Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041839/ng2312sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041839/ng2312Isup2.hkl |
CCDC reference: 663551
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.027
- wR factor = 0.071
- Data-to-parameter ratio = 8.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT128_ALERT_4_C Non-standard setting of Space group Pc .... Pn PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C7 - C8 ... 1.55 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C15 - C16 ... 1.55 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H100 .. H201 .. 2.12 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact Cl1 .. C7 .. 3.19 Ang.
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 3084 Count of symmetry unique reflns 2561 Completeness (_total/calc) 120.42% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 523 Fraction of Friedel pairs measured 0.204 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cr1 (9) 3.29 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cr2 (9) 3.33 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
To a stirred aqueous solution (45 ml) of cis-[Cr(tn)2Cl2]Cl (Pedersen, 1970) (2.4 g, 7.8 mmol) were slowly added H2C2O4.2H2O (1.2 g, 9.5 mmol) in 40 ml water. The solution was filtered and evaporated at room temperature. Orange crystal formed after about two weeks. Yield: 20%.
The coordinates of the H atoms of the water molecules were found from difference Fourier maps. H atoms bound to C and N atoms were also visible in difference maps and were placed using the HFIX commands in SHELXL97. All H atoms were allowed for as riding atoms (C—H 0.97 Å, N—H 0.90 Å, O—H 0.85 Å) with the constraint U(H) = 1.2Ueq(carrier) for all other H atoms. The Flack parameter refined to 0.017 (15) from 526 Friedel pairs (Flack, 1983).
The crystal structures of monomeric chromium(III) complexes Na[Cr(hm)(ox)2].3H2O (hm = histamine) and Na[Cr(PM)(ox)2].H2O (PM = pyridoxamine) (Sakagami et al., 1999), AsPh4[Cr(ox)(phen)].H2O and [NaCr(phen)(ox)2(H2O)].2H2O (phen = 1,10-phenanthroline) (Marinescu et al., 2000), AsPh4[Cr(bpm)(ox)2].H2O and Na[Cr(bpm)(ox)2].H2O (bpm = 2,2'-bipyrimidine) (De Munno et al., 1999), and PPh4[Cr(bipy)(ox)2].H2O (bipy = 2,2'-bipyridine) (Lescouëzec et al., 2003) contain two oxalato ligands and one neutral didentate terminal ligand. Among these examples, the complexes using the Na+ ion as balanced anions usually show beautiful one-, two- or three-dimensional supramolecular structures. The compound [Mn(4,4'-bipyridine-N,N'- dioxide)(H2O)4][Cr(bipy)(ox)2]2.8H2O comprises of [Cr(bipy)(ox)2]- anions and one-dimensional cationic chain [Mn(4,4'-bipyridine-N,N'- dioxide)(H2O)4]n2n+ (Bruda et al., 2001). The molecular structure of [Cr(en)2(ox)][Cr(en)(ox)2].2H2O (en = 1,2-ethylenediamine) consists of one [Cr(en)2(ox)]+ cation and one [Cr(en)(ox)2]- anion with one and two oxalato ligands, respectivley (Lethbridge et al., 1970). Herein we report a new monooxalato-containing chromium(III) complex [Cr(ox)(tn)2]Cl.H2O (I).
The crystal structure of (I) consists of two independent [Cr(tn)2(ox)]+ cations, two free Cl- as counteranions and two crystallization water molecules. (Figure 1). Each chromium atom in (I) is coordinated by four nitrogen atoms from two tn ligands and two oxalate oxygen atoms, yielding a distorted octahedral geometry. The four Cr—O bond distances (1.957 (2) to 1.994 (2) Å) are comparable to those in [Cr(en)2(ox)]+ unit of complex [Cr(en)2(ox)][Cr(en)(ox)2].2H2O. The Cr—N distances range from 2.063 (3) to 2.101 (3) Å for Cr1, and from 2.048 (3) to 2.093 (3) Å for Cr2. The bond angles between every adjacent two bonds around Cr atom are almost all close to 90 ° except O4—Cr1—O1 (82.30 (9) °) and O5—Cr2—O8 (82.47 (10) °), which leads to the distortion of coordination environment from the ideal octahedron. The ox ligands exhibit slightly deviation from planarity and the tn ligands show the typical chair-like conformation. The nearest Cr1···Cr2 separation is 6.061 Å.
There exist affluent hydrogen bonds in (I) (Figure 2). Firstly, the adjacent the adjacent two [Cr1(tn)2(ox)]+ units are linked by three N—H···O (N4—H4D···O3 [x + 1/2, -y + 2, z + 1/2], N1—H1D···O3 [x + 1/2, -y + 2, z + 1/2] and N2—H2A···O2 [x + 1/2, -y + 2, z + 1/2]) hydrogen bonds. Similarly, two [Cr2(tn)2(ox)]+ units are linked with two strong N—H···O (N5—H5A···O6 [x - 1/2, -y + 1, z - 1/2] and N7—H7A···O7 [x - 1/2, -y + 1, z - 1/2]) hydrogen bonds. Secondly, there are also three N—H···O (N1—H1A···O7 [x - 1, y, z], N3—H3A···O7 [x - 1, y, z], N6—H6A···O1 [x + 1, y, z]) hydrogen bonds between the nearest [Cr1(tn)2(ox)]+ and [Cr2(tn)2(ox)]+ units. Through all these N—H···O hydrogen bonds and seven N—H··· Cl hydrogen bonds, the two [Cr(tn)2(ox)]+ cationic units form two-dimensional layer-like structures. Finally, the layers form a three-dimensional network structure through hydrogen bond series N3···O2W···O1W [x - 1/2, -y + 1, z - 1/2]···O5 and two Owater···Cl hydrogen bonds.
For bis(oxalato)chromates, see: Bruda et al. (2001); De Munno et al. (1999); Lescouëzec et al. (2003); Sakagami et al. (1999). For mono(oxalato)chromates, see: Marinescu et al. (2000). For a chromium complex with an oxalate group in both the cation and anion, see: Lethbridge et al. (1970). For the synthesis of a precursor to the title compound, see: Pedersen (1970).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and XP (Sheldrick, 1998).
[Cr(C2O4)(C3H10N2)2]Cl·H2O | F(000) = 716 |
Mr = 341.74 | Dx = 1.567 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yac | Cell parameters from 25 reflections |
a = 8.9532 (17) Å | θ = 10.5–15.4° |
b = 12.038 (2) Å | µ = 1.00 mm−1 |
c = 13.645 (3) Å | T = 293 K |
β = 99.973 (14)° | Block, orange |
V = 1448.5 (5) Å3 | 0.30 × 0.25 × 0.10 mm |
Z = 4 |
Bruker P4 diffractometer | 3056 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ω scans | h = −1→10 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→1 |
Tmin = 0.742, Tmax = 0.905 | l = −16→16 |
3397 measured reflections | 3 standard reflections every 97 reflections |
3084 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.2592P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.071 | (Δ/σ)max = 0.001 |
S = 1.00 | Δρmax = 0.45 e Å−3 |
3084 reflections | Δρmin = −0.34 e Å−3 |
348 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.0164 (14) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 526 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.017 (15) |
[Cr(C2O4)(C3H10N2)2]Cl·H2O | V = 1448.5 (5) Å3 |
Mr = 341.74 | Z = 4 |
Monoclinic, Pn | Mo Kα radiation |
a = 8.9532 (17) Å | µ = 1.00 mm−1 |
b = 12.038 (2) Å | T = 293 K |
c = 13.645 (3) Å | 0.30 × 0.25 × 0.10 mm |
β = 99.973 (14)° |
Bruker P4 diffractometer | 3056 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.023 |
Tmin = 0.742, Tmax = 0.905 | 3 standard reflections every 97 reflections |
3397 measured reflections | intensity decay: none |
3084 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.071 | Δρmax = 0.45 e Å−3 |
S = 1.00 | Δρmin = −0.34 e Å−3 |
3084 reflections | Absolute structure: Flack (1983), with 526 Friedel pairs |
348 parameters | Absolute structure parameter: 0.017 (15) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.11216 (5) | 0.95504 (3) | 0.50724 (3) | 0.02451 (13) | |
Cr2 | 0.91647 (5) | 0.49199 (4) | 0.36494 (3) | 0.02758 (13) | |
Cl1 | 0.72903 (10) | 0.17592 (7) | 0.40994 (7) | 0.0437 (2) | |
Cl2 | 0.72668 (12) | 0.69845 (7) | 0.10465 (7) | 0.0501 (2) | |
O8 | 1.1124 (3) | 0.56581 (19) | 0.42017 (17) | 0.0377 (5) | |
O4 | 0.0934 (3) | 1.05364 (16) | 0.39174 (16) | 0.0315 (5) | |
O1 | −0.0788 (3) | 0.89196 (18) | 0.43131 (16) | 0.0311 (4) | |
O3 | −0.0479 (3) | 1.0854 (2) | 0.24315 (17) | 0.0447 (6) | |
N4 | 0.3109 (3) | 1.0355 (2) | 0.56628 (19) | 0.0302 (6) | |
H4A | 0.2864 | 1.1045 | 0.5831 | 0.036* | |
H4D | 0.3507 | 1.0003 | 0.6230 | 0.036* | |
O6 | 1.0014 (4) | 0.5508 (3) | 0.65332 (19) | 0.0585 (8) | |
O2 | −0.2401 (3) | 0.9151 (2) | 0.28784 (18) | 0.0416 (6) | |
O5 | 0.8982 (3) | 0.48382 (19) | 0.50579 (16) | 0.0372 (5) | |
C7 | −0.0216 (4) | 1.0350 (3) | 0.3227 (2) | 0.0326 (7) | |
N7 | 0.9481 (4) | 0.4989 (2) | 0.2183 (2) | 0.0388 (7) | |
H7A | 0.8791 | 0.4541 | 0.1822 | 0.047* | |
H7B | 0.9280 | 0.5686 | 0.1962 | 0.047* | |
N1 | 0.1263 (3) | 0.8508 (2) | 0.63199 (18) | 0.0321 (5) | |
H1A | 0.1693 | 0.7863 | 0.6184 | 0.038* | |
H1D | 0.1883 | 0.8828 | 0.6832 | 0.038* | |
N5 | 0.7049 (3) | 0.4228 (2) | 0.3303 (2) | 0.0343 (6) | |
H5A | 0.6725 | 0.4323 | 0.2646 | 0.041* | |
H5D | 0.7145 | 0.3492 | 0.3411 | 0.041* | |
N8 | 1.0256 (3) | 0.3378 (2) | 0.3778 (2) | 0.0337 (6) | |
H8A | 1.0494 | 0.3217 | 0.4430 | 0.040* | |
H8B | 0.9579 | 0.2866 | 0.3502 | 0.040* | |
C16 | 1.0020 (5) | 0.5343 (3) | 0.5649 (2) | 0.0386 (8) | |
N3 | 0.2297 (3) | 0.8394 (2) | 0.43456 (18) | 0.0313 (5) | |
H3A | 0.2635 | 0.7852 | 0.4782 | 0.038* | |
H3D | 0.1630 | 0.8083 | 0.3853 | 0.038* | |
O7 | 1.2405 (3) | 0.6304 (2) | 0.5638 (2) | 0.0460 (6) | |
N6 | 0.8089 (3) | 0.6469 (2) | 0.3501 (2) | 0.0353 (6) | |
H6A | 0.8791 | 0.6992 | 0.3713 | 0.042* | |
H6D | 0.7756 | 0.6591 | 0.2849 | 0.042* | |
N2 | −0.0082 (3) | 1.0630 (2) | 0.58323 (19) | 0.0332 (6) | |
H2A | 0.0574 | 1.0935 | 0.6334 | 0.040* | |
H2D | −0.0444 | 1.1184 | 0.5414 | 0.040* | |
C4 | 0.3594 (4) | 0.8806 (3) | 0.3915 (2) | 0.0375 (7) | |
H4B | 0.3233 | 0.9340 | 0.3396 | 0.045* | |
H4C | 0.4046 | 0.8190 | 0.3613 | 0.045* | |
C5 | 0.4799 (4) | 0.9351 (3) | 0.4691 (3) | 0.0417 (8) | |
H5B | 0.5050 | 0.8853 | 0.5254 | 0.050* | |
H5C | 0.5709 | 0.9459 | 0.4407 | 0.050* | |
C8 | −0.1270 (4) | 0.9398 (3) | 0.3463 (2) | 0.0303 (6) | |
C11 | 0.6798 (5) | 0.6637 (3) | 0.4033 (3) | 0.0442 (8) | |
H11A | 0.6455 | 0.7401 | 0.3950 | 0.053* | |
H11B | 0.7131 | 0.6504 | 0.4738 | 0.053* | |
C1 | −0.0201 (4) | 0.8257 (3) | 0.6641 (2) | 0.0367 (7) | |
H1B | −0.0043 | 0.7693 | 0.7156 | 0.044* | |
H1C | −0.0907 | 0.7962 | 0.6081 | 0.044* | |
C9 | 0.5841 (4) | 0.4639 (3) | 0.3831 (3) | 0.0432 (8) | |
H9A | 0.6153 | 0.4518 | 0.4540 | 0.052* | |
H9B | 0.4924 | 0.4213 | 0.3615 | 0.052* | |
C12 | 1.1642 (4) | 0.3234 (3) | 0.3342 (3) | 0.0438 (8) | |
H12A | 1.2000 | 0.2476 | 0.3450 | 0.053* | |
H12B | 1.2426 | 0.3724 | 0.3678 | 0.053* | |
C6 | 0.4317 (4) | 1.0457 (3) | 0.5058 (3) | 0.0393 (8) | |
H6B | 0.5191 | 1.0814 | 0.5453 | 0.047* | |
H6C | 0.3961 | 1.0930 | 0.4490 | 0.047* | |
C2 | −0.0870 (4) | 0.9273 (3) | 0.7031 (3) | 0.0413 (8) | |
H2B | −0.0125 | 0.9592 | 0.7556 | 0.050* | |
H2C | −0.1739 | 0.9052 | 0.7322 | 0.050* | |
C3 | −0.1370 (4) | 1.0163 (3) | 0.6254 (3) | 0.0383 (7) | |
H3B | −0.2104 | 0.9847 | 0.5720 | 0.046* | |
H3C | −0.1866 | 1.0757 | 0.6555 | 0.046* | |
C10 | 0.5496 (5) | 0.5868 (3) | 0.3646 (3) | 0.0497 (9) | |
H10A | 0.5201 | 0.5986 | 0.2936 | 0.060* | |
H10B | 0.4637 | 0.6066 | 0.3957 | 0.060* | |
C14 | 1.1000 (5) | 0.4677 (3) | 0.1975 (3) | 0.0495 (9) | |
H14A | 1.1761 | 0.5151 | 0.2359 | 0.059* | |
H14B | 1.1026 | 0.4797 | 0.1276 | 0.059* | |
C15 | 1.1322 (4) | 0.5803 (2) | 0.5151 (3) | 0.0368 (7) | |
C13 | 1.1372 (6) | 0.3483 (3) | 0.2232 (3) | 0.0527 (10) | |
H13A | 1.2274 | 0.3279 | 0.1969 | 0.063* | |
H13B | 1.0546 | 0.3021 | 0.1906 | 0.063* | |
O2W | 0.0565 (4) | 0.7737 (3) | 0.2347 (2) | 0.0611 (8) | |
O1W | 0.7699 (6) | 0.2955 (3) | 0.6197 (3) | 0.0797 (11) | |
H100 | 0.7126 | 0.2699 | 0.5685 | 0.26 (7)* | |
H101 | 0.8291 | 0.3453 | 0.6044 | 0.14 (3)* | |
H200 | −0.0276 | 0.7710 | 0.1948 | 0.10 (2)* | |
H201 | 0.1253 | 0.7580 | 0.2011 | 0.067 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.0265 (2) | 0.0242 (2) | 0.0218 (2) | −0.00091 (18) | 0.00145 (16) | 0.00035 (17) |
Cr2 | 0.0303 (2) | 0.0263 (2) | 0.0242 (2) | −0.0022 (2) | −0.00081 (18) | 0.00103 (16) |
Cl1 | 0.0445 (4) | 0.0343 (4) | 0.0525 (5) | 0.0006 (4) | 0.0088 (4) | 0.0070 (3) |
Cl2 | 0.0647 (6) | 0.0367 (4) | 0.0416 (4) | −0.0017 (4) | −0.0112 (4) | 0.0025 (3) |
O8 | 0.0386 (13) | 0.0371 (11) | 0.0346 (12) | −0.0069 (11) | −0.0010 (10) | 0.0013 (9) |
O4 | 0.0356 (12) | 0.0309 (10) | 0.0255 (10) | −0.0042 (9) | −0.0018 (9) | 0.0028 (8) |
O1 | 0.0329 (11) | 0.0302 (9) | 0.0284 (9) | −0.0042 (9) | 0.0002 (9) | −0.0004 (8) |
O3 | 0.0547 (15) | 0.0454 (13) | 0.0288 (11) | −0.0061 (12) | −0.0068 (11) | 0.0104 (10) |
N4 | 0.0295 (14) | 0.0301 (13) | 0.0290 (13) | −0.0015 (11) | −0.0002 (11) | −0.0013 (10) |
O6 | 0.071 (2) | 0.0729 (19) | 0.0276 (12) | −0.0007 (16) | −0.0035 (13) | −0.0113 (11) |
O2 | 0.0380 (14) | 0.0455 (13) | 0.0372 (12) | −0.0049 (11) | −0.0047 (11) | −0.0032 (10) |
O5 | 0.0426 (14) | 0.0399 (11) | 0.0275 (11) | −0.0033 (11) | 0.0013 (10) | 0.0037 (9) |
C7 | 0.0361 (18) | 0.0323 (15) | 0.0284 (15) | 0.0022 (13) | 0.0027 (14) | −0.0010 (12) |
N7 | 0.0513 (19) | 0.0346 (14) | 0.0296 (14) | 0.0042 (13) | 0.0042 (13) | 0.0025 (10) |
N1 | 0.0376 (14) | 0.0307 (12) | 0.0271 (12) | 0.0004 (11) | 0.0036 (11) | 0.0003 (10) |
N5 | 0.0342 (15) | 0.0298 (12) | 0.0353 (13) | −0.0013 (12) | −0.0045 (11) | 0.0033 (10) |
N8 | 0.0343 (13) | 0.0307 (12) | 0.0344 (13) | −0.0013 (12) | 0.0011 (11) | 0.0044 (10) |
C16 | 0.047 (2) | 0.0335 (15) | 0.0320 (17) | 0.0050 (15) | −0.0020 (15) | 0.0018 (13) |
N3 | 0.0369 (14) | 0.0280 (11) | 0.0287 (12) | −0.0016 (12) | 0.0053 (11) | −0.0004 (10) |
O7 | 0.0457 (14) | 0.0331 (12) | 0.0506 (13) | −0.0035 (11) | −0.0155 (12) | −0.0003 (10) |
N6 | 0.0403 (15) | 0.0284 (12) | 0.0351 (13) | −0.0018 (11) | 0.0006 (12) | 0.0004 (10) |
N2 | 0.0369 (15) | 0.0298 (12) | 0.0322 (13) | 0.0016 (11) | 0.0040 (12) | 0.0004 (10) |
C4 | 0.0375 (17) | 0.0385 (16) | 0.0389 (16) | 0.0003 (14) | 0.0134 (14) | −0.0021 (13) |
C5 | 0.0332 (18) | 0.0469 (18) | 0.0454 (18) | 0.0006 (16) | 0.0078 (15) | 0.0000 (15) |
C8 | 0.0313 (16) | 0.0316 (13) | 0.0266 (14) | −0.0004 (13) | 0.0016 (13) | −0.0035 (11) |
C11 | 0.049 (2) | 0.0338 (16) | 0.0510 (19) | 0.0076 (16) | 0.0115 (17) | −0.0059 (14) |
C1 | 0.0423 (18) | 0.0338 (15) | 0.0348 (15) | −0.0048 (14) | 0.0089 (15) | 0.0045 (13) |
C9 | 0.0368 (19) | 0.047 (2) | 0.0461 (19) | −0.0057 (16) | 0.0089 (16) | 0.0002 (15) |
C12 | 0.0383 (18) | 0.0419 (18) | 0.0520 (19) | 0.0068 (16) | 0.0099 (16) | 0.0086 (15) |
C6 | 0.0373 (18) | 0.0417 (18) | 0.0394 (17) | −0.0108 (15) | 0.0082 (15) | −0.0026 (13) |
C2 | 0.0440 (19) | 0.0444 (18) | 0.0372 (17) | 0.0018 (16) | 0.0119 (16) | 0.0037 (14) |
C3 | 0.0377 (18) | 0.0414 (17) | 0.0373 (17) | 0.0040 (15) | 0.0101 (15) | −0.0009 (13) |
C10 | 0.0367 (18) | 0.051 (2) | 0.060 (2) | 0.0076 (17) | 0.0059 (17) | −0.0041 (18) |
C14 | 0.061 (3) | 0.048 (2) | 0.043 (2) | 0.0012 (19) | 0.0209 (19) | 0.0090 (16) |
C15 | 0.0379 (18) | 0.0253 (13) | 0.0420 (18) | 0.0022 (14) | −0.0076 (15) | −0.0009 (14) |
C13 | 0.067 (3) | 0.045 (2) | 0.052 (2) | 0.0142 (19) | 0.027 (2) | 0.0023 (17) |
O2W | 0.0577 (18) | 0.081 (2) | 0.0442 (14) | 0.0030 (16) | 0.0067 (14) | −0.0099 (14) |
O1W | 0.118 (3) | 0.0555 (18) | 0.077 (2) | −0.015 (2) | 0.048 (2) | −0.0022 (16) |
Cr1—O4 | 1.957 (2) | N6—H6A | 0.9000 |
Cr1—O1 | 1.990 (2) | N6—H6D | 0.9000 |
Cr1—N4 | 2.063 (3) | N2—C3 | 1.486 (5) |
Cr1—N2 | 2.077 (3) | N2—H2A | 0.9000 |
Cr1—N3 | 2.095 (3) | N2—H2D | 0.9000 |
Cr1—N1 | 2.101 (3) | C4—C5 | 1.523 (5) |
Cr2—O5 | 1.959 (2) | C4—H4B | 0.9700 |
Cr2—O8 | 1.994 (2) | C4—H4C | 0.9700 |
Cr2—N5 | 2.048 (3) | C5—C6 | 1.511 (5) |
Cr2—N7 | 2.070 (3) | C5—H5B | 0.9700 |
Cr2—N8 | 2.091 (3) | C5—H5C | 0.9700 |
Cr2—N6 | 2.093 (3) | C11—C10 | 1.511 (6) |
O8—C15 | 1.288 (4) | C11—H11A | 0.9700 |
O4—C7 | 1.289 (4) | C11—H11B | 0.9700 |
O1—C8 | 1.299 (4) | C1—C2 | 1.500 (5) |
O3—C7 | 1.230 (4) | C1—H1B | 0.9700 |
N4—C6 | 1.475 (4) | C1—H1C | 0.9700 |
N4—H4A | 0.9000 | C9—C10 | 1.524 (5) |
N4—H4D | 0.9000 | C9—H9A | 0.9700 |
O6—C16 | 1.224 (4) | C9—H9B | 0.9700 |
O2—C8 | 1.213 (4) | C12—C13 | 1.521 (5) |
O5—C16 | 1.274 (5) | C12—H12A | 0.9700 |
C7—C8 | 1.554 (5) | C12—H12B | 0.9700 |
N7—C14 | 1.484 (6) | C6—H6B | 0.9700 |
N7—H7A | 0.9000 | C6—H6C | 0.9700 |
N7—H7B | 0.9000 | C2—C3 | 1.518 (5) |
N1—C1 | 1.483 (4) | C2—H2B | 0.9700 |
N1—H1A | 0.9000 | C2—H2C | 0.9700 |
N1—H1D | 0.9000 | C3—H3B | 0.9700 |
N5—C9 | 1.484 (5) | C3—H3C | 0.9700 |
N5—H5A | 0.9000 | C10—H10A | 0.9700 |
N5—H5D | 0.9000 | C10—H10B | 0.9700 |
N8—C12 | 1.476 (5) | C14—C13 | 1.503 (5) |
N8—H8A | 0.9000 | C14—H14A | 0.9700 |
N8—H8B | 0.9000 | C14—H14B | 0.9700 |
C16—C15 | 1.550 (5) | C13—H13A | 0.9700 |
N3—C4 | 1.475 (4) | C13—H13B | 0.9700 |
N3—H3A | 0.9000 | O2W—H200 | 0.8498 |
N3—H3D | 0.9000 | O2W—H201 | 0.8506 |
O7—C15 | 1.234 (4) | O1W—H100 | 0.8500 |
N6—C11 | 1.481 (5) | O1W—H101 | 0.8500 |
O4—Cr1—O1 | 82.29 (9) | Cr1—N2—H2A | 107.9 |
O4—Cr1—N4 | 88.73 (10) | C3—N2—H2D | 107.9 |
O1—Cr1—N4 | 170.97 (10) | Cr1—N2—H2D | 107.9 |
O4—Cr1—N2 | 92.45 (10) | H2A—N2—H2D | 107.2 |
O1—Cr1—N2 | 91.44 (10) | N3—C4—C5 | 112.4 (3) |
N4—Cr1—N2 | 89.91 (11) | N3—C4—H4B | 109.1 |
O4—Cr1—N3 | 90.12 (10) | C5—C4—H4B | 109.1 |
O1—Cr1—N3 | 87.51 (10) | N3—C4—H4C | 109.1 |
N4—Cr1—N3 | 91.54 (11) | C5—C4—H4C | 109.1 |
N2—Cr1—N3 | 177.08 (11) | H4B—C4—H4C | 107.9 |
O4—Cr1—N1 | 178.36 (11) | C6—C5—C4 | 113.7 (3) |
O1—Cr1—N1 | 96.87 (10) | C6—C5—H5B | 108.8 |
N4—Cr1—N1 | 92.13 (11) | C4—C5—H5B | 108.8 |
N2—Cr1—N1 | 86.15 (10) | C6—C5—H5C | 108.8 |
N3—Cr1—N1 | 91.26 (10) | C4—C5—H5C | 108.8 |
O5—Cr2—O8 | 82.47 (10) | H5B—C5—H5C | 107.7 |
O5—Cr2—N5 | 88.59 (11) | O2—C8—O1 | 126.1 (3) |
O8—Cr2—N5 | 170.49 (11) | O2—C8—C7 | 120.8 (3) |
O5—Cr2—N7 | 176.91 (14) | O1—C8—C7 | 113.1 (3) |
O8—Cr2—N7 | 95.09 (12) | N6—C11—C10 | 111.5 (3) |
N5—Cr2—N7 | 93.95 (13) | N6—C11—H11A | 109.3 |
O5—Cr2—N8 | 89.44 (11) | C10—C11—H11A | 109.3 |
O8—Cr2—N8 | 89.79 (11) | N6—C11—H11B | 109.3 |
N5—Cr2—N8 | 93.36 (11) | C10—C11—H11B | 109.3 |
N7—Cr2—N8 | 88.65 (11) | H11A—C11—H11B | 108.0 |
O5—Cr2—N6 | 91.39 (11) | N1—C1—C2 | 111.4 (3) |
O8—Cr2—N6 | 89.94 (11) | N1—C1—H1B | 109.3 |
N5—Cr2—N6 | 87.05 (11) | C2—C1—H1B | 109.3 |
N7—Cr2—N6 | 90.50 (11) | N1—C1—H1C | 109.3 |
N8—Cr2—N6 | 179.09 (12) | C2—C1—H1C | 109.3 |
C15—O8—Cr2 | 113.5 (2) | H1B—C1—H1C | 108.0 |
C7—O4—Cr1 | 115.4 (2) | N5—C9—C10 | 112.8 (3) |
C8—O1—Cr1 | 114.7 (2) | N5—C9—H9A | 109.0 |
C6—N4—Cr1 | 119.1 (2) | C10—C9—H9A | 109.0 |
C6—N4—H4A | 107.5 | N5—C9—H9B | 109.0 |
Cr1—N4—H4A | 107.5 | C10—C9—H9B | 109.0 |
C6—N4—H4D | 107.5 | H9A—C9—H9B | 107.8 |
Cr1—N4—H4D | 107.5 | N8—C12—C13 | 112.3 (3) |
H4A—N4—H4D | 107.0 | N8—C12—H12A | 109.2 |
C16—O5—Cr2 | 114.9 (2) | C13—C12—H12A | 109.2 |
O3—C7—O4 | 124.5 (3) | N8—C12—H12B | 109.2 |
O3—C7—C8 | 121.1 (3) | C13—C12—H12B | 109.2 |
O4—C7—C8 | 114.4 (3) | H12A—C12—H12B | 107.9 |
C14—N7—Cr2 | 117.2 (2) | N4—C6—C5 | 113.0 (3) |
C14—N7—H7A | 108.0 | N4—C6—H6B | 109.0 |
Cr2—N7—H7A | 108.0 | C5—C6—H6B | 109.0 |
C14—N7—H7B | 108.0 | N4—C6—H6C | 109.0 |
Cr2—N7—H7B | 108.0 | C5—C6—H6C | 109.0 |
H7A—N7—H7B | 107.2 | H6B—C6—H6C | 107.8 |
C1—N1—Cr1 | 115.4 (2) | C1—C2—C3 | 114.6 (3) |
C1—N1—H1A | 108.4 | C1—C2—H2B | 108.6 |
Cr1—N1—H1A | 108.4 | C3—C2—H2B | 108.6 |
C1—N1—H1D | 108.4 | C1—C2—H2C | 108.6 |
Cr1—N1—H1D | 108.4 | C3—C2—H2C | 108.6 |
H1A—N1—H1D | 107.5 | H2B—C2—H2C | 107.6 |
C9—N5—Cr2 | 118.3 (2) | N2—C3—C2 | 112.5 (3) |
C9—N5—H5A | 107.7 | N2—C3—H3B | 109.1 |
Cr2—N5—H5A | 107.7 | C2—C3—H3B | 109.1 |
C9—N5—H5D | 107.7 | N2—C3—H3C | 109.1 |
Cr2—N5—H5D | 107.7 | C2—C3—H3C | 109.1 |
H5A—N5—H5D | 107.1 | H3B—C3—H3C | 107.8 |
C12—N8—Cr2 | 118.9 (2) | C11—C10—C9 | 114.5 (3) |
C12—N8—H8A | 107.6 | C11—C10—H10A | 108.6 |
Cr2—N8—H8A | 107.6 | C9—C10—H10A | 108.6 |
C12—N8—H8B | 107.6 | C11—C10—H10B | 108.6 |
Cr2—N8—H8B | 107.6 | C9—C10—H10B | 108.6 |
H8A—N8—H8B | 107.0 | H10A—C10—H10B | 107.6 |
O6—C16—O5 | 125.1 (4) | N7—C14—C13 | 111.8 (3) |
O6—C16—C15 | 120.4 (3) | N7—C14—H14A | 109.3 |
O5—C16—C15 | 114.4 (3) | C13—C14—H14A | 109.3 |
C4—N3—Cr1 | 117.36 (19) | N7—C14—H14B | 109.3 |
C4—N3—H3A | 108.0 | C13—C14—H14B | 109.3 |
Cr1—N3—H3A | 108.0 | H14A—C14—H14B | 107.9 |
C4—N3—H3D | 108.0 | O7—C15—O8 | 124.5 (4) |
Cr1—N3—H3D | 108.0 | O7—C15—C16 | 121.3 (3) |
H3A—N3—H3D | 107.2 | O8—C15—C16 | 114.2 (3) |
C11—N6—Cr2 | 117.4 (2) | C14—C13—C12 | 114.3 (3) |
C11—N6—H6A | 108.0 | C14—C13—H13A | 108.7 |
Cr2—N6—H6A | 108.0 | C12—C13—H13A | 108.7 |
C11—N6—H6D | 108.0 | C14—C13—H13B | 108.7 |
Cr2—N6—H6D | 108.0 | C12—C13—H13B | 108.7 |
H6A—N6—H6D | 107.2 | H13A—C13—H13B | 107.6 |
C3—N2—Cr1 | 117.5 (2) | H200—O2W—H201 | 106.9 |
C3—N2—H2A | 107.9 | H100—O1W—H101 | 111.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···Cl2i | 0.90 | 2.46 | 3.353 (4) | 172 |
N4—H4D···O3ii | 0.90 | 2.02 | 2.913 (4) | 175 |
N7—H7A···O7iii | 0.90 | 2.12 | 2.994 (5) | 164 |
N7—H7B···Cl2 | 0.90 | 2.54 | 3.323 (4) | 145 |
N1—H1A···O7iv | 0.90 | 2.16 | 3.047 (4) | 170 |
N1—H1D···O3ii | 0.90 | 2.39 | 3.141 (5) | 141 |
N5—H5A···O6iii | 0.90 | 1.97 | 2.780 (4) | 149 |
N5—H5D···Cl1 | 0.90 | 2.28 | 3.160 (4) | 165 |
N8—H8A···Cl2v | 0.90 | 2.50 | 3.329 (3) | 154 |
N8—H8B···Cl1 | 0.90 | 2.69 | 3.383 (4) | 135 |
N3—H3A···O7iv | 0.90 | 2.23 | 3.064 (4) | 155 |
N3—H3D···O2W | 0.90 | 2.15 | 3.000 (4) | 157 |
N6—H6A···O1vi | 0.90 | 2.47 | 3.248 (4) | 145 |
N6—H6D···Cl2 | 0.90 | 2.47 | 3.360 (3) | 171 |
N2—H2A···O2ii | 0.90 | 2.53 | 3.363 (4) | 154 |
N2—H2D···Cl1vii | 0.90 | 2.56 | 3.323 (3) | 143 |
O1W—H100···Cl1 | 0.85 | 2.47 | 3.169 (4) | 140 |
O1W—H101···O5 | 0.85 | 2.29 | 3.082 (5) | 154 |
O2W—H200···Cl2iv | 0.85 | 2.49 | 3.298 (4) | 160 |
O2W—H201···O1Wiii | 0.85 | 1.95 | 2.800 (4) | 173 |
Symmetry codes: (i) x−1/2, −y+2, z+1/2; (ii) x+1/2, −y+2, z+1/2; (iii) x−1/2, −y+1, z−1/2; (iv) x−1, y, z; (v) x+1/2, −y+1, z+1/2; (vi) x+1, y, z; (vii) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cr(C2O4)(C3H10N2)2]Cl·H2O |
Mr | 341.74 |
Crystal system, space group | Monoclinic, Pn |
Temperature (K) | 293 |
a, b, c (Å) | 8.9532 (17), 12.038 (2), 13.645 (3) |
β (°) | 99.973 (14) |
V (Å3) | 1448.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.30 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.742, 0.905 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3397, 3084, 3056 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 1.00 |
No. of reflections | 3084 |
No. of parameters | 348 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.34 |
Absolute structure | Flack (1983), with 526 Friedel pairs |
Absolute structure parameter | 0.017 (15) |
Computer programs: XSCANS (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) and XP (Sheldrick, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···Cl2i | 0.900 | 2.460 | 3.353 (4) | 171.46 |
N4—H4D···O3ii | 0.900 | 2.015 | 2.913 (4) | 174.93 |
N7—H7A···O7iii | 0.900 | 2.119 | 2.994 (5) | 163.89 |
N7—H7B···Cl2 | 0.900 | 2.544 | 3.323 (4) | 145.27 |
N1—H1A···O7iv | 0.900 | 2.156 | 3.047 (4) | 169.98 |
N1—H1D···O3ii | 0.900 | 2.393 | 3.141 (5) | 140.69 |
N5—H5A···O6iii | 0.900 | 1.972 | 2.780 (4) | 148.59 |
N5—H5D···Cl1 | 0.900 | 2.283 | 3.160 (4) | 164.74 |
N8—H8A···Cl2v | 0.900 | 2.496 | 3.329 (3) | 154.18 |
N8—H8B···Cl1 | 0.900 | 2.687 | 3.383 (4) | 134.91 |
N3—H3A···O7iv | 0.900 | 2.227 | 3.064 (4) | 154.48 |
N3—H3D···O2W | 0.900 | 2.150 | 3.000 (4) | 157.17 |
N6—H6A···O1vi | 0.900 | 2.468 | 3.248 (4) | 145.22 |
N6—H6D···Cl2 | 0.900 | 2.469 | 3.360 (3) | 170.93 |
N2—H2A···O2ii | 0.900 | 2.533 | 3.363 (4) | 153.58 |
N2—H2D···Cl1vii | 0.900 | 2.560 | 3.323 (3) | 143.00 |
O1W—H100···Cl1 | 0.850 | 2.469 | 3.169 (4) | 140.19 |
O1W—H101···O5 | 0.850 | 2.294 | 3.082 (5) | 154.18 |
O2W—H200···Cl2iv | 0.850 | 2.486 | 3.298 (4) | 160.12 |
O2W—H201···O1Wiii | 0.850 | 1.954 | 2.800 (4) | 172.82 |
Symmetry codes: (i) x−1/2, −y+2, z+1/2; (ii) x+1/2, −y+2, z+1/2; (iii) x−1/2, −y+1, z−1/2; (iv) x−1, y, z; (v) x+1/2, −y+1, z+1/2; (vi) x+1, y, z; (vii) x−1, y+1, z. |
The crystal structures of monomeric chromium(III) complexes Na[Cr(hm)(ox)2].3H2O (hm = histamine) and Na[Cr(PM)(ox)2].H2O (PM = pyridoxamine) (Sakagami et al., 1999), AsPh4[Cr(ox)(phen)].H2O and [NaCr(phen)(ox)2(H2O)].2H2O (phen = 1,10-phenanthroline) (Marinescu et al., 2000), AsPh4[Cr(bpm)(ox)2].H2O and Na[Cr(bpm)(ox)2].H2O (bpm = 2,2'-bipyrimidine) (De Munno et al., 1999), and PPh4[Cr(bipy)(ox)2].H2O (bipy = 2,2'-bipyridine) (Lescouëzec et al., 2003) contain two oxalato ligands and one neutral didentate terminal ligand. Among these examples, the complexes using the Na+ ion as balanced anions usually show beautiful one-, two- or three-dimensional supramolecular structures. The compound [Mn(4,4'-bipyridine-N,N'- dioxide)(H2O)4][Cr(bipy)(ox)2]2.8H2O comprises of [Cr(bipy)(ox)2]- anions and one-dimensional cationic chain [Mn(4,4'-bipyridine-N,N'- dioxide)(H2O)4]n2n+ (Bruda et al., 2001). The molecular structure of [Cr(en)2(ox)][Cr(en)(ox)2].2H2O (en = 1,2-ethylenediamine) consists of one [Cr(en)2(ox)]+ cation and one [Cr(en)(ox)2]- anion with one and two oxalato ligands, respectivley (Lethbridge et al., 1970). Herein we report a new monooxalato-containing chromium(III) complex [Cr(ox)(tn)2]Cl.H2O (I).
The crystal structure of (I) consists of two independent [Cr(tn)2(ox)]+ cations, two free Cl- as counteranions and two crystallization water molecules. (Figure 1). Each chromium atom in (I) is coordinated by four nitrogen atoms from two tn ligands and two oxalate oxygen atoms, yielding a distorted octahedral geometry. The four Cr—O bond distances (1.957 (2) to 1.994 (2) Å) are comparable to those in [Cr(en)2(ox)]+ unit of complex [Cr(en)2(ox)][Cr(en)(ox)2].2H2O. The Cr—N distances range from 2.063 (3) to 2.101 (3) Å for Cr1, and from 2.048 (3) to 2.093 (3) Å for Cr2. The bond angles between every adjacent two bonds around Cr atom are almost all close to 90 ° except O4—Cr1—O1 (82.30 (9) °) and O5—Cr2—O8 (82.47 (10) °), which leads to the distortion of coordination environment from the ideal octahedron. The ox ligands exhibit slightly deviation from planarity and the tn ligands show the typical chair-like conformation. The nearest Cr1···Cr2 separation is 6.061 Å.
There exist affluent hydrogen bonds in (I) (Figure 2). Firstly, the adjacent the adjacent two [Cr1(tn)2(ox)]+ units are linked by three N—H···O (N4—H4D···O3 [x + 1/2, -y + 2, z + 1/2], N1—H1D···O3 [x + 1/2, -y + 2, z + 1/2] and N2—H2A···O2 [x + 1/2, -y + 2, z + 1/2]) hydrogen bonds. Similarly, two [Cr2(tn)2(ox)]+ units are linked with two strong N—H···O (N5—H5A···O6 [x - 1/2, -y + 1, z - 1/2] and N7—H7A···O7 [x - 1/2, -y + 1, z - 1/2]) hydrogen bonds. Secondly, there are also three N—H···O (N1—H1A···O7 [x - 1, y, z], N3—H3A···O7 [x - 1, y, z], N6—H6A···O1 [x + 1, y, z]) hydrogen bonds between the nearest [Cr1(tn)2(ox)]+ and [Cr2(tn)2(ox)]+ units. Through all these N—H···O hydrogen bonds and seven N—H··· Cl hydrogen bonds, the two [Cr(tn)2(ox)]+ cationic units form two-dimensional layer-like structures. Finally, the layers form a three-dimensional network structure through hydrogen bond series N3···O2W···O1W [x - 1/2, -y + 1, z - 1/2]···O5 and two Owater···Cl hydrogen bonds.