l-Histidinium sulfate

Kumar, R.P.; Athimoolam, S.; Bahadur, S.A.; Rajaram, R.K.

doi:10.1107/S1600536805021021

L-Histidinium sulfate

R. P. Kumar, S Athimoolam, S. A. Bahadur and R. K. Rajaram

The title compound, C₆H₁₁N₃O₂²⁺·SO₄²⁻, crystallizes with two cations and two anions in the asymmetric unit. In both diprotonated histidinium cations, the C^γ atom has a gauche-II conformation with respect to the amine N atom and it is in a trans position to the C atom. An extensive three-dimensional network of intermolecular N—H

O and O—H

O hydrogen bonds links the histidinium cations and sulfate anions, forming a crystal structure in which zigzag (Z1) head-to-tail sequences are observed for both the cations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805021021/cv6532sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805021021/cv6532Isup2.hkl Contains datablock I

CCDC reference: 282299

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.010 Å
R factor = 0.047
wR factor = 0.189
Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.774     0.999
            Tmin(prime) and Tmax expected:      0.927     0.960
            RR(prime) =      0.802
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.80
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S2
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               2368
           Count of symmetry unique reflns         1998
           Completeness (_total/calc)            118.52%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       370
           Fraction of Friedel pairs measured     0.185
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 2000) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

L-Histidinium sulfate top

Crystal data top

C₆H₁₁N₃O₂²⁺·SO₄²⁻	F(000) = 528
M_r = 253.25	D_x = 1.643 Mg m⁻³ D_m = 1.632 Mg m⁻³ D_m measured by flotation in a liquid mixture of CCl₄ and bromoform
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.8616 (6) Å	Cell parameters from 25 reflections
b = 5.8084 (6) Å	θ = 9.6–11.8°
c = 25.6901 (18) Å	µ = 0.34 mm⁻¹
β = 90.733 (8)°	T = 293 K
V = 1023.79 (16) Å³	Block, colourless
Z = 4	0.22 × 0.16 × 0.12 mm

Data collection top

Nonius MACH-3 sealed-tube diffractometer	2161 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.094
Graphite monochromator	θ_max = 25.0°, θ_min = 2.4°
ω–2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −1→6
T_min = 0.774, T_max = 0.999	l = −30→30
2571 measured reflections	3 standard reflections every 60 min
2368 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.1269P)² + 1.9828P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.189	(Δ/σ)_max < 0.001
S = 1.15	Δρ_max = 0.44 e Å⁻³
2368 reflections	Δρ_min = −0.51 e Å⁻³
294 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.131 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.09 (18)

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	U_iso*/U_eq
O1A	0.8595 (8)	0.7098 (12)	0.4952 (2)	0.0399 (15)
O1B	0.6669 (8)	0.4012 (12)	0.4855 (2)	0.0405 (16)
H1B	0.6364	0.4637	0.4580	0.061*
C11	0.7867 (9)	0.5338 (16)	0.5116 (2)	0.0254 (16)
C12	0.8271 (8)	0.4508 (14)	0.5668 (2)	0.0200 (13)
H12	0.8211	0.2823	0.5678	0.024*
N11	1.0260 (7)	0.5288 (12)	0.5821 (2)	0.0227 (12)
H11A	1.1083	0.4992	0.5565	0.034*
H11B	1.0646	0.4545	0.6107	0.034*
H11C	1.0243	0.6796	0.5883	0.034*
C13	0.6709 (9)	0.5518 (16)	0.6022 (3)	0.0286 (16)
H13A	0.6787	0.7184	0.6007	0.034*
H13B	0.5436	0.5073	0.5888	0.034*
C14	0.6867 (8)	0.4786 (15)	0.6575 (2)	0.0223 (15)
C15	0.7591 (9)	0.2871 (15)	0.6802 (3)	0.0243 (15)
H15	0.8212	0.1660	0.6635	0.029*
N12	0.7242 (7)	0.3041 (12)	0.7320 (2)	0.0224 (13)
H12A	0.7568	0.2032	0.7550	0.027*
C16	0.6329 (9)	0.4985 (14)	0.7415 (3)	0.0252 (16)
H16	0.5920	0.5491	0.7740	0.030*
N13	0.6094 (7)	0.6089 (11)	0.6970 (2)	0.0231 (13)
H13	0.5546	0.7412	0.6933	0.028*
O2A	0.3835 (9)	0.2315 (14)	0.9980 (2)	0.0498 (19)
O2B	0.1415 (7)	0.4673 (13)	1.01944 (19)	0.0371 (14)
H2B	0.1580	0.4115	1.0485	0.056*
C21	0.2661 (9)	0.3805 (15)	0.9878 (3)	0.0248 (16)
C22	0.2551 (8)	0.4796 (15)	0.9332 (2)	0.0216 (14)
H22	0.1882	0.6287	0.9338	0.026*
N21	0.4578 (7)	0.5110 (10)	0.9148 (2)	0.0205 (12)
H21A	0.5324	0.5621	0.9410	0.031*
H21B	0.4585	0.6128	0.8890	0.031*
H21C	0.5038	0.3769	0.9036	0.031*
C23	0.1437 (10)	0.3128 (16)	0.8970 (3)	0.0299 (17)
H23A	0.1985	0.1598	0.9010	0.036*
H23B	0.0087	0.3063	0.9076	0.036*
C24	0.1503 (8)	0.3791 (14)	0.8404 (3)	0.0234 (15)
C25	0.2247 (9)	0.2690 (14)	0.8000 (3)	0.0262 (16)
H25	0.2878	0.1273	0.8006	0.031*
N22	0.1904 (7)	0.4052 (12)	0.7568 (2)	0.0244 (14)
H22A	0.2234	0.3730	0.7255	0.029*
C26	0.0985 (9)	0.5934 (14)	0.7717 (3)	0.0257 (16)
H26	0.0595	0.7139	0.7501	0.031*
N23	0.0716 (7)	0.5810 (12)	0.8224 (2)	0.0226 (13)
H23	0.0141	0.6829	0.8410	0.027*
S1	0.2631 (2)	0.0470 (3)	0.64646 (6)	0.0232 (5)
O11	0.4123 (7)	0.0128 (12)	0.60718 (19)	0.0371 (15)
O12	0.0779 (8)	−0.0443 (14)	0.6272 (3)	0.0529 (18)
O13	0.2379 (7)	0.2988 (10)	0.65572 (19)	0.0259 (11)
O14	0.3275 (9)	−0.0596 (13)	0.6952 (2)	0.0463 (16)
S2	0.6944 (2)	0.9604 (3)	0.84857 (6)	0.0198 (5)
O21	0.7928 (8)	0.9489 (12)	0.7987 (2)	0.0348 (13)
O22	0.5024 (7)	0.8511 (12)	0.8439 (2)	0.0420 (16)
O23	0.6758 (8)	1.2003 (11)	0.8651 (3)	0.0443 (16)
O24	0.8172 (6)	0.8270 (11)	0.88683 (18)	0.0272 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.047 (3)	0.039 (4)	0.034 (3)	−0.018 (3)	−0.007 (2)	0.019 (3)
O1B	0.048 (3)	0.045 (4)	0.028 (3)	−0.023 (3)	−0.017 (2)	0.010 (3)
C11	0.023 (3)	0.030 (4)	0.023 (3)	−0.001 (3)	−0.001 (2)	0.005 (3)
C12	0.023 (3)	0.018 (3)	0.020 (3)	−0.002 (3)	−0.004 (2)	0.002 (3)
N11	0.021 (2)	0.022 (3)	0.025 (3)	0.005 (3)	−0.0024 (19)	−0.001 (3)
C13	0.024 (3)	0.031 (4)	0.030 (3)	0.009 (4)	0.003 (2)	0.007 (4)
C14	0.016 (3)	0.029 (4)	0.023 (3)	0.005 (3)	0.005 (2)	0.007 (3)
C15	0.022 (3)	0.020 (4)	0.031 (4)	0.002 (3)	0.002 (3)	0.004 (3)
N12	0.021 (2)	0.025 (3)	0.021 (3)	0.001 (3)	0.001 (2)	0.007 (3)
C16	0.019 (3)	0.028 (5)	0.029 (3)	−0.002 (3)	0.004 (2)	0.000 (3)
N13	0.020 (2)	0.020 (3)	0.030 (3)	0.005 (2)	0.004 (2)	−0.002 (3)
O2A	0.058 (3)	0.059 (5)	0.033 (3)	0.035 (4)	0.008 (3)	0.020 (3)
O2B	0.036 (2)	0.050 (4)	0.026 (2)	0.013 (3)	0.0069 (19)	0.005 (3)
C21	0.023 (3)	0.030 (4)	0.022 (3)	−0.001 (3)	−0.004 (2)	0.003 (3)
C22	0.019 (3)	0.024 (4)	0.022 (3)	0.007 (3)	0.004 (2)	0.003 (3)
N21	0.018 (2)	0.018 (3)	0.026 (2)	−0.001 (2)	−0.0013 (18)	0.002 (2)
C23	0.024 (3)	0.033 (5)	0.032 (4)	−0.009 (3)	−0.004 (3)	0.007 (4)
C24	0.011 (2)	0.024 (4)	0.035 (4)	−0.002 (3)	−0.005 (2)	0.001 (3)
C25	0.017 (3)	0.021 (4)	0.040 (4)	0.002 (3)	−0.005 (3)	−0.003 (3)
N22	0.017 (2)	0.032 (4)	0.024 (3)	0.003 (3)	−0.001 (2)	−0.006 (3)
C26	0.021 (3)	0.029 (4)	0.028 (3)	0.001 (3)	−0.006 (2)	0.001 (3)
N23	0.018 (2)	0.027 (4)	0.023 (3)	0.007 (3)	−0.0005 (19)	−0.003 (3)
S1	0.0213 (8)	0.0182 (9)	0.0301 (9)	0.0085 (7)	−0.0044 (6)	−0.0069 (7)
O11	0.030 (2)	0.048 (4)	0.033 (2)	0.017 (3)	−0.0081 (19)	−0.017 (3)
O12	0.030 (3)	0.045 (4)	0.084 (5)	0.001 (3)	−0.007 (3)	−0.031 (4)
O13	0.030 (2)	0.013 (3)	0.035 (3)	0.009 (2)	−0.0037 (19)	−0.006 (2)
O14	0.065 (4)	0.039 (4)	0.035 (3)	0.030 (4)	0.006 (3)	0.007 (3)
S2	0.0183 (7)	0.0152 (9)	0.0260 (8)	0.0034 (7)	0.0023 (5)	0.0013 (7)
O21	0.042 (3)	0.027 (3)	0.036 (3)	0.014 (3)	0.006 (2)	0.007 (3)
O22	0.022 (2)	0.038 (4)	0.066 (4)	−0.009 (3)	−0.010 (2)	0.023 (3)
O23	0.038 (3)	0.020 (3)	0.076 (4)	0.011 (3)	0.009 (3)	−0.017 (3)
O24	0.028 (2)	0.032 (3)	0.021 (2)	0.012 (2)	0.0005 (18)	−0.003 (2)

Geometric parameters (Å, º) top

O1A—C11	1.216 (10)	C22—N21	1.486 (7)
O1B—C11	1.305 (9)	C22—C23	1.540 (10)
O1B—H1B	0.8200	C22—H22	0.9800
C11—C12	1.519 (9)	N21—H21A	0.8900
C12—N11	1.487 (8)	N21—H21B	0.8900
C12—C13	1.532 (9)	N21—H21C	0.8900
C12—H12	0.9800	C23—C24	1.504 (10)
N11—H11A	0.8900	C23—H23A	0.9700
N11—H11B	0.8900	C23—H23B	0.9700
N11—H11C	0.8900	C24—C25	1.328 (11)
C13—C14	1.486 (9)	C24—N23	1.370 (10)
C13—H13A	0.9700	C25—N22	1.379 (10)
C13—H13B	0.9700	C25—H25	0.9300
C14—C15	1.348 (11)	N22—C26	1.321 (10)
C14—N13	1.377 (9)	N22—H22A	0.8600
C15—N12	1.358 (9)	C26—N23	1.320 (9)
C15—H15	0.9300	C26—H26	0.9300
N12—C16	1.316 (10)	N23—H23	0.8600
N12—H12A	0.8600	S1—O12	1.458 (6)
C16—N13	1.319 (9)	S1—O11	1.460 (5)
C16—H16	0.9300	S1—O14	1.460 (6)
N13—H13	0.8600	S1—O13	1.492 (6)
O2A—C21	1.208 (10)	S2—O21	1.458 (5)
O2B—C21	1.289 (9)	S2—O23	1.462 (7)
O2B—H2B	0.8200	S2—O22	1.466 (5)
C21—C22	1.518 (9)	S2—O24	1.502 (5)

C11—O1B—H1B	109.5	C21—C22—C23	109.8 (6)
O1A—C11—O1B	125.3 (6)	N21—C22—H22	109.7
O1A—C11—C12	121.3 (6)	C21—C22—H22	109.7
O1B—C11—C12	113.4 (7)	C23—C22—H22	109.7
N11—C12—C11	107.9 (5)	C22—N21—H21A	109.5
N11—C12—C13	111.9 (6)	C22—N21—H21B	109.5
C11—C12—C13	108.2 (5)	H21A—N21—H21B	109.5
N11—C12—H12	109.6	C22—N21—H21C	109.5
C11—C12—H12	109.6	H21A—N21—H21C	109.5
C13—C12—H12	109.6	H21B—N21—H21C	109.5
C12—N11—H11A	109.5	C24—C23—C22	113.7 (6)
C12—N11—H11B	109.5	C24—C23—H23A	108.8
H11A—N11—H11B	109.5	C22—C23—H23A	108.8
C12—N11—H11C	109.5	C24—C23—H23B	108.8
H11A—N11—H11C	109.5	C22—C23—H23B	108.8
H11B—N11—H11C	109.5	H23A—C23—H23B	107.7
C14—C13—C12	114.6 (6)	C25—C24—N23	107.6 (6)
C14—C13—H13A	108.6	C25—C24—C23	130.5 (8)
C12—C13—H13A	108.6	N23—C24—C23	122.0 (7)
C14—C13—H13B	108.6	C24—C25—N22	106.8 (7)
C12—C13—H13B	108.6	C24—C25—H25	126.6
H13A—C13—H13B	107.6	N22—C25—H25	126.6
C15—C14—N13	106.2 (6)	C26—N22—C25	108.7 (6)
C15—C14—C13	132.2 (7)	C26—N22—H22A	125.7
N13—C14—C13	121.5 (7)	C25—N22—H22A	125.7
C14—C15—N12	107.1 (7)	N23—C26—N22	108.3 (7)
C14—C15—H15	126.4	N23—C26—H26	125.9
N12—C15—H15	126.4	N22—C26—H26	125.9
C16—N12—C15	109.6 (6)	C26—N23—C24	108.7 (6)
C16—N12—H12A	125.2	C26—N23—H23	125.6
C15—N12—H12A	125.2	C24—N23—H23	125.6
N12—C16—N13	108.0 (6)	O12—S1—O11	109.3 (3)
N12—C16—H16	126.0	O12—S1—O14	113.0 (5)
N13—C16—H16	126.0	O11—S1—O14	109.1 (3)
C16—N13—C14	109.1 (6)	O12—S1—O13	108.0 (4)
C16—N13—H13	125.5	O11—S1—O13	109.1 (4)
C14—N13—H13	125.5	O14—S1—O13	108.3 (4)
C21—O2B—H2B	109.5	O21—S2—O23	110.0 (4)
O2A—C21—O2B	126.2 (7)	O21—S2—O22	109.5 (4)
O2A—C21—C22	119.7 (6)	O23—S2—O22	110.8 (4)
O2B—C21—C22	114.1 (6)	O21—S2—O24	106.8 (3)
N21—C22—C21	107.7 (5)	O23—S2—O24	110.6 (4)
N21—C22—C23	110.1 (5)	O22—S2—O24	109.0 (3)

O1A—C11—C12—N11	−30.1 (9)	O2A—C21—C22—N21	−41.6 (10)
O1B—C11—C12—N11	151.1 (7)	O2B—C21—C22—N21	139.3 (7)
O1A—C11—C12—C13	91.1 (8)	O2A—C21—C22—C23	78.4 (8)
O1B—C11—C12—C13	−87.7 (8)	O2B—C21—C22—C23	−100.8 (8)
N11—C12—C13—C14	−63.5 (9)	N21—C22—C23—C24	−53.1 (8)
C11—C12—C13—C14	177.9 (7)	C21—C22—C23—C24	−171.5 (6)
C12—C13—C14—C15	−28.0 (12)	C22—C23—C24—C25	117.6 (9)
C12—C13—C14—N13	156.3 (6)	C22—C23—C24—N23	−62.7 (8)
N13—C14—C15—N12	0.3 (7)	N23—C24—C25—N22	−0.1 (7)
C13—C14—C15—N12	−176.0 (7)	C23—C24—C25—N22	179.6 (6)
C14—C15—N12—C16	0.2 (8)	C24—C25—N22—C26	0.4 (8)
C15—N12—C16—N13	−0.6 (8)	C25—N22—C26—N23	−0.6 (7)
N12—C16—N13—C14	0.7 (7)	N22—C26—N23—C24	0.5 (7)
C15—C14—N13—C16	−0.6 (7)	C25—C24—N23—C26	−0.2 (7)
C13—C14—N13—C16	176.1 (6)	C23—C24—N23—C26	−180.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O11ⁱ	0.82	1.73	2.521 (7)	163
N11—H11A···O1Aⁱⁱ	0.89	2.15	2.834 (8)	133
N11—H11B···O13ⁱⁱⁱ	0.89	1.88	2.721 (8)	157
N11—H11C···O12^iv	0.89	1.92	2.757 (10)	156
N12—H12A···O21^v	0.86	1.87	2.719 (8)	169
N13—H13···O14^vi	0.86	1.94	2.729 (8)	152
O2B—H2B···O24^vii	0.82	1.74	2.554 (7)	173
N21—H21A···O2A^viii	0.89	1.93	2.790 (8)	161
N21—H21B···O22	0.89	1.83	2.708 (8)	168
N21—H21C···O23^v	0.89	1.86	2.679 (8)	152
N22—H22A···O13	0.86	1.85	2.694 (8)	168
N23—H23···O24^ix	0.86	1.99	2.811 (7)	160

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

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