3-Amino­pyridinium 2-hydr­oxy-2,2-diphenyl­acetate monohydrate

In the title compound, C₅H₇N₂⁺·C₁₄H₁₁O₃⁻·H₂O, the component species are connected by N—H...O and O—H...O hydrogen bonds. An R₁²(5) ring occurs.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.086
• Data-to-parameter ratio = 7.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.28
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2B    ...          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C5 H7 N2

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           25.99
           From the CIF: _reflns_number_total               1821
           Count of symmetry unique reflns         1827
           Completeness (_total/calc)             99.67%
           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
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          7

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

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

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S1. Comment

Supramolecular hydrogen bonded networks are an important area of current research (Zeng et al., 2005). Herein we report the supramolecular structure of the title compound, (I).

The asymmetric unit of (I) consists of one 2-aminopyridinium cation, one benzylate anion and one crystallization water (Fig. 1), in which 3-aminopyridinium cation interacts with benzylate anion through the doubly intermolecular N_protonized—H···O_hydroxyl (N1—H1A···O3) and N_protonized—H···O_carboxylate (N1—H1A···O2) hydrogen bonds, and builds a R₁²(5) ring (Table 1). The crystallization water, in which one of H atoms (H4A) acts as hydrogen bond donor is hydrogen bonded to carboxylate oxygen (O2) of benzylate anion. The other H atom (H4B) of water and hydroxyl H atom (H3A) of benzylate anion linked the adjacent asymmetric units by O_water—H···O_carboxylate and O_hydroxylH···O_water hydrogen bonds, respectively, into an infinite one-dimensional chain along the direction [001] (Fig. 2). Finally, infinite one-dimensional chains are further extended into a two-dimensional network running parallel to the plane (100) by N_amino—H···O_carboxylate hydrogen bonds (Fig.3).

Related literature

For background, see: Zeng et al. (2005).

S2. Experimental

A 5 ml e thanol solution of 3-aminopyridine (1.0 mmol, 0.094 g) was added to 20 ml hot aqueous solution of benzylic acid (1.0 mmol, 0.23 g) and the mixture was stirred for 15 minutes at 373 K. Then the solution was filtered, and the filtrate was kept at the room temperature. After a week, colourless plates of (I) were obtained.

S3. Refinement

Friedel-pair reflections were merged, since anormalous scattering effects were negligible. H atoms bonded to nitrogen atoms, hydroxyl group and water oxygen were located in a difference synthesis and refined isotropically with N—H = 0.85 (1) Å, O—H = 0.82 Å and H···H = 1.34 (1) Å, respectively. All the remaining H atoms were placed in calculated positions with C—H = 0.93 Å and were refined as riding with U_iso = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. An infinite one dimensional chain in (I) along the direction [001]. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.
	Fig. 3. Two dimensional network running parallel to the plane (100) in (I). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

3-Aminopyridinium 2-hydroxy-2,2-diphenylacetate monohydrate

Crystal data

C5H7N2^+·C14H11O3^−·H2O	F(000) = 720
Mr = 340.37	Dx = 1.327 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2804 reflections
a = 28.903 (6) Å	θ = 2.6–22.3°
b = 8.6828 (18) Å	µ = 0.09 mm^−1
c = 6.7900 (14) Å	T = 298 K
V = 1704.0 (6) Å^3	Plate, colourless
Z = 4	0.48 × 0.32 × 0.03 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1821 independent reflections
Radiation source: fine-focus sealed tube	1607 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω' scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −35→16
Tmin = 0.956, Tmax = 0.997	k = −7→10
6660 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.0365P] where P = (Fo^2 + 2Fc^2)/3
1821 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 0.13 e Å^−3
7 restraints	Δρmin = −0.17 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.

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
O1	0.17063 (6)	0.2495 (2)	0.7187 (3)	0.0457 (5)
O2	0.20716 (5)	0.4364 (2)	0.8757 (3)	0.0475 (5)
O3	0.13841 (5)	0.48577 (18)	1.1257 (3)	0.0378 (4)
H3A	0.1587 (7)	0.438 (3)	1.186 (4)	0.056 (9)*
O4	0.29689 (6)	0.3420 (3)	0.8495 (3)	0.0616 (6)
H4A	0.2694 (4)	0.363 (3)	0.848 (5)	0.059 (9)*
H4B	0.3028 (11)	0.307 (4)	0.959 (3)	0.062 (10)*
C6	0.17223 (7)	0.3540 (3)	0.8424 (4)	0.0334 (5)
C7	0.12734 (7)	0.3950 (2)	0.9587 (4)	0.0310 (5)
C14	0.10135 (7)	0.2479 (3)	1.0166 (4)	0.0344 (6)
C19	0.09745 (8)	0.2027 (3)	1.2115 (4)	0.0432 (6)
H19	0.1100	0.2637	1.3106	0.052*
C18	0.07485 (9)	0.0665 (3)	1.2595 (5)	0.0551 (8)
H18	0.0726	0.0369	1.3908	0.066*
C17	0.05596 (10)	−0.0240 (3)	1.1177 (6)	0.0618 (9)
H17	0.0413	−0.1157	1.1511	0.074*
C16	0.05879 (10)	0.0216 (3)	0.9236 (6)	0.0588 (8)
H16	0.0457	−0.0392	0.8256	0.071*
C15	0.08091 (8)	0.1569 (3)	0.8737 (5)	0.0452 (6)
H15	0.0821	0.1873	0.7425	0.054*
C8	0.09618 (7)	0.4964 (3)	0.8301 (4)	0.0325 (5)
C13	0.05536 (8)	0.5509 (3)	0.9120 (5)	0.0445 (7)
H13	0.0482	0.5276	1.0422	0.053*
C12	0.02522 (9)	0.6397 (3)	0.8016 (6)	0.0551 (8)
H12	−0.0022	0.6743	0.8576	0.066*
C11	0.03548 (10)	0.6771 (3)	0.6100 (6)	0.0594 (9)
H11	0.0151	0.7370	0.5365	0.071*
C10	0.07602 (10)	0.6254 (3)	0.5276 (5)	0.0542 (8)
H10	0.0833	0.6511	0.3983	0.065*
C9	0.10598 (9)	0.5353 (3)	0.6367 (4)	0.0440 (6)
H9	0.1332	0.5002	0.5792	0.053*
N1	0.22005 (8)	0.7051 (3)	1.0551 (3)	0.0437 (5)
H1A	0.2120 (9)	0.6156 (18)	1.015 (4)	0.051 (8)*
N2	0.32649 (8)	0.9158 (3)	1.1201 (4)	0.0565 (6)
H2A	0.3349 (11)	1.005 (2)	1.157 (6)	0.072 (10)*
H2B	0.3463 (8)	0.843 (2)	1.104 (5)	0.058 (10)*
C1	0.26516 (8)	0.7347 (3)	1.0651 (4)	0.0409 (6)
H1	0.2864	0.6564	1.0415	0.049*
C2	0.28080 (8)	0.8822 (3)	1.1107 (4)	0.0398 (6)
C3	0.24702 (10)	0.9941 (3)	1.1417 (5)	0.0456 (6)
H3	0.2559	1.0947	1.1696	0.055*
C4	0.20121 (9)	0.9583 (3)	1.1315 (5)	0.0497 (7)
H4	0.1791	1.0339	1.1547	0.060*
C5	0.18779 (10)	0.8111 (3)	1.0872 (4)	0.0490 (7)
H5	0.1566	0.7857	1.0797	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0465 (10)	0.0357 (9)	0.0550 (11)	0.0014 (8)	0.0115 (9)	−0.0106 (9)
O2	0.0306 (8)	0.0482 (11)	0.0635 (13)	−0.0051 (7)	0.0052 (8)	−0.0112 (10)
O3	0.0363 (9)	0.0364 (9)	0.0406 (10)	−0.0005 (7)	−0.0030 (8)	−0.0090 (8)
O4	0.0340 (10)	0.0979 (18)	0.0530 (15)	0.0072 (10)	0.0054 (10)	0.0192 (13)
C6	0.0330 (11)	0.0254 (11)	0.0418 (15)	0.0032 (10)	0.0010 (11)	0.0034 (11)
C7	0.0303 (11)	0.0272 (12)	0.0354 (13)	−0.0011 (9)	0.0003 (10)	−0.0039 (10)
C14	0.0257 (10)	0.0318 (12)	0.0458 (15)	0.0023 (9)	0.0045 (10)	−0.0006 (12)
C19	0.0386 (13)	0.0416 (14)	0.0493 (16)	−0.0028 (11)	0.0037 (12)	0.0042 (14)
C18	0.0568 (16)	0.0475 (17)	0.061 (2)	−0.0075 (14)	0.0100 (15)	0.0128 (15)
C17	0.0579 (17)	0.0372 (15)	0.090 (3)	−0.0154 (13)	0.0123 (19)	0.0087 (17)
C16	0.0597 (18)	0.0397 (15)	0.077 (2)	−0.0144 (14)	0.0030 (16)	−0.0113 (16)
C15	0.0469 (13)	0.0384 (14)	0.0502 (17)	−0.0052 (11)	0.0011 (13)	−0.0033 (13)
C8	0.0296 (11)	0.0231 (11)	0.0448 (14)	−0.0029 (9)	−0.0041 (11)	−0.0049 (11)
C13	0.0356 (13)	0.0389 (13)	0.0590 (18)	0.0016 (11)	0.0024 (12)	−0.0019 (14)
C12	0.0342 (13)	0.0440 (16)	0.087 (3)	0.0088 (12)	−0.0051 (14)	−0.0078 (17)
C11	0.0566 (17)	0.0378 (15)	0.084 (3)	0.0088 (13)	−0.0290 (18)	−0.0016 (17)
C10	0.0696 (19)	0.0459 (16)	0.0470 (18)	0.0066 (15)	−0.0138 (15)	0.0057 (14)
C9	0.0464 (14)	0.0409 (15)	0.0448 (16)	0.0057 (12)	−0.0001 (13)	−0.0017 (13)
N1	0.0516 (13)	0.0386 (13)	0.0409 (13)	−0.0107 (11)	−0.0026 (10)	−0.0010 (11)
N2	0.0500 (14)	0.0500 (16)	0.0696 (17)	−0.0082 (13)	0.0021 (13)	−0.0076 (15)
C1	0.0495 (15)	0.0355 (13)	0.0378 (14)	0.0014 (11)	0.0012 (11)	0.0014 (12)
C2	0.0461 (13)	0.0421 (14)	0.0314 (13)	−0.0053 (12)	0.0012 (12)	−0.0002 (12)
C3	0.0622 (15)	0.0324 (12)	0.0422 (15)	−0.0013 (13)	0.0058 (14)	−0.0028 (13)
C4	0.0539 (15)	0.0450 (16)	0.0502 (16)	0.0059 (13)	0.0034 (14)	0.0017 (14)
C5	0.0473 (14)	0.0541 (16)	0.0456 (17)	−0.0038 (14)	0.0023 (13)	0.0029 (14)

Geometric parameters (Å, º)

O1—C6	1.237 (3)	C13—H13	0.9300
O2—C6	1.258 (3)	C12—C11	1.374 (5)
O3—C7	1.417 (3)	C12—H12	0.9300
O3—H3A	0.826 (10)	C11—C10	1.374 (4)
O4—H4A	0.816 (10)	C11—H11	0.9300
O4—H4B	0.820 (10)	C10—C9	1.382 (4)
C6—C7	1.560 (3)	C10—H10	0.9300
C7—C8	1.533 (3)	C9—H9	0.9300
C7—C14	1.533 (3)	N1—C5	1.328 (4)
C14—C15	1.384 (4)	N1—C1	1.331 (3)
C14—C19	1.384 (4)	N1—H1A	0.855 (10)
C19—C18	1.390 (4)	N2—C2	1.354 (3)
C19—H19	0.9300	N2—H2A	0.848 (10)
C18—C17	1.357 (5)	N2—H2B	0.858 (10)
C18—H18	0.9300	C1—C2	1.393 (4)
C17—C16	1.379 (5)	C1—H1	0.9300
C17—H17	0.9300	C2—C3	1.393 (4)
C16—C15	1.379 (4)	C3—C4	1.361 (4)
C16—H16	0.9300	C3—H3	0.9300
C15—H15	0.9300	C4—C5	1.370 (4)
C8—C9	1.385 (4)	C4—H4	0.9300
C8—C13	1.388 (3)	C5—H5	0.9300
C13—C12	1.384 (4)
C7—O3—H3A	106 (2)	C8—C13—H13	119.7
H4A—O4—H4B	107 (3)	C11—C12—C13	120.6 (3)
O1—C6—O2	124.7 (2)	C11—C12—H12	119.7
O1—C6—C7	118.69 (19)	C13—C12—H12	119.7
O2—C6—C7	116.5 (2)	C12—C11—C10	119.5 (3)
O3—C7—C8	105.64 (17)	C12—C11—H11	120.3
O3—C7—C14	111.62 (19)	C10—C11—H11	120.3
C8—C7—C14	109.68 (18)	C11—C10—C9	120.1 (3)
O3—C7—C6	110.14 (17)	C11—C10—H10	120.0
C8—C7—C6	109.4 (2)	C9—C10—H10	120.0
C14—C7—C6	110.29 (17)	C10—C9—C8	121.2 (3)
C15—C14—C19	118.2 (2)	C10—C9—H9	119.4
C15—C14—C7	120.3 (2)	C8—C9—H9	119.4
C19—C14—C7	121.4 (2)	C5—N1—C1	123.1 (2)
C14—C19—C18	120.2 (3)	C5—N1—H1A	119.4 (19)
C14—C19—H19	119.9	C1—N1—H1A	117.3 (19)
C18—C19—H19	119.9	C2—N2—H2A	119 (2)
C17—C18—C19	121.0 (3)	C2—N2—H2B	119 (2)
C17—C18—H18	119.5	H2A—N2—H2B	121 (3)
C19—C18—H18	119.5	N1—C1—C2	120.5 (2)
C18—C17—C16	119.2 (3)	N1—C1—H1	119.8
C18—C17—H17	120.4	C2—C1—H1	119.8
C16—C17—H17	120.4	N2—C2—C3	121.8 (2)
C17—C16—C15	120.5 (3)	N2—C2—C1	121.7 (2)
C17—C16—H16	119.8	C3—C2—C1	116.5 (2)
C15—C16—H16	119.8	C4—C3—C2	121.0 (2)
C16—C15—C14	120.8 (3)	C4—C3—H3	119.5
C16—C15—H15	119.6	C2—C3—H3	119.5
C14—C15—H15	119.6	C3—C4—C5	119.9 (3)
C9—C8—C13	118.1 (2)	C3—C4—H4	120.0
C9—C8—C7	124.1 (2)	C5—C4—H4	120.0
C13—C8—C7	117.8 (2)	N1—C5—C4	119.0 (3)
C12—C13—C8	120.5 (3)	N1—C5—H5	120.5
C12—C13—H13	119.7	C4—C5—H5	120.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4^i	0.83 (1)	1.89 (1)	2.714 (3)	173 (3)
O4—H4A···O2	0.82 (1)	1.92 (1)	2.726 (2)	171 (3)
O4—H4B···O1^i	0.82 (1)	1.99 (1)	2.795 (3)	168 (3)
N1—H1A···O2	0.86 (1)	1.83 (1)	2.658 (3)	163 (3)
N1—H1A···O3	0.86 (1)	2.52 (2)	3.070 (3)	123 (2)
N2—H2A···O1^ii	0.85 (1)	2.17 (2)	2.975 (3)	158 (3)

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