Crystal structure of tris­(piperidinium) hydrogen sulfate sulfate

A novel mixed hydrogen sulfate–sulfate piperidinium salt comprises three protonated piperidinium cations, one hydrogen sulfate anion and one sulfate anion in the asymmetric unit. Strong hydrogen bonds exist between the cations and the anions giving rise to a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.083
• Data-to-parameter ratio = 21.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.162 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          7 Report
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          4 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        372 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrysAlis PRO (Rigaku Oxford, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford, 2015); data reduction: CrysAlis PRO (Rigaku Oxford, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1997); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Tris(piperidinium) hydrogen sulfate sulfate

Crystal data

3C5H12N^+·HSO4^−·SO4^2^−	F(000) = 976
Mr = 451.60	Dx = 1.434 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.592 (4) Å	Cell parameters from 12552 reflections
b = 17.922 (5) Å	θ = 2.2–29.4°
c = 11.161 (4) Å	µ = 0.30 mm^−1
β = 99.25 (2)°	T = 100 K
V = 2091.1 (12) Å^3	Block, colourless
Z = 4	0.20 × 0.18 × 0.16 mm

Data collection

Rigaku Oxford Xcalibur Atlas diffractometer	5411 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray source	4291 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.4°, θmin = 2.7°
ω scans	h = −14→14
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford, 2015), based on expressions of Clark & Reid (1995)]	k = −23→24
Tmin = 0.994, Tmax = 0.996	l = −15→15
35669 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 1.1863P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5411 reflections	Δρmax = 0.33 e Å^−3
254 parameters	Δρmin = −0.42 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.66217 (3)	0.57717 (2)	0.56541 (3)	0.01118 (9)
S2	0.39851 (3)	0.75550 (2)	0.40181 (3)	0.01134 (9)
O12	0.57890 (10)	0.58513 (6)	0.65614 (9)	0.0155 (2)
O21	0.39138 (10)	0.67389 (6)	0.42549 (10)	0.0183 (2)
O14	0.57685 (10)	0.58114 (6)	0.43754 (10)	0.0175 (2)
H14	0.5194	0.6134	0.4385	0.026*
O11	0.72505 (10)	0.50505 (6)	0.56684 (10)	0.0174 (2)
O13	0.75266 (10)	0.63911 (6)	0.57133 (10)	0.0180 (2)
O22	0.50129 (11)	0.79014 (7)	0.48587 (10)	0.0222 (3)
C25	0.19519 (15)	0.50258 (8)	0.72404 (14)	0.0154 (3)
H25A	0.2000	0.4735	0.8001	0.018*
H25B	0.1955	0.4669	0.6563	0.018*
N21	0.30210 (12)	0.60129 (7)	0.62212 (11)	0.0127 (3)
H21A	0.3029	0.5718	0.5559	0.015*
H21B	0.3716	0.6318	0.6293	0.015*
O23	0.27443 (10)	0.78993 (6)	0.41375 (9)	0.0142 (2)
O24	0.42147 (10)	0.76415 (6)	0.27366 (9)	0.0135 (2)
N11	0.32098 (12)	0.63977 (7)	0.14102 (11)	0.0131 (3)
H11A	0.3570	0.6768	0.1909	0.016*
H11B	0.3156	0.6560	0.0631	0.016*
N31	0.67984 (12)	0.73600 (7)	0.74774 (12)	0.0159 (3)
H31A	0.6901	0.7023	0.6890	0.019*
H31B	0.5947	0.7394	0.7510	0.019*
C14	0.21075 (15)	0.49250 (8)	0.09492 (14)	0.0164 (3)
H14A	0.2125	0.4710	0.1768	0.020*
H14B	0.1725	0.4551	0.0345	0.020*
C26	0.31146 (14)	0.55327 (8)	0.73257 (13)	0.0138 (3)
H26A	0.3169	0.5851	0.8057	0.017*
H26B	0.3901	0.5226	0.7403	0.017*
C23	0.06623 (15)	0.59747 (9)	0.59190 (15)	0.0176 (3)
H23A	0.0622	0.5662	0.5183	0.021*
H23B	−0.0121	0.6285	0.5828	0.021*
C16	0.40461 (14)	0.57238 (8)	0.15854 (14)	0.0152 (3)
H16A	0.4139	0.5557	0.2441	0.018*
H16B	0.4907	0.5850	0.1406	0.018*
C22	0.18310 (14)	0.64782 (8)	0.60349 (14)	0.0155 (3)
H22A	0.1799	0.6782	0.5290	0.019*
H22B	0.1837	0.6821	0.6731	0.019*
C24	0.07120 (15)	0.54724 (9)	0.70327 (15)	0.0189 (3)
H24A	0.0655	0.5782	0.7757	0.023*
H24B	−0.0027	0.5127	0.6912	0.023*
C12	0.18991 (14)	0.62418 (9)	0.16711 (14)	0.0160 (3)
H12A	0.1374	0.6701	0.1552	0.019*
H12B	0.1946	0.6080	0.2525	0.019*
C33	0.86970 (15)	0.80450 (9)	0.70869 (15)	0.0180 (3)
H33A	0.8828	0.7698	0.6428	0.022*
H33B	0.9023	0.8541	0.6895	0.022*
C35	0.89016 (16)	0.70228 (10)	0.86207 (16)	0.0217 (4)
H35A	0.9040	0.6641	0.8014	0.026*
H35B	0.9357	0.6860	0.9422	0.026*
C15	0.34720 (15)	0.50991 (8)	0.07536 (14)	0.0161 (3)
H15A	0.4007	0.4646	0.0915	0.019*
H15B	0.3466	0.5247	−0.0102	0.019*
C13	0.12870 (15)	0.56320 (9)	0.08232 (15)	0.0169 (3)
H13A	0.1182	0.5812	−0.0026	0.020*
H13B	0.0428	0.5515	0.1015	0.020*
C32	0.72742 (14)	0.81012 (8)	0.71454 (15)	0.0167 (3)
H32A	0.7129	0.8477	0.7758	0.020*
H32B	0.6804	0.8260	0.6348	0.020*
C36	0.74807 (16)	0.70877 (9)	0.86681 (16)	0.0205 (3)
H36A	0.7138	0.6595	0.8854	0.025*
H36B	0.7343	0.7440	0.9318	0.025*
C34	0.94462 (15)	0.77687 (10)	0.82831 (15)	0.0207 (3)
H34A	0.9390	0.8139	0.8930	0.025*
H34B	1.0358	0.7708	0.8205	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01134 (17)	0.01084 (17)	0.01124 (17)	0.00075 (13)	0.00142 (13)	−0.00154 (13)
S2	0.01054 (17)	0.01264 (17)	0.01101 (17)	0.00085 (13)	0.00228 (13)	−0.00016 (13)
O12	0.0153 (5)	0.0173 (5)	0.0147 (5)	0.0002 (4)	0.0049 (4)	−0.0014 (4)
O21	0.0207 (6)	0.0144 (5)	0.0214 (6)	0.0051 (4)	0.0077 (5)	0.0061 (4)
O14	0.0175 (6)	0.0209 (6)	0.0127 (5)	0.0071 (4)	−0.0014 (4)	−0.0035 (4)
O11	0.0208 (6)	0.0132 (5)	0.0174 (6)	0.0054 (4)	0.0013 (5)	−0.0018 (4)
O13	0.0147 (5)	0.0157 (5)	0.0246 (6)	−0.0029 (4)	0.0063 (5)	−0.0038 (4)
O22	0.0144 (5)	0.0339 (7)	0.0180 (6)	−0.0035 (5)	0.0013 (5)	−0.0088 (5)
C25	0.0189 (8)	0.0125 (7)	0.0154 (7)	−0.0006 (6)	0.0046 (6)	0.0019 (6)
N21	0.0109 (6)	0.0133 (6)	0.0140 (6)	−0.0009 (5)	0.0023 (5)	0.0015 (5)
O23	0.0130 (5)	0.0152 (5)	0.0152 (5)	0.0029 (4)	0.0043 (4)	0.0004 (4)
O24	0.0147 (5)	0.0141 (5)	0.0124 (5)	0.0001 (4)	0.0041 (4)	0.0008 (4)
N11	0.0151 (6)	0.0129 (6)	0.0114 (6)	−0.0017 (5)	0.0023 (5)	0.0004 (5)
N31	0.0110 (6)	0.0143 (6)	0.0231 (7)	−0.0014 (5)	0.0046 (5)	−0.0073 (5)
C14	0.0169 (7)	0.0141 (7)	0.0168 (8)	−0.0024 (6)	−0.0017 (6)	−0.0003 (6)
C26	0.0139 (7)	0.0143 (7)	0.0127 (7)	0.0006 (6)	0.0008 (6)	0.0028 (6)
C23	0.0122 (7)	0.0232 (8)	0.0177 (8)	0.0023 (6)	0.0027 (6)	0.0040 (6)
C16	0.0128 (7)	0.0157 (7)	0.0163 (7)	0.0006 (6)	0.0000 (6)	0.0016 (6)
C22	0.0159 (7)	0.0140 (7)	0.0168 (7)	0.0040 (6)	0.0034 (6)	0.0034 (6)
C24	0.0151 (7)	0.0226 (8)	0.0200 (8)	−0.0014 (6)	0.0058 (6)	0.0039 (6)
C12	0.0138 (7)	0.0170 (7)	0.0177 (8)	−0.0006 (6)	0.0042 (6)	−0.0001 (6)
C33	0.0148 (7)	0.0159 (7)	0.0236 (8)	−0.0010 (6)	0.0044 (7)	0.0003 (6)
C35	0.0195 (8)	0.0271 (9)	0.0196 (8)	0.0088 (7)	0.0061 (7)	0.0044 (7)
C15	0.0168 (8)	0.0148 (7)	0.0162 (7)	0.0008 (6)	0.0010 (6)	−0.0002 (6)
C13	0.0132 (7)	0.0173 (7)	0.0194 (8)	−0.0015 (6)	0.0001 (6)	0.0006 (6)
C32	0.0140 (7)	0.0147 (7)	0.0208 (8)	0.0008 (6)	0.0012 (6)	−0.0004 (6)
C36	0.0210 (8)	0.0185 (8)	0.0242 (9)	0.0035 (6)	0.0106 (7)	0.0043 (6)
C34	0.0124 (7)	0.0273 (9)	0.0217 (8)	−0.0013 (6)	0.0009 (6)	−0.0050 (7)

Geometric parameters (Å, º)

S1—O12	1.4529 (12)	C23—H23B	0.9900
S1—O14	1.5633 (12)	C23—C22	1.520 (2)
S1—O11	1.4530 (11)	C23—C24	1.529 (2)
S1—O13	1.4612 (11)	C16—H16A	0.9900
S2—O21	1.4904 (12)	C16—H16B	0.9900
S2—O22	1.4569 (12)	C16—C15	1.518 (2)
S2—O23	1.4773 (11)	C22—H22A	0.9900
S2—O24	1.4969 (12)	C22—H22B	0.9900
O14—H14	0.8400	C24—H24A	0.9900
C25—H25A	0.9900	C24—H24B	0.9900
C25—H25B	0.9900	C12—H12A	0.9900
C25—C26	1.521 (2)	C12—H12B	0.9900
C25—C24	1.523 (2)	C12—C13	1.521 (2)
N21—H21A	0.9100	C33—H33A	0.9900
N21—H21B	0.9100	C33—H33B	0.9900
N21—C26	1.4936 (19)	C33—C32	1.522 (2)
N21—C22	1.4978 (19)	C33—C34	1.522 (2)
N11—H11A	0.9100	C35—H35A	0.9900
N11—H11B	0.9100	C35—H35B	0.9900
N11—C16	1.4920 (19)	C35—C36	1.519 (2)
N11—C12	1.4900 (19)	C35—C34	1.527 (2)
N31—H31A	0.9100	C15—H15A	0.9900
N31—H31B	0.9100	C15—H15B	0.9900
N31—C32	1.489 (2)	C13—H13A	0.9900
N31—C36	1.489 (2)	C13—H13B	0.9900
C14—H14A	0.9900	C32—H32A	0.9900
C14—H14B	0.9900	C32—H32B	0.9900
C14—C15	1.528 (2)	C36—H36A	0.9900
C14—C13	1.530 (2)	C36—H36B	0.9900
C26—H26A	0.9900	C34—H34A	0.9900
C26—H26B	0.9900	C34—H34B	0.9900
C23—H23A	0.9900
O12—S1—O14	107.77 (7)	N21—C22—C23	109.68 (12)
O12—S1—O11	114.10 (7)	N21—C22—H22A	109.7
O12—S1—O13	111.17 (7)	N21—C22—H22B	109.7
O11—S1—O14	104.31 (6)	C23—C22—H22A	109.7
O11—S1—O13	112.28 (7)	C23—C22—H22B	109.7
O13—S1—O14	106.58 (7)	H22A—C22—H22B	108.2
O21—S2—O24	106.96 (6)	C25—C24—C23	110.44 (13)
O22—S2—O21	110.98 (7)	C25—C24—H24A	109.6
O22—S2—O23	110.32 (7)	C25—C24—H24B	109.6
O22—S2—O24	110.60 (7)	C23—C24—H24A	109.6
O23—S2—O21	108.83 (6)	C23—C24—H24B	109.6
O23—S2—O24	109.05 (6)	H24A—C24—H24B	108.1
S1—O14—H14	109.5	N11—C12—H12A	109.8
H25A—C25—H25B	108.0	N11—C12—H12B	109.8
C26—C25—H25A	109.3	N11—C12—C13	109.30 (12)
C26—C25—H25B	109.3	H12A—C12—H12B	108.3
C26—C25—C24	111.42 (13)	C13—C12—H12A	109.8
C24—C25—H25A	109.3	C13—C12—H12B	109.8
C24—C25—H25B	109.3	H33A—C33—H33B	108.0
H21A—N21—H21B	107.9	C32—C33—H33A	109.4
C26—N21—H21A	109.2	C32—C33—H33B	109.4
C26—N21—H21B	109.2	C34—C33—H33A	109.4
C26—N21—C22	112.22 (11)	C34—C33—H33B	109.4
C22—N21—H21A	109.2	C34—C33—C32	111.35 (14)
C22—N21—H21B	109.2	H35A—C35—H35B	108.0
H11A—N11—H11B	107.9	C36—C35—H35A	109.5
C16—N11—H11A	109.2	C36—C35—H35B	109.5
C16—N11—H11B	109.2	C36—C35—C34	110.94 (13)
C12—N11—H11A	109.2	C34—C35—H35A	109.5
C12—N11—H11B	109.2	C34—C35—H35B	109.5
C12—N11—C16	112.01 (11)	C14—C15—H15A	109.4
H31A—N31—H31B	107.9	C14—C15—H15B	109.4
C32—N31—H31A	109.1	C16—C15—C14	111.00 (13)
C32—N31—H31B	109.1	C16—C15—H15A	109.4
C32—N31—C36	112.30 (12)	C16—C15—H15B	109.4
C36—N31—H31A	109.1	H15A—C15—H15B	108.0
C36—N31—H31B	109.1	C14—C13—H13A	109.4
H14A—C14—H14B	108.1	C14—C13—H13B	109.4
C15—C14—H14A	109.5	C12—C13—C14	111.03 (13)
C15—C14—H14B	109.5	C12—C13—H13A	109.4
C15—C14—C13	110.74 (12)	C12—C13—H13B	109.4
C13—C14—H14A	109.5	H13A—C13—H13B	108.0
C13—C14—H14B	109.5	N31—C32—C33	109.20 (12)
C25—C26—H26A	109.6	N31—C32—H32A	109.8
C25—C26—H26B	109.6	N31—C32—H32B	109.8
N21—C26—C25	110.29 (12)	C33—C32—H32A	109.8
N21—C26—H26A	109.6	C33—C32—H32B	109.8
N21—C26—H26B	109.6	H32A—C32—H32B	108.3
H26A—C26—H26B	108.1	N31—C36—C35	109.60 (13)
H23A—C23—H23B	108.0	N31—C36—H36A	109.8
C22—C23—H23A	109.4	N31—C36—H36B	109.8
C22—C23—H23B	109.4	C35—C36—H36A	109.8
C22—C23—C24	111.05 (13)	C35—C36—H36B	109.8
C24—C23—H23A	109.4	H36A—C36—H36B	108.2
C24—C23—H23B	109.4	C33—C34—C35	109.69 (13)
N11—C16—H16A	109.6	C33—C34—H34A	109.7
N11—C16—H16B	109.6	C33—C34—H34B	109.7
N11—C16—C15	110.24 (12)	C35—C34—H34A	109.7
H16A—C16—H16B	108.1	C35—C34—H34B	109.7
C15—C16—H16A	109.6	H34A—C34—H34B	108.2
C15—C16—H16B	109.6
N11—C16—C15—C14	−55.57 (16)	C12—N11—C16—C15	59.41 (16)
N11—C12—C13—C14	57.09 (17)	C15—C14—C13—C12	−54.79 (17)
C26—C25—C24—C23	54.49 (17)	C13—C14—C15—C16	53.79 (17)
C26—N21—C22—C23	−58.61 (16)	C32—N31—C36—C35	−59.33 (17)
C16—N11—C12—C13	−59.86 (16)	C32—C33—C34—C35	55.93 (17)
C22—N21—C26—C25	57.84 (16)	C36—N31—C32—C33	59.01 (17)
C22—C23—C24—C25	−55.39 (18)	C36—C35—C34—C33	−55.78 (18)
C24—C25—C26—N21	−55.37 (16)	C34—C33—C32—N31	−57.02 (17)
C24—C23—C22—N21	56.89 (17)	C34—C35—C36—N31	57.05 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14···O21	0.84	1.72	2.5603 (16)	173
N21—H21A···O11^i	0.91	1.93	2.8226 (18)	166
N21—H21B···O12	0.91	2.32	2.9096 (19)	122
N21—H21B···O24^ii	0.91	2.47	3.0964 (18)	127
N11—H11A···O21	0.91	2.59	3.201 (2)	126
N11—H11A···O24	0.91	1.89	2.7904 (17)	171
N11—H11B···O22^iii	0.91	2.47	3.0474 (18)	122
N11—H11B···O23^iii	0.91	1.92	2.8039 (18)	164
N31—H31A···O12	0.91	2.41	3.0245 (18)	125
N31—H31A···O13	0.91	1.93	2.8240 (18)	167
N31—H31B···O24^ii	0.91	1.89	2.7978 (19)	172

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2.