Penta­aqua­[2-(5-carboxyl­ato-2-oxido-1-pyridinio)acetato]zinc(II) monohydrate

In the title compound, [Zn(C₈H₅NO₅)(H₂O)₅]·H₂O, the Zn^II atom is coordinated by one O atom from the 2-(5-carboxyl­ato-2-oxidopyridinium-1-yl)acetate ligand and by five water mol­ecules, forming a distorted octa­hedral geometry. Coordinated and uncoordinated water mol­ecules form O—H...O hydrogen bonds, leading to a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.084
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF019_ALERT_1_A  _diffrn_standards_number is missing
            Number of standards used in measurement.
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1WB   ..  H1WB    ..       1.91 Ang.

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  C8      ..       5.19 su
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C8 H15 N O10 Zn
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         16

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         18
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O5W -ZN1 -O5  -C7    103.10  0.50   1.555   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         12

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

   4 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
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The pyridinium carboxylate ligands, containing both of carboxylate and quaternary ammonium groups, have been extensively employed to design and construct novel complexes due to its versatile coordination behavior to metal ions (Zhang et al., 2003; Szafran et al., 2006; Yang et al., 2010). Herein, we report the synthesis and crystal structure of a new complex, [ZnL(H₂O)₅].H₂O (LH₂ = 5-carboxy-1-carboxymethyl-2-oxidopyridinium; He & Feng, 2007).

As shown in Fig. 1, the metal center Zn^II atom is six-coordinated by one O atom from one L^2- ligand [Zn—O 2.1039 (16) Å] and five water molecules [Zn—O 2.0554 (17)–2.0988 (19) Å], to form a distorted octahdral geometry. Notably, only one O atom from the flexible carboxylic groups of L^2- ligand coordinates to the Zn^II ion. As shown in Fig. 2, the complexes connected with each other by the O—H···O hydrogen bonds generate a three-dimensional structure.

Related literature

For related structures, see: Jiang et al. (2009); Szafran et al. (2006); Yang et al. (2010); Zhang et al. (2003); He & Feng (2007).

S2. Experimental

All the starting materials and solvents were obtained commercially and were used without further purification. A mixture of N-carboxymethyl-2-oxo-pyridine-5-carboxylic acid (0.1972 g, 1 mmol), ZnNO₃ (0.1901 g, 1 mmol), and purified water (15 ml) was sealed in a 25 ml stainless steel reactor and kept at 393 K for 3 d. Then, the reactor was cooled to room temperature at a speed of 5 K/h. A large quantity of colorless single crystals were filtered out of the mixture with the yield of 85%.

S3. Refinement

The C-bound H atoms were positioned geometrically and included in the refinement using a riding model, with C—H = 0.93 or 0.97 Å, and with U_iso(H) = 1.2U_eq(C). The O-bound H atoms was located in a difference Fourier map and refined, with the distance restraint of O—H = 0.82 (2) Å, and with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. Three-dimensional framework with hydrogen bonding interactions.

Pentaaqua[2-(5-carboxylato-2-oxido-1-pyridinio)acetato]zinc(II) monohydrate

Crystal data

[Zn(C8H5NO5)(H2O)5]·H2O	F(000) = 760
Mr = 368.60	Dx = 1.826 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6642 reflections
a = 10.9584 (4) Å	θ = 1.9–27.6°
b = 7.5548 (4) Å	µ = 1.89 mm^−1
c = 16.6510 (7) Å	T = 293 K
β = 103.498 (3)°	Prism, colourless
V = 1340.43 (10) Å^3	0.36 × 0.09 × 0.05 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	3086 independent reflections
Radiation source: fine-focus sealed tube	2233 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
ω scans	θmax = 27.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.824, Tmax = 0.918	k = −9→8
19343 measured reflections	l = −21→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0382P)^2] where P = (Fo^2 + 2Fc^2)/3
3086 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.48 e Å^−3
18 restraints	Δρmin = −0.80 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn1	0.14951 (2)	0.39964 (4)	0.404996 (17)	0.02275 (11)
O1	−0.56142 (14)	0.8182 (2)	0.07024 (11)	0.0314 (4)
O1W	0.0969 (2)	0.0417 (3)	0.59084 (15)	0.0564 (6)
H1WA	0.1593 (19)	−0.021 (4)	0.592 (2)	0.068*
H1WB	0.038 (2)	−0.002 (4)	0.5579 (17)	0.068*
O2	−0.70407 (16)	0.6153 (2)	0.01860 (11)	0.0357 (5)
O2W	0.16338 (18)	0.1231 (2)	0.40753 (11)	0.0324 (5)
H2WA	0.149 (2)	0.061 (3)	0.3650 (11)	0.039*
H2WB	0.207 (2)	0.071 (3)	0.4456 (11)	0.039*
O3	−0.30374 (16)	0.1584 (2)	0.26291 (11)	0.0322 (4)
O3W	0.13340 (17)	0.6755 (3)	0.41312 (11)	0.0331 (5)
H3WA	0.183 (2)	0.732 (3)	0.4479 (12)	0.040*
H3WB	0.120 (2)	0.730 (3)	0.3697 (10)	0.040*
O4	−0.08994 (16)	0.4075 (2)	0.22554 (10)	0.0290 (4)
O4W	0.12338 (18)	0.3724 (2)	0.52419 (11)	0.0306 (4)
H4WA	0.092 (2)	0.452 (2)	0.5466 (16)	0.037*
H4WB	0.103 (2)	0.276 (2)	0.5380 (16)	0.037*
O5	−0.04711 (15)	0.3999 (2)	0.36330 (10)	0.0263 (4)
O5W	0.33859 (16)	0.4349 (3)	0.45253 (12)	0.0348 (5)
H5WA	0.400 (2)	0.396 (3)	0.4376 (16)	0.042*
H5WB	0.357 (2)	0.520 (3)	0.4830 (15)	0.042*
O6W	0.17072 (18)	0.3938 (2)	0.28435 (11)	0.0302 (4)
H6WB	0.2178 (19)	0.467 (3)	0.2718 (16)	0.036*
H6WA	0.1020 (16)	0.399 (3)	0.2526 (15)	0.036*
N1	−0.34860 (18)	0.4432 (3)	0.22449 (12)	0.0223 (5)
C1	−0.4197 (2)	0.5668 (3)	0.17514 (15)	0.0233 (6)
H1A	−0.3972	0.6854	0.1826	0.028*
C2	−0.5222 (2)	0.5226 (3)	0.11561 (14)	0.0224 (5)
C3	−0.5541 (2)	0.3417 (3)	0.10731 (15)	0.0287 (6)
H3A	−0.6260	0.3074	0.0687	0.034*
C4	−0.4824 (2)	0.2166 (3)	0.15441 (15)	0.0279 (6)
H4A	−0.5046	0.0981	0.1462	0.033*
C5	−0.3744 (2)	0.2628 (3)	0.21590 (15)	0.0248 (6)
C6	−0.2487 (2)	0.4933 (3)	0.29580 (14)	0.0269 (6)
H6A	−0.2699	0.4489	0.3455	0.032*
H6B	−0.2454	0.6214	0.2996	0.032*
C7	−0.1195 (2)	0.4249 (3)	0.29292 (15)	0.0216 (5)
C8	−0.6009 (2)	0.6622 (3)	0.06435 (14)	0.0240 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02172 (18)	0.0210 (2)	0.02425 (17)	0.00083 (12)	0.00280 (12)	−0.00019 (12)
O1	0.0270 (10)	0.0199 (11)	0.0432 (11)	−0.0037 (8)	−0.0001 (8)	0.0073 (9)
O1W	0.0464 (15)	0.0551 (16)	0.0705 (17)	0.0124 (12)	0.0194 (12)	0.0136 (13)
O2	0.0303 (11)	0.0272 (11)	0.0393 (11)	−0.0024 (8)	−0.0125 (8)	−0.0002 (8)
O2W	0.0466 (13)	0.0209 (11)	0.0242 (10)	0.0051 (8)	−0.0032 (9)	−0.0027 (8)
O3	0.0332 (10)	0.0268 (11)	0.0346 (10)	0.0082 (8)	0.0040 (8)	0.0064 (8)
O3W	0.0361 (11)	0.0223 (11)	0.0341 (11)	0.0003 (8)	−0.0053 (9)	−0.0004 (8)
O4	0.0275 (10)	0.0371 (11)	0.0215 (9)	0.0010 (8)	0.0042 (8)	0.0006 (8)
O4W	0.0394 (12)	0.0296 (12)	0.0237 (10)	0.0038 (9)	0.0093 (8)	−0.0017 (8)
O5	0.0196 (9)	0.0366 (11)	0.0205 (9)	0.0013 (7)	0.0003 (7)	0.0007 (8)
O5W	0.0203 (10)	0.0372 (13)	0.0448 (12)	0.0009 (8)	0.0036 (9)	−0.0134 (9)
O6W	0.0278 (11)	0.0356 (12)	0.0258 (10)	−0.0059 (8)	0.0035 (8)	0.0019 (8)
N1	0.0183 (11)	0.0221 (13)	0.0242 (11)	0.0009 (9)	0.0002 (8)	−0.0009 (9)
C1	0.0237 (14)	0.0203 (15)	0.0260 (13)	0.0004 (10)	0.0058 (11)	0.0006 (11)
C2	0.0210 (13)	0.0208 (14)	0.0239 (13)	0.0004 (11)	0.0026 (10)	−0.0001 (11)
C3	0.0243 (14)	0.0286 (16)	0.0298 (14)	−0.0037 (11)	−0.0004 (11)	−0.0039 (12)
C4	0.0286 (14)	0.0187 (14)	0.0339 (14)	−0.0023 (11)	0.0025 (11)	−0.0032 (12)
C5	0.0255 (13)	0.0245 (16)	0.0262 (13)	0.0031 (11)	0.0096 (11)	0.0031 (11)
C6	0.0263 (14)	0.0267 (16)	0.0247 (13)	0.0027 (12)	−0.0002 (11)	−0.0034 (11)
C7	0.0221 (13)	0.0142 (14)	0.0267 (13)	−0.0036 (10)	0.0021 (10)	−0.0005 (10)
C8	0.0225 (13)	0.0264 (16)	0.0223 (13)	0.0027 (11)	0.0034 (10)	0.0002 (11)

Geometric parameters (Å, º)

Zn1—O5W	2.0554 (17)	O5W—H5WA	0.821 (16)
Zn1—O6W	2.0759 (18)	O5W—H5WB	0.812 (16)
Zn1—O4W	2.0805 (18)	O6W—H6WB	0.816 (15)
Zn1—O2W	2.0945 (18)	O6W—H6WA	0.814 (16)
Zn1—O3W	2.0988 (19)	N1—C1	1.362 (3)
Zn1—O5	2.1039 (16)	N1—C5	1.392 (3)
O1—C8	1.251 (3)	N1—C6	1.464 (3)
O1W—H1WA	0.829 (17)	C1—C2	1.355 (3)
O1W—H1WB	0.812 (17)	C1—H1A	0.9300
O2—C8	1.257 (3)	C2—C3	1.409 (4)
O2W—H2WA	0.832 (15)	C2—C8	1.498 (3)
O2W—H2WB	0.802 (15)	C3—C4	1.356 (3)
O3—C5	1.246 (3)	C3—H3A	0.9300
O3W—H3WA	0.813 (15)	C4—C5	1.416 (3)
O3W—H3WB	0.816 (15)	C4—H4A	0.9300
O4—C7	1.245 (3)	C6—C7	1.518 (3)
O4W—H4WA	0.823 (15)	C6—H6A	0.9700
O4W—H4WB	0.809 (15)	C6—H6B	0.9700
O5—C7	1.267 (3)
O5W—Zn1—O6W	92.57 (8)	H6WB—O6W—H6WA	110 (2)
O5W—Zn1—O4W	89.79 (8)	C1—N1—C5	122.35 (19)
O6W—Zn1—O4W	172.96 (8)	C1—N1—C6	121.7 (2)
O5W—Zn1—O2W	93.41 (8)	C5—N1—C6	115.59 (19)
O6W—Zn1—O2W	88.53 (7)	C2—C1—N1	122.1 (2)
O4W—Zn1—O2W	84.70 (7)	C2—C1—H1A	118.9
O5W—Zn1—O3W	86.50 (7)	N1—C1—H1A	118.9
O6W—Zn1—O3W	96.52 (7)	C1—C2—C3	117.1 (2)
O4W—Zn1—O3W	90.25 (7)	C1—C2—C8	120.8 (2)
O2W—Zn1—O3W	174.95 (8)	C3—C2—C8	122.0 (2)
O5W—Zn1—O5	171.74 (7)	C4—C3—C2	121.5 (2)
O6W—Zn1—O5	91.03 (7)	C4—C3—H3A	119.3
O4W—Zn1—O5	87.51 (7)	C2—C3—H3A	119.3
O2W—Zn1—O5	94.10 (7)	C3—C4—C5	121.4 (2)
O3W—Zn1—O5	85.71 (6)	C3—C4—H4A	119.3
H1WA—O1W—H1WB	107 (3)	C5—C4—H4A	119.3
Zn1—O2W—H2WA	123.1 (17)	O3—C5—N1	118.3 (2)
Zn1—O2W—H2WB	122.1 (18)	O3—C5—C4	126.2 (2)
H2WA—O2W—H2WB	111 (2)	N1—C5—C4	115.5 (2)
Zn1—O3W—H3WA	120.8 (18)	N1—C6—C7	114.4 (2)
Zn1—O3W—H3WB	116.6 (19)	N1—C6—H6A	108.7
H3WA—O3W—H3WB	109 (2)	C7—C6—H6A	108.7
Zn1—O4W—H4WA	121.7 (18)	N1—C6—H6B	108.7
Zn1—O4W—H4WB	118.0 (19)	C7—C6—H6B	108.7
H4WA—O4W—H4WB	111 (2)	H6A—C6—H6B	107.6
C7—O5—Zn1	132.66 (16)	O4—C7—O5	125.4 (2)
Zn1—O5W—H5WA	131.2 (19)	O4—C7—C6	120.3 (2)
Zn1—O5W—H5WB	114.9 (18)	O5—C7—C6	114.1 (2)
H5WA—O5W—H5WB	112 (2)	O1—C8—O2	124.0 (2)
Zn1—O6W—H6WB	117.0 (19)	O1—C8—C2	118.4 (2)
Zn1—O6W—H6WA	109.4 (19)	O2—C8—C2	117.6 (2)
O5W—Zn1—O5—C7	103.1 (5)	C1—N1—C5—C4	−2.3 (3)
O6W—Zn1—O5—C7	−12.8 (2)	C6—N1—C5—C4	171.2 (2)
O4W—Zn1—O5—C7	174.1 (2)	C3—C4—C5—O3	178.9 (2)
O2W—Zn1—O5—C7	−101.4 (2)	C3—C4—C5—N1	0.5 (4)
O3W—Zn1—O5—C7	83.6 (2)	C1—N1—C6—C7	−121.4 (2)
C5—N1—C1—C2	1.6 (4)	C5—N1—C6—C7	65.1 (3)
C6—N1—C1—C2	−171.5 (2)	Zn1—O5—C7—O4	21.6 (4)
N1—C1—C2—C3	1.0 (3)	Zn1—O5—C7—C6	−154.06 (16)
N1—C1—C2—C8	177.9 (2)	N1—C6—C7—O4	32.4 (3)
C1—C2—C3—C4	−2.8 (4)	N1—C6—C7—O5	−151.6 (2)
C8—C2—C3—C4	−179.6 (2)	C1—C2—C8—O1	9.1 (3)
C2—C3—C4—C5	2.1 (4)	C3—C2—C8—O1	−174.2 (2)
C1—N1—C5—O3	179.1 (2)	C1—C2—C8—O2	−170.0 (2)
C6—N1—C5—O3	−7.4 (3)	C3—C2—C8—O2	6.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^i	0.83 (2)	2.25 (2)	2.972 (3)	145 (3)
O1W—H1WB···O2W^ii	0.81 (2)	2.58 (3)	3.118 (3)	125 (3)
O2W—H2WA···O4^iii	0.83 (2)	1.89 (2)	2.716 (2)	169 (3)
O2W—H2WB···O2^i	0.80 (2)	1.96 (2)	2.742 (2)	163 (2)
O3W—H3WA···O2^iv	0.81 (2)	1.89 (2)	2.701 (2)	173 (2)
O3W—H3WB···O4^v	0.82 (2)	2.04 (2)	2.849 (2)	170 (3)
O4W—H4WA···O5^vi	0.82 (2)	2.02 (2)	2.810 (2)	160 (3)
O5W—H5WA···O1^iii	0.82 (2)	1.90 (2)	2.705 (2)	166 (3)
O5W—H5WB···O1^iv	0.81 (2)	1.95 (2)	2.742 (2)	164 (3)
O6W—H6WB···O3^v	0.82 (2)	1.89 (2)	2.697 (3)	171 (3)

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