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A second polymorphic form (form I) of the previously reported compound {2-[(2-hydroxy­ethyl)­iminio­methyl]­phen­olato-[kappa]O}dioxido{2-[(2-oxido­ethyl)­imino­methyl]­phenolato-[kappa]3O,N,O'}molybdenum(VI) (form II), [Mo(C9H9NO2)O2(C9­H11NO2)], is presented. The title structure differs from the previously reported polymorph [Glowiak, Jerzykiewicz, Sobczak & Ziólkowski (2003). Inorg. Chim. Acta, 356, 387-392] by the fact that the asymmetric unit contains three mol­ecules linked by O-H...O hydrogen bonds. These trimeric units are further linked through O-H...O hydrogen bonds to form a chain parallel to the [\overline{1}11] direction. As in the previous polymorph, each mol­ecule is built up from an MoO22+ cation surrounded by an O,N,O'-tridentate ligand (O-C6H4­CH=NCH2CH2O-) and weakly coordinated by a second zwitterionic ligand (O-C6H4CH=N+HC2H4OH). All com­plexes are chiral with the absolute configuration at Mo being C or A. The main difference between the two polymorphs results from the alternation of the chirality at Mo within the chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108000127/sk3193sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108000127/sk3193Isup2.hkl
Contains datablock I

CCDC reference: 681531

Comment top

Molybdenum oxo-complexes bearing polydentate ligands are known to be efficient epoxidation catalysts (Bruno et al., 2006; Herrmann et al., 2002; Martos-Calvente et al., 2004; Most et al., 2002; Valente et al., 2001; Wong et al., 1998; Zhao et al., 2003; Zhou et al., 2004; Sobczak & Ziolkowski, 2003). Thus, since we are interested in investigating the catalytic activity of MoVI complexes linked to tridentate ligands, we have synthesized and structurally characterized the title compound, (I), and compare it with the previously published polymorph, (II) (Głowiak et al., 2003).

Reaction of MoO2(sal)2 with ethanolamine (HOCH2CH2NH2) under the conditions described by Głowiak et al. (2003) led to a new polymorphic crystalline structure of MoO2(1,2-OC6H4CH NC2H4O)(1,2-O-C6H4CHN+HC2H4OH) with three crystallographically independent molecules per unit cell. The two polymorphs crystallize in triclinic space group P1 with different cell parameters [for (I), a = 10.096 Å, b = 13.565 Å, c = 21.879 Å, α = 81.68°, β = 86.40°, γ = 71.41°, V = 2810.9 Å3 and Z = 6; for (II), a = 8.483 Å, b = 10.187 Å, c = 11.034 Å, α = 105.26°, β = 95.29°, γ = 95.10°, V = 909.6 Å3 and Z = 2].

For both (I) and (II), the molecule is based on an MoO22+ cation surrounded by a doubly charged anionic ONO tridentate ligand (O-C6H4CH NCH2CH2O-) and weakly O-coordinated to a zwitterionic ligand (O-C6H4CHN+HC2H4OH) (Fig. 1). The zwitterionic form is stabilized by intramolecular N—H···O hydrogen bonds between the N+H group and the O atom within the same ligand linked to the Mo. A second weak interaction may be noted between the same N+H group and one of the O atoms of the tridentate ligand (O13, O23 or O33; Table 1).

All the crystallographically independent complexes are chiral at Mo, and the absolute configuration of each Mo could be determined as either C (clockwise) or A (anticlockwise) (Fig. 2) using the official nomenclature rules for such compounds (Brown et al., 1975; Hartung et al., 2006).

The title polymorph structure (I) differs from structure (II) by the fact that the asymmetric unit of (I) contains three molecules linked by O—H···O hydrogen bonds (Table 1) involving the hydroxyl O atom of the zwitterionic ligand of one molecule to an oxo O atom attached to the Mo atom of another molecule. These trimeric units are further linked through O—H···O hydrogen bonds of the same type to form a chain parallel to the [111] direction (Fig. 3).

Although the chirality is different for each molecule, they have roughly the same conformation. Indeed, an overlay analysis calculated using structure matching software (Watkin et al., 2003; Collins et al., 2006) shows that the three molecules can be superimposed (Fig. 4, Table 2). A similar overlay analysis of the two polymorphs indicates that the largest deviation occurs for the dangling hydroxyl O atom (Fig. 4) not coordinated to the Mo atom and involved in hydrogen bonding, which is not surprising owing to the different packing observed in the two isomers. However, it is worth pointing out that in compound (II), the chain is formed from complexes having the same configuration C (or A), whereas in compound (I), the chain is built up from trimeric units linked by translation to form infinite (CAC)n [or (ACA)n] chains (Fig. 2).

As observed in polymorph (II), there are also intramolecular hydrogen bonds between the dangling NH (N12, N22 or N32) group of the monodentate ligand and the O atom (O15, O25 or O35) within the same ligand. Moreover, the position of the dangling CH2NHCH2CH2OH chain over the chelating ligand is certainly induced by a second weak N—H···O interaction involving one of the O atoms (O13, O23 or O33) of the tridentate ligand (Table 1).

Related literature top

For related literature, see: Brown et al. (1975); Bruno et al. (2006); Collins et al. (2006); Głowiak et al. (2003); Hartung et al. (2006); Herrmann et al. (2002); Martos-Calvente, De La Pena O'Shea, Campos-Martin, Fierro & Gutierrez-Puebla (2004); Most et al. (2002); Sobczak & Ziolkowski (2003); Spek (2003); Valente et al. (2001); Watkin et al. (2003); Wong et al. (1998); Yamanouchi & Yamada (1974); Zhao et al. (2003); Zhou et al. (2004).

Experimental top

Less than two equivalents of HOCH2CH2NH2 (0.3 ml, 4.97 mmol) were added to an ethanol solution (10 ml) of one equivalent of MoO2(sal)2 (0.92 g, 2.48 mmol), previously synthesized following a literature procedure (Yamanouchi & Yamada, 1974). The mixture was maintained under reflux for 30 min. The white precipitate that formed was separated off. The solution was subsequently cooled to room temperature and left to stand in air. Evaporation of the filtrate gave air-stable yellow crystals of the title compound, (I). The IR spectrum of the yellow crystals in KBr pellets showed no visible difference with the compound synthesized previously (Głowiak et al., 2003)

Refinement top

All H atoms were fixed geometrically and treated as riding, with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene), O—H = 0.84 Å and N—H = 0.88 Å, with Uiso(H) = 1.2Ueq(C), 1.5Ueq(C) or 1.2Ueq(N). [Please check revised text, which has been amended to include N-bound H-atom treatment]

The two polymorphs have the same space group P1 but no relation between them could be found. Moreover, the simulated powder patterns produced using PLATON (Spek, 2003) are different (Fig. 5).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997), CAMERON (Pearce et al., 2000) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.
[Figure 2] Fig. 2. Scheme showing the two enantiomers, C and A, with the priority numbers used to define the absolute configuration shown as subscripted indices.
[Figure 3] Fig. 3. A partial packing view of compound (I), showing the formation of chains along [111] built from hydrogen bonds. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 4] Fig. 4. Overlays of the different molecules within the title compound, A, B and C, and an overlay of the two polymorphs, D.
[Figure 5] Fig. 5. A view of the simulated powder patterns for polymorphs (I) (top?) and (II) (bottom?).
{2-[(2-hydroxyethyl)iminiomethyl]phenolato-κO}dioxido(2-[(2-oxidoethyl)iminomethyl]phenolato-κ3O,N,O')molybdenum(VI) top
Crystal data top
[Mo(C9H9NO2)O2(C9H11NO2)]Z = 6
Mr = 456.30F(000) = 1392
Triclinic, P1Dx = 1.617 Mg m3
a = 10.0953 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.5645 (8) ÅCell parameters from 15657 reflections
c = 21.8864 (14) Åθ = 2.8–31.9°
α = 81.731 (5)°µ = 0.74 mm1
β = 86.437 (5)°T = 180 K
γ = 71.422 (5)°Box, pale yellow
V = 2810.9 (3) Å30.76 × 0.33 × 0.27 mm
Data collection top
Oxford Diffraction Xcalibur
diffractometer
13842 independent reflections
Radiation source: fine-focus sealed tube10817 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.2632 pixels mm-1θmax = 28.3°, θmin = 2.8°
ω and ϕ scansh = 1213
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
k = 1518
Tmin = 0.762, Tmax = 0.834l = 2629
24992 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0361P)2 + 4.7867P]
where P = (Fo2 + 2Fc2)/3
13844 reflections(Δ/σ)max = 0.004
733 parametersΔρmax = 1.02 e Å3
0 restraintsΔρmin = 1.10 e Å3
Crystal data top
[Mo(C9H9NO2)O2(C9H11NO2)]γ = 71.422 (5)°
Mr = 456.30V = 2810.9 (3) Å3
Triclinic, P1Z = 6
a = 10.0953 (5) ÅMo Kα radiation
b = 13.5645 (8) ŵ = 0.74 mm1
c = 21.8864 (14) ÅT = 180 K
α = 81.731 (5)°0.76 × 0.33 × 0.27 mm
β = 86.437 (5)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer
13842 independent reflections
Absorption correction: multi-scan
[CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
10817 reflections with I > 2σ(I)
Tmin = 0.762, Tmax = 0.834Rint = 0.026
24992 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.15Δρmax = 1.02 e Å3
13844 reflectionsΔρmin = 1.10 e Å3
733 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mo10.71809 (3)0.19222 (2)0.475213 (12)0.01746 (7)
N110.5452 (3)0.3365 (2)0.43393 (14)0.0260 (6)
N120.5260 (3)0.2633 (2)0.64495 (14)0.0254 (6)
H120.55030.25080.60680.031*
O110.8554 (3)0.1098 (2)0.51756 (11)0.0303 (6)
O120.7026 (3)0.1273 (2)0.41596 (11)0.0288 (6)
O130.5537 (2)0.16546 (18)0.52010 (10)0.0212 (5)
O140.8136 (2)0.28157 (19)0.42987 (11)0.0233 (5)
O150.6753 (3)0.2953 (2)0.54756 (12)0.0329 (6)
O160.2490 (3)0.4049 (2)0.64413 (13)0.0364 (7)
H10.22890.41940.68030.055*
C110.4164 (4)0.3460 (3)0.43072 (17)0.0293 (8)
H110.35710.40870.40900.035*
C120.3551 (3)0.2671 (3)0.45820 (16)0.0236 (7)
C130.2169 (4)0.2794 (3)0.44314 (18)0.0310 (8)
H130.16780.33960.41610.037*
C140.1492 (4)0.2069 (3)0.46633 (18)0.0324 (9)
H140.05610.21630.45510.039*
C150.2224 (4)0.1203 (3)0.50650 (17)0.0265 (7)
H150.17880.06920.52250.032*
C160.3572 (3)0.1065 (3)0.52369 (15)0.0225 (7)
H160.40450.04700.55160.027*
C170.4244 (3)0.1803 (3)0.50001 (15)0.0198 (6)
C180.6036 (4)0.4172 (3)0.4035 (2)0.0452 (11)
H18A0.61130.46390.43310.054*
H18B0.54470.46010.36880.054*
C190.7468 (4)0.3561 (3)0.3805 (2)0.0372 (9)
H19A0.73760.32050.34530.045*
H19B0.80200.40410.36650.045*
C1510.7445 (3)0.3347 (3)0.57998 (16)0.0221 (7)
C1520.8559 (4)0.3709 (3)0.55523 (17)0.0276 (8)
H1520.88390.36490.51330.033*
C1530.9240 (4)0.4144 (3)0.59054 (18)0.0287 (8)
H1530.99900.43770.57300.034*
C1540.8838 (4)0.4250 (3)0.65295 (18)0.0319 (8)
H1540.93110.45560.67720.038*
C1550.7763 (4)0.3909 (3)0.67812 (17)0.0297 (8)
H1550.74920.39800.72000.036*
C1560.7051 (3)0.3453 (3)0.64296 (16)0.0223 (7)
C1570.5952 (4)0.3095 (3)0.67180 (16)0.0248 (7)
H1570.57150.32040.71350.030*
C1580.4103 (4)0.2304 (3)0.67364 (18)0.0312 (8)
H15A0.40480.23710.71830.037*
H15B0.42620.15590.66920.037*
C1590.2741 (4)0.2975 (3)0.64349 (17)0.0275 (8)
H15C0.27610.28370.60020.033*
H15D0.19610.27700.66530.033*
Mo20.01883 (3)0.53892 (2)0.809053 (13)0.01874 (7)
N210.0744 (3)0.6883 (2)0.77954 (13)0.0235 (6)
N220.0970 (3)0.5974 (2)0.98532 (13)0.0260 (6)
H220.09450.58420.94730.031*
O210.0617 (3)0.4533 (2)0.84618 (12)0.0312 (6)
O220.1074 (3)0.4814 (2)0.74740 (11)0.0307 (6)
O230.1930 (2)0.50697 (19)0.85537 (10)0.0232 (5)
O240.1414 (2)0.6334 (2)0.76566 (11)0.0269 (5)
O250.0497 (2)0.6286 (2)0.88798 (11)0.0271 (5)
O260.2359 (3)0.7519 (2)0.97421 (13)0.0411 (7)
H20.23520.77001.00940.062*
C210.1957 (4)0.6992 (3)0.77746 (16)0.0254 (7)
H210.20450.76580.76140.030*
C220.3198 (4)0.6158 (3)0.79830 (16)0.0226 (7)
C230.4504 (4)0.6287 (3)0.78206 (18)0.0298 (8)
H230.45400.69180.75780.036*
C240.5748 (4)0.5519 (3)0.80037 (19)0.0322 (8)
H240.66250.56170.78880.039*
C250.5676 (4)0.4606 (3)0.83587 (18)0.0317 (8)
H250.65160.40690.84830.038*
C260.4408 (4)0.4461 (3)0.85348 (17)0.0283 (8)
H260.43890.38330.87850.034*
C270.3144 (3)0.5228 (3)0.83497 (15)0.0213 (7)
C280.0473 (4)0.7740 (3)0.7553 (2)0.0379 (10)
H28A0.01840.82570.72540.046*
H28B0.10270.81020.78920.046*
C290.1300 (4)0.7212 (3)0.72414 (19)0.0375 (9)
H29A0.22400.77070.71380.045*
H29B0.08190.69790.68550.045*
C2510.1637 (4)0.6622 (3)0.92073 (15)0.0201 (6)
C2520.2977 (4)0.6989 (3)0.89577 (16)0.0249 (7)
H2520.30800.69790.85300.030*
C2530.4152 (4)0.7365 (3)0.93184 (18)0.0315 (8)
H2530.50480.76080.91370.038*
C2540.4038 (4)0.7394 (3)0.99515 (18)0.0335 (9)
H2540.48500.76521.01980.040*
C2550.2743 (4)0.7046 (3)1.02084 (16)0.0293 (8)
H2550.26610.70641.06360.035*
C2560.1531 (4)0.6661 (3)0.98503 (15)0.0209 (7)
C2570.0207 (4)0.6349 (3)1.01292 (16)0.0258 (7)
H2570.01880.64231.05530.031*
C2580.2334 (4)0.5749 (3)1.01142 (18)0.0319 (8)
H25A0.28800.50041.00960.038*
H25B0.22280.58681.05530.038*
C2590.3101 (4)0.6446 (3)0.97604 (18)0.0338 (9)
H25C0.40160.63000.99540.041*
H25D0.32820.62720.93330.041*
Mo30.29709 (3)0.85939 (2)1.145206 (13)0.02017 (7)
N310.1199 (3)0.9983 (2)1.10182 (14)0.0278 (7)
N320.1088 (3)0.9258 (2)1.31410 (13)0.0248 (6)
H320.13060.91531.27550.030*
O310.4360 (3)0.7835 (2)1.18894 (11)0.0287 (5)
O320.2880 (3)0.7881 (2)1.08792 (12)0.0340 (6)
O330.1351 (2)0.82979 (18)1.19075 (10)0.0218 (5)
O340.3888 (3)0.9492 (2)1.09707 (11)0.0309 (6)
O350.2487 (2)0.96756 (19)1.21485 (11)0.0236 (5)
O360.1670 (3)1.0694 (2)1.30853 (12)0.0318 (6)
H30.19681.08781.34320.048*
C310.0107 (4)1.0097 (3)1.10216 (17)0.0303 (8)
H310.07161.07281.08150.036*
C320.0713 (4)0.9304 (3)1.13274 (16)0.0263 (7)
C330.2108 (4)0.9420 (3)1.12042 (19)0.0352 (9)
H330.26431.00251.09480.042*
C340.2702 (4)0.8674 (4)1.1449 (2)0.0405 (10)
H340.36490.87661.13650.049*
C350.1939 (4)0.7788 (3)1.18182 (18)0.0331 (9)
H350.23480.72581.19730.040*
C360.0578 (4)0.7669 (3)1.19635 (17)0.0268 (7)
H360.00680.70671.22290.032*
C370.0056 (3)0.8423 (3)1.17235 (15)0.0209 (7)
C380.1751 (5)1.0778 (3)1.0679 (2)0.0458 (11)
H38A0.18111.12851.09520.055*
H38B0.11511.11651.03260.055*
C390.3194 (5)1.0170 (4)1.0457 (2)0.0466 (11)
H39A0.31170.97611.01280.056*
H39B0.37171.06571.02880.056*
C3510.3250 (3)1.0002 (2)1.24838 (15)0.0185 (6)
C3520.4348 (4)1.0372 (3)1.22344 (16)0.0255 (7)
H3520.45841.03691.18080.031*
C3530.5077 (4)1.0737 (3)1.26071 (17)0.0284 (8)
H3530.58151.09831.24300.034*
C3540.4780 (4)1.0762 (3)1.32357 (18)0.0300 (8)
H3540.53071.10171.34830.036*
C3550.3712 (4)1.0410 (3)1.34896 (16)0.0254 (7)
H3550.34901.04311.39170.030*
C3560.2940 (3)1.0019 (3)1.31282 (15)0.0204 (6)
C3570.1830 (4)0.9670 (3)1.34139 (16)0.0238 (7)
H3570.16260.97471.38370.029*
C3580.0091 (4)0.8953 (3)1.34268 (17)0.0288 (8)
H35A0.01700.90511.38690.035*
H35B0.00660.82021.34000.035*
C3590.1432 (4)0.9608 (3)1.31059 (17)0.0263 (7)
H35C0.13920.94371.26790.032*
H35D0.22260.94241.33250.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.01563 (13)0.02193 (14)0.01543 (13)0.00617 (11)0.00184 (10)0.00307 (10)
N110.0202 (15)0.0218 (15)0.0330 (16)0.0050 (12)0.0009 (12)0.0011 (12)
N120.0212 (15)0.0293 (16)0.0239 (15)0.0061 (12)0.0018 (12)0.0022 (12)
O110.0195 (12)0.0398 (15)0.0281 (13)0.0078 (11)0.0074 (10)0.0066 (11)
O120.0337 (14)0.0322 (14)0.0241 (13)0.0118 (11)0.0015 (10)0.0117 (10)
O130.0170 (11)0.0274 (12)0.0205 (11)0.0097 (10)0.0036 (9)0.0004 (9)
O140.0187 (12)0.0263 (13)0.0248 (12)0.0082 (10)0.0005 (9)0.0004 (10)
O150.0304 (14)0.0515 (17)0.0305 (14)0.0258 (13)0.0093 (11)0.0241 (12)
O160.0403 (16)0.0247 (13)0.0407 (16)0.0073 (12)0.0181 (13)0.0082 (12)
C110.0236 (18)0.0230 (18)0.036 (2)0.0016 (14)0.0033 (15)0.0034 (15)
C120.0157 (16)0.0250 (17)0.0296 (18)0.0048 (13)0.0017 (13)0.0068 (14)
C130.0177 (17)0.031 (2)0.039 (2)0.0006 (15)0.0048 (15)0.0017 (16)
C140.0147 (17)0.041 (2)0.043 (2)0.0061 (15)0.0047 (15)0.0149 (18)
C150.0198 (17)0.0330 (19)0.0329 (19)0.0148 (15)0.0051 (14)0.0116 (15)
C160.0207 (16)0.0260 (17)0.0230 (17)0.0095 (14)0.0031 (13)0.0072 (13)
C170.0169 (15)0.0235 (16)0.0234 (16)0.0107 (13)0.0069 (12)0.0109 (13)
C180.028 (2)0.025 (2)0.073 (3)0.0043 (16)0.004 (2)0.015 (2)
C190.029 (2)0.035 (2)0.042 (2)0.0111 (17)0.0033 (17)0.0133 (17)
C1510.0189 (16)0.0227 (17)0.0268 (17)0.0065 (13)0.0014 (13)0.0093 (13)
C1520.0267 (18)0.034 (2)0.0290 (18)0.0149 (16)0.0034 (15)0.0152 (15)
C1530.0187 (17)0.0259 (18)0.046 (2)0.0116 (14)0.0084 (15)0.0056 (16)
C1540.034 (2)0.032 (2)0.034 (2)0.0113 (16)0.0154 (16)0.0081 (16)
C1550.033 (2)0.0306 (19)0.0236 (18)0.0046 (16)0.0056 (15)0.0085 (15)
C1560.0205 (16)0.0183 (16)0.0252 (17)0.0008 (13)0.0045 (13)0.0036 (13)
C1570.0227 (17)0.0255 (18)0.0216 (17)0.0022 (14)0.0016 (13)0.0004 (13)
C1580.0287 (19)0.030 (2)0.033 (2)0.0105 (16)0.0064 (15)0.0026 (15)
C1590.0203 (17)0.0293 (19)0.0322 (19)0.0059 (14)0.0060 (14)0.0090 (15)
Mo20.02038 (14)0.02072 (14)0.01609 (13)0.00746 (11)0.00021 (10)0.00332 (10)
N210.0202 (14)0.0229 (15)0.0250 (15)0.0047 (12)0.0005 (11)0.0003 (11)
N220.0305 (16)0.0285 (16)0.0220 (15)0.0139 (13)0.0039 (12)0.0009 (12)
O210.0305 (14)0.0331 (14)0.0328 (14)0.0162 (12)0.0002 (11)0.0002 (11)
O220.0339 (15)0.0337 (14)0.0251 (13)0.0094 (12)0.0038 (11)0.0100 (11)
O230.0204 (12)0.0261 (12)0.0201 (12)0.0053 (10)0.0011 (9)0.0026 (9)
O240.0213 (12)0.0329 (14)0.0257 (13)0.0075 (11)0.0052 (10)0.0013 (10)
O250.0207 (12)0.0405 (15)0.0212 (12)0.0074 (11)0.0033 (10)0.0139 (11)
O260.063 (2)0.0342 (16)0.0326 (15)0.0223 (15)0.0184 (14)0.0010 (12)
C210.0266 (18)0.0202 (17)0.0291 (18)0.0080 (14)0.0003 (14)0.0015 (14)
C220.0197 (16)0.0233 (17)0.0247 (17)0.0056 (13)0.0003 (13)0.0059 (13)
C230.0258 (19)0.0269 (19)0.039 (2)0.0111 (15)0.0011 (16)0.0036 (16)
C240.0187 (18)0.038 (2)0.046 (2)0.0145 (16)0.0039 (16)0.0156 (18)
C250.0241 (18)0.030 (2)0.039 (2)0.0032 (15)0.0030 (16)0.0111 (16)
C260.0266 (19)0.0265 (18)0.0301 (19)0.0057 (15)0.0037 (15)0.0026 (15)
C270.0202 (16)0.0254 (17)0.0199 (16)0.0081 (13)0.0013 (12)0.0068 (13)
C280.028 (2)0.0234 (19)0.056 (3)0.0040 (16)0.0066 (18)0.0089 (17)
C290.032 (2)0.039 (2)0.036 (2)0.0079 (18)0.0082 (17)0.0084 (17)
C2510.0241 (17)0.0188 (16)0.0197 (16)0.0095 (13)0.0029 (13)0.0054 (12)
C2520.0229 (17)0.0286 (18)0.0253 (17)0.0101 (14)0.0013 (14)0.0060 (14)
C2530.0228 (18)0.036 (2)0.036 (2)0.0108 (16)0.0057 (15)0.0039 (16)
C2540.030 (2)0.033 (2)0.038 (2)0.0105 (16)0.0162 (17)0.0120 (17)
C2550.041 (2)0.0304 (19)0.0211 (17)0.0168 (17)0.0071 (15)0.0066 (14)
C2560.0275 (18)0.0197 (16)0.0186 (16)0.0115 (14)0.0016 (13)0.0036 (12)
C2570.038 (2)0.0227 (17)0.0210 (17)0.0167 (15)0.0011 (15)0.0004 (13)
C2580.0285 (19)0.034 (2)0.036 (2)0.0129 (16)0.0104 (16)0.0000 (16)
C2590.041 (2)0.039 (2)0.031 (2)0.0233 (19)0.0015 (17)0.0090 (17)
Mo30.02375 (15)0.02210 (15)0.01581 (14)0.00820 (12)0.00104 (11)0.00358 (10)
N310.0316 (17)0.0255 (16)0.0284 (16)0.0138 (13)0.0099 (13)0.0053 (12)
N320.0208 (14)0.0286 (16)0.0235 (15)0.0068 (12)0.0012 (11)0.0012 (12)
O310.0223 (13)0.0344 (14)0.0268 (13)0.0053 (11)0.0026 (10)0.0034 (11)
O320.0429 (16)0.0366 (15)0.0266 (14)0.0148 (13)0.0008 (12)0.0117 (11)
O330.0220 (12)0.0241 (12)0.0217 (12)0.0110 (10)0.0040 (9)0.0001 (9)
O340.0361 (15)0.0411 (15)0.0222 (12)0.0233 (13)0.0000 (11)0.0002 (11)
O350.0241 (12)0.0306 (13)0.0223 (12)0.0144 (10)0.0001 (9)0.0106 (10)
O360.0334 (15)0.0239 (13)0.0348 (15)0.0066 (11)0.0088 (12)0.0031 (11)
C310.034 (2)0.0241 (18)0.0301 (19)0.0056 (15)0.0121 (16)0.0031 (15)
C320.0211 (17)0.0322 (19)0.0241 (18)0.0040 (15)0.0046 (14)0.0074 (14)
C330.0244 (19)0.041 (2)0.036 (2)0.0018 (17)0.0104 (16)0.0091 (17)
C340.027 (2)0.055 (3)0.044 (2)0.0123 (19)0.0011 (17)0.023 (2)
C350.030 (2)0.042 (2)0.037 (2)0.0201 (18)0.0080 (16)0.0183 (18)
C360.0274 (18)0.0269 (18)0.0291 (18)0.0113 (15)0.0021 (14)0.0078 (14)
C370.0212 (16)0.0249 (17)0.0196 (16)0.0081 (13)0.0008 (12)0.0106 (13)
C380.055 (3)0.032 (2)0.051 (3)0.023 (2)0.018 (2)0.0179 (19)
C390.061 (3)0.051 (3)0.033 (2)0.033 (2)0.005 (2)0.0150 (19)
C3510.0180 (15)0.0142 (15)0.0220 (16)0.0017 (12)0.0028 (12)0.0048 (12)
C3520.0249 (18)0.0270 (18)0.0259 (18)0.0091 (14)0.0011 (14)0.0063 (14)
C3530.0213 (17)0.0297 (19)0.035 (2)0.0086 (15)0.0027 (15)0.0035 (15)
C3540.0280 (19)0.0292 (19)0.035 (2)0.0068 (15)0.0125 (15)0.0103 (16)
C3550.0218 (17)0.0298 (19)0.0217 (17)0.0016 (14)0.0072 (13)0.0068 (14)
C3560.0187 (16)0.0207 (16)0.0207 (16)0.0034 (13)0.0037 (12)0.0044 (12)
C3570.0236 (17)0.0228 (17)0.0202 (16)0.0008 (14)0.0015 (13)0.0011 (13)
C3580.0220 (17)0.0306 (19)0.033 (2)0.0096 (15)0.0022 (15)0.0019 (15)
C3590.0217 (17)0.0276 (18)0.0287 (18)0.0059 (14)0.0023 (14)0.0065 (14)
Geometric parameters (Å, º) top
Mo1—O111.704 (2)C25—H250.9500
Mo1—O121.710 (2)C26—C271.404 (5)
Mo1—O141.914 (2)C26—H260.9500
Mo1—O131.982 (2)C28—C291.506 (6)
Mo1—O152.194 (2)C28—H28A0.9900
Mo1—N112.281 (3)C28—H28B0.9900
N11—C111.270 (4)C29—H29A0.9900
N11—C181.463 (5)C29—H29B0.9900
N12—C1571.290 (5)C251—C2521.400 (5)
N12—C1581.455 (4)C251—C2561.428 (4)
N12—H120.8800C252—C2531.380 (5)
O13—C171.347 (4)C252—H2520.9500
O14—C191.410 (4)C253—C2541.405 (5)
O15—C1511.299 (4)C253—H2530.9500
O16—C1591.399 (4)C254—C2551.368 (6)
O16—H10.8400C254—H2540.9500
C11—C121.443 (5)C255—C2561.405 (5)
C11—H110.9500C255—H2550.9500
C12—C171.400 (5)C256—C2571.416 (5)
C12—C131.406 (5)C257—H2570.9500
C13—C141.390 (5)C258—C2591.508 (5)
C13—H130.9500C258—H25A0.9900
C14—C151.390 (5)C258—H25B0.9900
C14—H140.9500C259—H25C0.9900
C15—C161.382 (5)C259—H25D0.9900
C15—H150.9500Mo3—O311.705 (2)
C16—C171.403 (4)Mo3—O321.713 (2)
C16—H160.9500Mo3—O341.918 (2)
C18—C191.515 (6)Mo3—O331.982 (2)
C18—H18A0.9900Mo3—O352.193 (2)
C18—H18B0.9900Mo3—N312.281 (3)
C19—H19A0.9900N31—C311.278 (5)
C19—H19B0.9900N31—C381.458 (5)
C151—C1521.414 (5)N32—C3571.284 (5)
C151—C1561.425 (5)N32—C3581.458 (4)
C152—C1531.369 (5)N32—H320.8800
C152—H1520.9500O33—C371.343 (4)
C153—C1541.415 (5)O34—C391.411 (5)
C153—H1530.9500O35—C3511.307 (4)
C154—C1551.367 (5)O36—C3591.409 (4)
C154—H1540.9500O36—H30.8400
C155—C1561.407 (5)C31—C321.463 (5)
C155—H1550.9500C31—H310.9500
C156—C1571.425 (5)C32—C331.405 (5)
C157—H1570.9500C32—C371.406 (5)
C158—C1591.516 (5)C33—C341.365 (6)
C158—H15A0.9900C33—H330.9500
C158—H15B0.9900C34—C351.377 (6)
C159—H15C0.9900C34—H340.9500
C159—H15D0.9900C35—C361.383 (5)
Mo2—O211.709 (2)C35—H350.9500
Mo2—O221.714 (2)C36—C371.398 (5)
Mo2—O241.919 (2)C36—H360.9500
Mo2—O231.979 (2)C38—C391.516 (7)
Mo2—O252.205 (2)C38—H38A0.9900
Mo2—N212.267 (3)C38—H38B0.9900
N21—C211.277 (4)C39—H39A0.9900
N21—C281.460 (5)C39—H39B0.9900
N22—C2571.285 (5)C351—C3521.408 (5)
N22—C2581.448 (5)C351—C3561.427 (4)
N22—H220.8800C352—C3531.369 (5)
O23—C271.349 (4)C352—H3520.9500
O24—C291.422 (5)C353—C3541.393 (5)
O25—C2511.305 (4)C353—H3530.9500
O26—C2591.405 (5)C354—C3551.370 (5)
O26—H20.8400C354—H3540.9500
C21—C221.442 (5)C355—C3561.405 (5)
C21—H210.9500C355—H3550.9500
C22—C231.402 (5)C356—C3571.427 (5)
C22—C271.409 (5)C357—H3570.9500
C23—C241.390 (5)C358—C3591.512 (5)
C23—H230.9500C358—H35A0.9900
C24—C251.384 (6)C358—H35B0.9900
C24—H240.9500C359—H35C0.9900
C25—C261.379 (5)C359—H35D0.9900
O11—Mo1—O12105.87 (13)N21—C28—C29104.4 (3)
O11—Mo1—O1498.02 (11)N21—C28—H28A110.9
O12—Mo1—O1497.57 (11)C29—C28—H28A110.9
O11—Mo1—O13103.18 (11)N21—C28—H28B110.9
O12—Mo1—O1392.42 (11)C29—C28—H28B110.9
O14—Mo1—O13153.09 (10)H28A—C28—H28B108.9
O11—Mo1—O1588.17 (12)O24—C29—C28107.8 (3)
O12—Mo1—O15164.04 (11)O24—C29—H29A110.2
O14—Mo1—O1587.72 (10)C28—C29—H29A110.2
O13—Mo1—O1576.69 (9)O24—C29—H29B110.2
O11—Mo1—N11163.69 (12)C28—C29—H29B110.2
O12—Mo1—N1189.81 (12)H29A—C29—H29B108.5
O14—Mo1—N1175.01 (10)O25—C251—C252123.5 (3)
O13—Mo1—N1180.12 (10)O25—C251—C256119.1 (3)
O15—Mo1—N1176.97 (11)C252—C251—C256117.3 (3)
C11—N11—C18121.8 (3)C253—C252—C251121.5 (3)
C11—N11—Mo1127.1 (2)C253—C252—H252119.2
C18—N11—Mo1110.8 (2)C251—C252—H252119.2
C157—N12—C158124.2 (3)C252—C253—C254120.7 (4)
C157—N12—H12117.9C252—C253—H253119.6
C158—N12—H12117.9C254—C253—H253119.6
C17—O13—Mo1130.2 (2)C255—C254—C253119.2 (3)
C19—O14—Mo1119.8 (2)C255—C254—H254120.4
C151—O15—Mo1138.1 (2)C253—C254—H254120.4
C159—O16—H1109.5C254—C255—C256121.1 (3)
N11—C11—C12123.7 (3)C254—C255—H255119.4
N11—C11—H11118.1C256—C255—H255119.4
C12—C11—H11118.1C255—C256—C257119.3 (3)
C17—C12—C13118.2 (3)C255—C256—C251120.1 (3)
C17—C12—C11123.7 (3)C257—C256—C251120.6 (3)
C13—C12—C11118.1 (3)N22—C257—C256125.1 (3)
C14—C13—C12122.6 (3)N22—C257—H257117.5
C14—C13—H13118.7C256—C257—H257117.5
C12—C13—H13118.7N22—C258—C259110.0 (3)
C13—C14—C15117.7 (3)N22—C258—H25A109.7
C13—C14—H14121.2C259—C258—H25A109.7
C15—C14—H14121.2N22—C258—H25B109.7
C16—C15—C14121.6 (3)C259—C258—H25B109.7
C16—C15—H15119.2H25A—C258—H25B108.2
C14—C15—H15119.2O26—C259—C258113.0 (3)
C15—C16—C17120.2 (3)O26—C259—H25C109.0
C15—C16—H16119.9C258—C259—H25C109.0
C17—C16—H16119.9O26—C259—H25D109.0
O13—C17—C12122.4 (3)C258—C259—H25D109.0
O13—C17—C16117.9 (3)H25C—C259—H25D107.8
C12—C17—C16119.7 (3)O31—Mo3—O32105.83 (13)
N11—C18—C19104.4 (3)O31—Mo3—O3497.69 (12)
N11—C18—H18A110.9O32—Mo3—O3497.01 (12)
C19—C18—H18A110.9O31—Mo3—O33103.37 (11)
N11—C18—H18B110.9O32—Mo3—O3392.38 (12)
C19—C18—H18B110.9O34—Mo3—O33153.62 (11)
H18A—C18—H18B108.9O31—Mo3—O3587.58 (11)
O14—C19—C18107.6 (3)O32—Mo3—O35164.75 (11)
O14—C19—H19A110.2O34—Mo3—O3588.15 (10)
C18—C19—H19A110.2O33—Mo3—O3577.18 (9)
O14—C19—H19B110.2O31—Mo3—N31163.01 (12)
C18—C19—H19B110.2O32—Mo3—N3190.51 (12)
H19A—C19—H19B108.5O34—Mo3—N3175.27 (11)
O15—C151—C152123.0 (3)O33—Mo3—N3180.07 (10)
O15—C151—C156119.2 (3)O35—Mo3—N3176.88 (10)
C152—C151—C156117.8 (3)C31—N31—C38120.8 (3)
C153—C152—C151121.2 (3)C31—N31—Mo3128.7 (2)
C153—C152—H152119.4C38—N31—Mo3110.4 (2)
C151—C152—H152119.4C357—N32—C358124.5 (3)
C152—C153—C154120.6 (3)C357—N32—H32117.8
C152—C153—H153119.7C358—N32—H32117.8
C154—C153—H153119.7C37—O33—Mo3131.2 (2)
C155—C154—C153119.5 (3)C39—O34—Mo3118.7 (2)
C155—C154—H154120.3C351—O35—Mo3133.8 (2)
C153—C154—H154120.3C359—O36—H3109.5
C154—C155—C156121.1 (3)N31—C31—C32123.3 (3)
C154—C155—H155119.5N31—C31—H31118.4
C156—C155—H155119.5C32—C31—H31118.4
C155—C156—C157118.7 (3)C33—C32—C37119.2 (4)
C155—C156—C151119.9 (3)C33—C32—C31118.2 (3)
C157—C156—C151121.4 (3)C37—C32—C31122.6 (3)
N12—C157—C156124.3 (3)C34—C33—C32120.7 (4)
N12—C157—H157117.9C34—C33—H33119.7
C156—C157—H157117.9C32—C33—H33119.7
N12—C158—C159110.2 (3)C33—C34—C35120.5 (4)
N12—C158—H15A109.6C33—C34—H34119.7
C159—C158—H15A109.6C35—C34—H34119.7
N12—C158—H15B109.6C34—C35—C36120.0 (4)
C159—C158—H15B109.6C34—C35—H35120.0
H15A—C158—H15B108.1C36—C35—H35120.0
O16—C159—C158113.0 (3)C35—C36—C37120.8 (4)
O16—C159—H15C109.0C35—C36—H36119.6
C158—C159—H15C109.0C37—C36—H36119.6
O16—C159—H15D109.0O33—C37—C36118.2 (3)
C158—C159—H15D109.0O33—C37—C32123.0 (3)
H15C—C159—H15D107.8C36—C37—C32118.7 (3)
O21—Mo2—O22105.80 (13)N31—C38—C39104.8 (3)
O21—Mo2—O2497.06 (12)N31—C38—H38A110.8
O22—Mo2—O2497.98 (12)C39—C38—H38A110.8
O21—Mo2—O23104.10 (11)N31—C38—H38B110.8
O22—Mo2—O2392.35 (11)C39—C38—H38B110.8
O24—Mo2—O23152.94 (10)H38A—C38—H38B108.9
O21—Mo2—O2586.57 (11)O34—C39—C38107.2 (3)
O22—Mo2—O25165.35 (11)O34—C39—H39A110.3
O24—Mo2—O2588.01 (10)C38—C39—H39A110.3
O23—Mo2—O2576.76 (9)O34—C39—H39B110.3
O21—Mo2—N21160.95 (12)C38—C39—H39B110.3
O22—Mo2—N2192.58 (12)H39A—C39—H39B108.5
O24—Mo2—N2175.05 (10)O35—C351—C352122.9 (3)
O23—Mo2—N2179.58 (10)O35—C351—C356119.3 (3)
O25—Mo2—N2175.99 (10)C352—C351—C356117.8 (3)
C21—N21—C28121.2 (3)C353—C352—C351120.0 (3)
C21—N21—Mo2127.4 (2)C353—C352—H352120.0
C28—N21—Mo2111.1 (2)C351—C352—H352120.0
C257—N22—C258125.6 (3)C352—C353—C354122.6 (3)
C257—N22—H22117.2C352—C353—H353118.7
C258—N22—H22117.2C354—C353—H353118.7
C27—O23—Mo2128.1 (2)C355—C354—C353118.6 (3)
C29—O24—Mo2120.6 (2)C355—C354—H354120.7
C251—O25—Mo2137.6 (2)C353—C354—H354120.7
C259—O26—H2109.5C354—C355—C356121.0 (3)
N21—C21—C22123.4 (3)C354—C355—H355119.5
N21—C21—H21118.3C356—C355—H355119.5
C22—C21—H21118.3C355—C356—C351119.9 (3)
C23—C22—C27119.0 (3)C355—C356—C357118.9 (3)
C23—C22—C21118.5 (3)C351—C356—C357121.2 (3)
C27—C22—C21122.4 (3)N32—C357—C356124.8 (3)
C24—C23—C22121.9 (3)N32—C357—H357117.6
C24—C23—H23119.0C356—C357—H357117.6
C22—C23—H23119.0N32—C358—C359110.4 (3)
C25—C24—C23118.2 (3)N32—C358—H35A109.6
C25—C24—H24120.9C359—C358—H35A109.6
C23—C24—H24120.9N32—C358—H35B109.6
C26—C25—C24121.3 (4)C359—C358—H35B109.6
C26—C25—H25119.4H35A—C358—H35B108.1
C24—C25—H25119.4O36—C359—C358112.7 (3)
C25—C26—C27121.1 (3)O36—C359—H35C109.1
C25—C26—H26119.5C358—C359—H35C109.1
C27—C26—H26119.5O36—C359—H35D109.1
O23—C27—C26118.9 (3)C358—C359—H35D109.1
O23—C27—C22122.6 (3)H35C—C359—H35D107.8
C26—C27—C22118.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O16—H1···O220.841.962.748 (4)156
O26—H2···O320.841.902.719 (4)164
O36—H3···O12i0.841.892.714 (4)169
N12—H12···O150.881.922.599 (4)133
N12—H12···O130.882.353.165 (4)153
N22—H22···O250.881.902.577 (4)132
N22—H22···O230.882.413.230 (4)155
N32—H32···O350.881.942.609 (4)132
N32—H32···O330.882.323.124 (4)153
Symmetry code: (i) x1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Mo(C9H9NO2)O2(C9H11NO2)]
Mr456.30
Crystal system, space groupTriclinic, P1
Temperature (K)180
a, b, c (Å)10.0953 (5), 13.5645 (8), 21.8864 (14)
α, β, γ (°)81.731 (5), 86.437 (5), 71.422 (5)
V3)2810.9 (3)
Z6
Radiation typeMo Kα
µ (mm1)0.74
Crystal size (mm)0.76 × 0.33 × 0.27
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer
Absorption correctionMulti-scan
[CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
Tmin, Tmax0.762, 0.834
No. of measured, independent and
observed [I > 2σ(I)] reflections
24992, 13842, 10817
Rint0.026
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.105, 1.15
No. of reflections13844
No. of parameters733
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.02, 1.10

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997), CAMERON (Pearce et al., 2000) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O16—H1···O220.841.962.748 (4)156
O26—H2···O320.841.902.719 (4)164
O36—H3···O12i0.841.892.714 (4)169
N12—H12···O150.881.922.599 (4)133
N12—H12···O130.882.353.165 (4)153
N22—H22···O250.881.902.577 (4)132
N22—H22···O230.882.413.230 (4)155
N32—H32···O350.881.942.609 (4)132
N32—H32···O330.882.323.124 (4)153
Symmetry code: (i) x1, y+1, z+1.
Structure matching between the three independent molecules of (I) and between the two polymorphs, (I) and (II) top
A is the structure match between molecules 1 and 2 in the title structure; B is the structure match between molecules 1 and 3 in the title structure; C is the structure match between molecules 2 and 3 in the title structure; D is the structure match between the two polymorphs.
OverlayR.m.s. position (Å)R.m.s. bond (Å)R.m.s. torsion (°)
A0.14590.00712.8944
B0.10840.00853.7916
C0.17020.00895.2911
D0.1820.7839.806
 

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