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The title compound, catena-poly­[[di­aqua­barium(II)-bis­[di-μ-oxalato-[(1,10-phenanthroline)­chromate(III)]]] tetrahydrate], [Ba{Cr(C2O4)2(C12H8N2)}2(H2O)6]n, with ten-coordinate bar­ium(II) and six-coordinate chromium(III), consists of infinite chains along the b axis and exhibits stacking with π-interactions between the chains. Even though the crystal is racemic, only one of the enantiomers of the chromium anion is present in the single chain due to the twofold axis passing through the barium, making the chains chiral.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005931/br6013sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005931/br6013Isup2.hkl
Contains datablock I

CCDC reference: 165631

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.007 Å
  • H-atom completeness 58%
  • R factor = 0.044
  • wR factor = 0.125
  • Data-to-parameter ratio = 15.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(30) - C(31) = 1.54 Ang. PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(40) - C(41) = 1.54 Ang. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C32 H28 Ba1 Cr2 N4 O22 Atom count from the _atom_site data: C32 H16 Ba1 Cr2 N4 O22 ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.945 Tmax scaled 0.719 Tmin scaled 0.560 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C32 H28 Ba Cr2 N4 O22 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 128.00 128.00 0.00 H 112.00 64.00 48.00 Ba 4.00 4.00 0.00 Cr 8.00 8.00 0.00 N 16.00 16.00 0.00 O 88.00 88.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 1061.92 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 32.00 384.35 H 1.01 16.00 16.13 Ba 137.33 1.00 137.33 Cr 52.00 2.00 103.99 N 14.01 4.00 56.03 O 16.00 22.00 351.98 Calculated formula weight 1049.81 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

The structure of several compounds with the [Cr(ox)2(L—L)]1- (ox = oxalate, L—L = phen or bipy, phen = 1,10-phenanthroline, bipy = bipyridine) anion have been published. By using different counter-ions, such as Na+, K+, Mn2+ and Ba2+, one-dimensional chains as well as two- and three-dimensional nets have been obtained (Rochon & Massaerweh, 1999; De Munno et al., 1999; Marinescu et al., 2000). In Ba[Cr(ox)2(bipy)]2, the complex forms a three-dimensional network. This is, however, not the case for the title compound, (I), which forms an infinite one-dimensional structure similar to [Mn(Cr(ox)2(bipy))2]n (Rochon et al., 1996).

The title compound has an asymmetric unit containing one barium and one chromium with two oxalates and one 1,10-phenanthroline (Fig. 1). Barium exhibits a ten-coordinate environment with four oxalates and two water molecules and chromium coordinates two oxalates and one phenanthroline in a distorted octahedral environment. The asymmetric unit forms infinite chains along the b axis and has a twofold symmetry. The two chromium complex anions acts as a bridge between the barium ions with solvent water located in the cavities around barium. Within the chains, the Ba···Ba distance is 10.154 (1) Å and the bridging Cr atoms are 6.892 (12) Å apart. The four chains in the unit cell are related to each other by a twofold screw axis and a c-glide plane normal to the b axis. This results in the enantiomers forming layers along the c axis which are stacked together by π-interactions. These interactions result in the phenanthrolines being 3.4 Å apart with a parallel displacement of 3 Å, not uncommon in aromatic compounds containing heteroatoms (Janiak, 2000). Even though the structure contains both enantiomers of the octahedral Cr anion, only one of the enantiomers, Δ or Λ, are found in the individual chains. This makes the chains chiral as in the [Mn(Cr(bipy)(ox)2)2]n analog (Rochon et al., 1996).

The structure, which differs from its bipyridine analog, shows the importance of π-interactions in crystal design which in this case plays a key role in the topology of the framework.

Experimental top

The compound was synthesized according to the method described by Broomhead (1962).

Refinement top

No H atoms were assigned to the water molecules. A correction for intensity decay was applied by the default method in XCAD4 (Harms & Wocadlo, 1995)

Computing details top

Data collection: CAD-4 Software (Enraf Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).

Figures top
[Figure 1] Fig. 1. View of (I) shown with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. View of the chain in (I) along the twofold axis.
(I) top
Crystal data top
[Ba{Cr(C2O4)(C12H8N2)}2(H2O)6]F(000) = 2112
Mr = 1061.92Dx = 1.822 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 26.1127 (18) ÅCell parameters from 25 reflections
b = 10.1535 (6) Åθ = 3.1–27°
c = 14.6165 (9) ŵ = 1.65 mm1
β = 92.367 (7)°T = 293 K
V = 3872.0 (4) Å3Prism, red-violet
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Enraf-Nonius CAD4
diffractometer
Rint = 0.028
ω–2θ scansθmax = 27.0°, θmin = 3.1°
Absorption correction: ψ scan
(North et al., 1968)
h = 033
Tmin = 0.593, Tmax = 0.760k = 012
4442 measured reflectionsl = 1818
4203 independent reflections4 standard reflections every 120 min
2749 reflections with I > 2σ(I) intensity decay: 21%
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.0627P)2 + 13.8292P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.125(Δ/σ)max < 0.001
S = 1.01Δρmax = 2.09 e Å3
4203 reflectionsΔρmin = 1.15 e Å3
276 parameters
Crystal data top
[Ba{Cr(C2O4)(C12H8N2)}2(H2O)6]V = 3872.0 (4) Å3
Mr = 1061.92Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.1127 (18) ŵ = 1.65 mm1
b = 10.1535 (6) ÅT = 293 K
c = 14.6165 (9) Å0.3 × 0.2 × 0.2 mm
β = 92.367 (7)°
Data collection top
Enraf-Nonius CAD4
diffractometer
2749 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.028
Tmin = 0.593, Tmax = 0.7604 standard reflections every 120 min
4442 measured reflections intensity decay: 21%
4203 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.125H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0627P)2 + 13.8292P]
where P = (Fo2 + 2Fc2)/3
4203 reflectionsΔρmax = 2.09 e Å3
276 parametersΔρmin = 1.15 e Å3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba10.00000.19519 (4)0.25000.04879 (17)
Cr10.12873 (2)0.30660 (7)0.31223 (5)0.03088 (18)
O310.08888 (13)0.2245 (3)0.2111 (2)0.0419 (8)
O410.13193 (12)0.4773 (3)0.2522 (2)0.0377 (7)
O300.12214 (13)0.1320 (3)0.3675 (2)0.0406 (8)
O400.06779 (12)0.3803 (3)0.3649 (2)0.0440 (8)
O420.01774 (13)0.5577 (4)0.3532 (3)0.0539 (10)
O430.08790 (14)0.6623 (3)0.2355 (3)0.0539 (10)
O320.08312 (15)0.0601 (4)0.3428 (3)0.0576 (11)
O330.04474 (17)0.0415 (4)0.1793 (3)0.0674 (12)
N100.19900 (14)0.2695 (3)0.2577 (3)0.0307 (8)
C200.22668 (16)0.3678 (4)0.3985 (3)0.0303 (9)
N110.17661 (14)0.3707 (4)0.4188 (3)0.0330 (8)
C140.32903 (18)0.3626 (5)0.3474 (4)0.0411 (11)
H140.36290.36270.33000.049*
C160.26598 (18)0.4108 (4)0.4587 (3)0.0363 (10)
C150.31785 (18)0.4081 (5)0.4308 (4)0.0429 (12)
H150.34400.43800.47060.051*
C210.23855 (16)0.3161 (4)0.3115 (3)0.0276 (8)
C110.2588 (2)0.2188 (5)0.1437 (3)0.0426 (12)
H110.26460.18620.08560.051*
C190.1640 (2)0.4145 (5)0.5008 (3)0.0428 (11)
H190.12970.41720.51530.051*
C170.2519 (2)0.4555 (5)0.5455 (3)0.0443 (12)
H170.27670.48400.58840.053*
C300.09358 (18)0.0522 (5)0.3209 (4)0.0398 (11)
C120.2987 (2)0.2629 (5)0.1989 (4)0.0417 (11)
H120.33200.25860.17870.050*
C100.2089 (2)0.2232 (5)0.1754 (3)0.0389 (11)
H100.18200.19280.13770.047*
C180.2015 (2)0.4564 (5)0.5655 (4)0.0490 (13)
H180.19190.48510.62270.059*
C310.07281 (18)0.1075 (5)0.2282 (4)0.0419 (11)
C130.28988 (17)0.3142 (4)0.2850 (3)0.0324 (9)
C400.05581 (17)0.4951 (5)0.3340 (4)0.0407 (11)
C410.09411 (16)0.5538 (5)0.2681 (4)0.0370 (11)
O10.36785 (19)0.2633 (7)0.5205 (3)0.0965 (18)
O20.4493 (2)0.1237 (7)0.4398 (3)0.101 (2)
O30.0172 (3)0.1943 (6)0.0574 (5)0.120 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0269 (2)0.0271 (2)0.0914 (4)0.0000.0089 (2)0.000
Cr10.0273 (4)0.0251 (4)0.0402 (4)0.0008 (3)0.0001 (3)0.0015 (3)
O310.0376 (17)0.0360 (18)0.051 (2)0.0055 (14)0.0129 (15)0.0056 (15)
O410.0328 (16)0.0311 (16)0.050 (2)0.0026 (13)0.0076 (14)0.0053 (15)
O300.0453 (19)0.0297 (16)0.046 (2)0.0032 (15)0.0082 (15)0.0062 (15)
O400.0292 (16)0.043 (2)0.061 (2)0.0036 (15)0.0101 (15)0.0083 (17)
O420.0343 (18)0.058 (2)0.070 (3)0.0122 (17)0.0070 (17)0.001 (2)
O430.0349 (18)0.0303 (18)0.096 (3)0.0001 (14)0.0032 (19)0.0125 (19)
O320.054 (2)0.036 (2)0.082 (3)0.0136 (17)0.013 (2)0.0138 (19)
O330.070 (3)0.060 (3)0.070 (3)0.026 (2)0.027 (2)0.006 (2)
N100.0331 (18)0.0250 (18)0.034 (2)0.0033 (15)0.0014 (15)0.0022 (15)
C200.035 (2)0.0209 (19)0.036 (2)0.0017 (17)0.0014 (18)0.0003 (18)
N110.038 (2)0.0270 (18)0.034 (2)0.0006 (16)0.0037 (16)0.0027 (16)
C140.029 (2)0.037 (3)0.057 (3)0.001 (2)0.001 (2)0.006 (2)
C160.045 (3)0.027 (2)0.037 (3)0.001 (2)0.006 (2)0.004 (2)
C150.039 (3)0.037 (3)0.052 (3)0.007 (2)0.013 (2)0.002 (2)
C210.031 (2)0.0210 (19)0.031 (2)0.0018 (17)0.0009 (16)0.0008 (18)
C110.056 (3)0.038 (3)0.035 (3)0.010 (2)0.010 (2)0.006 (2)
C190.051 (3)0.036 (3)0.043 (3)0.003 (2)0.015 (2)0.003 (2)
C170.065 (3)0.033 (2)0.034 (3)0.002 (2)0.007 (2)0.005 (2)
C300.031 (2)0.029 (2)0.058 (3)0.0009 (19)0.001 (2)0.002 (2)
C120.040 (3)0.038 (3)0.047 (3)0.010 (2)0.008 (2)0.005 (2)
C100.049 (3)0.034 (3)0.034 (3)0.003 (2)0.004 (2)0.005 (2)
C180.080 (4)0.038 (3)0.029 (3)0.002 (3)0.006 (3)0.005 (2)
C310.032 (2)0.039 (3)0.054 (3)0.004 (2)0.004 (2)0.001 (2)
C130.034 (2)0.027 (2)0.037 (2)0.0023 (19)0.0004 (18)0.0039 (19)
C400.028 (2)0.042 (3)0.052 (3)0.000 (2)0.003 (2)0.004 (2)
C410.026 (2)0.031 (2)0.054 (3)0.0017 (18)0.005 (2)0.000 (2)
O10.060 (3)0.159 (5)0.071 (3)0.016 (3)0.011 (2)0.035 (4)
O20.110 (4)0.139 (5)0.054 (3)0.056 (4)0.012 (3)0.013 (3)
O30.150 (6)0.096 (5)0.117 (5)0.016 (4)0.034 (5)0.010 (4)
Geometric parameters (Å, º) top
Ba1—O43i2.729 (4)O33—C311.206 (6)
Ba1—O322.861 (4)N10—C101.327 (6)
Ba1—O32.869 (7)N10—C211.357 (6)
Ba1—O332.883 (4)C20—N111.353 (6)
Ba1—O42i2.955 (4)C20—C161.395 (6)
Cr1—O401.946 (3)C20—C211.422 (6)
Cr1—O411.946 (3)N11—C191.332 (6)
Cr1—O301.959 (3)C14—C151.348 (7)
Cr1—O311.959 (3)C14—C131.428 (7)
Cr1—N112.062 (4)C16—C171.410 (7)
Cr1—N102.065 (4)C16—C151.431 (7)
O31—C311.288 (6)C21—C131.410 (6)
O41—C411.285 (5)C11—C121.368 (7)
O30—C301.278 (6)C11—C101.400 (7)
O40—C401.284 (6)C19—C181.398 (8)
O42—C401.223 (6)C17—C181.359 (8)
O42—Ba1ii2.955 (4)C30—C311.544 (7)
O43—C411.209 (6)C12—C131.391 (7)
O43—Ba1ii2.729 (4)C40—C411.538 (7)
O32—C301.219 (6)
O43i—Ba1—O43iii115.97 (15)O30—Cr1—N1192.01 (14)
O43i—Ba1—O32iv147.28 (13)O31—Cr1—N11172.36 (14)
O43iii—Ba1—O32iv70.54 (12)O40—Cr1—N10167.71 (15)
O43i—Ba1—O3270.54 (12)O41—Cr1—N1086.16 (14)
O43iii—Ba1—O32147.28 (13)O30—Cr1—N1095.06 (14)
O32iv—Ba1—O32122.73 (15)O31—Cr1—N1094.81 (15)
O43i—Ba1—O376.04 (19)N11—Cr1—N1080.11 (15)
O43iii—Ba1—O3104.15 (18)C31—O31—Cr1114.4 (3)
O32iv—Ba1—O371.35 (19)C41—O41—Cr1114.1 (3)
O32—Ba1—O3108.47 (18)C30—O30—Cr1114.4 (3)
O43i—Ba1—O3iv104.15 (18)C40—O40—Cr1113.7 (3)
O43iii—Ba1—O3iv76.04 (19)C40—O42—Ba1ii115.9 (3)
O32iv—Ba1—O3iv108.47 (18)C41—O43—Ba1ii123.5 (3)
O32—Ba1—O3iv71.36 (19)C30—O32—Ba1119.9 (3)
O3—Ba1—O3iv179.7 (3)C31—O33—Ba1119.7 (4)
O43i—Ba1—O3393.41 (12)C10—N10—C21118.4 (4)
O43iii—Ba1—O33145.54 (12)C10—N10—Cr1128.6 (3)
O32iv—Ba1—O3375.00 (12)C21—N10—Cr1112.4 (3)
O32—Ba1—O3357.29 (11)N11—C20—C16123.1 (4)
O3—Ba1—O3364.10 (16)N11—C20—C21116.9 (4)
O3iv—Ba1—O33115.58 (17)C16—C20—C21119.9 (4)
O43i—Ba1—O33iv145.54 (12)C19—N11—C20118.8 (4)
O43iii—Ba1—O33iv93.41 (12)C19—N11—Cr1128.4 (3)
O32iv—Ba1—O33iv57.29 (11)C20—N11—Cr1112.8 (3)
O32—Ba1—O33iv75.00 (12)C15—C14—C13121.3 (4)
O3—Ba1—O33iv115.58 (17)C20—C16—C17117.1 (5)
O3iv—Ba1—O33iv64.10 (16)C20—C16—C15119.6 (4)
O33—Ba1—O33iv67.0 (2)C17—C16—C15123.3 (5)
O43i—Ba1—O42i58.33 (11)C14—C15—C16120.5 (4)
O43iii—Ba1—O42i67.96 (11)N10—C21—C13123.1 (4)
O32iv—Ba1—O42i138.49 (11)N10—C21—C20117.2 (4)
O32—Ba1—O42i93.73 (11)C13—C21—C20119.7 (4)
O3—Ba1—O42i118.43 (16)C12—C11—C10119.5 (4)
O3iv—Ba1—O42i61.91 (15)N11—C19—C18121.2 (5)
O33—Ba1—O42i146.51 (11)C18—C17—C16119.1 (5)
O33iv—Ba1—O42i125.60 (12)O32—C30—O30125.8 (5)
O43i—Ba1—O42iii67.96 (11)O32—C30—C31119.7 (5)
O43iii—Ba1—O42iii58.33 (11)O30—C30—C31114.4 (4)
O32iv—Ba1—O42iii93.73 (11)C11—C12—C13120.3 (5)
O32—Ba1—O42iii138.49 (11)N10—C10—C11122.1 (4)
O3—Ba1—O42iii61.91 (15)C17—C18—C19120.6 (5)
O3iv—Ba1—O42iii118.43 (16)O33—C31—O31126.2 (5)
O33—Ba1—O42iii125.60 (12)O33—C31—C30120.1 (5)
O33iv—Ba1—O42iii146.51 (11)O31—C31—C30113.6 (4)
O42i—Ba1—O42iii63.75 (16)C12—C13—C21116.7 (4)
O40—Cr1—O4183.52 (14)C12—C13—C14124.4 (4)
O40—Cr1—O3095.62 (15)C21—C13—C14118.9 (4)
O41—Cr1—O30176.56 (14)O42—C40—O40125.5 (5)
O40—Cr1—O3192.56 (15)O42—C40—C41119.9 (5)
O41—Cr1—O3194.00 (14)O40—C40—C41114.7 (4)
O30—Cr1—O3182.70 (14)O43—C41—O41124.8 (5)
O40—Cr1—N1193.45 (15)O43—C41—C40121.4 (4)
O41—Cr1—N1191.37 (15)O41—C41—C40113.8 (4)
Symmetry codes: (i) x, y+1, z; (ii) x, y1, z; (iii) x, y+1, z+1/2; (iv) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Ba{Cr(C2O4)(C12H8N2)}2(H2O)6]
Mr1061.92
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)26.1127 (18), 10.1535 (6), 14.6165 (9)
β (°) 92.367 (7)
V3)3872.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.65
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerEnraf-Nonius CAD4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.593, 0.760
No. of measured, independent and
observed [I > 2σ(I)] reflections
4442, 4203, 2749
Rint0.028
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.125, 1.01
No. of reflections4203
No. of parameters276
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0627P)2 + 13.8292P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.09, 1.15

Computer programs: CAD-4 Software (Enraf Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top
Ba1—O43i2.729 (4)Cr1—O411.946 (3)
Ba1—O322.861 (4)Cr1—O301.959 (3)
Ba1—O32.869 (7)Cr1—O311.959 (3)
Ba1—O332.883 (4)Cr1—N112.062 (4)
Ba1—O42i2.955 (4)Cr1—N102.065 (4)
Cr1—O401.946 (3)
O32—Ba1—O3357.29 (11)O30—Cr1—O3182.70 (14)
O43i—Ba1—O42i58.33 (11)N11—Cr1—N1080.11 (15)
O40—Cr1—O4183.52 (14)
Symmetry code: (i) x, y+1, z.
 

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