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In the search for potential ferroelectric materials, molecular-based one-, two- and three-dimensional cadmium(II) organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature. A new cadmium dicyanamide complex, poly[4-dimethylamino-1-ethylpyridin-1-ium [tri-μ-dicyanamido-κ6N1:N5-cadmium(II)]], {(C9H15N2)[Cd(C2N3)3]}n, was synthesized by the reaction of 4-dimethylamino-1-ethylpyridin-1-ium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution. In the crystal structure, each CdII cation is octahedrally coordinated by six terminal N atoms from six anionic dicyanamide (dca) ligands. Neighbouring CdII cations are linked together by dicyanamide bridges to form a two-dimensional coordination polymer. The organic cations are not involved in the formation of the supramolecular network.
Supporting information
CCDC reference: 1412135
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Poly[4-dimethylamino-1-ethylpyridin-1-ium
[tri-µ-dicyanamido-
κ6N1:
N5-cadmium(II)]]
top
Crystal data top
(C9H15N2)[Cd(C2N3)3] | F(000) = 920 |
Mr = 461.78 | Dx = 1.569 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2c 2b | Cell parameters from 2313 reflections |
a = 7.7042 (15) Å | θ = 3.0–30.5° |
b = 14.457 (3) Å | µ = 1.14 mm−1 |
c = 17.549 (4) Å | T = 293 K |
V = 1954.5 (7) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.26 × 0.25 mm |
Data collection top
Rigaku SCXmini diffractometer | 1674 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −10→6 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −18→18 |
Tmin = 0.726, Tmax = 0.763 | l = −22→22 |
12742 measured reflections | 3 standard reflections every 180 reflections |
2313 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0288P)2 + 3.5336P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max < 0.001 |
2313 reflections | Δρmax = 0.71 e Å−3 |
135 parameters | Δρmin = −0.68 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0819 (12) |
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 | Uiso*/Ueq | Occ. (<1) |
N4 | 0.4868 (6) | 0.1538 (5) | 0.5628 (4) | 0.147 (3) | |
Cd1 | 1.0000 | 0.0000 | 0.5000 | 0.03462 (13) | |
C8 | 0.8972 (5) | 0.0452 (3) | 0.3147 (2) | 0.0455 (10) | |
N6 | 0.8310 (8) | 0.0675 (7) | 0.2500 | 0.103 (3) | |
C7 | 0.6357 (6) | 0.1231 (3) | 0.5438 (3) | 0.0554 (12) | |
N7 | 1.2099 (5) | 0.1165 (3) | 0.5082 (2) | 0.0505 (9) | |
N3 | 0.7743 (5) | 0.1009 (3) | 0.5357 (2) | 0.0561 (10) | |
N5 | 0.9464 (5) | 0.0313 (3) | 0.37423 (19) | 0.0535 (9) | |
C9 | 1.3433 (5) | 0.1308 (3) | 0.5305 (3) | 0.0511 (11) | |
N1 | −0.0430 (6) | 0.1777 (3) | 0.7500 | 0.0427 (11) | |
N2 | 0.3536 (6) | 0.3695 (3) | 0.7500 | 0.0426 (11) | |
C5 | −0.2009 (8) | 0.1208 (4) | 0.7500 | 0.0510 (15) | |
H5A | −0.2011 | 0.0813 | 0.7947 | 0.061* | 0.50 |
H5B | −0.2011 | 0.0813 | 0.7053 | 0.061* | 0.50 |
C3 | 0.2322 (7) | 0.3040 (4) | 0.7500 | 0.0367 (12) | |
C2 | 0.1607 (6) | 0.2682 (3) | 0.6814 (2) | 0.0430 (10) | |
H2 | 0.2064 | 0.2865 | 0.6348 | 0.052* | |
C1 | 0.0266 (5) | 0.2076 (3) | 0.6834 (2) | 0.0459 (10) | |
H1 | −0.0190 | 0.1858 | 0.6377 | 0.055* | |
C4 | 0.4247 (6) | 0.4055 (3) | 0.8219 (2) | 0.0540 (11) | |
H4A | 0.3315 | 0.4269 | 0.8537 | 0.081* | |
H4B | 0.5023 | 0.4558 | 0.8114 | 0.081* | |
H4C | 0.4867 | 0.3571 | 0.8478 | 0.081* | |
C6 | −0.3625 (10) | 0.1798 (5) | 0.7500 | 0.074 (2) | |
H6A | −0.4632 | 0.1407 | 0.7500 | 0.111* | |
H6B | −0.3635 | 0.2182 | 0.7053 | 0.111* | 0.50 |
H6C | −0.3635 | 0.2182 | 0.7947 | 0.111* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N4 | 0.036 (3) | 0.227 (7) | 0.178 (7) | 0.039 (3) | −0.032 (3) | −0.141 (6) |
Cd1 | 0.02607 (19) | 0.0542 (2) | 0.02363 (18) | 0.00032 (17) | −0.00107 (15) | −0.00130 (16) |
C8 | 0.030 (2) | 0.077 (3) | 0.029 (2) | 0.006 (2) | 0.0046 (16) | −0.001 (2) |
N6 | 0.053 (4) | 0.231 (9) | 0.024 (3) | 0.057 (5) | 0.000 | 0.000 |
C7 | 0.034 (2) | 0.073 (3) | 0.059 (3) | 0.006 (2) | −0.006 (2) | −0.024 (2) |
N7 | 0.0354 (19) | 0.065 (2) | 0.051 (2) | −0.0069 (16) | −0.0029 (17) | −0.0034 (18) |
N3 | 0.036 (2) | 0.073 (2) | 0.059 (2) | 0.0111 (18) | −0.0014 (18) | −0.014 (2) |
N5 | 0.056 (2) | 0.075 (2) | 0.0294 (18) | 0.000 (2) | −0.0025 (16) | 0.0042 (17) |
C9 | 0.032 (2) | 0.067 (3) | 0.054 (3) | 0.011 (2) | −0.0070 (19) | −0.020 (2) |
N1 | 0.046 (3) | 0.039 (2) | 0.043 (3) | 0.004 (2) | 0.000 | 0.000 |
N2 | 0.036 (3) | 0.057 (3) | 0.035 (2) | 0.001 (2) | 0.000 | 0.000 |
C5 | 0.047 (4) | 0.046 (3) | 0.060 (4) | −0.001 (3) | 0.000 | 0.000 |
C3 | 0.036 (3) | 0.043 (3) | 0.032 (3) | 0.007 (2) | 0.000 | 0.000 |
C2 | 0.053 (2) | 0.046 (2) | 0.030 (2) | 0.0033 (18) | 0.0053 (18) | −0.0016 (16) |
C1 | 0.054 (3) | 0.047 (2) | 0.036 (2) | 0.003 (2) | −0.0003 (19) | −0.0071 (18) |
C4 | 0.047 (2) | 0.072 (3) | 0.043 (2) | −0.004 (2) | 0.000 (2) | −0.008 (2) |
C6 | 0.056 (5) | 0.073 (5) | 0.094 (6) | 0.013 (4) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Cd1—N5i | 2.291 (3) | N2—C3 | 1.332 (7) |
Cd1—N5 | 2.291 (3) | N2—C4 | 1.471 (5) |
Cd1—N7 | 2.339 (4) | N2—C4v | 1.471 (5) |
Cd1—N7i | 2.339 (4) | C5—C6 | 1.509 (9) |
Cd1—N3 | 2.355 (4) | C5—H5A | 0.9700 |
Cd1—N3i | 2.355 (4) | C5—H5B | 0.9700 |
C7—N3 | 1.124 (5) | C3—C2 | 1.421 (5) |
N4—C7 | 1.275 (6) | C3—C2v | 1.421 (5) |
N4—C9ii | 1.286 (6) | C2—C1 | 1.355 (6) |
C8—N5 | 1.130 (5) | C2—H2 | 0.9300 |
C8—N6 | 1.285 (5) | C1—H1 | 0.9300 |
N6—C8iii | 1.285 (5) | C4—H4A | 0.9600 |
N7—C9 | 1.119 (5) | C4—H4B | 0.9600 |
C9—N4iv | 1.286 (6) | C4—H4C | 0.9600 |
N1—C1v | 1.357 (5) | C6—H6A | 0.9600 |
N1—C1 | 1.357 (5) | C6—H6B | 0.9600 |
N1—C5 | 1.469 (7) | C6—H6C | 0.9600 |
| | | |
C7—N4—C9ii | 124.6 (5) | C4—N2—C4v | 118.3 (5) |
N5i—Cd1—N5 | 180.00 (5) | N1—C5—C6 | 111.5 (5) |
N5i—Cd1—N7 | 87.62 (13) | N1—C5—H5A | 109.3 |
N5—Cd1—N7 | 92.38 (13) | C6—C5—H5A | 109.3 |
N5i—Cd1—N7i | 92.38 (13) | N1—C5—H5B | 109.3 |
N5—Cd1—N7i | 87.62 (13) | C6—C5—H5B | 109.3 |
N7—Cd1—N7i | 180.00 (13) | H5A—C5—H5B | 108.0 |
N5i—Cd1—N3 | 89.98 (14) | N2—C3—C2 | 122.1 (3) |
N5—Cd1—N3 | 90.02 (14) | N2—C3—C2v | 122.1 (3) |
N7—Cd1—N3 | 92.78 (14) | C2—C3—C2v | 115.8 (5) |
N7i—Cd1—N3 | 87.22 (14) | C1—C2—C3 | 120.6 (4) |
N5i—Cd1—N3i | 90.02 (14) | C1—C2—H2 | 119.7 |
N5—Cd1—N3i | 89.98 (14) | C3—C2—H2 | 119.7 |
N7—Cd1—N3i | 87.22 (14) | C2—C1—N1 | 122.0 (4) |
N7i—Cd1—N3i | 92.78 (14) | C2—C1—H1 | 119.0 |
N3—Cd1—N3i | 180.00 (18) | N1—C1—H1 | 119.0 |
N5—C8—N6 | 174.1 (6) | N2—C4—H4A | 109.5 |
C8iii—N6—C8 | 124.1 (6) | N2—C4—H4B | 109.5 |
N3—C7—N4 | 171.0 (5) | H4A—C4—H4B | 109.5 |
C9—N7—Cd1 | 142.2 (4) | N2—C4—H4C | 109.5 |
C7—N3—Cd1 | 155.8 (4) | H4A—C4—H4C | 109.5 |
C8—N5—Cd1 | 170.8 (4) | H4B—C4—H4C | 109.5 |
N7—C9—N4iv | 172.6 (5) | C5—C6—H6A | 109.5 |
C1v—N1—C1 | 119.0 (5) | C5—C6—H6B | 109.5 |
C1v—N1—C5 | 120.4 (3) | H6A—C6—H6B | 109.5 |
C1—N1—C5 | 120.4 (3) | C5—C6—H6C | 109.5 |
C3—N2—C4 | 120.8 (2) | H6A—C6—H6C | 109.5 |
C3—N2—C4v | 120.8 (2) | H6B—C6—H6C | 109.5 |
| | | |
N5—C8—N6—C8iii | 164 (6) | N7i—Cd1—N5—C8 | 42 (3) |
C9ii—N4—C7—N3 | −167 (4) | N3—Cd1—N5—C8 | −46 (3) |
N5i—Cd1—N7—C9 | 44.9 (6) | N3i—Cd1—N5—C8 | 134 (3) |
N5—Cd1—N7—C9 | −135.1 (6) | Cd1—N7—C9—N4iv | −108 (5) |
N7i—Cd1—N7—C9 | 147 (16) | C1v—N1—C5—C6 | 87.3 (4) |
N3—Cd1—N7—C9 | 134.8 (6) | C1—N1—C5—C6 | −87.3 (4) |
N3i—Cd1—N7—C9 | −45.2 (6) | C4—N2—C3—C2 | 179.8 (4) |
N4—C7—N3—Cd1 | 140 (4) | C4v—N2—C3—C2 | −2.5 (8) |
N5i—Cd1—N3—C7 | −105.0 (10) | C4—N2—C3—C2v | 2.5 (8) |
N5—Cd1—N3—C7 | 75.0 (10) | C4v—N2—C3—C2v | −179.8 (4) |
N7—Cd1—N3—C7 | 167.4 (10) | N2—C3—C2—C1 | −174.1 (4) |
N7i—Cd1—N3—C7 | −12.6 (10) | C2v—C3—C2—C1 | 3.4 (7) |
N3i—Cd1—N3—C7 | 12 (100) | C3—C2—C1—N1 | −0.9 (7) |
N6—C8—N5—Cd1 | 54 (8) | C1v—N1—C1—C2 | −1.8 (8) |
N5i—Cd1—N5—C8 | −14 (100) | C5—N1—C1—C2 | 172.8 (4) |
N7—Cd1—N5—C8 | −138 (3) | | |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z; (iii) x, y, −z+1/2; (iv) x+1, y, z; (v) x, y, −z+3/2. |
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