A novel one-dimensional tubular cadmium(II) coordination polymer based on 5-(carboxyl­atometh­oxy)benzene-1,3-di­carboxyl­ate containing 4-amino­pyridinium ions

A novel coordination polymer, poly[4-amino­pyridinium [di­aqua­[μ₃-5-(carboxyl­atometh­oxy)benzene-1,3-di­carboxyl­ato]cadmium(II)] dihydrate], {(C₅H₇N₂)[Cd(C₁₀H₅O₇)(H₂O)₂]·2H₂O}_n or {(HpAPy)[Cd(OABDC)(H₂O)₂]·2H₂O}_n [HpAPy is 4-amino­pyridinium and H₃OABDC is 5-(carb­oxy­meth­oxy)benzene-1,3-di­carb­oxy­lic acid], was synthesized under hydro­thermal conditions. Single-crystal analysis revealed that the anionic complex has a centrosymmetric one-dimensional tub­ular arrangement. The pyridine N atom of the 4-amino­pyridine mol­ecule is proton­ated and this cation balances the charge of the tubular anionic coordination polymer. Neighbouring tubes are crosslinked into a three-dimensional framework through multiple hy­dro­gen bonds involving solvent water mol­ecules and OABDC³⁻ ligands.

Computing details

Data collection: SMART (Bruker 2003); cell refinement: SMART (Bruker 2003); data reduction: SAINT (Bruker 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[4-aminopyridinium [diaqua[µ₃-5-(carboxylatomethoxy)benzene-1,3-dicarboxylato]cadmium(II)] dihydrate]

Crystal data

(C5H7N2)[Cd(C10H5O7)(H2O)2]·2H2O	F(000) = 1040
Mr = 516.74	Dx = 1.892 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.6330 (9) Å	Cell parameters from 5042 reflections
b = 22.831 (3) Å	θ = 2.2–28.2°
c = 12.5639 (12) Å	µ = 1.27 mm^−1
β = 124.061 (5)°	T = 293 K
V = 1813.9 (4) Å^3	Plan, colorless
Z = 4	0.32 × 0.19 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3378 independent reflections
Radiation source: fine-focus sealed tube	3111 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
phi and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker 2003)	h = −9→9
Tmin = 0.748, Tmax = 0.938	k = −27→20
9391 measured reflections	l = −15→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0205P)^2 + 1.7606P] where P = (Fo^2 + 2Fc^2)/3
3378 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.38 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 > 2sigma(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
Cd1	0.36956 (3)	0.843899 (8)	−0.193156 (17)	0.02262 (7)
O1	0.6153 (3)	0.91537 (8)	−0.05618 (16)	0.0292 (4)
O2	0.6185 (3)	0.83260 (8)	0.03349 (18)	0.0296 (4)
O3	0.8671 (3)	1.12550 (10)	0.07663 (19)	0.0405 (5)
O4	0.9262 (3)	1.10200 (9)	0.26378 (18)	0.0336 (5)
O5	1.2531 (3)	1.02772 (8)	0.31654 (17)	0.0274 (4)
O6	1.2991 (3)	0.87236 (9)	0.61330 (17)	0.0328 (5)
O7	1.2302 (4)	0.79265 (9)	0.49319 (19)	0.0387 (5)
O8	0.6288 (3)	0.78678 (10)	−0.1825 (2)	0.0403 (5)
H8A	0.7471	0.7896	−0.1106	0.060*
H8B	0.6503	0.7850	−0.2412	0.060*
O9	0.1932 (3)	0.75911 (9)	−0.21459 (19)	0.0366 (5)
H9A	0.2130	0.7416	−0.1493	0.055*
H9B	0.1661	0.7351	−0.2721	0.055*
C1	0.6947 (4)	0.88223 (12)	0.0408 (2)	0.0244 (6)
C2	0.8871 (4)	0.90230 (11)	0.1675 (2)	0.0212 (5)
C3	0.9758 (4)	0.95718 (12)	0.1765 (2)	0.0234 (6)
H3	0.9183	0.9813	0.1048	0.028*
C4	1.1515 (4)	0.97514 (11)	0.2944 (2)	0.0221 (5)
C5	1.2365 (4)	0.93926 (11)	0.4014 (2)	0.0225 (6)
H5	1.3537	0.9516	0.4800	0.027*
C6	1.1471 (4)	0.88507 (11)	0.3917 (2)	0.0216 (5)
C7	0.9732 (4)	0.86674 (12)	0.2740 (2)	0.0224 (5)
H7	0.9142	0.8301	0.2670	0.027*
C8	1.1710 (4)	1.06869 (12)	0.2145 (3)	0.0273 (6)
H8C	1.1399	1.0482	0.1381	0.033*
H8D	1.2799	1.0974	0.2363	0.033*
C9	0.9724 (4)	1.10101 (12)	0.1824 (3)	0.0262 (6)
C10	1.2332 (4)	0.84705 (12)	0.5091 (2)	0.0252 (6)
N1	0.4150 (4)	0.96019 (12)	0.1140 (2)	0.0447 (7)
H1A	0.4385	0.9961	0.1047	0.067*
H1B	0.3335	0.9360	0.0536	0.067*
N2	0.7573 (4)	0.88886 (13)	0.4708 (2)	0.0446 (7)
H2N	0.8302	0.8740	0.5472	0.067*
C11	0.5282 (5)	0.93762 (13)	0.2305 (3)	0.0311 (6)
C12	0.6807 (5)	0.97066 (14)	0.3373 (3)	0.0366 (7)
H12	0.7048	1.0097	0.3280	0.044*
C13	0.7910 (5)	0.94477 (15)	0.4533 (3)	0.0424 (8)
H13	0.8942	0.9663	0.5239	0.051*
C14	0.6161 (5)	0.85641 (15)	0.3724 (3)	0.0428 (8)
H14	0.5953	0.8177	0.3861	0.051*
C15	0.5020 (5)	0.87861 (14)	0.2528 (3)	0.0360 (7)
H15	0.4052	0.8550	0.1843	0.043*
O10	0.0458 (3)	0.79050 (10)	0.0480 (2)	0.0421 (5)
H10A	0.1123	0.7646	0.0348	0.063*
H10B	0.0621	0.8229	0.0205	0.063*
O11	0.7362 (4)	0.71619 (10)	0.1371 (2)	0.0498 (6)
H11A	0.6708	0.7476	0.0991	0.075*
H11B	0.8681	0.7224	0.1752	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02148 (12)	0.02322 (12)	0.01727 (11)	−0.00099 (8)	0.00724 (9)	0.00012 (7)
O1	0.0292 (10)	0.0305 (11)	0.0171 (9)	−0.0027 (8)	0.0062 (8)	0.0007 (8)
O2	0.0276 (10)	0.0268 (11)	0.0243 (10)	−0.0067 (8)	0.0084 (9)	−0.0023 (8)
O3	0.0415 (13)	0.0406 (13)	0.0268 (11)	0.0063 (10)	0.0115 (10)	0.0115 (10)
O4	0.0294 (11)	0.0429 (12)	0.0273 (10)	0.0079 (9)	0.0152 (9)	0.0025 (9)
O5	0.0253 (10)	0.0216 (10)	0.0263 (10)	−0.0011 (8)	0.0089 (8)	0.0033 (8)
O6	0.0411 (12)	0.0370 (12)	0.0162 (9)	0.0040 (9)	0.0135 (9)	0.0029 (8)
O7	0.0549 (14)	0.0259 (11)	0.0290 (11)	−0.0007 (10)	0.0196 (10)	0.0035 (9)
O8	0.0390 (12)	0.0486 (13)	0.0333 (11)	0.0118 (10)	0.0202 (10)	0.0030 (10)
O9	0.0499 (13)	0.0287 (11)	0.0337 (11)	−0.0127 (10)	0.0249 (10)	−0.0066 (9)
C1	0.0190 (13)	0.0329 (16)	0.0187 (13)	0.0005 (11)	0.0090 (11)	−0.0035 (11)
C2	0.0187 (13)	0.0250 (14)	0.0177 (12)	0.0027 (11)	0.0089 (11)	−0.0012 (10)
C3	0.0240 (13)	0.0258 (14)	0.0191 (12)	0.0040 (11)	0.0112 (11)	0.0040 (11)
C4	0.0198 (13)	0.0214 (13)	0.0259 (13)	0.0011 (10)	0.0133 (11)	−0.0011 (11)
C5	0.0195 (13)	0.0251 (14)	0.0169 (12)	0.0020 (10)	0.0065 (11)	−0.0029 (10)
C6	0.0231 (13)	0.0228 (13)	0.0192 (12)	0.0050 (11)	0.0121 (11)	0.0016 (10)
C7	0.0236 (13)	0.0213 (13)	0.0216 (13)	−0.0002 (11)	0.0121 (11)	−0.0029 (11)
C8	0.0295 (15)	0.0245 (14)	0.0312 (14)	−0.0007 (12)	0.0189 (13)	0.0035 (12)
C9	0.0272 (14)	0.0206 (13)	0.0256 (14)	−0.0045 (11)	0.0115 (12)	−0.0019 (11)
C10	0.0232 (14)	0.0291 (16)	0.0226 (14)	0.0009 (11)	0.0124 (12)	0.0027 (12)
N1	0.0489 (17)	0.0364 (15)	0.0333 (14)	0.0016 (13)	0.0135 (13)	0.0012 (12)
N2	0.0473 (17)	0.0564 (19)	0.0258 (13)	0.0177 (14)	0.0178 (13)	0.0093 (13)
C11	0.0292 (15)	0.0347 (17)	0.0291 (15)	0.0065 (12)	0.0162 (13)	−0.0009 (13)
C12	0.0363 (17)	0.0348 (17)	0.0365 (16)	0.0003 (14)	0.0191 (14)	−0.0080 (14)
C13	0.0385 (18)	0.050 (2)	0.0310 (16)	0.0052 (15)	0.0148 (14)	−0.0128 (15)
C14	0.046 (2)	0.0399 (19)	0.0452 (19)	0.0077 (15)	0.0273 (17)	0.0068 (15)
C15	0.0327 (17)	0.0334 (17)	0.0341 (16)	−0.0027 (13)	0.0139 (14)	−0.0030 (13)
O10	0.0505 (14)	0.0364 (12)	0.0462 (13)	0.0055 (10)	0.0313 (12)	0.0046 (10)
O11	0.0507 (14)	0.0451 (14)	0.0489 (14)	−0.0029 (11)	0.0251 (12)	0.0042 (11)

Geometric parameters (Å, º)

Cd1—O6^i	2.2716 (18)	C5—C6	1.385 (4)
Cd1—O4^ii	2.273 (2)	C5—H5	0.9300
Cd1—O9	2.2859 (19)	C6—C7	1.388 (4)
Cd1—O8	2.311 (2)	C6—C10	1.508 (4)
Cd1—O1	2.3509 (18)	C7—H7	0.9300
Cd1—O2	2.3927 (19)	C8—C9	1.523 (4)
Cd1—C1	2.719 (3)	C8—H8C	0.9700
O1—C1	1.264 (3)	C8—H8D	0.9700
O2—C1	1.253 (3)	N1—C11	1.319 (4)
O3—C9	1.236 (3)	N1—H1A	0.8606
O4—C9	1.255 (3)	N1—H1B	0.8589
O4—Cd1^ii	2.2729 (19)	N2—C14	1.322 (4)
O5—C4	1.370 (3)	N2—C13	1.344 (4)
O5—C8	1.418 (3)	N2—H2N	0.8648
O6—C10	1.251 (3)	C11—C12	1.405 (4)
O6—Cd1^iii	2.2715 (18)	C11—C15	1.413 (4)
O7—C10	1.256 (3)	C12—C13	1.345 (4)
O8—H8A	0.8502	C12—H12	0.9300
O8—H8B	0.8407	C13—H13	0.9300
O9—H9A	0.8461	C14—C15	1.345 (4)
O9—H9B	0.8362	C14—H14	0.9300
C1—C2	1.511 (3)	C15—H15	0.9300
C2—C7	1.377 (4)	O10—H10A	0.8528
C2—C3	1.398 (4)	O10—H10B	0.8548
C3—C4	1.391 (4)	O11—H11A	0.8506
C3—H3	0.9300	O11—H11B	0.8505
C4—C5	1.387 (4)
O6^i—Cd1—O4^ii	80.72 (7)	C5—C4—C3	120.5 (2)
O6^i—Cd1—O9	110.21 (7)	C6—C5—C4	120.2 (2)
O4^ii—Cd1—O9	91.35 (8)	C6—C5—H5	119.9
O6^i—Cd1—O8	84.54 (7)	C4—C5—H5	119.9
O4^ii—Cd1—O8	163.86 (7)	C5—C6—C7	119.6 (2)
O9—Cd1—O8	87.57 (8)	C5—C6—C10	120.3 (2)
O6^i—Cd1—O1	101.45 (7)	C7—C6—C10	120.1 (2)
O4^ii—Cd1—O1	96.86 (7)	C2—C7—C6	120.6 (2)
O9—Cd1—O1	148.19 (7)	C2—C7—H7	119.7
O8—Cd1—O1	92.47 (7)	C6—C7—H7	119.7
O6^i—Cd1—O2	149.20 (7)	O5—C8—C9	115.5 (2)
O4^ii—Cd1—O2	118.44 (7)	O5—C8—H8C	108.4
O9—Cd1—O2	94.11 (7)	C9—C8—H8C	108.4
O8—Cd1—O2	77.70 (7)	O5—C8—H8D	108.4
O1—Cd1—O2	55.07 (6)	C9—C8—H8D	108.4
O6^i—Cd1—C1	126.21 (8)	H8C—C8—H8D	107.5
O4^ii—Cd1—C1	110.66 (8)	O3—C9—O4	123.9 (3)
O9—Cd1—C1	121.37 (8)	O3—C9—C8	117.1 (2)
O8—Cd1—C1	83.43 (8)	O4—C9—C8	119.0 (2)
O1—Cd1—C1	27.67 (7)	O6—C10—O7	125.7 (2)
O2—Cd1—C1	27.44 (7)	O6—C10—C6	117.2 (2)
C1—O1—Cd1	92.61 (16)	O7—C10—C6	117.0 (2)
C1—O2—Cd1	90.95 (15)	C11—N1—H1A	117.8
C9—O4—Cd1^ii	111.27 (17)	C11—N1—H1B	115.4
C4—O5—C8	118.8 (2)	H1A—N1—H1B	126.5
C10—O6—Cd1^iii	134.75 (18)	C14—N2—C13	120.7 (3)
Cd1—O8—H8A	112.5	C14—N2—H2N	119.9
Cd1—O8—H8B	123.9	C13—N2—H2N	119.4
H8A—O8—H8B	108.9	N1—C11—C12	121.9 (3)
Cd1—O9—H9A	120.8	N1—C11—C15	121.0 (3)
Cd1—O9—H9B	120.1	C12—C11—C15	117.1 (3)
H9A—O9—H9B	110.6	C13—C12—C11	118.7 (3)
O2—C1—O1	121.2 (2)	C13—C12—H12	120.7
O2—C1—C2	119.3 (2)	C11—C12—H12	120.7
O1—C1—C2	119.5 (2)	N2—C13—C12	122.2 (3)
O2—C1—Cd1	61.62 (13)	N2—C13—H13	118.9
O1—C1—Cd1	59.73 (13)	C12—C13—H13	118.9
C2—C1—Cd1	175.40 (18)	N2—C14—C15	120.8 (3)
C7—C2—C3	120.2 (2)	N2—C14—H14	119.6
C7—C2—C1	119.9 (2)	C15—C14—H14	119.6
C3—C2—C1	119.9 (2)	C14—C15—C11	120.4 (3)
C4—C3—C2	119.0 (2)	C14—C15—H15	119.8
C4—C3—H3	120.5	C11—C15—H15	119.8
C2—C3—H3	120.5	H10A—O10—H10B	106.5
O5—C4—C5	114.6 (2)	H11A—O11—H11B	108.2
O5—C4—C3	124.9 (2)
O6^i—Cd1—O1—C1	−155.73 (16)	Cd1—C1—C2—C3	79 (2)
O4^ii—Cd1—O1—C1	122.39 (16)	C7—C2—C3—C4	−0.1 (4)
O9—Cd1—O1—C1	18.6 (2)	C1—C2—C3—C4	179.2 (2)
O8—Cd1—O1—C1	−70.81 (16)	C8—O5—C4—C5	−176.7 (2)
O2—Cd1—O1—C1	2.32 (15)	C8—O5—C4—C3	2.8 (4)
O6^i—Cd1—O2—C1	43.3 (2)	C2—C3—C4—O5	−179.8 (2)
O4^ii—Cd1—O2—C1	−80.06 (17)	C2—C3—C4—C5	−0.3 (4)
O9—Cd1—O2—C1	−173.83 (16)	O5—C4—C5—C6	179.6 (2)
O8—Cd1—O2—C1	99.56 (17)	C3—C4—C5—C6	0.1 (4)
O1—Cd1—O2—C1	−2.33 (15)	C4—C5—C6—C7	0.5 (4)
Cd1—O2—C1—O1	4.2 (3)	C4—C5—C6—C10	−177.4 (2)
Cd1—O2—C1—C2	−174.8 (2)	C3—C2—C7—C6	0.7 (4)
Cd1—O1—C1—O2	−4.2 (3)	C1—C2—C7—C6	−178.6 (2)
Cd1—O1—C1—C2	174.8 (2)	C5—C6—C7—C2	−1.0 (4)
O6^i—Cd1—C1—O2	−154.17 (14)	C10—C6—C7—C2	176.9 (2)
O4^ii—Cd1—C1—O2	112.24 (16)	C4—O5—C8—C9	75.2 (3)
O9—Cd1—C1—O2	7.21 (19)	Cd1^ii—O4—C9—O3	−1.3 (3)
O8—Cd1—C1—O2	−75.89 (16)	Cd1^ii—O4—C9—C8	177.78 (18)
O1—Cd1—C1—O2	175.9 (3)	O5—C8—C9—O3	−162.5 (2)
O6^i—Cd1—C1—O1	29.95 (19)	O5—C8—C9—O4	18.4 (4)
O4^ii—Cd1—C1—O1	−63.64 (17)	Cd1^iii—O6—C10—O7	−16.9 (5)
O9—Cd1—C1—O1	−168.67 (14)	Cd1^iii—O6—C10—C6	162.28 (18)
O8—Cd1—C1—O1	108.23 (16)	C5—C6—C10—O6	35.5 (4)
O2—Cd1—C1—O1	−175.9 (3)	C7—C6—C10—O6	−142.4 (3)
O6^i—Cd1—C1—C2	−52 (2)	C5—C6—C10—O7	−145.3 (3)
O4^ii—Cd1—C1—C2	−145 (2)	C7—C6—C10—O7	36.8 (4)
O9—Cd1—C1—C2	110 (2)	N1—C11—C12—C13	−179.7 (3)
O8—Cd1—C1—C2	27 (2)	C15—C11—C12—C13	−0.3 (4)
O1—Cd1—C1—C2	−82 (2)	C14—N2—C13—C12	1.9 (5)
O2—Cd1—C1—C2	102 (2)	C11—C12—C13—N2	−1.4 (5)
O2—C1—C2—C7	−1.7 (4)	C13—N2—C14—C15	−0.4 (5)
O1—C1—C2—C7	179.3 (2)	N2—C14—C15—C11	−1.3 (5)
Cd1—C1—C2—C7	−102 (2)	N1—C11—C15—C14	−179.0 (3)
O2—C1—C2—C3	179.0 (2)	C12—C11—C15—C14	1.6 (5)
O1—C1—C2—C3	−0.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O10^iv	0.85	2.02	2.863 (3)	172
O8—H8B···O11^v	0.84	1.97	2.809 (3)	173
O9—H9A···O7^vi	0.85	1.89	2.732 (3)	174
O9—H9B···O10^v	0.84	1.99	2.773 (3)	155
N2—H2N···O4^vii	0.86	2.11	2.824 (3)	140
N2—H2N···O11^viii	0.86	2.63	3.243 (4)	129
O10—H10A···O7^vi	0.85	1.82	2.673 (3)	175
O10—H10B···O3^ii	0.85	1.98	2.781 (3)	157
O11—H11B···O9^ix	0.85	2.10	2.946 (3)	174
O11—H11A···O2	0.85	2.06	2.873 (3)	160
N1—H1A···O1^ii	0.86	2.09	2.910 (3)	160
N1—H1B···O3^ii	0.86	2.05	2.902 (3)	174

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