Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005931/br6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005931/br6013Isup2.hkl |
CCDC reference: 165631
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)
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).
Fig. 1. View of (I) shown with 50% probability displacement ellipsoids. | |
Fig. 2. View of the chain in (I) along the twofold axis. |
[Ba{Cr(C2O4)(C12H8N2)}2(H2O)6] | F(000) = 2112 |
Mr = 1061.92 | Dx = 1.822 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 26.1127 (18) Å | Cell parameters from 25 reflections |
b = 10.1535 (6) Å | θ = 3.1–27° |
c = 14.6165 (9) Å | µ = 1.65 mm−1 |
β = 92.367 (7)° | T = 293 K |
V = 3872.0 (4) Å3 | Prism, red-violet |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
Enraf-Nonius CAD4 diffractometer | Rint = 0.028 |
ω–2θ scans | θmax = 27.0°, θmin = 3.1° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→33 |
Tmin = 0.593, Tmax = 0.760 | k = 0→12 |
4442 measured reflections | l = −18→18 |
4203 independent reflections | 4 standard reflections every 120 min |
2749 reflections with I > 2σ(I) | intensity decay: 21% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-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 = 1.01 | Δρmax = 2.09 e Å−3 |
4203 reflections | Δρmin = −1.15 e Å−3 |
276 parameters |
[Ba{Cr(C2O4)(C12H8N2)}2(H2O)6] | V = 3872.0 (4) Å3 |
Mr = 1061.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.1127 (18) Å | µ = 1.65 mm−1 |
b = 10.1535 (6) Å | T = 293 K |
c = 14.6165 (9) Å | 0.3 × 0.2 × 0.2 mm |
β = 92.367 (7)° |
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 = 0.760 | 4 standard reflections every 120 min |
4442 measured reflections | intensity decay: 21% |
4203 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0627P)2 + 13.8292P] where P = (Fo2 + 2Fc2)/3 |
4203 reflections | Δρmax = 2.09 e Å−3 |
276 parameters | Δρmin = −1.15 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ba1 | 0.0000 | 0.19519 (4) | 0.2500 | 0.04879 (17) | |
Cr1 | 0.12873 (2) | −0.30660 (7) | 0.31223 (5) | 0.03088 (18) | |
O31 | 0.08888 (13) | −0.2245 (3) | 0.2111 (2) | 0.0419 (8) | |
O41 | 0.13193 (12) | −0.4773 (3) | 0.2522 (2) | 0.0377 (7) | |
O30 | 0.12214 (13) | −0.1320 (3) | 0.3675 (2) | 0.0406 (8) | |
O40 | 0.06779 (12) | −0.3803 (3) | 0.3649 (2) | 0.0440 (8) | |
O42 | 0.01774 (13) | −0.5577 (4) | 0.3532 (3) | 0.0539 (10) | |
O43 | 0.08790 (14) | −0.6623 (3) | 0.2355 (3) | 0.0539 (10) | |
O32 | 0.08312 (15) | 0.0601 (4) | 0.3428 (3) | 0.0576 (11) | |
O33 | 0.04474 (17) | −0.0415 (4) | 0.1793 (3) | 0.0674 (12) | |
N10 | 0.19900 (14) | −0.2695 (3) | 0.2577 (3) | 0.0307 (8) | |
C20 | 0.22668 (16) | −0.3678 (4) | 0.3985 (3) | 0.0303 (9) | |
N11 | 0.17661 (14) | −0.3707 (4) | 0.4188 (3) | 0.0330 (8) | |
C14 | 0.32903 (18) | −0.3626 (5) | 0.3474 (4) | 0.0411 (11) | |
H14 | 0.3629 | −0.3627 | 0.3300 | 0.049* | |
C16 | 0.26598 (18) | −0.4108 (4) | 0.4587 (3) | 0.0363 (10) | |
C15 | 0.31785 (18) | −0.4081 (5) | 0.4308 (4) | 0.0429 (12) | |
H15 | 0.3440 | −0.4380 | 0.4706 | 0.051* | |
C21 | 0.23855 (16) | −0.3161 (4) | 0.3115 (3) | 0.0276 (8) | |
C11 | 0.2588 (2) | −0.2188 (5) | 0.1437 (3) | 0.0426 (12) | |
H11 | 0.2646 | −0.1862 | 0.0856 | 0.051* | |
C19 | 0.1640 (2) | −0.4145 (5) | 0.5008 (3) | 0.0428 (11) | |
H19 | 0.1297 | −0.4172 | 0.5153 | 0.051* | |
C17 | 0.2519 (2) | −0.4555 (5) | 0.5455 (3) | 0.0443 (12) | |
H17 | 0.2767 | −0.4840 | 0.5884 | 0.053* | |
C30 | 0.09358 (18) | −0.0522 (5) | 0.3209 (4) | 0.0398 (11) | |
C12 | 0.2987 (2) | −0.2629 (5) | 0.1989 (4) | 0.0417 (11) | |
H12 | 0.3320 | −0.2586 | 0.1787 | 0.050* | |
C10 | 0.2089 (2) | −0.2232 (5) | 0.1754 (3) | 0.0389 (11) | |
H10 | 0.1820 | −0.1928 | 0.1377 | 0.047* | |
C18 | 0.2015 (2) | −0.4564 (5) | 0.5655 (4) | 0.0490 (13) | |
H18 | 0.1919 | −0.4851 | 0.6227 | 0.059* | |
C31 | 0.07281 (18) | −0.1075 (5) | 0.2282 (4) | 0.0419 (11) | |
C13 | 0.28988 (17) | −0.3142 (4) | 0.2850 (3) | 0.0324 (9) | |
C40 | 0.05581 (17) | −0.4951 (5) | 0.3340 (4) | 0.0407 (11) | |
C41 | 0.09411 (16) | −0.5538 (5) | 0.2681 (4) | 0.0370 (11) | |
O1 | 0.36785 (19) | 0.2633 (7) | 0.5205 (3) | 0.0965 (18) | |
O2 | 0.4493 (2) | 0.1237 (7) | 0.4398 (3) | 0.101 (2) | |
O3 | 0.0172 (3) | 0.1943 (6) | 0.0574 (5) | 0.120 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.0269 (2) | 0.0271 (2) | 0.0914 (4) | 0.000 | −0.0089 (2) | 0.000 |
Cr1 | 0.0273 (4) | 0.0251 (4) | 0.0402 (4) | 0.0008 (3) | −0.0001 (3) | −0.0015 (3) |
O31 | 0.0376 (17) | 0.0360 (18) | 0.051 (2) | 0.0055 (14) | −0.0129 (15) | −0.0056 (15) |
O41 | 0.0328 (16) | 0.0311 (16) | 0.050 (2) | −0.0026 (13) | 0.0076 (14) | −0.0053 (15) |
O30 | 0.0453 (19) | 0.0297 (16) | 0.046 (2) | 0.0032 (15) | −0.0082 (15) | −0.0062 (15) |
O40 | 0.0292 (16) | 0.043 (2) | 0.061 (2) | −0.0036 (15) | 0.0101 (15) | −0.0083 (17) |
O42 | 0.0343 (18) | 0.058 (2) | 0.070 (3) | −0.0122 (17) | 0.0070 (17) | −0.001 (2) |
O43 | 0.0349 (18) | 0.0303 (18) | 0.096 (3) | 0.0001 (14) | −0.0032 (19) | −0.0125 (19) |
O32 | 0.054 (2) | 0.036 (2) | 0.082 (3) | 0.0136 (17) | −0.013 (2) | −0.0138 (19) |
O33 | 0.070 (3) | 0.060 (3) | 0.070 (3) | 0.026 (2) | −0.027 (2) | −0.006 (2) |
N10 | 0.0331 (18) | 0.0250 (18) | 0.034 (2) | −0.0033 (15) | −0.0014 (15) | 0.0022 (15) |
C20 | 0.035 (2) | 0.0209 (19) | 0.036 (2) | −0.0017 (17) | 0.0014 (18) | −0.0003 (18) |
N11 | 0.038 (2) | 0.0270 (18) | 0.034 (2) | 0.0006 (16) | 0.0037 (16) | 0.0027 (16) |
C14 | 0.029 (2) | 0.037 (3) | 0.057 (3) | −0.001 (2) | −0.001 (2) | −0.006 (2) |
C16 | 0.045 (3) | 0.027 (2) | 0.037 (3) | 0.001 (2) | −0.006 (2) | −0.004 (2) |
C15 | 0.039 (3) | 0.037 (3) | 0.052 (3) | 0.007 (2) | −0.013 (2) | −0.002 (2) |
C21 | 0.031 (2) | 0.0210 (19) | 0.031 (2) | −0.0018 (17) | 0.0009 (16) | −0.0008 (18) |
C11 | 0.056 (3) | 0.038 (3) | 0.035 (3) | −0.010 (2) | 0.010 (2) | 0.006 (2) |
C19 | 0.051 (3) | 0.036 (3) | 0.043 (3) | −0.003 (2) | 0.015 (2) | 0.003 (2) |
C17 | 0.065 (3) | 0.033 (2) | 0.034 (3) | 0.002 (2) | −0.007 (2) | 0.005 (2) |
C30 | 0.031 (2) | 0.029 (2) | 0.058 (3) | 0.0009 (19) | −0.001 (2) | −0.002 (2) |
C12 | 0.040 (3) | 0.038 (3) | 0.047 (3) | −0.010 (2) | 0.008 (2) | −0.005 (2) |
C10 | 0.049 (3) | 0.034 (3) | 0.034 (3) | −0.003 (2) | −0.004 (2) | 0.005 (2) |
C18 | 0.080 (4) | 0.038 (3) | 0.029 (3) | −0.002 (3) | 0.006 (3) | 0.005 (2) |
C31 | 0.032 (2) | 0.039 (3) | 0.054 (3) | 0.004 (2) | −0.004 (2) | −0.001 (2) |
C13 | 0.034 (2) | 0.027 (2) | 0.037 (2) | −0.0023 (19) | 0.0004 (18) | −0.0039 (19) |
C40 | 0.028 (2) | 0.042 (3) | 0.052 (3) | 0.000 (2) | −0.003 (2) | 0.004 (2) |
C41 | 0.026 (2) | 0.031 (2) | 0.054 (3) | 0.0017 (18) | −0.005 (2) | 0.000 (2) |
O1 | 0.060 (3) | 0.159 (5) | 0.071 (3) | −0.016 (3) | 0.011 (2) | −0.035 (4) |
O2 | 0.110 (4) | 0.139 (5) | 0.054 (3) | 0.056 (4) | 0.012 (3) | 0.013 (3) |
O3 | 0.150 (6) | 0.096 (5) | 0.117 (5) | 0.016 (4) | 0.034 (5) | 0.010 (4) |
Ba1—O43i | 2.729 (4) | O33—C31 | 1.206 (6) |
Ba1—O32 | 2.861 (4) | N10—C10 | 1.327 (6) |
Ba1—O3 | 2.869 (7) | N10—C21 | 1.357 (6) |
Ba1—O33 | 2.883 (4) | C20—N11 | 1.353 (6) |
Ba1—O42i | 2.955 (4) | C20—C16 | 1.395 (6) |
Cr1—O40 | 1.946 (3) | C20—C21 | 1.422 (6) |
Cr1—O41 | 1.946 (3) | N11—C19 | 1.332 (6) |
Cr1—O30 | 1.959 (3) | C14—C15 | 1.348 (7) |
Cr1—O31 | 1.959 (3) | C14—C13 | 1.428 (7) |
Cr1—N11 | 2.062 (4) | C16—C17 | 1.410 (7) |
Cr1—N10 | 2.065 (4) | C16—C15 | 1.431 (7) |
O31—C31 | 1.288 (6) | C21—C13 | 1.410 (6) |
O41—C41 | 1.285 (5) | C11—C12 | 1.368 (7) |
O30—C30 | 1.278 (6) | C11—C10 | 1.400 (7) |
O40—C40 | 1.284 (6) | C19—C18 | 1.398 (8) |
O42—C40 | 1.223 (6) | C17—C18 | 1.359 (8) |
O42—Ba1ii | 2.955 (4) | C30—C31 | 1.544 (7) |
O43—C41 | 1.209 (6) | C12—C13 | 1.391 (7) |
O43—Ba1ii | 2.729 (4) | C40—C41 | 1.538 (7) |
O32—C30 | 1.219 (6) | ||
O43i—Ba1—O43iii | 115.97 (15) | O30—Cr1—N11 | 92.01 (14) |
O43i—Ba1—O32iv | 147.28 (13) | O31—Cr1—N11 | 172.36 (14) |
O43iii—Ba1—O32iv | 70.54 (12) | O40—Cr1—N10 | 167.71 (15) |
O43i—Ba1—O32 | 70.54 (12) | O41—Cr1—N10 | 86.16 (14) |
O43iii—Ba1—O32 | 147.28 (13) | O30—Cr1—N10 | 95.06 (14) |
O32iv—Ba1—O32 | 122.73 (15) | O31—Cr1—N10 | 94.81 (15) |
O43i—Ba1—O3 | 76.04 (19) | N11—Cr1—N10 | 80.11 (15) |
O43iii—Ba1—O3 | 104.15 (18) | C31—O31—Cr1 | 114.4 (3) |
O32iv—Ba1—O3 | 71.35 (19) | C41—O41—Cr1 | 114.1 (3) |
O32—Ba1—O3 | 108.47 (18) | C30—O30—Cr1 | 114.4 (3) |
O43i—Ba1—O3iv | 104.15 (18) | C40—O40—Cr1 | 113.7 (3) |
O43iii—Ba1—O3iv | 76.04 (19) | C40—O42—Ba1ii | 115.9 (3) |
O32iv—Ba1—O3iv | 108.47 (18) | C41—O43—Ba1ii | 123.5 (3) |
O32—Ba1—O3iv | 71.36 (19) | C30—O32—Ba1 | 119.9 (3) |
O3—Ba1—O3iv | 179.7 (3) | C31—O33—Ba1 | 119.7 (4) |
O43i—Ba1—O33 | 93.41 (12) | C10—N10—C21 | 118.4 (4) |
O43iii—Ba1—O33 | 145.54 (12) | C10—N10—Cr1 | 128.6 (3) |
O32iv—Ba1—O33 | 75.00 (12) | C21—N10—Cr1 | 112.4 (3) |
O32—Ba1—O33 | 57.29 (11) | N11—C20—C16 | 123.1 (4) |
O3—Ba1—O33 | 64.10 (16) | N11—C20—C21 | 116.9 (4) |
O3iv—Ba1—O33 | 115.58 (17) | C16—C20—C21 | 119.9 (4) |
O43i—Ba1—O33iv | 145.54 (12) | C19—N11—C20 | 118.8 (4) |
O43iii—Ba1—O33iv | 93.41 (12) | C19—N11—Cr1 | 128.4 (3) |
O32iv—Ba1—O33iv | 57.29 (11) | C20—N11—Cr1 | 112.8 (3) |
O32—Ba1—O33iv | 75.00 (12) | C15—C14—C13 | 121.3 (4) |
O3—Ba1—O33iv | 115.58 (17) | C20—C16—C17 | 117.1 (5) |
O3iv—Ba1—O33iv | 64.10 (16) | C20—C16—C15 | 119.6 (4) |
O33—Ba1—O33iv | 67.0 (2) | C17—C16—C15 | 123.3 (5) |
O43i—Ba1—O42i | 58.33 (11) | C14—C15—C16 | 120.5 (4) |
O43iii—Ba1—O42i | 67.96 (11) | N10—C21—C13 | 123.1 (4) |
O32iv—Ba1—O42i | 138.49 (11) | N10—C21—C20 | 117.2 (4) |
O32—Ba1—O42i | 93.73 (11) | C13—C21—C20 | 119.7 (4) |
O3—Ba1—O42i | 118.43 (16) | C12—C11—C10 | 119.5 (4) |
O3iv—Ba1—O42i | 61.91 (15) | N11—C19—C18 | 121.2 (5) |
O33—Ba1—O42i | 146.51 (11) | C18—C17—C16 | 119.1 (5) |
O33iv—Ba1—O42i | 125.60 (12) | O32—C30—O30 | 125.8 (5) |
O43i—Ba1—O42iii | 67.96 (11) | O32—C30—C31 | 119.7 (5) |
O43iii—Ba1—O42iii | 58.33 (11) | O30—C30—C31 | 114.4 (4) |
O32iv—Ba1—O42iii | 93.73 (11) | C11—C12—C13 | 120.3 (5) |
O32—Ba1—O42iii | 138.49 (11) | N10—C10—C11 | 122.1 (4) |
O3—Ba1—O42iii | 61.91 (15) | C17—C18—C19 | 120.6 (5) |
O3iv—Ba1—O42iii | 118.43 (16) | O33—C31—O31 | 126.2 (5) |
O33—Ba1—O42iii | 125.60 (12) | O33—C31—C30 | 120.1 (5) |
O33iv—Ba1—O42iii | 146.51 (11) | O31—C31—C30 | 113.6 (4) |
O42i—Ba1—O42iii | 63.75 (16) | C12—C13—C21 | 116.7 (4) |
O40—Cr1—O41 | 83.52 (14) | C12—C13—C14 | 124.4 (4) |
O40—Cr1—O30 | 95.62 (15) | C21—C13—C14 | 118.9 (4) |
O41—Cr1—O30 | 176.56 (14) | O42—C40—O40 | 125.5 (5) |
O40—Cr1—O31 | 92.56 (15) | O42—C40—C41 | 119.9 (5) |
O41—Cr1—O31 | 94.00 (14) | O40—C40—C41 | 114.7 (4) |
O30—Cr1—O31 | 82.70 (14) | O43—C41—O41 | 124.8 (5) |
O40—Cr1—N11 | 93.45 (15) | O43—C41—C40 | 121.4 (4) |
O41—Cr1—N11 | 91.37 (15) | O41—C41—C40 | 113.8 (4) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, 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] |
Mr | 1061.92 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 26.1127 (18), 10.1535 (6), 14.6165 (9) |
β (°) | 92.367 (7) |
V (Å3) | 3872.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.593, 0.760 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4442, 4203, 2749 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.125, 1.01 |
No. of reflections | 4203 |
No. of parameters | 276 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0627P)2 + 13.8292P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 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).
Ba1—O43i | 2.729 (4) | Cr1—O41 | 1.946 (3) |
Ba1—O32 | 2.861 (4) | Cr1—O30 | 1.959 (3) |
Ba1—O3 | 2.869 (7) | Cr1—O31 | 1.959 (3) |
Ba1—O33 | 2.883 (4) | Cr1—N11 | 2.062 (4) |
Ba1—O42i | 2.955 (4) | Cr1—N10 | 2.065 (4) |
Cr1—O40 | 1.946 (3) | ||
O32—Ba1—O33 | 57.29 (11) | O30—Cr1—O31 | 82.70 (14) |
O43i—Ba1—O42i | 58.33 (11) | N11—Cr1—N10 | 80.11 (15) |
O40—Cr1—O41 | 83.52 (14) |
Symmetry code: (i) x, y+1, z. |
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.