In the crystal structure of the title salt, C5H15N32+·C2O42-·2H2O, all four O atoms of the oxalate anion are involved in hydrogen bonding with the piperazine dication and the water molecules of crystallization.
Supporting information
CCDC reference: 238791
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.037
- wR factor = 0.100
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.22
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C6 - C7 ... 1.55 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker 1997); cell refinement: SMART; data reduction: SAINT (Bruker 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
4-Ammonio-1-methylpiperazin-1-ium oxalate dihydrate
top
Crystal data top
C5H15N32+·C2O42−·2H2O | F(000) = 520 |
Mr = 241.25 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 977 reflections |
a = 10.000 (2) Å | θ = 2.7–25.9° |
b = 9.9641 (16) Å | µ = 0.12 mm−1 |
c = 11.661 (4) Å | T = 293 K |
β = 97.502 (8)° | Block, colourless |
V = 1152.0 (5) Å3 | 0.20 × 0.16 × 0.14 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2262 independent reflections |
Radiation source: fine-focus sealed tube | 1839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 26.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→12 |
Tmin = 0.975, Tmax = 0.985 | k = −11→12 |
6250 measured reflections | l = −14→13 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0481P)2 + 0.3395P] where P = (Fo2 + 2Fc2)/3 |
2262 reflections | (Δ/σ)max = 0.001 |
147 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.24 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 | |
O1 | 0.26264 (14) | 0.43963 (14) | 0.44414 (10) | 0.0510 (4) | |
O2 | 0.29901 (12) | 0.40403 (12) | 0.63406 (9) | 0.0402 (3) | |
O3 | 0.10290 (13) | 0.22009 (12) | 0.42331 (9) | 0.0443 (3) | |
O4 | 0.08637 (13) | 0.23480 (12) | 0.61146 (9) | 0.0444 (3) | |
N1 | 0.67008 (13) | 1.12376 (13) | 0.71835 (10) | 0.0306 (3) | |
H1A | 0.6470 | 1.2082 | 0.7006 | 0.046* | |
H1B | 0.7478 | 1.1048 | 0.6924 | 0.046* | |
H1C | 0.6794 | 1.1133 | 0.7948 | 0.046* | |
N2 | 0.56581 (12) | 1.03395 (12) | 0.66489 (10) | 0.0259 (3) | |
N3 | 0.35869 (12) | 0.83775 (12) | 0.67036 (10) | 0.0267 (3) | |
H3 | 0.3602 | 0.8249 | 0.7478 | 0.032* | |
C1 | 0.60150 (15) | 0.89563 (15) | 0.69901 (13) | 0.0301 (3) | |
H1D | 0.6067 | 0.8862 | 0.7823 | 0.036* | |
H1E | 0.6888 | 0.8729 | 0.6766 | 0.036* | |
C2 | 0.49450 (15) | 0.80286 (15) | 0.63955 (13) | 0.0316 (3) | |
H2A | 0.4933 | 0.8094 | 0.5564 | 0.038* | |
H2B | 0.5162 | 0.7109 | 0.6623 | 0.038* | |
C3 | 0.32795 (15) | 0.98175 (15) | 0.64508 (13) | 0.0305 (3) | |
H3A | 0.2424 | 1.0049 | 0.6706 | 0.037* | |
H3B | 0.3205 | 0.9971 | 0.5623 | 0.037* | |
C4 | 0.43810 (15) | 1.06936 (15) | 0.70628 (13) | 0.0298 (3) | |
H4A | 0.4174 | 1.1631 | 0.6902 | 0.036* | |
H4B | 0.4451 | 1.0555 | 0.7892 | 0.036* | |
C5 | 0.25238 (17) | 0.74923 (17) | 0.60941 (14) | 0.0389 (4) | |
H5A | 0.1663 | 0.7736 | 0.6311 | 0.058* | |
H5B | 0.2719 | 0.6575 | 0.6304 | 0.058* | |
H5C | 0.2504 | 0.7595 | 0.5273 | 0.058* | |
C6 | 0.24082 (15) | 0.38177 (15) | 0.53491 (12) | 0.0286 (3) | |
C7 | 0.13305 (15) | 0.26904 (15) | 0.52110 (12) | 0.0276 (3) | |
O5 | 0.42322 (12) | 0.63537 (12) | 0.37787 (11) | 0.0463 (3) | |
H5D | 0.3777 | 0.5733 | 0.4044 | 0.056* | |
H5E | 0.5014 | 0.6073 | 0.3686 | 0.056* | |
O6 | 0.89242 (13) | 0.05165 (12) | 0.62264 (13) | 0.0546 (4) | |
H6A | 0.9094 | −0.0294 | 0.6071 | 0.066* | |
H6B | 0.9576 | 0.1035 | 0.6133 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0639 (9) | 0.0569 (8) | 0.0315 (6) | −0.0329 (7) | 0.0036 (6) | 0.0089 (6) |
O2 | 0.0422 (7) | 0.0475 (7) | 0.0301 (6) | −0.0133 (5) | 0.0017 (5) | −0.0021 (5) |
O3 | 0.0609 (8) | 0.0423 (7) | 0.0311 (6) | −0.0205 (6) | 0.0107 (5) | −0.0082 (5) |
O4 | 0.0559 (8) | 0.0468 (7) | 0.0338 (6) | −0.0241 (6) | 0.0182 (5) | −0.0059 (5) |
N1 | 0.0321 (7) | 0.0321 (7) | 0.0280 (6) | −0.0071 (5) | 0.0057 (5) | −0.0039 (5) |
N2 | 0.0266 (6) | 0.0243 (6) | 0.0272 (6) | −0.0030 (5) | 0.0044 (5) | −0.0015 (5) |
N3 | 0.0303 (7) | 0.0271 (6) | 0.0234 (6) | −0.0030 (5) | 0.0058 (5) | 0.0013 (5) |
C1 | 0.0281 (8) | 0.0289 (8) | 0.0339 (8) | 0.0033 (6) | 0.0060 (6) | 0.0015 (6) |
C2 | 0.0348 (8) | 0.0259 (8) | 0.0354 (8) | 0.0026 (6) | 0.0094 (6) | −0.0017 (6) |
C3 | 0.0288 (8) | 0.0273 (8) | 0.0357 (8) | 0.0020 (6) | 0.0059 (6) | 0.0044 (6) |
C4 | 0.0316 (8) | 0.0243 (8) | 0.0349 (8) | 0.0027 (6) | 0.0097 (6) | −0.0008 (6) |
C5 | 0.0402 (9) | 0.0361 (9) | 0.0401 (9) | −0.0125 (7) | 0.0045 (7) | −0.0016 (7) |
C6 | 0.0299 (8) | 0.0286 (8) | 0.0280 (7) | −0.0019 (6) | 0.0063 (6) | 0.0001 (6) |
C7 | 0.0295 (8) | 0.0256 (7) | 0.0284 (7) | −0.0008 (6) | 0.0071 (6) | 0.0001 (6) |
O5 | 0.0411 (7) | 0.0343 (7) | 0.0656 (8) | −0.0046 (5) | 0.0148 (6) | 0.0116 (6) |
O6 | 0.0432 (7) | 0.0352 (7) | 0.0918 (10) | −0.0091 (6) | 0.0328 (7) | −0.0051 (7) |
Geometric parameters (Å, º) top
O1—C6 | 1.2492 (18) | C1—H1E | 0.9700 |
O2—C6 | 1.2446 (18) | C2—H2A | 0.9700 |
O3—C7 | 1.2407 (18) | C2—H2B | 0.9700 |
O4—C7 | 1.2542 (17) | C3—C4 | 1.510 (2) |
N1—N2 | 1.4515 (16) | C3—H3A | 0.9700 |
N1—H1A | 0.8900 | C3—H3B | 0.9700 |
N1—H1B | 0.8900 | C4—H4A | 0.9700 |
N1—H1C | 0.8900 | C4—H4B | 0.9700 |
N2—C1 | 1.4656 (19) | C5—H5A | 0.9600 |
N2—C4 | 1.4661 (19) | C5—H5B | 0.9600 |
N3—C5 | 1.4886 (19) | C5—H5C | 0.9600 |
N3—C3 | 1.4888 (19) | C6—C7 | 1.550 (2) |
N3—C2 | 1.491 (2) | O5—H5D | 0.8500 |
N3—H3 | 0.9100 | O5—H5E | 0.8500 |
C1—C2 | 1.512 (2) | O6—H6A | 0.8498 |
C1—H1D | 0.9700 | O6—H6B | 0.8498 |
| | | |
N2—N1—H1A | 109.5 | N3—C3—C4 | 110.16 (12) |
N2—N1—H1B | 109.5 | N3—C3—H3A | 109.6 |
H1A—N1—H1B | 109.5 | C4—C3—H3A | 109.6 |
N2—N1—H1C | 109.5 | N3—C3—H3B | 109.6 |
H1A—N1—H1C | 109.5 | C4—C3—H3B | 109.6 |
H1B—N1—H1C | 109.5 | H3A—C3—H3B | 108.1 |
N1—N2—C1 | 109.11 (11) | N2—C4—C3 | 108.56 (12) |
N1—N2—C4 | 108.54 (11) | N2—C4—H4A | 110.0 |
C1—N2—C4 | 109.19 (11) | C3—C4—H4A | 110.0 |
C5—N3—C3 | 111.12 (12) | N2—C4—H4B | 110.0 |
C5—N3—C2 | 111.29 (12) | C3—C4—H4B | 110.0 |
C3—N3—C2 | 110.37 (11) | H4A—C4—H4B | 108.4 |
C5—N3—H3 | 108.0 | N3—C5—H5A | 109.5 |
C3—N3—H3 | 108.0 | N3—C5—H5B | 109.5 |
C2—N3—H3 | 108.0 | H5A—C5—H5B | 109.5 |
N2—C1—C2 | 108.52 (12) | N3—C5—H5C | 109.5 |
N2—C1—H1D | 110.0 | H5A—C5—H5C | 109.5 |
C2—C1—H1D | 110.0 | H5B—C5—H5C | 109.5 |
N2—C1—H1E | 110.0 | O2—C6—O1 | 126.35 (14) |
C2—C1—H1E | 110.0 | O2—C6—C7 | 117.38 (13) |
H1D—C1—H1E | 108.4 | O1—C6—C7 | 116.25 (13) |
N3—C2—C1 | 111.06 (12) | O3—C7—O4 | 126.35 (14) |
N3—C2—H2A | 109.4 | O3—C7—C6 | 117.55 (13) |
C1—C2—H2A | 109.4 | O4—C7—C6 | 116.09 (12) |
N3—C2—H2B | 109.4 | H5D—O5—H5E | 110.6 |
C1—C2—H2B | 109.4 | H6A—O6—H6B | 111.8 |
H2A—C2—H2B | 108.0 | | |
| | | |
N1—N2—C1—C2 | −178.12 (11) | N1—N2—C4—C3 | 176.51 (11) |
C4—N2—C1—C2 | 63.40 (15) | C1—N2—C4—C3 | −64.66 (15) |
C5—N3—C2—C1 | 178.37 (12) | N3—C3—C4—N2 | 60.16 (15) |
C3—N3—C2—C1 | 54.50 (15) | O2—C6—C7—O3 | −159.88 (15) |
N2—C1—C2—N3 | −58.28 (15) | O1—C6—C7—O3 | 18.6 (2) |
C5—N3—C3—C4 | −179.13 (12) | O2—C6—C7—O4 | 19.0 (2) |
C2—N3—C3—C4 | −55.16 (15) | O1—C6—C7—O4 | −162.49 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O5i | 0.89 | 1.90 | 2.7598 (18) | 163 |
N1—H1B···O6ii | 0.89 | 1.83 | 2.7118 (18) | 172 |
N1—H1C···O1iii | 0.89 | 1.90 | 2.7482 (18) | 158 |
N3—H3···O4iv | 0.91 | 1.89 | 2.7318 (18) | 154 |
O5—H5E···O2v | 0.85 | 2.00 | 2.8267 (18) | 163 |
O5—H5D···O1 | 0.85 | 1.86 | 2.7026 (16) | 172 |
O6—H6A···O3vi | 0.85 | 1.93 | 2.7617 (18) | 164 |
O6—H6B···O4vii | 0.85 | 1.84 | 2.6787 (16) | 170 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y+1, z; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1; (vii) x+1, y, z. |