282 (3)	C14—C15	1.372 (3)
N2—C9	1.481 (3)	C14—H14	0.9300
N3—C23	1.137 (3)	C15—C16	1.404 (3)
C1—C2	1.386 (3)	C15—H15	0.9300
C1—C6	1.416 (3)	C17—C18	1.408 (3)
C2—C3	1.384 (3)	C17—C22	1.415 (3)
C2—H2	0.9300	C18—C19	1.377 (4)
C3—C4	1.378 (4)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.379 (4)
C4—C5	1.363 (4)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.364 (4)
C5—C6	1.407 (3)	C20—H20	0.9300
C5—H5	0.9300	C21—C22	1.390 (3)
C6—C7	1.440 (3)	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.440 (3)
C8—C9	1.508 (3)	O1W—H2W	0.95 (4)
C8—H8A	0.9700	O1W—H1W	0.85 (4)
O2—Mn1—O1	94.96 (6)	N2—C9—H9A	110.3
O2—Mn1—N2	91.39 (6)	C8—C9—H9A	110.3
O1—Mn1—N2	167.03 (7)	N2—C9—H9B	110.3
O2—Mn1—N1	167.92 (7)	C8—C9—H9B	110.3
O1—Mn1—N1	89.72 (6)	H9A—C9—H9B	108.6
N2—Mn1—N1	81.95 (7)	N2—C10—C11	125.37 (18)
O2—Mn1—O3	97.57 (6)	N2—C10—H10	117.3
O1—Mn1—O3	99.41 (6)	C11—C10—H10	117.3
N2—Mn1—O3	90.94 (6)	C12—C11—C16	119.10 (19)
N1—Mn1—O3	92.63 (6)	C12—C11—C10	117.85 (18)
C1—O1—Mn1	122.21 (11)	C16—C11—C10	123.04 (18)
C16—O2—Mn1	129.88 (12)	C13—C12—C11	121.9 (2)
C17—O3—Mn1	133.20 (13)	C13—C12—H12	119.0
C7—N1—C8	122.58 (17)	C11—C12—H12	119.0
C7—N1—Mn1	123.87 (14)	C12—C13—C14	118.5 (2)
C8—N1—Mn1	113.34 (13)	C12—C13—H13	120.8
C10—N2—C9	120.55 (16)	C14—C13—H13	120.8
C10—N2—Mn1	126.90 (14)	C15—C14—C13	121.3 (2)
C9—N2—Mn1	112.45 (13)	C15—C14—H14	119.4
O1—C1—C2	118.93 (18)	C13—C14—H14	119.4
O1—C1—C6	122.07 (17)	C14—C15—C16	121.0 (2)
C2—C1—C6	118.97 (18)	C14—C15—H15	119.5
C3—C2—C1	120.1 (2)	C16—C15—H15	119.5
C3—C2—H2	119.9	O2—C16—C15	118.44 (18)
C1—C2—H2	119.9	O2—C16—C11	123.35 (17)
C4—C3—C2	121.2 (2)	C15—C16—C11	118.21 (18)
C4—C3—H3	119.4	O3—C17—C18	122.64 (19)
C2—C3—H3	119.4	O3—C17—C22	121.23 (19)
C5—C4—C3	119.7 (2)	C18—C17—C22	116.13 (19)
C5—C4—H4	120.1	C19—C18—C17	121.0 (2)
C3—C4—H4	120.1	C19—C18—H18	119.5
C4—C5—C6	120.8 (2)	C17—C18—H18	119.5
C4—C5—H5	119.6	C18—C19—C20	121.4 (2)
C6—C5—H5	119.6	C18—C19—H19	119.3
C5—C6—C1	119.1 (2)	C20—C19—H19	119.3
C5—C6—C7	118.39 (19)	C21—C20—C19	119.5 (2)
C1—C6—C7	122.49 (18)	C21—C20—H20	120.3
N1—C7—C6	124.71 (19)	C19—C20—H20	120.3
N1—C7—H7	117.6	C20—C21—C22	120.3 (2)
C6—C7—H7	117.6	C20—C21—H21	119.9
N1—C8—C9	106.19 (17)	C22—C21—H21	119.9
N1—C8—H8A	110.5	C21—C22—C17	121.7 (2)
C9—C8—H8A	110.5	C21—C22—C23	119.8 (2)
N1—C8—H8B	110.5	C17—C22—C23	118.5 (2)
C9—C8—H8B	110.5	N3—C23—C22	177.3 (3)
H8A—C8—H8B	108.7	H2W—O1W—H1W	100 (4)
N2—C9—C8	107.04 (16)
O2—Mn1—O1—C1	149.32 (14)	C8—N1—C7—C6	179.83 (19)
N2—Mn1—O1—C1	−91.7 (3)	Mn1—N1—C7—C6	−5.8 (3)
N1—Mn1—O1—C1	−41.83 (15)	C5—C6—C7—N1	167.2 (2)
O3—Mn1—O1—C1	50.79 (15)	C1—C6—C7—N1	−14.3 (3)
O1—Mn1—O2—C16	169.06 (15)	C7—N1—C8—C9	138.9 (2)
N2—Mn1—O2—C16	0.38 (16)	Mn1—N1—C8—C9	−36.0 (2)
N1—Mn1—O2—C16	56.6 (4)	C10—N2—C9—C8	145.0 (2)
O3—Mn1—O2—C16	−90.75 (16)	Mn1—N2—C9—C8	−38.2 (2)
O2—Mn1—O3—C17	−106.03 (19)	N1—C8—C9—N2	46.5 (2)
O1—Mn1—O3—C17	−9.7 (2)	C9—N2—C10—C11	175.19 (19)
N2—Mn1—O3—C17	162.44 (19)	Mn1—N2—C10—C11	−1.0 (3)
N1—Mn1—O3—C17	80.46 (19)	N2—C10—C11—C12	−179.9 (2)
O2—Mn1—N1—C7	140.7 (3)	N2—C10—C11—C16	−1.1 (3)
O1—Mn1—N1—C7	27.74 (16)	C16—C11—C12—C13	−1.2 (3)
N2—Mn1—N1—C7	−162.23 (17)	C10—C11—C12—C13	177.7 (2)
O3—Mn1—N1—C7	−71.66 (17)	C11—C12—C13—C14	−0.4 (3)
O2—Mn1—N1—C8	−44.5 (4)	C12—C13—C14—C15	1.3 (3)
O1—Mn1—N1—C8	−157.44 (14)	C13—C14—C15—C16	−0.6 (3)
N2—Mn1—N1—C8	12.58 (14)	Mn1—O2—C16—C15	177.54 (13)
O3—Mn1—N1—C8	103.15 (14)	Mn1—O2—C16—C11	−2.3 (3)
O2—Mn1—N2—C10	1.26 (17)	C14—C15—C16—O2	179.23 (18)
O1—Mn1—N2—C10	−118.1 (3)	C14—C15—C16—C11	−0.9 (3)
N1—Mn1—N2—C10	−168.63 (18)	C12—C11—C16—O2	−178.37 (18)
O3—Mn1—N2—C10	98.85 (18)	C10—C11—C16—O2	2.8 (3)
O2—Mn1—N2—C9	−175.21 (14)	C12—C11—C16—C15	1.8 (3)
O1—Mn1—N2—C9	65.4 (3)	C10—C11—C16—C15	−177.01 (18)
N1—Mn1—N2—C9	14.90 (13)	Mn1—O3—C17—C18	69.0 (3)
O3—Mn1—N2—C9	−77.62 (14)	Mn1—O3—C17—C22	−111.8 (2)
Mn1—O1—C1—C2	−146.56 (15)	O3—C17—C18—C19	179.1 (2)
Mn1—O1—C1—C6	35.5 (2)	C22—C17—C18—C19	−0.2 (3)
O1—C1—C2—C3	−179.0 (2)	C17—C18—C19—C20	−0.4 (4)
C6—C1—C2—C3	−1.0 (3)	C18—C19—C20—C21	0.5 (4)
C1—C2—C3—C4	0.8 (4)	C19—C20—C21—C22	0.0 (4)
C2—C3—C4—C5	1.1 (4)	C20—C21—C22—C17	−0.7 (4)
C3—C4—C5—C6	−2.7 (4)	C20—C21—C22—C23	177.4 (2)
C4—C5—C6—C1	2.4 (3)	O3—C17—C22—C21	−178.5 (2)
C4—C5—C6—C7	−179.1 (2)	C18—C17—C22—C21	0.8 (3)
O1—C1—C6—C5	177.34 (18)	O3—C17—C22—C23	3.4 (3)
C2—C1—C6—C5	−0.6 (3)	C18—C17—C22—C23	−177.28 (19)
O1—C1—C6—C7	−1.1 (3)	C21—C22—C23—N3	−16 (6)
C2—C1—C6—C7	−179.04 (19)	C17—C22—C23—N3	162 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2	0.86 (4)	2.24 (5)	2.959 (3)	141 (4)
O1W—H2W···O3ii	0.96 (4)	1.91 (4)	2.840 (3)	163 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2	0.86 (4)	2.24 (5)	2.959 (3)	141 (4)
O1W—H2W⋯O3i	0.96 (4)	1.91 (4)	2.840 (3)	163 (4)

Symmetry code: (i) .