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The title compound, C18H26N4O11, is a proton-transfer compound obtained from pyridine-2,6-dicarboxylic acid and piperazine. The asymmetric unit contains one half-cation, one anion and 1.5 water mol­ecules. There is a centre of inversion at the centre of the cation ring and one water molecule lies on a twofold rotation axis. In the crystal structure, inter­molecular O—H...O, N—H...O and N—H...N hydrogen bonds play an important role in the construction of the three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806029011/hk2087sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806029011/hk2087Isup2.hkl
Contains datablock I

CCDC reference: 609296

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.058
  • wR factor = 0.186
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C DIFMN02_ALERT_2_C The minimum difference density is < -0.1*ZMAX*0.75 _refine_diff_density_min given = -0.760 Test value = -0.600 DIFMN03_ALERT_1_C The minimum difference density is < -0.1*ZMAX*0.75 The relevant atom site should be identified. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............ -0.76 e/A    PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 9 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C4 H12 N2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C7 H4 N O4 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 H2 O
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 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 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Piperazinium bis(6-carboxypyridine-2-carboxylate) trihydrate top
Crystal data top
C4H12N22+·2C7H4NO4·3H2OF(000) = 1000
Mr = 474.43Dx = 1.527 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 986 reflections
a = 16.966 (3) Åθ = 2.7–26.4°
b = 13.406 (2) ŵ = 0.13 mm1
c = 10.3516 (17) ÅT = 120 K
β = 118.795 (3)°Cube, colorless
V = 2063.3 (6) Å30.50 × 0.50 × 0.50 mm
Z = 4
Data collection top
Bruker Smart 1000 CCD area-detector
diffractometer
2034 independent reflections
Radiation source: fine-focus sealed tube1656 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 2020
Tmin = 0.939, Tmax = 0.939k = 1616
9040 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.1254P)2 + 3.9531P]
where P = (Fo2 + 2Fc2)/3
2034 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.76 e Å3
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
xyzUiso*/Ueq
O10.26196 (12)0.06324 (12)0.7471 (2)0.0301 (5)
O20.33517 (11)0.04719 (12)0.68274 (19)0.0278 (4)
O30.30594 (13)0.40324 (12)0.7350 (2)0.0349 (5)
H30.27900.46200.75340.052*
O40.36348 (19)0.46825 (15)0.6040 (3)0.0579 (7)
N10.33499 (12)0.21736 (14)0.6749 (2)0.0206 (4)
C10.31340 (15)0.03987 (17)0.6958 (2)0.0227 (5)
C20.35128 (14)0.12472 (16)0.6458 (2)0.0214 (5)
C30.39901 (15)0.10432 (18)0.5704 (3)0.0254 (5)
H3A0.40900.03750.55110.031*
C40.43156 (16)0.18376 (18)0.5245 (3)0.0283 (5)
H4A0.46460.17230.47330.034*
C50.41544 (16)0.27950 (18)0.5539 (3)0.0271 (5)
H5A0.43700.33530.52350.032*
C60.36676 (14)0.29269 (16)0.6294 (2)0.0218 (5)
C70.34594 (15)0.39734 (17)0.6568 (3)0.0243 (5)
N1A0.24316 (12)0.25881 (14)0.8562 (2)0.0218 (4)
H1AA0.24720.23110.77830.026*
H1AB0.22740.32480.83440.026*
C1A0.17249 (15)0.20586 (17)0.8762 (2)0.0230 (5)
H1AC0.11350.21370.78640.028*
H1AD0.18670.13380.89140.028*
C2A0.16755 (14)0.24798 (17)1.0077 (2)0.0232 (5)
H2AA0.12220.21051.02250.028*
H2AB0.14830.31860.98860.028*
O1W0.50000.13389 (18)0.75000.0356 (6)
H1WA0.45940.08990.72780.053*
O2W0.4980 (2)0.5775 (3)0.6001 (4)0.0895 (11)
H2WA0.45050.54740.58650.134*
H2WB0.53030.54440.67810.134*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0394 (10)0.0209 (9)0.0440 (10)0.0037 (7)0.0312 (9)0.0049 (7)
O20.0286 (9)0.0202 (8)0.0400 (10)0.0005 (6)0.0209 (8)0.0030 (7)
O30.0489 (11)0.0204 (9)0.0543 (12)0.0034 (7)0.0400 (10)0.0025 (7)
O40.104 (2)0.0240 (10)0.0908 (18)0.0072 (10)0.0828 (17)0.0112 (10)
N10.0182 (9)0.0223 (10)0.0187 (9)0.0001 (7)0.0067 (7)0.0004 (7)
C10.0218 (10)0.0224 (11)0.0240 (11)0.0009 (8)0.0111 (9)0.0029 (8)
C20.0203 (10)0.0230 (11)0.0192 (10)0.0007 (8)0.0080 (8)0.0020 (8)
C30.0262 (11)0.0260 (12)0.0254 (11)0.0014 (9)0.0135 (9)0.0030 (9)
C40.0301 (12)0.0331 (13)0.0275 (12)0.0018 (10)0.0184 (10)0.0004 (10)
C50.0281 (12)0.0296 (12)0.0265 (12)0.0015 (9)0.0156 (10)0.0024 (9)
C60.0201 (10)0.0239 (12)0.0185 (10)0.0009 (8)0.0071 (9)0.0007 (8)
C70.0253 (11)0.0240 (12)0.0247 (11)0.0007 (9)0.0129 (9)0.0015 (9)
N1A0.0252 (10)0.0206 (9)0.0222 (9)0.0010 (7)0.0135 (8)0.0003 (7)
C1A0.0244 (11)0.0209 (11)0.0240 (11)0.0016 (8)0.0118 (9)0.0017 (8)
C2A0.0223 (11)0.0241 (11)0.0247 (11)0.0022 (8)0.0126 (9)0.0011 (9)
O1W0.0254 (12)0.0247 (12)0.0538 (16)0.0000.0168 (12)0.000
O2W0.0662 (18)0.092 (2)0.107 (3)0.0038 (16)0.0396 (18)0.033 (2)
Geometric parameters (Å, º) top
O1—C11.261 (3)C6—C71.507 (3)
O2—C11.251 (3)N1A—C1A1.491 (3)
O3—C71.285 (3)N1A—C2Ai1.494 (3)
O3—H30.9748N1A—H1AA0.9200
O4—C71.203 (3)N1A—H1AB0.9200
N1—C61.333 (3)C1A—C2A1.513 (3)
N1—C21.338 (3)C1A—H1AC0.9900
C1—C21.515 (3)C1A—H1AD0.9900
C2—C31.396 (3)C2A—N1Ai1.494 (3)
C3—C41.385 (3)C2A—H2AA0.9900
C3—H3A0.9500C2A—H2AB0.9900
C4—C51.377 (3)O1W—H1WA0.8501
C4—H4A0.9500O2W—H2WA0.8499
C5—C61.395 (3)O2W—H2WB0.8501
C5—H5A0.9500
C7—O3—H3127.8O4—C7—C6121.2 (2)
C6—N1—C2117.44 (19)O3—C7—C6114.75 (19)
O2—C1—O1125.3 (2)C1A—N1A—C2Ai110.97 (17)
O2—C1—C2117.9 (2)C1A—N1A—H1AA109.4
O1—C1—C2116.82 (19)C2Ai—N1A—H1AA109.4
N1—C2—C3123.1 (2)C1A—N1A—H1AB109.4
N1—C2—C1116.89 (19)C2Ai—N1A—H1AB109.4
C3—C2—C1120.0 (2)H1AA—N1A—H1AB108.0
C4—C3—C2118.4 (2)N1A—C1A—C2A110.12 (18)
C4—C3—H3A120.8N1A—C1A—H1AC109.6
C2—C3—H3A120.8C2A—C1A—H1AC109.6
C5—C4—C3119.1 (2)N1A—C1A—H1AD109.6
C5—C4—H4A120.4C2A—C1A—H1AD109.6
C3—C4—H4A120.4H1AC—C1A—H1AD108.2
C4—C5—C6118.4 (2)N1Ai—C2A—C1A110.82 (18)
C4—C5—H5A120.8N1Ai—C2A—H2AA109.5
C6—C5—H5A120.8C1A—C2A—H2AA109.5
N1—C6—C5123.5 (2)N1Ai—C2A—H2AB109.5
N1—C6—C7117.87 (19)C1A—C2A—H2AB109.5
C5—C6—C7118.6 (2)H2AA—C2A—H2AB108.1
O4—C7—O3124.0 (2)H2WA—O2W—H2WB92.0
C6—N1—C2—C30.3 (3)C2—N1—C6—C50.0 (3)
C6—N1—C2—C1178.96 (18)C2—N1—C6—C7177.83 (18)
O2—C1—C2—N1173.12 (19)C4—C5—C6—N10.1 (4)
O1—C1—C2—N17.1 (3)C4—C5—C6—C7177.7 (2)
O2—C1—C2—C38.1 (3)N1—C6—C7—O4171.4 (2)
O1—C1—C2—C3171.7 (2)C5—C6—C7—O46.6 (4)
N1—C2—C3—C40.4 (3)N1—C6—C7—O36.3 (3)
C1—C2—C3—C4179.1 (2)C5—C6—C7—O3175.8 (2)
C2—C3—C4—C50.3 (3)C2Ai—N1A—C1A—C2A56.9 (2)
C3—C4—C5—C60.1 (3)N1A—C1A—C2A—N1Ai56.8 (2)
Symmetry code: (i) x+1/2, y1/2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O1ii0.981.522.483 (3)167
N1A—H1AA···N10.922.223.012 (3)144
N1A—H1AA···O10.922.302.932 (2)125
N1A—H1AB···O2ii0.921.982.859 (2)159
O1W—H1WA···O20.852.012.789 (2)152
O2W—H2WA···O40.851.902.728 (5)166
O2W—H2WB···O4iii0.852.343.180 (5)172
Symmetry codes: (ii) x+1/2, y1/2, z+3/2; (iii) x+1, y, z+3/2.
 

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