Piperazinium aqua­bis­(oxalato)­oxovanadate(IV) sesquihydrate

Lin, L.; Wu, S.-F.; Huang, C.-C.; Zhang, H.-H.; Huang, X.-H.; Lian, Z.-X.

doi:10.1107/S1600536804008918

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Piperazinium aquabis(oxalato)oxovanadate(IV) sesquihydrate

L. Lin, S.-F. Wu, C.-C. Huang, H.-H. Zhang, X.-H. Huang and Z.-X. Lian

A mononuclear V^IV 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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804008918/cv6297sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804008918/cv6297Isup2.hkl Contains datablock I

CCDC reference: 239074

checkCIF report

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

Computing details top

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
M_r = 376.18	D_x = 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	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 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(F_o²) + (0.056P)²] where P = (F_o² + 2F_c²)/3
3285 reflections	(Δ/σ)_max = 0.001
226 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −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	U_iso*/U_eq	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···O5^iv	0.90	1.92	2.774 (3)	158
O2—H101···O10^v	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.

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