1-(Amino­carbon­yl)ethyl­ammonium hydrogensquarate monohydrate

Cations of the title compound, C₃H₉N₂O⁺·C₄HO₄⁻·H₂O, are connected by inter­molecular N_ammonium—H...O_amide hydrogen bonds into helical chains propagating in the [010] direction. These chains are further linked by N_ammonium—H...O hydrogen bonds to the hydrogensquarate anions, which in turn form O—H...O-bridged chains in the [100] direction, thereby giving rise to a three-dimensional network. The water O atoms participate in two O—H...O hydrogen bonds to the anions and one O...H—N_amide bridge to the cation.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.049
• wR factor = 0.134
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =      19.14
            Cell volume su given      =      17.00
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.10
PLAT417_ALERT_2_C Short Inter D-H..H-D       HW1    ..  H22     ..       2.14 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.829(10) ......       4.00 su-Rat
              OW   -HW1     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.828(10) ......       4.00 su-Rat
              OW   -HW2     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(4), Rep   0.829(10) ......       4.00 su-Rat
              O1#  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(4), Rep   0.828(10) ......       4.00 su-Rat
              O1#  -H2#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.98(4), Rep   1.975(15) ......       2.67 su-Rat
              H1#  -O4'     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.93(4), Rep   1.931(15) ......       2.67 su-Rat
              H2#  -O2'     1.555   2.646

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               1580
           Count of symmetry unique reflns         1585
           Completeness (_total/calc)             99.68%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   8 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: R3m/V (Siemens, 1989); cell refinement: R3m/V; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

1-(Aminocarbonyl)ethylammonium hydrogensquarate monohydrate

Crystal data

C3H9N2O^+·C4HO4^−·H2O	F(000) = 232
Mr = 220.19	Dx = 1.453 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 20 reflections
a = 6.2189 (12) Å	θ = 7.9–16.8°
b = 6.4643 (13) Å	µ = 0.13 mm^−1
c = 12.790 (3) Å	T = 294 K
β = 101.80 (3)°	Prism, colourless
V = 503.31 (17) Å^3	0.44 × 0.34 × 0.24 mm
Z = 2

Data collection

Siemens P4 four-circle diffractometer	1260 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 30.0°, θmin = 3.3°
Profile fitted scans	h = 0→8
Absorption correction: ψ scan (SHELXTL; Sheldrick, 1995)	k = 0→9
Tmin = 0.941, Tmax = 0.975	l = −17→17
1708 measured reflections	3 standard reflections every 100 reflections
1580 independent reflections	intensity decay: 0.5%

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.2429P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1580 reflections	Δρmax = 0.36 e Å^−3
145 parameters	Δρmin = −0.30 e Å^−3
3 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.21 (2)

Special details

Experimental. The IR spectrum of (I) (KBr pellet) exhibits characteristic sharp bands for ν (OH) connected through a hydrogen bond. A band of intermediate intensity appears at 3546 cm^-1 and a strong one at 3397 cm^-1 could be assigned to ν (OH) of the water molecule. The bands at 3107 and 3292 cm^-1 in the Raman spectrum of (I) are attributed to the ν NH₂ of the amido group. Corresponding IR bands appear at values of 3110 and 3290 cm^-1, that coincide with the literature data for the alanine zwitterion. The bands at 3100 and 3053 and 3036 cm^-1 can tentatively be assigned to the ν NH₃ group, an assignment that is supported by quantum chemical calculations, but is still uncertain because the IR, LD and theoretical ab initio UHF data for some amino acids and amino acid amides show multiple 3400–2200 cm^-1 bands corresponding to ν NH₃ stretching vibrations. Weak Raman bands at 3001, 2985 and 2952 cm^-1 belong to C—H stretching vibrations of the methyl group. The aminocarbonyl group exhibits the following bands in the IR spectrum: an antisymmetric stretching vibration at 3397 cm^-1 and a symmetric one at 3200 cm^-1, as a shoulder of the very intensive band at 3397 cm^-1. Whereas a very intensive ν (C═O) (amide I) band of (I) is observed at 1673 cm^-1(IR), the corresponding band is very weak in the Raman spectrum.

The –NH₂ deformation (amide II) appears in the region 1610±30 cm^-1 (Roeges, 1994). We assign the band at 1604 cm^-1 (IR) and 1606 cm^-1 (Raman) to amide II modes. The C—N stretching vibration (amide III) is at 1382 cm^-1 but in this case the attribution is not certain. The –NH₂ rocking mode absorbs at 1129 cm^-1 and is weak in both the IR and Raman spectra. A very weak Raman counterpart at 790 cm^-1 is observed for the amide VII band absorbing at 789 cm^-1 in the IR. The amide V band 711 cm^-1 is a mixed vibration attributed to the –NH₂ wag with a contribution from the C═O out-of-plane deformation. The band belonging to the asymmetric scissoring vibration of the –NH₃ group is observed at 1630 cm^-1 (IR) and 1632 cm^-1 (Raman) and other prominent bands are those at 1609 and 1491 cm^-1 (IR) belonging to the second asymmetric and symmetric deformation vibrations of the –NH₃ group, respectively. Corresponding bands are at 1608 and 1486 cm^-1 in the Raman spectrum. For the –NH₃ rocks, three bands can be taken into account at 1170, 1112 and 934 cm^-1. Characteristic for the hydrogensquarate anions are a weak IR band at 1815 cm^-1 and a moderately intensive Raman band at 1810 cm^-1, which can be assigned to mixed C—O and C═O vibrations. The strong Raman bands at 1141 and 639 cm^-1, as well as the intermediate band at 1073 cm^-1, are attributed to the in and out-of-plane vibrations of the aforementioned anion. CH₃ deformation vibrations are observed at 1490, 1349 and 1209 cm^-1. Our assignment is fully in accordance with previous literature data and the vibrational spectra of (I) may, therefore, be compared with those of a series of protonated natural amino acids amides. On the basis of this comparison, the expected ranges of the different characteristic vibrations having analytical value have now been clearly established.

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
C1	0.0210 (5)	0.6305 (6)	0.1258 (2)	0.0344 (7)
O1	0.0783 (4)	0.6750 (5)	0.04183 (17)	0.0456 (7)
N1	0.1123 (5)	0.4822 (6)	0.1920 (2)	0.0456 (8)
H11	0.2185	0.4101	0.1773	0.055*
H12	0.0652	0.4582	0.2495	0.055*
N2	−0.1306 (4)	0.9707 (5)	0.14607 (19)	0.0330 (6)
H21	−0.0055	1.0056	0.1899	0.043*
H22	−0.2410	1.0420	0.1631	0.043*
H23	−0.1214	0.9992	0.0791	0.043*
C2	−0.1708 (5)	0.7457 (6)	0.1564 (2)	0.0321 (6)
H2	−0.1780	0.7134	0.2305	0.039*
C3	−0.3852 (6)	0.6860 (9)	0.0828 (4)	0.0579 (11)
H31	−0.5035	0.7635	0.1016	0.078*
H32	−0.4112	0.5408	0.0900	0.078*
H33	−0.3767	0.7160	0.0103	0.078*
C1'	0.9777 (4)	0.4504 (6)	0.5568 (2)	0.0313 (6)
O1'	1.1776 (3)	0.4469 (5)	0.59316 (17)	0.0400 (6)
C2'	0.7797 (4)	0.4674 (6)	0.6049 (2)	0.0333 (6)
O2'	0.7486 (4)	0.4875 (5)	0.69767 (16)	0.0440 (7)
C3'	0.6445 (4)	0.4499 (6)	0.4994 (2)	0.0339 (6)
O3'	0.4349 (3)	0.4414 (6)	0.45781 (17)	0.0457 (7)
H3'	0.3651	0.4414	0.5057	0.059*
C4'	0.8323 (4)	0.4388 (6)	0.4489 (2)	0.0310 (6)
O4'	0.8591 (4)	0.4239 (5)	0.35564 (17)	0.0412 (6)
OW	0.5373 (4)	0.2129 (5)	0.21028 (18)	0.0400 (6)
HW1	0.631 (6)	0.262 (8)	0.259 (3)	0.054*
HW2	0.469 (6)	0.135 (6)	0.243 (3)	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0359 (14)	0.0411 (18)	0.0284 (13)	0.0025 (13)	0.0118 (11)	−0.0038 (13)
O1	0.0560 (14)	0.0508 (16)	0.0377 (12)	0.0049 (13)	0.0275 (10)	0.0019 (12)
N1	0.0470 (14)	0.049 (2)	0.0461 (15)	0.0158 (15)	0.0226 (12)	0.0089 (15)
N2	0.0308 (11)	0.0424 (15)	0.0277 (11)	0.0010 (12)	0.0108 (8)	−0.0015 (12)
C2	0.0280 (13)	0.0404 (17)	0.0300 (13)	0.0001 (12)	0.0104 (10)	0.0021 (13)
C3	0.0330 (16)	0.061 (3)	0.075 (3)	−0.0104 (19)	−0.0009 (16)	0.005 (2)
C1'	0.0310 (12)	0.0338 (15)	0.0325 (13)	−0.0006 (14)	0.0140 (10)	−0.0011 (14)
O1'	0.0266 (9)	0.0541 (15)	0.0403 (11)	0.0030 (12)	0.0093 (8)	0.0010 (13)
C2'	0.0272 (11)	0.0437 (18)	0.0319 (13)	0.0036 (14)	0.0126 (10)	−0.0005 (14)
O2'	0.0344 (10)	0.072 (2)	0.0276 (10)	0.0068 (13)	0.0117 (8)	−0.0018 (12)
C3'	0.0303 (12)	0.0433 (18)	0.0303 (13)	0.0017 (16)	0.0115 (10)	0.0013 (15)
O3'	0.0276 (10)	0.0750 (19)	0.0355 (11)	−0.0002 (14)	0.0091 (8)	−0.0019 (14)
C4'	0.0269 (12)	0.0354 (16)	0.0330 (13)	−0.0015 (14)	0.0114 (10)	0.0001 (13)
O4'	0.0423 (11)	0.0547 (17)	0.0307 (10)	−0.0052 (12)	0.0174 (8)	−0.0023 (11)
OW	0.0371 (12)	0.0495 (16)	0.0354 (11)	0.0009 (11)	0.0120 (9)	0.0020 (11)

Geometric parameters (Å, º)

C1—O1	1.233 (4)	C3—H33	0.9600
C1—N1	1.327 (4)	C1'—O1'	1.235 (3)
C1—C2	1.523 (4)	C1'—C2'	1.489 (4)
N1—H11	0.8600	C1'—C4'	1.489 (4)
N1—H12	0.8600	C2'—O2'	1.248 (3)
N2—C2	1.486 (5)	C2'—C3'	1.441 (4)
N2—H21	0.8900	C3'—O3'	1.305 (3)
N2—H22	0.8900	C3'—C4'	1.447 (4)
N2—H23	0.8900	O3'—H3'	0.8200
C2—C3	1.517 (5)	C4'—O4'	1.242 (3)
C2—H2	0.9800	OW—HW1	0.829 (10)
C3—H31	0.9600	OW—HW2	0.828 (10)
C3—H32	0.9600
O1—C1—N1	124.2 (3)	C2—C3—H32	109.5
O1—C1—C2	119.4 (3)	H31—C3—H32	109.5
N1—C1—C2	116.4 (3)	C2—C3—H33	109.5
C1—N1—H11	120.0	H31—C3—H33	109.5
C1—N1—H12	120.0	H32—C3—H33	109.5
H11—N1—H12	120.0	O1'—C1'—C2'	134.4 (3)
C2—N2—H21	109.5	O1'—C1'—C4'	136.2 (2)
C2—N2—H22	109.5	C2'—C1'—C4'	89.4 (2)
H21—N2—H22	109.5	O2'—C2'—C3'	136.4 (3)
C2—N2—H23	109.5	O2'—C2'—C1'	134.7 (3)
H21—N2—H23	109.5	C3'—C2'—C1'	88.9 (2)
H22—N2—H23	109.5	O3'—C3'—C2'	136.7 (3)
N2—C2—C3	109.6 (3)	O3'—C3'—C4'	130.3 (3)
N2—C2—C1	107.5 (2)	C2'—C3'—C4'	93.0 (2)
C3—C2—C1	110.6 (3)	C3'—O3'—H3'	109.5
N2—C2—H2	109.7	O4'—C4'—C3'	135.4 (3)
C3—C2—H2	109.7	O4'—C4'—C1'	136.0 (2)
C1—C2—H2	109.7	C3'—C4'—C1'	88.7 (2)
C2—C3—H31	109.5	HW1—OW—HW2	102 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···OW	0.86	2.32	3.134 (4)	157
N1—H12···O4′^i	0.86	2.06	2.890 (3)	162
N2—H21···O2′^ii	0.89	1.92	2.777 (3)	160
N2—H22···OW^iii	0.89	1.96	2.843 (4)	175
N2—H23···O1^iv	0.89	1.98	2.819 (4)	156
O3′—H3′···O1′^i	0.82	1.77	2.587 (3)	171
OW—HW1···O4′	0.83 (1)	1.98 (2)	2.793 (4)	169 (5)
OW—HW2···O2′^v	0.83 (1)	1.93 (2)	2.743 (4)	167 (4)

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