A mononuclear VIV complex, (C4H12N2)[VO(C2O4)2(H2O)]·1.5H2O, with bis(oxalate) ligands, has been synthesized under hydrothermal conditions. The structure contains aquabis(oxalato)oxovanadium(IV) complex anions, [VO(C2O4)2(H2O)]2-, and diprotonated piperazine cations, [C4N2H12]2+. The ions are connected through hydrogen bonds to form a three-dimensional network with micropores, where uncoordinated water molecules are located with the some degree of disorder. The V center has distorted octahedral geometry with one terminal O atom, four O atoms from two oxalate groups and one water O atom. The two oxalate groups are cis arranged. The V-O bond lengths are in the range 1.599 (2)-2.216 (2) Å.
Supporting information
CCDC reference: 239074
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- H-atom completeness 83%
- Disorder in solvent or counterion
- R factor = 0.035
- wR factor = 0.105
- Data-to-parameter ratio = 14.5
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact OW2 .. OW4 .. 1.85 Ang.
PLAT430_ALERT_2_A Short Inter D...A Contact OW2 .. OW3 .. 2.30 Ang.
Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact OW1 .. O8 .. 2.69 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact O8 .. OW2 .. 2.81 Ang.
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.03
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 17.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >OW1
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <OW2
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.55 Ang.
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C3 - C4 ... 1.55 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
PLAT751_ALERT_4_C Bond Calc 0.90790, Rep 0.9078(19) ...... Senseless su
O2 -H101 1.555 1.555
PLAT751_ALERT_4_C Bond Calc 0.88422, Rep 0.8840(17) ...... Senseless su
O2 -H102 1.555 1.555
PLAT752_ALERT_4_C Angle Calc 124.35, Rep 124.33(15) ...... Senseless su
V1 -O2 -H101 1.555 1.555 1.555
PLAT752_ALERT_4_C Angle Calc 129.04, Rep 129.03(15) ...... Senseless su
V1 -O2 -H102 1.555 1.555 1.555
PLAT752_ALERT_4_C Angle Calc 101.54, Rep 101.56(17) ...... Senseless su
H101 -O2 -H102 1.555 1.555 1.555
PLAT755_ALERT_4_C D-H Calc 0.90790, Rep 0.9078(19) ...... Senseless su
O2 -H101 1.555 1.555
PLAT755_ALERT_4_C D-H Calc 0.88422, Rep 0.8840(17) ...... Senseless su
O2 -H102 1.555 1.555
PLAT755_ALERT_4_C D-H Calc 0.88422, Rep 0.8840(17) ...... Senseless su
O2 -H102 1.555 1.555
PLAT756_ALERT_4_C H...A Calc 1.79897, Rep 1.7990(18) ...... Senseless su
H101 -O10 1.555 4.766
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 4.10 Deg.
OW3 -OW3 -OW4 3.775 1.555 3.775
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 3.90 Deg.
OW3 -OW4 -OW3 1.555 1.555 3.775
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C4 H12 N2
Alert level G
FORMU01_ALERT_2_G 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:C8 H17 N2 O11.5 V1
Atom count from the _atom_site data: C8 H14 N2 O11.5 V1
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C8 H17 N2 O11.50 V
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 32.00 32.00 0.00
H 68.00 56.00 12.00
N 8.00 8.00 0.00
O 46.00 46.00 0.00
V 4.00 4.00 0.00
2 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
25 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
12 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
13 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97/2 (Sheldrick, 1997).
Piperazinium aquabis(oxalato)oxovanadium(IV) sesquihydrate
top
Crystal data top
(C4H12N2)[VO(C2O4)2(H2O)]·1.5H2O | F(000) = 776 |
Mr = 376.18 | Dx = 1.705 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 9.9464 (9) Å | Cell parameters from 25 reflections |
b = 12.5099 (12) Å | θ = 12–18° |
c = 12.5779 (9) Å | µ = 0.74 mm−1 |
β = 110.585 (3)° | T = 298 K |
V = 1465.1 (2) Å3 | Block, green |
Z = 4 | 0.35 × 0.32 × 0.30 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2183 reflections with I > 2σ(I) |
Radiation source: rotor target | Rint = 0.043 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
Detector resolution: none pixels mm-1 | h = 0→12 |
R–AXISCS3 scanner | k = 0→16 |
13526 measured reflections | l = −16→15 |
3285 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3 |
3285 reflections | (Δ/σ)max = 0.001 |
226 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
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. |
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) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
V1 | 0.61679 (4) | 0.93837 (3) | 0.35257 (3) | 0.02692 (14) | |
O1 | 0.5324 (2) | 1.03345 (15) | 0.38665 (15) | 0.0394 (5) | |
O2 | 0.7453 (2) | 1.02828 (15) | 0.29454 (15) | 0.0392 (5) | |
O3 | 0.78632 (18) | 0.91570 (14) | 0.49334 (13) | 0.0325 (4) | |
O4 | 0.84148 (19) | 0.84619 (17) | 0.66723 (14) | 0.0418 (5) | |
O5 | 0.54576 (17) | 0.81248 (15) | 0.41843 (14) | 0.0325 (4) | |
O6 | 0.5941 (2) | 0.72013 (16) | 0.57875 (15) | 0.0420 (5) | |
O7 | 0.46784 (18) | 0.91893 (14) | 0.19589 (14) | 0.0333 (4) | |
O8 | 0.41469 (19) | 0.84600 (16) | 0.02395 (14) | 0.0400 (5) | |
O9 | 0.70361 (17) | 0.80965 (14) | 0.27413 (13) | 0.0307 (4) | |
O10 | 0.65436 (19) | 0.71803 (15) | 0.11191 (14) | 0.0379 (5) | |
C1 | 0.7639 (3) | 0.8544 (2) | 0.5683 (2) | 0.0301 (6) | |
C2 | 0.6232 (3) | 0.7885 (2) | 0.5208 (2) | 0.0303 (6) | |
C3 | 0.4903 (3) | 0.8557 (2) | 0.1242 (2) | 0.0290 (6) | |
C4 | 0.6280 (3) | 0.7875 (2) | 0.1730 (2) | 0.0284 (6) | |
N1 | 1.0004 (2) | 0.79140 (18) | 0.37570 (17) | 0.0320 (5) | |
H1A | 1.0384 | 0.7903 | 0.4520 | 0.038* | |
H1B | 0.9043 | 0.7952 | 0.3554 | 0.038* | |
N2 | 1.2525 (2) | 0.77930 (18) | 0.31653 (18) | 0.0350 (5) | |
H2A | 1.2153 | 0.7791 | 0.2401 | 0.042* | |
H2B | 1.3487 | 0.7755 | 0.3376 | 0.042* | |
C5 | 1.0395 (3) | 0.6918 (2) | 0.3301 (2) | 0.0412 (7) | |
H5A | 0.9933 | 0.6904 | 0.2482 | 0.049* | |
H5B | 1.0059 | 0.6306 | 0.3611 | 0.049* | |
C6 | 1.0533 (3) | 0.8871 (2) | 0.3327 (2) | 0.0381 (6) | |
H6A | 1.0305 | 0.9508 | 0.3668 | 0.046* | |
H6B | 1.0053 | 0.8922 | 0.2511 | 0.046* | |
C7 | 1.2122 (3) | 0.8809 (2) | 0.3600 (2) | 0.0390 (7) | |
H7A | 1.2433 | 0.9412 | 0.3259 | 0.047* | |
H7B | 1.2608 | 0.8849 | 0.4416 | 0.047* | |
C8 | 1.1992 (3) | 0.6849 (2) | 0.3607 (3) | 0.0419 (7) | |
H8A | 1.2452 | 0.6816 | 0.4426 | 0.050* | |
H8B | 1.2234 | 0.6203 | 0.3287 | 0.050* | |
OW1 | 0.7528 (3) | 0.9925 (3) | 0.0892 (2) | 0.0617 (8) | 0.75 |
OW2 | 0.8407 (8) | 1.0581 (7) | 0.1183 (6) | 0.0369 (17) | 0.25 |
OW3 | 1.0009 (13) | 1.0138 (10) | 0.0312 (8) | 0.059 (3) | 0.25 |
OW4 | 1.0159 (9) | 1.0437 (8) | 0.0987 (8) | 0.055 (3) | 0.25 |
H101 | 0.7674 | 1.0978 | 0.3134 | 0.066* | |
H102 | 0.7597 | 1.0238 | 0.2292 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.0304 (2) | 0.0250 (2) | 0.0252 (2) | 0.0004 (2) | 0.00967 (17) | −0.00032 (19) |
O1 | 0.0498 (11) | 0.0361 (11) | 0.0362 (10) | 0.0109 (9) | 0.0198 (9) | 0.0004 (8) |
O2 | 0.0504 (11) | 0.0339 (11) | 0.0381 (10) | −0.0112 (9) | 0.0214 (9) | −0.0008 (8) |
O3 | 0.0329 (9) | 0.0341 (11) | 0.0280 (9) | −0.0064 (8) | 0.0076 (8) | 0.0036 (8) |
O4 | 0.0442 (11) | 0.0489 (13) | 0.0271 (11) | −0.0046 (10) | 0.0061 (9) | 0.0035 (9) |
O5 | 0.0308 (9) | 0.0352 (11) | 0.0309 (10) | −0.0063 (8) | 0.0103 (8) | 0.0018 (8) |
O6 | 0.0485 (12) | 0.0405 (12) | 0.0386 (11) | −0.0086 (10) | 0.0173 (9) | 0.0075 (9) |
O7 | 0.0334 (9) | 0.0330 (11) | 0.0302 (9) | 0.0086 (8) | 0.0070 (8) | −0.0041 (8) |
O8 | 0.0398 (11) | 0.0465 (13) | 0.0270 (10) | 0.0098 (9) | 0.0033 (8) | −0.0028 (8) |
O9 | 0.0291 (9) | 0.0333 (10) | 0.0264 (9) | 0.0046 (8) | 0.0056 (7) | −0.0026 (8) |
O10 | 0.0449 (11) | 0.0356 (11) | 0.0317 (10) | 0.0135 (9) | 0.0118 (8) | −0.0030 (8) |
C1 | 0.0331 (14) | 0.0267 (14) | 0.0314 (15) | 0.0011 (11) | 0.0125 (12) | −0.0011 (11) |
C2 | 0.0347 (14) | 0.0288 (14) | 0.0300 (14) | 0.0024 (12) | 0.0149 (11) | −0.0008 (11) |
C3 | 0.0294 (13) | 0.0266 (14) | 0.0302 (14) | 0.0007 (11) | 0.0097 (11) | 0.0019 (11) |
C4 | 0.0291 (13) | 0.0260 (14) | 0.0315 (14) | 0.0025 (11) | 0.0125 (11) | 0.0035 (11) |
N1 | 0.0249 (11) | 0.0411 (14) | 0.0292 (11) | −0.0013 (10) | 0.0086 (9) | −0.0009 (10) |
N2 | 0.0296 (11) | 0.0413 (14) | 0.0365 (12) | −0.0062 (10) | 0.0145 (10) | −0.0107 (10) |
C5 | 0.0485 (17) | 0.0384 (17) | 0.0429 (16) | −0.0169 (14) | 0.0240 (13) | −0.0095 (13) |
C6 | 0.0352 (14) | 0.0359 (16) | 0.0448 (16) | 0.0040 (13) | 0.0160 (12) | 0.0064 (13) |
C7 | 0.0386 (15) | 0.0355 (16) | 0.0456 (16) | −0.0089 (13) | 0.0184 (13) | −0.0096 (13) |
C8 | 0.0509 (18) | 0.0331 (16) | 0.0491 (17) | 0.0033 (14) | 0.0269 (14) | −0.0011 (13) |
OW1 | 0.078 (2) | 0.067 (2) | 0.0439 (17) | 0.018 (2) | 0.0254 (16) | 0.0096 (16) |
OW2 | 0.041 (4) | 0.038 (4) | 0.035 (4) | 0.007 (4) | 0.017 (3) | 0.011 (4) |
OW3 | 0.064 (6) | 0.071 (8) | 0.052 (9) | 0.008 (6) | 0.033 (9) | −0.007 (7) |
OW4 | 0.024 (4) | 0.057 (7) | 0.066 (7) | −0.017 (4) | −0.009 (5) | 0.042 (5) |
Geometric parameters (Å, º) top
V1—O1 | 1.5990 (18) | N1—H1B | 0.9000 |
V1—O3 | 1.9898 (16) | N2—C8 | 1.480 (3) |
V1—O5 | 2.0192 (17) | N2—C7 | 1.492 (3) |
V1—O7 | 2.0211 (16) | N2—H2A | 0.9000 |
V1—O2 | 2.0221 (18) | N2—H2B | 0.9000 |
V1—O9 | 2.2162 (17) | C5—C8 | 1.500 (4) |
O2—H101 | 0.9078 (19) | C5—H5A | 0.9700 |
O2—H102 | 0.8840 (17) | C5—H5B | 0.9700 |
O3—C1 | 1.294 (3) | C6—C7 | 1.497 (4) |
O4—C1 | 1.216 (3) | C6—H6A | 0.9700 |
O5—C2 | 1.283 (3) | C6—H6B | 0.9700 |
O6—C2 | 1.222 (3) | C7—H7A | 0.9700 |
O7—C3 | 1.277 (3) | C7—H7B | 0.9700 |
O8—C3 | 1.226 (3) | C8—H8A | 0.9700 |
O9—C4 | 1.260 (3) | C8—H8B | 0.9700 |
O10—C4 | 1.247 (3) | OW1—OW2 | 1.161 (8) |
C1—C2 | 1.551 (4) | OW3—OW3i | 0.853 (16) |
C3—C4 | 1.546 (3) | OW3—OW4 | 0.891 (12) |
N1—C5 | 1.480 (3) | OW3—OW4i | 1.739 (17) |
N1—C6 | 1.484 (3) | OW4—OW3i | 1.739 (17) |
N1—H1A | 0.9000 | | |
| | | |
O1—V1—O3 | 103.18 (8) | C5—N1—H1B | 109.4 |
O1—V1—O5 | 100.24 (9) | C6—N1—H1B | 109.4 |
O3—V1—O5 | 80.39 (7) | H1A—N1—H1B | 108.0 |
O1—V1—O7 | 94.41 (8) | C8—N2—C7 | 111.4 (2) |
O3—V1—O7 | 162.15 (7) | C8—N2—H2A | 109.3 |
O5—V1—O7 | 93.66 (7) | C7—N2—H2A | 109.3 |
O1—V1—O2 | 98.12 (9) | C8—N2—H2B | 109.3 |
O3—V1—O2 | 87.42 (7) | C7—N2—H2B | 109.3 |
O5—V1—O2 | 159.85 (8) | H2A—N2—H2B | 108.0 |
O7—V1—O2 | 93.14 (7) | N1—C5—C8 | 110.4 (2) |
O1—V1—O9 | 169.55 (8) | N1—C5—H5A | 109.6 |
O3—V1—O9 | 87.23 (7) | C8—C5—H5A | 109.6 |
O5—V1—O9 | 82.14 (7) | N1—C5—H5B | 109.6 |
O7—V1—O9 | 75.24 (6) | C8—C5—H5B | 109.6 |
O2—V1—O9 | 81.30 (7) | H5A—C5—H5B | 108.1 |
V1—O2—H101 | 124.33 (15) | N1—C6—C7 | 110.8 (2) |
V1—O2—H102 | 129.03 (15) | N1—C6—H6A | 109.5 |
H101—O2—H102 | 101.56 (17) | C7—C6—H6A | 109.5 |
C1—O3—V1 | 115.04 (15) | N1—C6—H6B | 109.5 |
C2—O5—V1 | 114.90 (16) | C7—C6—H6B | 109.5 |
C3—O7—V1 | 120.87 (16) | H6A—C6—H6B | 108.1 |
C4—O9—V1 | 114.93 (15) | N2—C7—C6 | 110.9 (2) |
O4—C1—O3 | 125.8 (2) | N2—C7—H7A | 109.5 |
O4—C1—C2 | 120.7 (2) | C6—C7—H7A | 109.5 |
O3—C1—C2 | 113.5 (2) | N2—C7—H7B | 109.5 |
O6—C2—O5 | 125.3 (3) | C6—C7—H7B | 109.5 |
O6—C2—C1 | 120.9 (2) | H7A—C7—H7B | 108.0 |
O5—C2—C1 | 113.9 (2) | N2—C8—C5 | 110.1 (2) |
O8—C3—O7 | 126.3 (2) | N2—C8—H8A | 109.6 |
O8—C3—C4 | 119.4 (2) | C5—C8—H8A | 109.6 |
O7—C3—C4 | 114.3 (2) | N2—C8—H8B | 109.6 |
O10—C4—O9 | 126.5 (2) | C5—C8—H8B | 109.6 |
O10—C4—C3 | 119.3 (2) | H8A—C8—H8B | 108.1 |
O9—C4—C3 | 114.2 (2) | OW3i—OW3—OW4 | 172 (3) |
C5—N1—C6 | 111.28 (19) | OW3i—OW3—OW4i | 4.1 (13) |
C5—N1—H1A | 109.4 | OW4—OW3—OW4i | 176.1 (13) |
C6—N1—H1A | 109.4 | OW3—OW4—OW3i | 3.9 (13) |
Symmetry code: (i) −x+2, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O10ii | 0.90 | 1.94 | 2.826 (3) | 169 |
N1—H1B···O9 | 0.90 | 1.90 | 2.783 (3) | 165 |
N2—H2A···O6iii | 0.90 | 1.96 | 2.848 (3) | 168 |
N2—H2B···O5iv | 0.90 | 1.92 | 2.774 (3) | 158 |
O2—H101···O10v | 0.9078 (19) | 1.7990 (18) | 2.681 (3) | 163.30 (13) |
O2—H102···OW1 | 0.8840 (17) | 1.781 (3) | 2.647 (3) | 165.96 (17) |
O2—H102···OW2 | 0.8840 (17) | 1.889 (7) | 2.726 (7) | 157.2 (3) |
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+1, y, z; (v) −x+3/2, y+1/2, −z+1/2. |