Piperazinium nitrate

Crystals of the title compound, C₄H₁₁N₂⁺·NO₃⁻, are built up from singly protonated piperazinium residues and nitrate anions. The components are linked by hydrogen bonds into a three-dimensional framework. The piperazinium residues are linked together via N—H...N hydrogen bonds into chains in the form of stacks along the [100] direction.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.043
• wR factor = 0.108
• Data-to-parameter ratio = 19.7

checkCIF/PLATON results

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Computing details

Data collection: KM-4 CCD Software (Kuma, 2001); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

C4H11N2^+·NO3^−	F(000) = 320
Mr = 149.16	Dx = 1.365 Mg m^−3 Dm = 1.36 Mg m^−3 Dm measured by flotation
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 937 reflections
a = 4.4420 (9) Å	θ = 3.2–29.5°
b = 12.953 (3) Å	µ = 0.12 mm^−1
c = 12.677 (3) Å	T = 295 K
β = 95.62 (3)°	Parallelepiped, colourless
V = 725.9 (3) Å^3	0.42 × 0.35 × 0.22 mm
Z = 4

Data collection

Kuma KM-4 with CCD area-detector diffractometer	1874 independent reflections
Radiation source: fine-focus sealed tube	939 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.5°, θmin = 3.2°
ω scans	h = −5→5
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990)	k = −17→16
Tmin = 0.948, Tmax = 0.970	l = −16→17
8599 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.0421P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.003
1874 reflections	Δρmax = 0.14 e Å^−3
95 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL-97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (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.

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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.9850 (2)	0.04477 (10)	0.26449 (9)	0.0658 (4)
O1	0.9832 (2)	0.14018 (8)	0.25769 (7)	0.0678 (4)
O2	0.9157 (3)	0.00830 (8)	0.34873 (10)	0.0794 (5)
O3	1.0575 (3)	−0.00589 (10)	0.19074 (12)	0.0913 (5)
N1	0.2485 (2)	0.29227 (10)	0.55572 (9)	0.0551 (4)
H1	0.201 (3)	0.3301 (11)	0.6059 (12)	0.083*
C2	0.4173 (3)	0.35955 (10)	0.49228 (12)	0.0605 (4)
H21	0.5880	0.3887	0.5358	0.091*
H22	0.2891	0.4159	0.4645	0.091*
C3	0.5269 (3)	0.30026 (12)	0.40327 (10)	0.0612 (4)
H31	0.3558	0.2746	0.3573	0.092*
H32	0.6452	0.3449	0.3618	0.092*
N4	0.7157 (2)	0.21240 (9)	0.44595 (9)	0.0595 (4)
H41	0.7705	0.1741	0.3917	0.089*
H42	0.8851	0.2369	0.4821	0.089*
C5	0.5545 (3)	0.14682 (10)	0.51619 (12)	0.0634 (4)
H51	0.6891	0.0934	0.5468	0.095*
H52	0.3847	0.1136	0.4758	0.095*
C6	0.4442 (3)	0.21019 (12)	0.60193 (10)	0.0611 (4)
H61	0.3326	0.1670	0.6470	0.092*
H62	0.6147	0.2400	0.6451	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0668 (8)	0.0634 (7)	0.0665 (9)	0.0022 (6)	0.0031 (6)	−0.0072 (7)
O1	0.0925 (10)	0.0529 (6)	0.0635 (8)	0.0051 (6)	0.0367 (7)	0.0050 (5)
O2	0.0889 (12)	0.0702 (8)	0.0831 (9)	−0.0069 (8)	0.0319 (8)	0.0288 (7)
O3	0.0996 (12)	0.0889 (10)	0.0874 (10)	0.0188 (8)	0.0213 (9)	−0.0565 (8)
N1	0.0439 (7)	0.0659 (8)	0.0570 (8)	−0.0032 (6)	0.0126 (6)	−0.0235 (6)
C2	0.0564 (9)	0.0409 (8)	0.0808 (11)	0.0017 (7)	−0.0104 (8)	0.0021 (7)
C3	0.0588 (9)	0.0803 (10)	0.0438 (8)	−0.0210 (8)	0.0015 (7)	0.0138 (8)
N4	0.0414 (7)	0.0761 (9)	0.0626 (8)	−0.0072 (6)	0.0131 (6)	−0.0329 (6)
C5	0.0571 (9)	0.0403 (8)	0.0893 (12)	0.0004 (7)	−0.0110 (8)	0.0037 (8)
C6	0.0640 (10)	0.0761 (10)	0.0426 (8)	−0.0261 (8)	0.0025 (7)	0.0110 (8)

Geometric parameters (Å, º)

N2—O3	1.2114 (15)	C3—H31	0.9700
N2—O2	1.2340 (14)	C3—H32	0.9700
N2—O1	1.2388 (15)	N4—C5	1.4669 (18)
N1—C2	1.4445 (18)	N4—H41	0.9000
N1—C6	1.4592 (19)	N4—H42	0.9000
N1—H1	0.846 (15)	C5—C6	1.483 (2)
C2—C3	1.486 (2)	C5—H51	0.9700
C2—H21	0.9700	C5—H52	0.9700
C2—H22	0.9700	C6—H61	0.9700
C3—N4	1.4841 (18)	C6—H62	0.9700
O3—N2—O2	124.63 (14)	C5—N4—C3	111.92 (10)
O3—N2—O1	119.14 (14)	C5—N4—H41	109.2
O2—N2—O1	116.22 (12)	C3—N4—H41	109.2
C2—N1—C6	109.99 (10)	C5—N4—H42	109.2
C2—N1—H1	104.5 (10)	C3—N4—H42	109.2
C6—N1—H1	107.6 (10)	H41—N4—H42	107.9
N1—C2—C3	109.72 (12)	N4—C5—C6	109.90 (11)
N1—C2—H21	109.7	N4—C5—H51	109.7
C3—C2—H21	109.7	C6—C5—H51	109.7
N1—C2—H22	109.7	N4—C5—H52	109.7
C3—C2—H22	109.7	C6—C5—H52	109.7
H21—C2—H22	108.2	H51—C5—H52	108.2
N4—C3—C2	109.57 (11)	N1—C6—C5	109.61 (11)
N4—C3—H31	109.8	N1—C6—H61	109.7
C2—C3—H31	109.8	C5—C6—H61	109.7
N4—C3—H32	109.8	N1—C6—H62	109.7
C2—C3—H32	109.8	C5—C6—H62	109.7
H31—C3—H32	108.2	H61—C6—H62	108.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O1	0.90	2.07	2.9222 (14)	158
N4—H41···O2	0.90	2.32	3.0849 (15)	142
N4—H42···N1^i	0.90	1.92	2.8219 (16)	178
N1—H1···O1^ii	0.846 (15)	2.270 (15)	3.0486 (15)	153.2 (12)

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