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The asymmetric unit of the title compound, C
4H
12N
22+·C
2O
42−·H
2O, contains one water molecule, one anion and two half-cations, both cations having chair conformations. The crystal structure is stabilized by intra- and intermolecular O—H
O and N—H
O hydrogen bonds, linking the molecules into a three-dimensional framework, which results in the formation of a supramolecular structure based on a hydrogen-bonded network.
Supporting information
CCDC reference: 601612
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.005 Å
- R factor = 0.071
- wR factor = 0.168
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.94
Alert level C
REFLT03_ALERT_3_C Reflection count < 95% complete
From the CIF: _diffrn_reflns_theta_max 26.02
From the CIF: _diffrn_reflns_theta_full 26.02
From the CIF: _reflns_number_total 1591
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 1693
Completeness (_total/calc) 93.98%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.94
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.55 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 14
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.18 Ratio
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
7 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
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
piperazinium oxalate monohydrate
top
Crystal data top
C4H12N22+·C2O42−·H2O | F(000) = 416 |
Mr = 194.19 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1292 reflections |
a = 11.983 (3) Å | θ = 3.7–28.4° |
b = 6.4802 (18) Å | µ = 0.13 mm−1 |
c = 11.256 (3) Å | T = 120 K |
β = 96.858 (6)° | Cube, colourless |
V = 867.8 (4) Å3 | 0.02 × 0.02 × 0.02 mm |
Z = 4 | |
Data collection top
Bruker Smart 1000 CCD area-detector diffractometer | 1591 independent reflections |
Radiation source: fine-focus sealed tube | 930 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
φ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −11→14 |
Tmin = 0.998, Tmax = 0.998 | k = −7→7 |
4334 measured reflections | l = −13→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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0845P)] where P = (Fo2 + 2Fc2)/3 |
1591 reflections | (Δ/σ)max = 0.001 |
118 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.32 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 | 0.2538 (2) | −0.1275 (4) | 0.8455 (2) | 0.0199 (6) | |
O2 | 0.1052 (2) | 0.0230 (4) | 0.7409 (2) | 0.0181 (6) | |
O3 | 0.2384 (2) | 0.1518 (4) | 0.5788 (2) | 0.0191 (6) | |
O4 | 0.3903 (2) | 0.0522 (4) | 0.7014 (2) | 0.0183 (6) | |
C1 | 0.2090 (3) | −0.0179 (5) | 0.7619 (3) | 0.0134 (8) | |
C2 | 0.2852 (3) | 0.0705 (5) | 0.6720 (3) | 0.0146 (8) | |
N1A | 0.0297 (2) | 0.1325 (5) | 0.1011 (3) | 0.0141 (7) | |
H1AA | 0.0748 | 0.2336 | 0.1388 | 0.017* | |
H1AB | −0.0227 | 0.0956 | 0.1507 | 0.017* | |
C1A | −0.0287 (3) | 0.2149 (6) | −0.0135 (3) | 0.0155 (8) | |
H1AE | 0.0276 | 0.2649 | −0.0643 | 0.019* | |
H1AF | −0.0768 | 0.3329 | 0.0034 | 0.019* | |
C2A | 0.0995 (3) | −0.0502 (6) | 0.0788 (3) | 0.0162 (8) | |
H2AA | 0.1355 | −0.1055 | 0.1560 | 0.019* | |
H2AB | 0.1597 | −0.0081 | 0.0307 | 0.019* | |
N1B | 0.4990 (2) | 0.3562 (5) | 0.5969 (3) | 0.0149 (7) | |
H1BA | 0.4658 | 0.2490 | 0.6331 | 0.018* | |
H1BB | 0.5640 | 0.3914 | 0.6446 | 0.018* | |
C1B | 0.5272 (3) | 0.2882 (6) | 0.4768 (3) | 0.0169 (8) | |
H1BE | 0.4581 | 0.2402 | 0.4274 | 0.020* | |
H1BF | 0.5809 | 0.1717 | 0.4867 | 0.020* | |
C2B | 0.4219 (3) | 0.5355 (6) | 0.5850 (3) | 0.0174 (8) | |
H2BA | 0.4059 | 0.5803 | 0.6654 | 0.021* | |
H2BB | 0.3499 | 0.4949 | 0.5386 | 0.021* | |
O1S | 0.2643 (3) | 0.0599 (5) | 0.3416 (3) | 0.0484 (11) | |
H1SA | 0.2602 | 0.0859 | 0.4150 | 0.073* | |
H1SB | 0.2656 | −0.0698 | 0.3305 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0208 (15) | 0.0210 (14) | 0.0185 (13) | 0.0027 (12) | 0.0046 (11) | 0.0063 (11) |
O2 | 0.0116 (13) | 0.0217 (15) | 0.0213 (13) | −0.0017 (11) | 0.0039 (10) | 0.0021 (11) |
O3 | 0.0189 (14) | 0.0223 (15) | 0.0167 (13) | 0.0032 (12) | 0.0044 (10) | 0.0034 (11) |
O4 | 0.0144 (13) | 0.0187 (14) | 0.0230 (13) | 0.0010 (11) | 0.0073 (11) | 0.0034 (11) |
C1 | 0.0135 (18) | 0.0116 (19) | 0.0152 (17) | −0.0016 (15) | 0.0024 (14) | −0.0048 (14) |
C2 | 0.0143 (19) | 0.0095 (19) | 0.0205 (18) | 0.0009 (15) | 0.0043 (15) | −0.0023 (15) |
N1A | 0.0129 (16) | 0.0137 (16) | 0.0169 (15) | −0.0057 (13) | 0.0064 (12) | −0.0018 (12) |
C1A | 0.0123 (19) | 0.0136 (19) | 0.0217 (19) | 0.0023 (15) | 0.0060 (15) | 0.0042 (15) |
C2A | 0.0127 (18) | 0.0183 (19) | 0.0177 (17) | 0.0018 (16) | 0.0026 (14) | 0.0030 (15) |
N1B | 0.0134 (16) | 0.0135 (16) | 0.0180 (15) | −0.0065 (13) | 0.0036 (12) | 0.0032 (12) |
C1B | 0.0136 (19) | 0.0169 (19) | 0.0209 (19) | −0.0020 (16) | 0.0052 (15) | −0.0050 (16) |
C2B | 0.0131 (18) | 0.021 (2) | 0.0199 (18) | −0.0018 (16) | 0.0082 (15) | 0.0002 (16) |
O1S | 0.099 (3) | 0.0253 (18) | 0.0213 (16) | −0.0035 (19) | 0.0097 (17) | −0.0028 (14) |
Geometric parameters (Å, º) top
O1—C1 | 1.248 (4) | C2A—H2AB | 0.9900 |
O2—C1 | 1.267 (4) | N1B—C2B | 1.481 (5) |
O3—C2 | 1.246 (4) | N1B—C1B | 1.497 (5) |
O4—C2 | 1.268 (4) | N1B—H1BA | 0.9200 |
C1—C2 | 1.552 (5) | N1B—H1BB | 0.9200 |
N1A—C2A | 1.488 (5) | C1B—C2Bii | 1.505 (5) |
N1A—C1A | 1.491 (5) | C1B—H1BE | 0.9900 |
N1A—H1AA | 0.9200 | C1B—H1BF | 0.9900 |
N1A—H1AB | 0.9200 | C2B—C1Bii | 1.505 (5) |
C1A—C2Ai | 1.501 (5) | C2B—H2BA | 0.9900 |
C1A—H1AE | 0.9900 | C2B—H2BB | 0.9900 |
C1A—H1AF | 0.9900 | O1S—H1SA | 0.8501 |
C2A—C1Ai | 1.501 (5) | O1S—H1SB | 0.8500 |
C2A—H2AA | 0.9900 | | |
| | | |
O1—C1—O2 | 125.7 (3) | C1Ai—C2A—H2AB | 109.5 |
O1—C1—C2 | 117.9 (3) | H2AA—C2A—H2AB | 108.1 |
O2—C1—C2 | 116.3 (3) | C2B—N1B—C1B | 110.8 (3) |
O3—C2—O4 | 126.3 (3) | C2B—N1B—H1BA | 109.5 |
O3—C2—C1 | 117.7 (3) | C1B—N1B—H1BA | 109.5 |
O4—C2—C1 | 116.0 (3) | C2B—N1B—H1BB | 109.5 |
C2A—N1A—C1A | 110.8 (3) | C1B—N1B—H1BB | 109.5 |
C2A—N1A—H1AA | 109.5 | H1BA—N1B—H1BB | 108.1 |
C1A—N1A—H1AA | 109.5 | N1B—C1B—C2Bii | 110.0 (3) |
C2A—N1A—H1AB | 109.5 | N1B—C1B—H1BE | 109.7 |
C1A—N1A—H1AB | 109.5 | C2Bii—C1B—H1BE | 109.7 |
H1AA—N1A—H1AB | 108.1 | N1B—C1B—H1BF | 109.7 |
N1A—C1A—C2Ai | 110.4 (3) | C2Bii—C1B—H1BF | 109.7 |
N1A—C1A—H1AE | 109.6 | H1BE—C1B—H1BF | 108.2 |
C2Ai—C1A—H1AE | 109.6 | N1B—C2B—C1Bii | 110.7 (3) |
N1A—C1A—H1AF | 109.6 | N1B—C2B—H2BA | 109.5 |
C2Ai—C1A—H1AF | 109.6 | C1Bii—C2B—H2BA | 109.5 |
H1AE—C1A—H1AF | 108.1 | N1B—C2B—H2BB | 109.5 |
N1A—C2A—C1Ai | 110.6 (3) | C1Bii—C2B—H2BB | 109.5 |
N1A—C2A—H2AA | 109.5 | H2BA—C2B—H2BB | 108.1 |
C1Ai—C2A—H2AA | 109.5 | H1SA—O1S—H1SB | 110.0 |
N1A—C2A—H2AB | 109.5 | | |
| | | |
O1—C1—C2—O3 | 169.0 (3) | C2A—N1A—C1A—C2Ai | 57.1 (4) |
O2—C1—C2—O3 | −8.8 (5) | C1A—N1A—C2A—C1Ai | −57.2 (4) |
O1—C1—C2—O4 | −11.0 (5) | C2B—N1B—C1B—C2Bii | 57.3 (4) |
O2—C1—C2—O4 | 171.2 (3) | C1B—N1B—C2B—C1Bii | −57.7 (4) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1BA···O4 | 0.92 | 1.79 | 2.707 (4) | 175 |
N1A—H1AA···O2iii | 0.92 | 1.96 | 2.818 (4) | 154 |
N1A—H1AA···O3iii | 0.92 | 2.27 | 2.902 (4) | 125 |
N1A—H1AB···O2iv | 0.92 | 1.83 | 2.735 (4) | 167 |
N1B—H1BB···O1v | 0.92 | 2.18 | 2.958 (4) | 142 |
N1B—H1BB···O4v | 0.92 | 2.04 | 2.794 (4) | 138 |
O1S—H1SA···O3 | 0.85 | 1.94 | 2.789 (4) | 175 |
O1S—H1SB···O1vi | 0.85 | 1.98 | 2.805 (4) | 165 |
Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) −x, −y, −z+1; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y−1/2, z−1/2. |
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