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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): m684.
Published online 2008 April 18. doi:  10.1107/S1600536808010246
PMCID: PMC2961198

(−)545-fac-Δ-Tris(l-prolinato)cobalt(III) trihydrate

Abstract

The absolute configuration of the octa­hedral fac-CoN3O3 title complex, [Co(C5H8NO2)3]·3H2O, has been determined by single-crystal X-ray analysis. A three-dimensional network of hydrogen bonds is observed between the proline carboxyl­ate groups and the three uncoordinated water mol­ecules.

Related literature

For related literature, see: Denning & Piper (1965 [triangle]).

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Object name is e-64-0m684-scheme1.jpg

Experimental

Crystal data

  • [Co(C5H8NO2)3]·3H2O
  • M r = 455.35
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m684-efi1.jpg
  • a = 10.1673 (9) Å
  • b = 10.8433 (10) Å
  • c = 17.2157 (14) Å
  • V = 1898.0 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.96 mm−1
  • T = 173 (2) K
  • 0.13 × 0.08 × 0.07 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.885, T max = 0.936
  • 13762 measured reflections
  • 4522 independent reflections
  • 2969 reflections with I > 2σ(I)
  • R int = 0.122

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.107
  • S = 0.92
  • 4522 reflections
  • 274 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.85 e Å−3
  • Δρmin = −0.51 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2596 Friedel pairs
  • Flack parameter: 0.04 (2)

Data collection: SMART-W2K/NT (Bruker, 2003 [triangle]); cell refinement: SAINT-W2K/NT (Bruker, 2003 [triangle]); data reduction: SAINT-W2K/NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL-NT; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL-NT.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010246/tk2254sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010246/tk2254Isup2.hkl

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

supplementary crystallographic information

Comment

The optical activity, absolute configuration, and rearrangement of tris(L-prolinato)cobalt(III) complexes were studied by Denning & Piper (1965), in which the absolute configurations were assigned based on circular dichroism (CD) studies and 1H NMR spectra. In this work, single crystals of the (-)545-fac-[Co(L-pro)3] isomer (I) suitable for single-crystal X-ray analysis have been prepared. This has allowed the determination of the absolute configuration of (I) as Δ. The UV-Vis and CD spectra of (I) in H2O show good agreement with the reported spectra (Denning & Piper, 1965). The molecular structure, Fig. 1, shows three deprotonated proline molecules to chelate the cobalt(III) ion to form octahedral fac-CoN3O3 geometry. The three lattice water form a three-dimensional network of hydrogen bonds with the uncoordinated carbonyl groups of the proline molecules (Table 1 & Fig. 2).

Experimental

The title compound was prepared according to the literature method (Denning & Piper, 1965). Single crystals suitable for single-crystal X-ray analysis were obtained by vapor diffusion of ethanol into the aqueous solution of (I) at room temperature. Analysis found: C 39.59, H 6.58, N 9.10; C15H30CoN3O9 C29H34F6O2S2 requires: C 39.57, H 6.64, N 9.23.

Refinement

The water- and N-bound H atoms were located in difference maps and refined with Uiso(H) = 1.5Ueq(O) or 1.5Ueq(N); see Table 1 for O-H and N-H bond distances. The remaining H atoms were placed in calculated positions, with C—H = 1.00 Å (for CH) and 0.99 Å (for CH2) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
ORTEP drawing for (I), showing atom labelling scheme and displacement ellipsoids at the 50% probability level. All hydrogen atoms are omitted for clarity.
Fig. 2.
Three-dimensional network structure of hydrogen bonds viewed in projection down the a axis. Dashed lines indicate the hydrogen-bonding interactions. All hydrogen atoms are omitted for clarity.

Crystal data

[Co(C5H8NO2)3]·3H2OF000 = 960
Mr = 455.35Dx = 1.594 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 705 reflections
a = 10.1673 (9) Åθ = 2.2–17.1º
b = 10.8433 (10) ŵ = 0.96 mm1
c = 17.2157 (14) ÅT = 173 (2) K
V = 1898.0 (3) Å3Block, pink
Z = 40.13 × 0.08 × 0.07 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer4522 independent reflections
Radiation source: fine-focus sealed tube2969 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.122
Detector resolution: 8.366 pixels mm-1θmax = 27.9º
T = 173(2) Kθmin = 2.2º
[var phi] and ω scansh = −13→7
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)k = −14→14
Tmin = 0.885, Tmax = 0.936l = −22→22
13762 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.062  w = 1/[σ2(Fo2) + (0.0283P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107(Δ/σ)max < 0.001
S = 0.92Δρmax = 0.85 e Å3
4522 reflectionsΔρmin = −0.51 e Å3
274 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2596 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.04 (2)

Special details

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)

xyzUiso*/Ueq
C10.3689 (5)0.9795 (5)0.1401 (3)0.0220 (11)
H1A0.43640.93960.10630.026*
C20.4210 (5)1.1046 (5)0.1661 (3)0.0309 (15)
H2A0.39401.12300.22010.037*
H2B0.51821.10740.16270.037*
C30.3589 (5)1.1948 (4)0.1093 (3)0.0248 (11)
H3A0.35611.27940.13090.030*
H3B0.40621.19580.05910.030*
C40.2218 (5)1.1408 (5)0.1008 (3)0.0251 (12)
H4A0.16781.15760.14750.030*
H4B0.17661.17490.05460.030*
C50.3343 (5)0.8910 (5)0.2056 (3)0.0216 (12)
C60.0485 (5)0.7863 (5)−0.0354 (3)0.0168 (11)
H6A−0.01940.7199−0.03090.020*
C70.0427 (5)0.8403 (5)−0.1185 (3)0.0226 (12)
H7A0.13160.8630−0.13720.027*
H7B0.00290.7809−0.15530.027*
C8−0.0437 (5)0.9539 (4)−0.1089 (3)0.0223 (11)
H8A−0.02861.0141−0.15120.027*
H8B−0.13810.9316−0.10740.027*
C90.0024 (5)1.0038 (5)−0.0315 (3)0.0213 (12)
H9A0.08931.0442−0.03640.026*
H9B−0.06141.0637−0.01010.026*
C100.1804 (5)0.7331 (5)−0.0136 (3)0.0172 (11)
C11−0.0584 (5)0.8563 (5)0.2340 (3)0.0208 (12)
H11A−0.00410.84480.28190.025*
C12−0.1937 (5)0.9052 (5)0.2579 (3)0.0311 (15)
H12A−0.26430.85980.23050.037*
H12B−0.20690.89600.31460.037*
C13−0.1946 (5)1.0400 (5)0.2351 (3)0.0258 (13)
H13A−0.15941.09250.27730.031*
H13B−0.28441.06810.22160.031*
C14−0.1050 (5)1.0419 (5)0.1647 (3)0.0205 (12)
H14A−0.15231.01320.11780.025*
H14B−0.07101.12610.15510.025*
C15−0.0597 (5)0.7356 (5)0.1891 (3)0.0180 (11)
Co10.12024 (6)0.87354 (6)0.11104 (3)0.01537 (16)
N10.2469 (4)1.0046 (4)0.0916 (2)0.0190 (10)
H1C0.26980.99570.04700.023*
N20.0110 (4)0.8912 (4)0.01862 (19)0.0144 (9)
H2C−0.0700.87570.03380.017*
N30.0039 (4)0.9561 (4)0.1851 (2)0.0194 (11)
H3C0.04600.99000.21080.023*
O10.2224 (3)0.8373 (3)0.20056 (17)0.0198 (9)
O20.4133 (3)0.8715 (4)0.25896 (18)0.0321 (9)
O30.2340 (3)0.7768 (3)0.04792 (18)0.0182 (8)
O40.2308 (3)0.6524 (3)−0.05483 (18)0.0275 (9)
O50.0152 (3)0.7314 (3)0.12902 (16)0.0189 (8)
O6−0.1273 (4)0.6473 (3)0.21062 (17)0.0246 (8)
O70.1135 (5)0.9744 (5)0.4313 (3)0.0419 (12)
H7C0.096 (6)1.024 (6)0.392 (4)0.063*
H7D0.051 (7)0.966 (8)0.442 (4)0.063*
O80.2893 (4)0.7736 (4)0.3961 (2)0.0383 (11)
H8C0.227 (6)0.835 (6)0.404 (3)0.057*
H8D0.328 (6)0.796 (6)0.360 (3)0.057*
O90.3649 (5)0.5837 (4)0.5018 (3)0.0461 (13)
H9C0.356 (8)0.640 (6)0.475 (4)0.069*
H9D0.328 (7)0.531 (6)0.485 (4)0.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.016 (3)0.027 (3)0.023 (2)−0.002 (3)0.002 (2)−0.003 (2)
C20.024 (3)0.034 (4)0.035 (3)−0.010 (3)0.000 (2)−0.007 (3)
C30.029 (3)0.019 (3)0.027 (2)−0.006 (2)0.009 (3)−0.002 (3)
C40.031 (3)0.019 (3)0.025 (3)0.003 (3)0.006 (2)−0.004 (3)
C50.028 (3)0.016 (3)0.021 (3)0.005 (2)0.002 (2)−0.005 (2)
C60.018 (3)0.018 (3)0.015 (2)−0.005 (2)0.004 (2)−0.008 (2)
C70.024 (3)0.035 (3)0.009 (2)−0.001 (2)−0.001 (2)−0.002 (2)
C80.019 (3)0.030 (3)0.018 (2)0.000 (2)−0.001 (3)0.009 (3)
C90.022 (3)0.018 (3)0.024 (3)0.000 (2)0.000 (2)0.003 (2)
C100.015 (3)0.017 (3)0.019 (3)−0.002 (2)0.007 (2)−0.001 (2)
C110.028 (3)0.015 (3)0.019 (2)−0.001 (3)0.003 (2)0.000 (2)
C120.031 (3)0.025 (4)0.037 (3)−0.006 (3)0.014 (3)0.001 (3)
C130.018 (3)0.029 (3)0.030 (3)0.000 (3)0.004 (2)−0.003 (3)
C140.022 (3)0.015 (3)0.025 (3)0.003 (3)−0.003 (3)0.001 (2)
C150.017 (3)0.018 (3)0.019 (3)−0.002 (2)−0.006 (2)−0.002 (2)
Co10.0161 (3)0.0153 (3)0.0147 (3)−0.0008 (3)−0.0009 (3)−0.0009 (3)
N10.020 (2)0.019 (2)0.018 (2)0.0016 (19)−0.0008 (19)−0.0008 (17)
N20.013 (2)0.015 (2)0.0159 (19)0.0001 (19)−0.0015 (17)0.0004 (18)
N30.026 (3)0.012 (2)0.021 (2)−0.004 (2)−0.003 (2)−0.0027 (18)
O10.021 (2)0.023 (2)0.0158 (17)0.0023 (17)−0.0061 (16)0.0040 (15)
O20.033 (2)0.040 (2)0.0236 (18)0.001 (2)−0.0133 (16)0.003 (2)
O30.0158 (18)0.019 (2)0.0199 (17)0.0037 (16)−0.0049 (15)−0.0045 (15)
O40.0225 (19)0.034 (3)0.0261 (19)0.0057 (18)0.0014 (16)−0.0104 (18)
O50.0215 (18)0.016 (2)0.0194 (19)−0.0054 (16)−0.0042 (15)−0.0002 (14)
O60.0259 (18)0.021 (2)0.0270 (17)−0.005 (2)−0.0014 (17)0.0053 (15)
O70.041 (3)0.046 (3)0.039 (2)0.009 (3)−0.003 (3)0.0153 (19)
O80.049 (3)0.034 (3)0.032 (2)−0.001 (2)0.002 (2)0.004 (2)
O90.048 (3)0.036 (3)0.055 (3)−0.005 (3)−0.006 (3)0.004 (2)

Geometric parameters (Å, °)

C1—N11.520 (6)C11—N31.510 (6)
C1—C51.521 (7)C11—C151.520 (7)
C1—C21.523 (7)C11—C121.530 (7)
C1—H1A1.0000C11—H11A1.0000
C2—C31.520 (7)C12—C131.514 (7)
C2—H2A0.9900C12—H12A0.9900
C2—H2B0.9900C12—H12B0.9900
C3—C41.518 (6)C13—C141.516 (6)
C3—H3A0.9900C13—H13A0.9900
C3—H3B0.9900C13—H13B0.9900
C4—N11.507 (6)C14—N31.488 (6)
C4—H4A0.9900C14—H14A0.9900
C4—H4B0.9900C14—H14B0.9900
C5—O21.238 (5)C15—O61.235 (6)
C5—O11.282 (6)C15—O51.285 (5)
C6—C101.508 (6)Co1—O11.900 (3)
C6—N21.518 (6)Co1—O51.900 (3)
C6—C71.546 (6)Co1—O31.903 (3)
C6—H6A1.0000Co1—N11.947 (4)
C7—C81.522 (7)Co1—N21.950 (3)
C7—H7A0.9900Co1—N31.956 (4)
C7—H7B0.9900N1—H1C0.8117
C8—C91.513 (6)N2—H2C0.8806
C8—H8A0.9900N3—H3C0.7180
C8—H8B0.9900O7—H7C0.88 (6)
C9—N21.497 (6)O7—H7D0.66 (7)
C9—H9A0.9900O8—H8C0.93 (6)
C9—H9B0.9900O8—H8D0.77 (6)
C10—O41.237 (6)O9—H9C0.77 (6)
C10—O31.282 (5)O9—H9D0.74 (6)
N1—C1—C5109.4 (4)C13—C12—C11105.7 (4)
N1—C1—C2106.6 (4)C13—C12—H12A110.6
C5—C1—C2115.2 (4)C11—C12—H12A110.6
N1—C1—H1A108.5C13—C12—H12B110.6
C5—C1—H1A108.5C11—C12—H12B110.6
C2—C1—H1A108.5H12A—C12—H12B108.7
C3—C2—C1103.9 (4)C12—C13—C14102.5 (4)
C3—C2—H2A111.0C12—C13—H13A111.3
C1—C2—H2A111.0C14—C13—H13A111.3
C3—C2—H2B111.0C12—C13—H13B111.3
C1—C2—H2B111.0C14—C13—H13B111.3
H2A—C2—H2B109.0H13A—C13—H13B109.2
C4—C3—C2101.3 (4)N3—C14—C13104.5 (4)
C4—C3—H3A111.5N3—C14—H14A110.9
C2—C3—H3A111.5C13—C14—H14A110.9
C4—C3—H3B111.5N3—C14—H14B110.9
C2—C3—H3B111.5C13—C14—H14B110.9
H3A—C3—H3B109.3H14A—C14—H14B108.9
N1—C4—C3103.5 (4)O6—C15—O5123.0 (5)
N1—C4—H4A111.1O6—C15—C11121.3 (4)
C3—C4—H4A111.1O5—C15—C11115.8 (4)
N1—C4—H4B111.1O1—Co1—O590.41 (14)
C3—C4—H4B111.1O1—Co1—O390.97 (14)
H4A—C4—H4B109.0O5—Co1—O389.27 (14)
O2—C5—O1123.3 (5)O1—Co1—N185.92 (15)
O2—C5—C1120.5 (5)O5—Co1—N1172.63 (16)
O1—C5—C1116.2 (4)O3—Co1—N184.41 (15)
C10—C6—N2111.0 (4)O1—Co1—N2173.64 (17)
C10—C6—C7114.1 (4)O5—Co1—N283.85 (15)
N2—C6—C7105.9 (4)O3—Co1—N286.24 (15)
C10—C6—H6A108.6N1—Co1—N299.48 (16)
N2—C6—H6A108.6O1—Co1—N384.07 (15)
C7—C6—H6A108.6O5—Co1—N385.70 (16)
C8—C7—C6103.2 (4)O3—Co1—N3172.90 (16)
C8—C7—H7A111.1N1—Co1—N3100.25 (17)
C6—C7—H7A111.1N2—Co1—N398.17 (16)
C8—C7—H7B111.1C4—N1—C1104.8 (4)
C6—C7—H7B111.1C4—N1—Co1125.9 (3)
H7A—C7—H7B109.1C1—N1—Co1108.3 (3)
C9—C8—C7101.9 (4)C4—N1—H1C105.4
C9—C8—H8A111.4C1—N1—H1C105.4
C7—C8—H8A111.4Co1—N1—H1C105.4
C9—C8—H8B111.4C9—N2—C6105.8 (3)
C7—C8—H8B111.4C9—N2—Co1125.7 (3)
H8A—C8—H8B109.3C6—N2—Co1106.5 (3)
N2—C9—C8103.6 (4)C9—N2—H2C105.8
N2—C9—H9A111.0C6—N2—H2C105.8
C8—C9—H9A111.0Co1—N2—H2C105.8
N2—C9—H9B111.0C14—N3—C11105.5 (4)
C8—C9—H9B111.0C14—N3—Co1125.6 (3)
H9A—C9—H9B109.0C11—N3—Co1106.8 (3)
O4—C10—O3124.0 (5)C14—N3—H3C105.8
O4—C10—C6119.8 (5)C11—N3—H3C105.8
O3—C10—C6116.2 (4)Co1—N3—H3C105.8
N3—C11—C15109.7 (4)C5—O1—Co1116.5 (3)
N3—C11—C12106.2 (4)C10—O3—Co1114.7 (3)
C15—C11—C12115.3 (4)C15—O5—Co1115.8 (3)
N3—C11—H11A108.5H7C—O7—H7D95 (7)
C15—C11—H11A108.5H8C—O8—H8D104 (6)
C12—C11—H11A108.5H9C—O9—H9D108 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O9—H9D···O4i0.74 (6)2.19 (7)2.907 (6)164 (8)
O8—H8D···O20.77 (6)2.11 (6)2.880 (5)173 (7)
O7—H7D···O9ii0.66 (7)2.20 (6)2.848 (7)167 (9)
O9—H9C···O80.77 (6)2.09 (7)2.853 (6)166 (8)
O8—H8C···O70.93 (6)1.96 (6)2.882 (7)172 (5)

Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2254).

References

  • Bruker (2003). SAINT-W2K/NT and SMART-W2K/NT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Denning, R. G. & Piper, T. S. (1965). Inorg. Chem.5, 1056–1065.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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