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The title compound, (C8H12N)2[Co2(C2O4)3(H2O)4], was prepared under hydro­thermal conditions. The structure consists of chiral organic cations and complex anions. Hydrogen bonds and C–H...π(ar­yl) inter­actions give a herring-bone arrangement of the cations along the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020016/hy2056sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020016/hy2056Isup2.hkl
Contains datablock I

CCDC reference: 650510

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.012 Å
  • R factor = 0.033
  • wR factor = 0.102
  • Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.839 0.951 RT(exp) = 1.134 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT057_ALERT_3_C Correction for Absorption Required RT(exp) ... 1.14 PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 12 PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.56 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C3 - C4 ... 1.56 Ang. PLAT731_ALERT_1_C Bond Calc 1.558(17), Rep 1.558(6) ...... 2.83 su-Ra C1 -C2 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 1.556(11), Rep 1.556(5) ...... 2.20 su-Ra C4 -C3 1.555 1.555 PLAT732_ALERT_1_C Angle Calc 81.0(2), Rep 81.01(9) ...... 2.22 su-Ra O3 -CO -O4 1.555 1.555 1.555 PLAT732_ALERT_1_C Angle Calc 79.46(19), Rep 79.45(9) ...... 2.11 su-Ra O1 -CO -O2 1.555 1.555 1.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.50 From the CIF: _reflns_number_total 2268 Count of symmetry unique reflns 1418 Completeness (_total/calc) 159.94% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 850 Fraction of Friedel pairs measured 0.599 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11 = . R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The crystal structure of the title compound, (I)(Fig. 1), consists of bicobalt oxalate complex anions [Co2(C2O4)3(H2O)4]2- and organic cations (C8H12N)+, joined into a two-dimensional sheet by hydrogen bonds. Owing to the presence of the chiral organic cation, the compound crystallizes in the polar space group C2. In the anion, there are two types of oxalates. One as tetradentate ligand bridges two Co atoms, each is coordinated by another type of oxalate as bidentate ligand in the same plane. Each Co atom is also bonded by two water molecules above and below the equatorial plane to produce a negative step-lamella. The bond angles around the Co atom range from 81.01 (9)° to 100.2 (2) °, and from 178.1 (2)° to 178.7 (2)°. The Co—O distances span from 2.062 (5)Å to 2.114 (3) Å. The organic cation contains a stereogenic center in its R configuration and has a normal structure similar to that described elsewhere (Shan & Huang, 2001). The cations are anchored in the pockets on the both faces of the puckered anionic lamella through hydrogen bonds with the distances ranging from 2.678 (8)Å to 2.976 (7)Å (Table 1), thus resulting in the formation of cation–anion–cation slab-sandwich layers with an arrangement of the cations held together by close C–H···π(aryl) interactions in a herring bone motif (Fig.2).

Related literature top

For related structure, see: Shan & Huang (2001).

Experimental top

Compound (I) was prepared by the hydrothermal reaction of Co(C2O4).2H2O(0.130 g, 0.71 mmol), (R)-(+)-1-phenylethylamine (0.062 g, 0.51 mmol) and water (0.6 ml) at 383 K for 3 d in a sealed thick-walled Pyrex tube. Light pink crystals of (I) were obtained in 40–50% yield.

Refinement top

H atoms on C and N atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å (aryl), 0.98Å (CH) and 0.96Å (CH3) and N—H = 0.89 Å and Uiso(H) = 1.2Ueq(C,N). H atoms on water molecules were located in a difference Fourier map and fixed with Uiso(H) = 1.2Ueq(O).

Structure description top

The crystal structure of the title compound, (I)(Fig. 1), consists of bicobalt oxalate complex anions [Co2(C2O4)3(H2O)4]2- and organic cations (C8H12N)+, joined into a two-dimensional sheet by hydrogen bonds. Owing to the presence of the chiral organic cation, the compound crystallizes in the polar space group C2. In the anion, there are two types of oxalates. One as tetradentate ligand bridges two Co atoms, each is coordinated by another type of oxalate as bidentate ligand in the same plane. Each Co atom is also bonded by two water molecules above and below the equatorial plane to produce a negative step-lamella. The bond angles around the Co atom range from 81.01 (9)° to 100.2 (2) °, and from 178.1 (2)° to 178.7 (2)°. The Co—O distances span from 2.062 (5)Å to 2.114 (3) Å. The organic cation contains a stereogenic center in its R configuration and has a normal structure similar to that described elsewhere (Shan & Huang, 2001). The cations are anchored in the pockets on the both faces of the puckered anionic lamella through hydrogen bonds with the distances ranging from 2.678 (8)Å to 2.976 (7)Å (Table 1), thus resulting in the formation of cation–anion–cation slab-sandwich layers with an arrangement of the cations held together by close C–H···π(aryl) interactions in a herring bone motif (Fig.2).

For related structure, see: Shan & Huang (2001).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. [Symmetry code: (i) 1 - x, y, 1 - z.]
[Figure 2] Fig. 2. A packing diagram of (I), showing the cation–anion–cation slab-sandwich layers with a herring-bone arrangement of the cations.
(R)-1-Phenylethylaminium µ-oxalato-κ4O,O':O''O'''-bis[diaqua(oxalato-κ2O,O')cobalt(II)] top
Crystal data top
(C8H12N)2[Co2(C2O4)3(H2O)4]F(000) = 720
Mr = 698.36Dx = 1.639 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 4453 reflections
a = 10.973 (2) Åθ = 1.2–27.1°
b = 7.5560 (15) ŵ = 1.25 mm1
c = 17.067 (3) ÅT = 296 K
β = 90.33 (3)°Plate, pink
V = 1415.0 (5) Å30.24 × 0.12 × 0.04 mm
Z = 2
Data collection top
Siemens Quantum CCD
diffractometer
1938 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Graphite monochromatorθmax = 25.5°, θmin = 1.2°
ω scansh = 1310
3658 measured reflectionsk = 98
2268 independent reflectionsl = 2019
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0589P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2268 reflectionsΔρmax = 0.45 e Å3
193 parametersΔρmin = 0.52 e Å3
38 restraintsAbsolute structure: Flack (1983), 850 Fridel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.11 (3)
Crystal data top
(C8H12N)2[Co2(C2O4)3(H2O)4]V = 1415.0 (5) Å3
Mr = 698.36Z = 2
Monoclinic, C2Mo Kα radiation
a = 10.973 (2) ŵ = 1.25 mm1
b = 7.5560 (15) ÅT = 296 K
c = 17.067 (3) Å0.24 × 0.12 × 0.04 mm
β = 90.33 (3)°
Data collection top
Siemens Quantum CCD
diffractometer
1938 reflections with I > 2σ(I)
3658 measured reflectionsRint = 0.020
2268 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.102Δρmax = 0.45 e Å3
S = 1.13Δρmin = 0.52 e Å3
2268 reflectionsAbsolute structure: Flack (1983), 850 Fridel pairs
193 parametersAbsolute structure parameter: 0.11 (3)
38 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.29291 (4)0.98018 (18)0.41036 (3)0.02253 (17)
O10.4159 (6)0.8027 (5)0.4631 (3)0.0242 (13)
O20.4163 (5)1.1583 (6)0.4624 (3)0.0266 (13)
O30.1732 (5)1.1586 (6)0.3606 (3)0.0262 (14)
O40.1735 (6)0.8017 (6)0.3563 (3)0.0286 (15)
O50.0023 (6)0.8057 (7)0.2907 (3)0.0379 (16)
O60.0019 (5)1.1607 (6)0.2925 (3)0.0341 (15)
O70.3966 (2)0.9858 (9)0.30858 (15)0.0317 (6)
H7A0.44800.88820.29920.038*
H7B0.44911.07600.30100.038*
O80.1915 (2)0.9809 (10)0.51531 (15)0.0314 (6)
H8A0.14651.08920.52200.038*
H8B0.14870.87600.52440.038*
N10.2561 (3)0.4834 (10)0.28541 (18)0.0278 (7)
H1A0.33710.48220.28330.042*
H1B0.23060.39500.31560.042*
H1C0.23120.58600.30540.042*
C10.50000.8799 (16)0.50000.019 (2)
C20.50001.0861 (15)0.50000.021 (3)
C40.0833 (8)0.8815 (10)0.3241 (4)0.0194 (16)
C30.0844 (9)1.0873 (11)0.3269 (5)0.0275 (19)
C90.3493 (6)0.6631 (9)0.1348 (3)0.0599 (19)
H90.41340.59780.15600.072*
C80.3753 (9)0.8048 (11)0.0842 (4)0.081 (2)
H80.45530.83450.07220.098*
C70.2813 (10)0.8964 (11)0.0536 (5)0.086 (3)
H70.29750.98980.01980.103*
C60.1660 (9)0.8583 (11)0.0701 (4)0.083 (3)
H60.10330.92410.04770.100*
C50.1388 (7)0.7174 (10)0.1216 (4)0.067 (2)
H50.05820.69210.13370.080*
C100.2306 (8)0.6182 (9)0.1538 (4)0.0395 (18)
C110.2044 (4)0.4618 (12)0.2043 (2)0.0307 (12)
H110.11570.45170.20890.037*
C120.2513 (8)0.2897 (8)0.1688 (4)0.045 (2)
H12A0.21890.27630.11680.068*
H12B0.22580.19170.20050.068*
H12C0.33870.29280.16670.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0218 (3)0.0158 (3)0.0299 (3)0.0009 (6)0.00417 (19)0.0013 (6)
O10.034 (3)0.010 (3)0.029 (3)0.001 (3)0.008 (3)0.003 (2)
O20.018 (3)0.023 (3)0.039 (3)0.002 (3)0.006 (2)0.005 (3)
O30.023 (3)0.018 (3)0.038 (3)0.004 (2)0.007 (3)0.002 (2)
O40.033 (4)0.016 (3)0.037 (3)0.001 (3)0.007 (3)0.001 (2)
O50.038 (4)0.031 (4)0.044 (3)0.004 (3)0.020 (3)0.005 (3)
O60.032 (4)0.021 (3)0.050 (3)0.010 (3)0.006 (3)0.000 (3)
O70.0339 (13)0.0203 (14)0.0412 (15)0.001 (3)0.0077 (11)0.007 (3)
O80.0361 (13)0.0150 (12)0.0432 (15)0.001 (3)0.0063 (11)0.002 (3)
N10.0297 (15)0.0213 (15)0.0323 (16)0.002 (4)0.0005 (13)0.003 (4)
C10.011 (5)0.029 (5)0.017 (4)0.0000.001 (4)0.000
C20.030 (6)0.005 (4)0.029 (5)0.0000.004 (5)0.000
C40.014 (4)0.024 (4)0.019 (4)0.001 (3)0.002 (3)0.000 (3)
C30.039 (5)0.015 (3)0.029 (4)0.004 (4)0.002 (4)0.001 (3)
C90.073 (5)0.070 (5)0.037 (3)0.032 (4)0.000 (3)0.005 (3)
C80.109 (6)0.082 (5)0.053 (4)0.043 (5)0.008 (4)0.003 (4)
C70.149 (7)0.053 (4)0.056 (4)0.010 (5)0.007 (5)0.001 (3)
C60.132 (7)0.062 (4)0.056 (4)0.045 (5)0.011 (5)0.010 (4)
C50.086 (5)0.064 (4)0.050 (4)0.038 (4)0.003 (4)0.009 (4)
C100.055 (4)0.031 (4)0.033 (3)0.003 (3)0.007 (3)0.008 (3)
C110.0267 (18)0.032 (4)0.034 (2)0.005 (3)0.0019 (16)0.001 (3)
C120.076 (5)0.027 (4)0.033 (4)0.002 (4)0.003 (4)0.010 (3)
Geometric parameters (Å, º) top
Co—O32.062 (5)C1—C21.558 (6)
Co—O72.083 (3)C2—O2i1.243 (7)
Co—O42.091 (5)C4—C31.556 (5)
Co—O12.102 (5)C9—C101.387 (10)
Co—O22.103 (6)C9—C81.406 (10)
Co—O82.114 (3)C9—H90.9300
O1—C11.257 (8)C8—C71.345 (12)
O2—C21.243 (7)C8—H80.9300
O3—C31.250 (10)C7—C61.329 (12)
O4—C41.281 (9)C7—H70.9300
O5—C41.237 (9)C6—C51.414 (11)
O6—C31.242 (10)C6—H60.9300
O7—H7A0.9420C5—C101.368 (10)
O7—H7B0.9020C5—H50.9300
O8—H8A0.9630C10—C111.491 (11)
O8—H8B0.9349C11—C121.525 (11)
N1—C111.503 (5)C11—H110.9800
N1—H1A0.8900C12—H12A0.9600
N1—H1B0.8900C12—H12B0.9600
N1—H1C0.8900C12—H12C0.9600
C1—O1i1.257 (8)
O3—Co—O789.6 (2)O5—C4—O4124.3 (8)
O3—Co—O481.01 (9)O5—C4—C3118.9 (9)
O7—Co—O489.4 (2)O4—C4—C3116.8 (9)
O3—Co—O1178.7 (2)O6—C3—O3128.0 (8)
O7—Co—O191.0 (2)O6—C3—C4115.2 (9)
O4—Co—O1100.2 (2)O3—C3—C4116.8 (9)
O3—Co—O299.4 (2)C10—C9—C8121.6 (8)
O7—Co—O289.2 (2)C10—C9—H9119.2
O4—Co—O2178.5 (3)C8—C9—H9119.2
O1—Co—O279.45 (9)C7—C8—C9118.2 (8)
O3—Co—O890.6 (2)C7—C8—H8120.9
O7—Co—O8178.1 (2)C9—C8—H8120.9
O4—Co—O892.5 (2)C6—C7—C8122.4 (8)
O1—Co—O888.7 (2)C6—C7—H7118.8
O2—Co—O888.9 (2)C8—C7—H7118.8
C1—O1—Co112.7 (6)C7—C6—C5119.9 (8)
C2—O2—Co114.2 (6)C7—C6—H6120.0
C3—O3—Co113.6 (5)C5—C6—H6120.0
C4—O4—Co111.5 (5)C10—C5—C6120.4 (8)
Co—O7—H7A117.1C10—C5—H5119.8
Co—O7—H7B119.1C6—C5—H5119.8
H7A—O7—H7B100.6C5—C10—C9117.5 (7)
Co—O8—H8A112.0C5—C10—C11121.5 (7)
Co—O8—H8B113.9C9—C10—C11120.9 (7)
H8A—O8—H8B116.2C10—C11—N1111.9 (6)
C11—N1—H1A109.5C10—C11—C12112.3 (4)
C11—N1—H1B109.5N1—C11—C12109.4 (6)
H1A—N1—H1B109.5C10—C11—H11107.7
C11—N1—H1C109.5N1—C11—H11107.7
H1A—N1—H1C109.5C12—C11—H11107.7
H1B—N1—H1C109.5C11—C12—H12A109.5
O1—C1—O1i124.7 (12)C11—C12—H12B109.5
O1—C1—C2117.6 (6)H12A—C12—H12B109.5
O1i—C1—C2117.6 (6)C11—C12—H12C109.5
O2i—C2—O2128.0 (12)H12A—C12—H12C109.5
O2i—C2—C1116.0 (6)H12B—C12—H12C109.5
O2—C2—C1116.0 (6)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O40.891.952.843 (8)176
N1—H1B···O3ii0.892.052.918 (8)166
N1—H1A···O6iii0.892.232.976 (7)141
N1—H1A···O5iii0.892.212.973 (7)143
O8—H8B···O2iv0.931.812.737 (9)172
O8—H8A···O1v0.961.772.728 (9)172
O7—H7B···O5vi0.901.822.678 (8)157
O7—H7A···O6iii0.941.812.712 (8)159
Symmetry codes: (ii) x, y1, z; (iii) x+1/2, y1/2, z; (iv) x+1/2, y1/2, z+1; (v) x+1/2, y+1/2, z+1; (vi) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula(C8H12N)2[Co2(C2O4)3(H2O)4]
Mr698.36
Crystal system, space groupMonoclinic, C2
Temperature (K)296
a, b, c (Å)10.973 (2), 7.5560 (15), 17.067 (3)
β (°) 90.33 (3)
V3)1415.0 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.25
Crystal size (mm)0.24 × 0.12 × 0.04
Data collection
DiffractometerSiemens Quantum CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3658, 2268, 1938
Rint0.020
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.102, 1.13
No. of reflections2268
No. of parameters193
No. of restraints38
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.52
Absolute structureFlack (1983), 850 Fridel pairs
Absolute structure parameter0.11 (3)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O40.891.952.843 (8)176
N1—H1B···O3i0.892.052.918 (8)166
N1—H1A···O6ii0.892.232.976 (7)141
N1—H1A···O5ii0.892.212.973 (7)143
O8—H8B···O2iii0.931.812.737 (9)172
O8—H8A···O1iv0.961.772.728 (9)172
O7—H7B···O5v0.901.822.678 (8)157
O7—H7A···O6ii0.941.812.712 (8)159
Symmetry codes: (i) x, y1, z; (ii) x+1/2, y1/2, z; (iii) x+1/2, y1/2, z+1; (iv) x+1/2, y+1/2, z+1; (v) x+1/2, y+1/2, z.
 

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