3-(Pyridin-4-yl)acetyl­acetone: Cd^II and Hg^II compete for nitro­gen coordination

3-(Pyridin-4-yl)acetyl­acetone (HacacPy) acts as a pyridine-type ligand towards Cd^II and Hg^II halides. With CdBr₂, the one-dimensional polymer [Cd(μ-Br)₂(HacacPy)Cd(μ-Br)₂(HacacPy)₂]_∞ is obtained in which five- and six-coordinated Cd^II cations alternate in the chain direction. Reaction of HacacPy with HgBr₂ results in [Hg(μ-Br)Br(HacacPy)]_∞, a polymer in which each Hg^II centre is tetra­coordinated. In both compounds, each metal(II) cation is N-coordinated by at least one HacacPy ligand. Equimolar reaction between these Cd^II and Hg^II derivatives, either conducted in ethanol as solvent or via grinding in the solid state, leads to ligand redistribution and the formation of the well-ordered bimetallic polymer catena-poly[[bromido­mercury(II)]-μ-bromido-[aqua­bis­[4-hy­droxy-3-(pyridin-4-yl)pent-3-en-2-one]cadmium(II)]-di-μ-bromido], [CdHgBr₄(C₁₀H₁₁NO₂)₂(H₂O)]_n or [{HgBr}(μ-Br){(HacacPy)₂Cd(H₂O)}(μ-Br)₂]_∞. Hg^II and Cd^II cations alternate in the [100] direction. The HacacPy ligands do not bind to the Hg^II cations, which are tetra­coordinated by three bridging and one terminal bromide ligand. The Cd^II centres adopt an only slightly distorted octa­hedral coordination. Three bromide ligands link them in a (2 + 1) pattern to neighbouring Hg^II atoms; two HacacPy ligands in a cis configuration, acting as N-atom donors, and a terminal aqua ligand complete the coordination sphere. Classical O—H...Br hydrogen bonds stabilize the polymeric chain. O—H...O hydrogen bonds between aqua H atoms and the uncoordinated carbonyl group of an HacacPy ligand in a neighbouring strand in the c direction link the chains into layers in the (010) plane.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXS2013 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).

catena-Poly[[bromidomercury(II)]-µ-bromido-[aquabis[4-hydroxy-3-(pyridin-4-yl)pent-3-en-2-one]cadmium(II)]-di-µ-bromido]

Crystal data

[CdHgBr4(C10H11NO2)2(H2O)]	F(000) = 1864
Mr = 1005.04	Dx = 2.413 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.3985 (4) Å	Cell parameters from 8666 reflections
b = 16.4980 (9) Å	θ = 2.5–29.8°
c = 22.9089 (13) Å	µ = 12.12 mm^−1
β = 98.3739 (10)°	T = 100 K
V = 2766.5 (3) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.22 mm

Data collection

Bruker SMART CCD area detector diffractometer	6965 reflections with I > 2σ(I)
Radiation source: microsource	Rint = 0.077
/w scans	θmax = 30.7°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.152, Tmax = 0.176	k = −23→23
41116 measured reflections	l = −31→32
8192 independent reflections

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + 2.393P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
8192 reflections	Δρmax = 2.46 e Å^−3
314 parameters	Δρmin = −2.62 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. Intensity data were collected on a Bruker D8 goniometer with APEX CCD area detector in ω scan mode using Mo Kα radiation (λ = 0.71073 Å) from an Incoatec microsource with multilayer optics. A temperature of 100 (2) K was maintained with the help of an Oxford Cryostream 700 instrument. Data were integrated with SAINT-Plus (Bruker, 2009) and corrected for absorption by multi-scan methods with SADABS (Bruker, 2008). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008). Full-matrix least-square refinements based on F² were performed with SHELXL15 (Sheldrick, 2013; Sheldrick, 2015). Non-hydrogen atoms were assigned anisotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.68524 (4)	0.17451 (2)	0.22881 (2)	0.01122 (7)
Hg1	0.22664 (2)	0.07782 (2)	0.21609 (2)	0.01756 (5)
Br1	0.54434 (6)	0.03216 (2)	0.27445 (2)	0.01554 (9)
Br2	0.34237 (6)	0.20703 (3)	0.16500 (2)	0.01677 (9)
Br3	0.02521 (6)	0.14092 (3)	0.29030 (2)	0.01538 (9)
Br4	0.06595 (6)	−0.03192 (3)	0.15085 (2)	0.02262 (11)
O1	0.4826 (4)	0.42594 (19)	0.54933 (13)	0.0187 (7)
O2	0.1736 (4)	0.3680 (2)	0.51344 (14)	0.0196 (7)
H2A	0.244 (6)	0.405 (2)	0.527 (2)	0.024*
O3	1.2651 (4)	0.53508 (18)	0.04863 (13)	0.0161 (6)
O4	0.9732 (4)	0.60551 (18)	0.04417 (14)	0.0171 (6)
H4A	1.078 (4)	0.587 (3)	0.041 (2)	0.021*
O5	0.7288 (4)	0.0970 (2)	0.14901 (14)	0.0215 (7)
H5D	0.812 (6)	0.062 (3)	0.151 (2)	0.026*
H5E	0.646 (6)	0.085 (3)	0.1214 (18)	0.026*
N1	0.6150 (5)	0.2469 (2)	0.30959 (15)	0.0138 (7)
N2	0.8038 (5)	0.2825 (2)	0.18219 (16)	0.0153 (7)
C1	0.7395 (6)	0.4108 (3)	0.4984 (2)	0.0216 (10)
H1A	0.7901	0.4549	0.5245	0.032*
H1B	0.7502	0.4246	0.4574	0.032*
H1C	0.8073	0.3607	0.5094	0.032*
C2	0.5425 (6)	0.3988 (3)	0.50437 (18)	0.0150 (8)
C3	0.4233 (6)	0.3552 (2)	0.45993 (18)	0.0130 (8)
C4	0.2434 (6)	0.3410 (3)	0.46707 (19)	0.0148 (8)
C5	0.1121 (6)	0.2926 (3)	0.4263 (2)	0.0190 (9)
H5A	0.0926	0.2401	0.4444	0.028*
H5B	0.1611	0.2839	0.3893	0.028*
H5C	−0.0043	0.3217	0.4182	0.028*
C6	0.4950 (6)	0.3192 (3)	0.40736 (18)	0.0140 (8)
C7	0.4664 (7)	0.3558 (3)	0.35250 (19)	0.0196 (9)
H7	0.4061	0.4067	0.3474	0.023*
C8	0.5268 (7)	0.3175 (3)	0.30474 (19)	0.0192 (9)
H8	0.5041	0.3427	0.2671	0.023*
C9	0.6482 (6)	0.2128 (3)	0.36329 (18)	0.0178 (9)
H9	0.7135	0.1631	0.3676	0.021*
C10	0.5915 (6)	0.2471 (3)	0.41226 (18)	0.0159 (8)
H10	0.6187	0.2213	0.4496	0.019*
C11	1.3212 (6)	0.4032 (3)	0.0893 (2)	0.0202 (9)
H11A	1.4228	0.4059	0.0663	0.030*
H11B	1.2498	0.3540	0.0788	0.030*
H11C	1.3694	0.4022	0.1314	0.030*
C12	1.2011 (6)	0.4761 (3)	0.07605 (18)	0.0142 (8)
C13	1.0228 (6)	0.4790 (2)	0.09139 (17)	0.0126 (8)
C14	0.9127 (6)	0.5463 (3)	0.07306 (18)	0.0146 (8)
C15	0.7178 (6)	0.5540 (3)	0.0834 (2)	0.0186 (9)
H15A	0.6887	0.6112	0.0886	0.028*
H15B	0.7005	0.5236	0.1190	0.028*
H15C	0.6369	0.5320	0.0494	0.028*
C16	0.9488 (6)	0.4107 (3)	0.12313 (18)	0.0132 (8)
C17	0.9903 (6)	0.4013 (3)	0.18402 (19)	0.0185 (9)
H17	1.0692	0.4388	0.2066	0.022*
C18	0.9170 (6)	0.3377 (3)	0.21124 (19)	0.0183 (9)
H18	0.9477	0.3323	0.2528	0.022*
C19	0.7655 (7)	0.2911 (3)	0.1238 (2)	0.0256 (11)
H19	0.6882	0.2522	0.1022	0.031*
C20	0.8325 (8)	0.3536 (3)	0.0932 (2)	0.0280 (12)
H20	0.7991	0.3575	0.0517	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01266 (14)	0.01237 (14)	0.00929 (13)	−0.00074 (11)	0.00379 (11)	0.00038 (10)
Hg1	0.01380 (9)	0.01914 (9)	0.01978 (9)	−0.00108 (6)	0.00262 (7)	−0.00211 (6)
Br1	0.0132 (2)	0.01363 (19)	0.0191 (2)	0.00017 (15)	0.00026 (16)	0.00325 (15)
Br2	0.0140 (2)	0.0188 (2)	0.0174 (2)	0.00166 (16)	0.00197 (16)	0.00562 (16)
Br3	0.01242 (19)	0.0220 (2)	0.01179 (19)	0.00235 (16)	0.00190 (15)	0.00032 (15)
Br4	0.0205 (2)	0.0214 (2)	0.0244 (2)	0.00285 (18)	−0.00176 (18)	−0.00940 (18)
O1	0.0154 (15)	0.0303 (18)	0.0109 (14)	−0.0003 (13)	0.0036 (12)	−0.0047 (12)
O2	0.0132 (15)	0.0296 (19)	0.0167 (16)	−0.0016 (13)	0.0042 (12)	−0.0026 (13)
O3	0.0164 (15)	0.0186 (15)	0.0141 (14)	−0.0055 (12)	0.0049 (12)	0.0011 (12)
O4	0.0209 (16)	0.0120 (14)	0.0195 (16)	0.0009 (13)	0.0064 (13)	0.0022 (12)
O5	0.0157 (16)	0.0338 (19)	0.0138 (15)	0.0110 (14)	−0.0016 (13)	−0.0081 (14)
N1	0.0162 (18)	0.0157 (17)	0.0101 (16)	0.0008 (14)	0.0037 (13)	−0.0008 (13)
N2	0.0141 (17)	0.0181 (18)	0.0144 (17)	−0.0032 (14)	0.0038 (14)	0.0015 (14)
C1	0.013 (2)	0.032 (3)	0.020 (2)	−0.0016 (18)	0.0034 (18)	−0.0038 (19)
C2	0.018 (2)	0.015 (2)	0.0119 (19)	0.0009 (17)	0.0030 (16)	−0.0002 (16)
C3	0.015 (2)	0.0147 (19)	0.0099 (18)	0.0017 (16)	0.0046 (15)	−0.0013 (15)
C4	0.015 (2)	0.015 (2)	0.015 (2)	0.0032 (16)	0.0010 (16)	0.0009 (16)
C5	0.016 (2)	0.017 (2)	0.023 (2)	−0.0047 (17)	0.0014 (18)	−0.0014 (17)
C6	0.0112 (19)	0.016 (2)	0.015 (2)	−0.0028 (16)	0.0046 (16)	−0.0015 (16)
C7	0.028 (2)	0.017 (2)	0.014 (2)	0.0071 (19)	0.0071 (18)	0.0016 (16)
C8	0.032 (3)	0.016 (2)	0.011 (2)	0.0028 (18)	0.0074 (18)	0.0032 (16)
C9	0.021 (2)	0.019 (2)	0.013 (2)	0.0052 (18)	0.0009 (17)	0.0013 (16)
C10	0.020 (2)	0.019 (2)	0.0093 (19)	0.0045 (17)	0.0025 (16)	0.0016 (16)
C11	0.018 (2)	0.019 (2)	0.024 (2)	0.0012 (18)	0.0047 (18)	−0.0005 (18)
C12	0.015 (2)	0.015 (2)	0.0122 (19)	−0.0017 (16)	0.0010 (16)	−0.0045 (15)
C13	0.0128 (19)	0.0156 (19)	0.0092 (18)	−0.0048 (16)	0.0007 (15)	−0.0006 (15)
C14	0.016 (2)	0.016 (2)	0.0120 (19)	−0.0016 (17)	0.0037 (16)	−0.0029 (16)
C15	0.016 (2)	0.021 (2)	0.019 (2)	0.0008 (18)	0.0022 (17)	−0.0034 (18)
C16	0.0113 (19)	0.016 (2)	0.0134 (19)	0.0003 (15)	0.0051 (16)	0.0002 (15)
C17	0.026 (2)	0.015 (2)	0.013 (2)	−0.0051 (18)	−0.0005 (18)	0.0016 (16)
C18	0.024 (2)	0.017 (2)	0.013 (2)	−0.0061 (18)	−0.0012 (17)	−0.0018 (16)
C19	0.032 (3)	0.032 (3)	0.013 (2)	−0.016 (2)	0.0004 (19)	0.0013 (19)
C20	0.043 (3)	0.029 (3)	0.011 (2)	−0.018 (2)	−0.001 (2)	0.0019 (18)

Geometric parameters (Å, º)

Cd1—O5	2.292 (3)	C5—H5A	0.9800
Cd1—N2	2.315 (4)	C5—H5B	0.9800
Cd1—N1	2.324 (3)	C5—H5C	0.9800
Cd1—Br3^i	2.7542 (5)	C6—C10	1.382 (6)
Cd1—Br2	2.7892 (5)	C6—C7	1.383 (6)
Cd1—Br1	2.8306 (5)	C7—C8	1.392 (6)
Hg1—Br4	2.5312 (5)	C7—H7	0.9500
Hg1—Br3	2.6330 (5)	C8—H8	0.9500
Hg1—Br2	2.6342 (5)	C9—C10	1.376 (6)
Hg1—Br1	2.6390 (4)	C9—H9	0.9500
Br3—Cd1^ii	2.7542 (5)	C10—H10	0.9500
O1—C2	1.261 (5)	C11—C12	1.500 (6)
O2—C4	1.324 (5)	C11—H11A	0.9800
O2—H2A	0.829 (19)	C11—H11B	0.9800
O3—C12	1.285 (5)	C11—H11C	0.9800
O4—C14	1.295 (5)	C12—C13	1.414 (6)
O4—H4A	0.843 (19)	C13—C14	1.405 (6)
O5—H5D	0.846 (19)	C13—C16	1.488 (6)
O5—H5E	0.838 (19)	C14—C15	1.500 (6)
N1—C8	1.332 (5)	C15—H15A	0.9800
N1—C9	1.342 (5)	C15—H15B	0.9800
N2—C19	1.335 (5)	C15—H15C	0.9800
N2—C18	1.345 (5)	C16—C20	1.388 (6)
C1—C2	1.497 (6)	C16—C17	1.393 (6)
C1—H1A	0.9800	C17—C18	1.372 (6)
C1—H1B	0.9800	C17—H17	0.9500
C1—H1C	0.9800	C18—H18	0.9500
C2—C3	1.438 (6)	C19—C20	1.378 (6)
C3—C4	1.384 (6)	C19—H19	0.9500
C3—C6	1.507 (6)	C20—H20	0.9500
C4—C5	1.480 (6)
O5—Cd1—N2	87.41 (13)	H5A—C5—H5C	109.5
O5—Cd1—N1	174.61 (13)	H5B—C5—H5C	109.5
N2—Cd1—N1	96.64 (12)	C10—C6—C7	117.3 (4)
O5—Cd1—Br3^i	94.12 (8)	C10—C6—C3	120.8 (4)
N2—Cd1—Br3^i	90.67 (9)	C7—C6—C3	121.9 (4)
N1—Cd1—Br3^i	89.41 (9)	C6—C7—C8	119.5 (4)
O5—Cd1—Br2	84.95 (8)	C6—C7—H7	120.3
N2—Cd1—Br2	89.25 (9)	C8—C7—H7	120.3
N1—Cd1—Br2	91.53 (9)	N1—C8—C7	122.7 (4)
Br3^i—Cd1—Br2	179.063 (17)	N1—C8—H8	118.6
O5—Cd1—Br1	86.21 (9)	C7—C8—H8	118.6
N2—Cd1—Br1	173.61 (9)	N1—C9—C10	122.6 (4)
N1—Cd1—Br1	89.72 (9)	N1—C9—H9	118.7
Br3^i—Cd1—Br1	90.128 (15)	C10—C9—H9	118.7
Br2—Cd1—Br1	89.851 (15)	C9—C10—C6	120.2 (4)
Br4—Hg1—Br3	113.746 (16)	C9—C10—H10	119.9
Br4—Hg1—Br2	118.138 (17)	C6—C10—H10	119.9
Br3—Hg1—Br2	102.595 (15)	C12—C11—H11A	109.5
Br4—Hg1—Br1	113.707 (15)	C12—C11—H11B	109.5
Br3—Hg1—Br1	109.382 (15)	H11A—C11—H11B	109.5
Br2—Hg1—Br1	97.638 (14)	C12—C11—H11C	109.5
Hg1—Br1—Cd1	85.690 (14)	H11A—C11—H11C	109.5
Hg1—Br2—Cd1	86.626 (14)	H11B—C11—H11C	109.5
Hg1—Br3—Cd1^ii	108.057 (16)	O3—C12—C13	121.3 (4)
C4—O2—H2A	104 (4)	O3—C12—C11	117.1 (4)
C14—O4—H4A	99 (3)	C13—C12—C11	121.5 (4)
Cd1—O5—H5D	122 (4)	C14—C13—C12	118.2 (4)
Cd1—O5—H5E	124 (4)	C14—C13—C16	120.4 (4)
H5D—O5—H5E	109 (5)	C12—C13—C16	121.3 (4)
C8—N1—C9	117.7 (4)	O4—C14—C13	121.4 (4)
C8—N1—Cd1	123.1 (3)	O4—C14—C15	115.4 (4)
C9—N1—Cd1	118.8 (3)	C13—C14—C15	123.2 (4)
C19—N2—C18	116.8 (4)	C14—C15—H15A	109.5
C19—N2—Cd1	120.3 (3)	C14—C15—H15B	109.5
C18—N2—Cd1	122.9 (3)	H15A—C15—H15B	109.5
C2—C1—H1A	109.5	C14—C15—H15C	109.5
C2—C1—H1B	109.5	H15A—C15—H15C	109.5
H1A—C1—H1B	109.5	H15B—C15—H15C	109.5
C2—C1—H1C	109.5	C20—C16—C17	116.7 (4)
H1A—C1—H1C	109.5	C20—C16—C13	121.2 (4)
H1B—C1—H1C	109.5	C17—C16—C13	122.0 (4)
O1—C2—C3	120.2 (4)	C18—C17—C16	119.7 (4)
O1—C2—C1	119.3 (4)	C18—C17—H17	120.1
C3—C2—C1	120.4 (4)	C16—C17—H17	120.1
C4—C3—C2	120.1 (4)	N2—C18—C17	123.5 (4)
C4—C3—C6	118.9 (4)	N2—C18—H18	118.3
C2—C3—C6	120.8 (4)	C17—C18—H18	118.3
O2—C4—C3	122.1 (4)	N2—C19—C20	123.3 (4)
O2—C4—C5	113.0 (4)	N2—C19—H19	118.4
C3—C4—C5	124.8 (4)	C20—C19—H19	118.4
C4—C5—H5A	109.5	C19—C20—C16	120.0 (4)
C4—C5—H5B	109.5	C19—C20—H20	120.0
H5A—C5—H5B	109.5	C16—C20—H20	120.0
C4—C5—H5C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.83 (2)	1.80 (4)	2.504 (4)	141 (4)
O4—H4A···O3	0.84 (2)	1.62 (4)	2.441 (4)	165 (5)
O5—H5D···Br4^i	0.85 (2)	2.44 (5)	3.274 (3)	175 (4)
O5—H5E···O1^iii	0.84 (2)	1.91 (4)	2.732 (4)	168 (4)

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