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As part of an exploration of new coordination polymers, a cadmium-dicyanamide complex, namely poly[benzyltriethylammonium [tri-μ-dicyanamido-κ6N1:N5-cadmium(II)]], {(C13H22N)[Cd(C2N3)3]}n, has been synthesized by the reaction of benzyltriethylammonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution, and characterized by single-crystal X-ray diffraction at room temperature. In the crystal structure, each CdII cation is coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands to furnish a slightly distorted octahedral geometry. Neighbouring CdII cations are linked by dicyanamide bridges to construct a two-dimensional anionic layer coordination polymer. One amide N atom in the bridging dca ligand is disordered over two sites. The cations lie between the anionic frameworks and there are no hydrogen-bond interactions between the cations and anions. The organic cations are not involved in the formation of the supramolecular network.
Supporting information
CCDC reference: 1563912
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).
Poly[benzyltriethylammonium
[tri-µ-dicyanamido-
κ6N1:
N5-cadmium(II)]]
top
Crystal data top
(C13H22N)[Cd(C2N3)3] | Z = 2 |
Mr = 502.88 | F(000) = 508 |
Triclinic, P1 | Dx = 1.520 Mg m−3 |
a = 7.3585 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7960 (18) Å | Cell parameters from 11505 reflections |
c = 17.619 (3) Å | θ = 3.0–27.5° |
α = 79.56 (3)° | µ = 1.02 mm−1 |
β = 84.69 (3)° | T = 293 K |
γ = 78.96 (3)° | Bulk, colorless |
V = 1098.8 (4) Å3 | 0.18 × 0.16 × 0.12 mm |
Data collection top
Rigaku SCXmini diffractometer | 3230 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −9→9 |
Tmin = 0.832, Tmax = 0.885 | k = −11→11 |
11505 measured reflections | l = −22→22 |
5034 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0362P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.095 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.35 e Å−3 |
5034 reflections | Δρmin = −0.52 e Å−3 |
287 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b) |
0 restraints | Extinction coefficient: 0.015 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N2A | 1.008 (7) | 0.209 (9) | 0.565 (5) | 0.069 (18) | 0.31 (9) |
N2B | 1.052 (3) | 0.194 (2) | 0.527 (2) | 0.060 (6) | 0.69 (9) |
C1 | 0.8673 (6) | 0.2400 (4) | 0.5257 (2) | 0.0422 (10) | |
C2 | 1.1490 (6) | 0.2952 (5) | 0.5387 (3) | 0.0527 (11) | |
C3 | 0.3755 (6) | 0.5243 (4) | 0.3161 (2) | 0.0441 (10) | |
C4 | 0.3657 (5) | 0.5219 (4) | 0.1887 (2) | 0.0409 (9) | |
C5 | 0.8709 (7) | 0.2451 (5) | −0.0072 (3) | 0.0484 (11) | |
C6 | 1.1609 (6) | 0.2968 (5) | −0.0227 (3) | 0.0525 (11) | |
C7 | 0.5071 (6) | 0.0699 (5) | 0.1697 (2) | 0.0503 (11) | |
H7A | 0.4204 | 0.1681 | 0.1590 | 0.060* | |
H7B | 0.6312 | 0.0940 | 0.1600 | 0.060* | |
C8 | 0.4809 (7) | −0.0331 (5) | 0.1136 (2) | 0.0713 (15) | |
H8A | 0.5710 | −0.1283 | 0.1211 | 0.107* | |
H8B | 0.4965 | 0.0213 | 0.0617 | 0.107* | |
H8C | 0.3584 | −0.0581 | 0.1222 | 0.107* | |
C9 | 0.6043 (5) | −0.1565 (4) | 0.2742 (2) | 0.0483 (10) | |
H9A | 0.5838 | −0.1955 | 0.3289 | 0.058* | |
H9B | 0.5664 | −0.2288 | 0.2458 | 0.058* | |
C10 | 0.8095 (6) | −0.1581 (5) | 0.2566 (3) | 0.0706 (15) | |
H10A | 0.8332 | −0.1272 | 0.2020 | 0.106* | |
H10B | 0.8769 | −0.2621 | 0.2728 | 0.106* | |
H10C | 0.8489 | −0.0861 | 0.2839 | 0.106* | |
C11 | 0.5286 (6) | 0.1181 (4) | 0.3000 (2) | 0.0481 (10) | |
H11A | 0.4394 | 0.2150 | 0.2898 | 0.058* | |
H11B | 0.6496 | 0.1417 | 0.2806 | 0.058* | |
C12 | 0.5320 (7) | 0.0663 (5) | 0.3865 (3) | 0.0702 (14) | |
H12A | 0.4249 | 0.0199 | 0.4051 | 0.105* | |
H12B | 0.5309 | 0.1555 | 0.4109 | 0.105* | |
H12C | 0.6423 | −0.0096 | 0.3984 | 0.105* | |
C13 | 0.2811 (5) | −0.0201 (4) | 0.2750 (2) | 0.0408 (9) | |
H13A | 0.2539 | −0.0930 | 0.2442 | 0.049* | |
H13B | 0.2712 | −0.0690 | 0.3288 | 0.049* | |
C14 | 0.1359 (5) | 0.1248 (4) | 0.2633 (2) | 0.0413 (9) | |
C15 | 0.0674 (6) | 0.2007 (5) | 0.3255 (2) | 0.0572 (12) | |
H15 | 0.1120 | 0.1611 | 0.3742 | 0.069* | |
C16 | −0.1330 (6) | 0.3964 (5) | 0.2443 (3) | 0.0649 (13) | |
H16 | −0.2212 | 0.4881 | 0.2377 | 0.078* | |
C17 | −0.0669 (7) | 0.3349 (6) | 0.3151 (3) | 0.0687 (14) | |
H17 | −0.1128 | 0.3840 | 0.3572 | 0.082* | |
C18 | −0.0681 (6) | 0.3213 (5) | 0.1827 (3) | 0.0618 (13) | |
H18 | −0.1129 | 0.3617 | 0.1341 | 0.074* | |
C19 | 0.0639 (6) | 0.1858 (5) | 0.1930 (2) | 0.0532 (11) | |
H19 | 0.1050 | 0.1347 | 0.1512 | 0.064* | |
Cd1 | 0.5000 | 0.5000 | 0.5000 | 0.03740 (13) | |
Cd2 | 0.5000 | 0.5000 | 0.0000 | 0.03956 (13) | |
N1 | 0.7130 (5) | 0.2634 (4) | 0.5163 (2) | 0.0535 (9) | |
N3 | 1.2574 (5) | 0.3682 (4) | 0.5432 (2) | 0.0578 (10) | |
N4 | 0.4349 (5) | 0.4909 (4) | 0.37519 (19) | 0.0595 (10) | |
N5 | 0.2965 (5) | 0.5754 (4) | 0.25095 (19) | 0.0566 (10) | |
N6 | 0.4137 (5) | 0.4821 (4) | 0.13087 (19) | 0.0598 (10) | |
N7 | 0.7258 (5) | 0.6384 (4) | 0.0165 (2) | 0.0638 (11) | |
N8 | 0.7192 (5) | 0.2654 (4) | 0.0148 (2) | 0.0547 (10) | |
N9 | 1.0417 (6) | 0.2129 (5) | −0.0336 (3) | 0.0899 (16) | |
N10 | 0.4810 (4) | 0.0024 (3) | 0.25477 (17) | 0.0392 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N2A | 0.032 (13) | 0.07 (2) | 0.09 (3) | −0.024 (13) | −0.020 (15) | 0.048 (19) |
N2B | 0.036 (5) | 0.048 (5) | 0.098 (13) | −0.005 (4) | −0.013 (7) | −0.016 (6) |
C1 | 0.045 (3) | 0.036 (2) | 0.044 (2) | −0.006 (2) | −0.009 (2) | −0.0011 (19) |
C2 | 0.039 (3) | 0.050 (3) | 0.064 (3) | −0.005 (2) | −0.012 (2) | 0.006 (2) |
C3 | 0.057 (3) | 0.039 (2) | 0.041 (2) | −0.014 (2) | −0.002 (2) | −0.0137 (19) |
C4 | 0.048 (2) | 0.037 (2) | 0.037 (2) | −0.0118 (18) | −0.0069 (19) | 0.0040 (18) |
C5 | 0.048 (3) | 0.048 (3) | 0.054 (3) | −0.013 (2) | −0.004 (2) | −0.017 (2) |
C6 | 0.043 (3) | 0.060 (3) | 0.058 (3) | −0.009 (2) | 0.009 (2) | −0.024 (2) |
C7 | 0.057 (3) | 0.051 (3) | 0.038 (2) | −0.008 (2) | 0.005 (2) | 0.000 (2) |
C8 | 0.096 (4) | 0.072 (3) | 0.042 (3) | −0.004 (3) | 0.014 (3) | −0.020 (2) |
C9 | 0.052 (3) | 0.030 (2) | 0.061 (3) | −0.0052 (19) | −0.006 (2) | −0.006 (2) |
C10 | 0.053 (3) | 0.053 (3) | 0.103 (4) | −0.005 (2) | −0.004 (3) | −0.010 (3) |
C11 | 0.054 (3) | 0.035 (2) | 0.060 (3) | −0.0106 (19) | −0.014 (2) | −0.011 (2) |
C12 | 0.100 (4) | 0.054 (3) | 0.063 (3) | −0.008 (3) | −0.036 (3) | −0.017 (2) |
C13 | 0.046 (2) | 0.039 (2) | 0.039 (2) | −0.0151 (19) | −0.0016 (18) | −0.0040 (18) |
C14 | 0.044 (2) | 0.041 (2) | 0.039 (2) | −0.0147 (19) | −0.0001 (19) | −0.0043 (19) |
C15 | 0.057 (3) | 0.073 (3) | 0.038 (2) | −0.004 (2) | 0.001 (2) | −0.010 (2) |
C16 | 0.046 (3) | 0.055 (3) | 0.091 (4) | −0.003 (2) | −0.002 (3) | −0.014 (3) |
C17 | 0.068 (3) | 0.068 (3) | 0.071 (3) | 0.001 (3) | 0.008 (3) | −0.034 (3) |
C18 | 0.069 (3) | 0.053 (3) | 0.058 (3) | 0.000 (2) | −0.020 (3) | −0.001 (2) |
C19 | 0.057 (3) | 0.053 (3) | 0.048 (3) | −0.002 (2) | −0.005 (2) | −0.013 (2) |
Cd1 | 0.0338 (2) | 0.0476 (3) | 0.0326 (2) | −0.01028 (19) | −0.00500 (18) | −0.00673 (19) |
Cd2 | 0.0349 (3) | 0.0529 (3) | 0.0308 (2) | −0.0088 (2) | −0.00123 (18) | −0.0063 (2) |
N1 | 0.041 (2) | 0.051 (2) | 0.070 (3) | −0.0054 (18) | −0.008 (2) | −0.0132 (19) |
N3 | 0.044 (2) | 0.067 (2) | 0.062 (2) | −0.0242 (19) | −0.0067 (18) | 0.006 (2) |
N4 | 0.082 (3) | 0.063 (2) | 0.036 (2) | −0.009 (2) | −0.0104 (19) | −0.0152 (18) |
N5 | 0.065 (3) | 0.064 (2) | 0.038 (2) | 0.010 (2) | −0.0126 (18) | −0.0169 (18) |
N6 | 0.077 (3) | 0.067 (3) | 0.0310 (19) | −0.006 (2) | 0.0025 (19) | −0.0070 (18) |
N7 | 0.048 (2) | 0.074 (3) | 0.078 (3) | −0.019 (2) | −0.002 (2) | −0.027 (2) |
N8 | 0.044 (2) | 0.057 (2) | 0.062 (2) | −0.0072 (19) | −0.0043 (19) | −0.0070 (19) |
N9 | 0.047 (2) | 0.094 (3) | 0.149 (5) | −0.024 (2) | 0.022 (3) | −0.077 (3) |
N10 | 0.047 (2) | 0.0297 (15) | 0.0398 (18) | −0.0085 (14) | −0.0019 (15) | −0.0029 (13) |
Geometric parameters (Å, º) top
Cd1—N3i | 2.309 (3) | C8—H8A | 0.9600 |
Cd1—N3ii | 2.309 (3) | C8—H8B | 0.9600 |
Cd1—N4iii | 2.312 (3) | C8—H8C | 0.9600 |
Cd1—N4 | 2.312 (3) | C9—C10 | 1.512 (5) |
Cd1—N1iii | 2.343 (3) | C9—N10 | 1.514 (4) |
Cd1—N1 | 2.343 (3) | C9—H9A | 0.9700 |
Cd2—N7 | 2.307 (4) | C9—H9B | 0.9700 |
Cd2—N7iv | 2.307 (4) | C10—H10A | 0.9600 |
Cd2—N6 | 2.320 (3) | C10—H10B | 0.9600 |
Cd2—N6iv | 2.320 (3) | C10—H10C | 0.9600 |
Cd2—N8 | 2.353 (4) | C11—N10 | 1.509 (4) |
Cd2—N8iv | 2.353 (4) | C11—C12 | 1.510 (5) |
N3—Cd1v | 2.309 (3) | C11—H11A | 0.9700 |
N7—C6vi | 1.119 (5) | C11—H11B | 0.9700 |
N2A—C1 | 1.26 (3) | C12—H12A | 0.9600 |
N2A—C2 | 1.40 (2) | C12—H12B | 0.9600 |
N2B—C2 | 1.293 (17) | C12—H12C | 0.9600 |
N2B—C1 | 1.339 (17) | C13—C14 | 1.495 (5) |
C1—N1 | 1.136 (5) | C13—N10 | 1.522 (4) |
C2—N3 | 1.132 (5) | C13—H13A | 0.9700 |
C3—N4 | 1.135 (5) | C13—H13B | 0.9700 |
C3—N5 | 1.301 (5) | C14—C19 | 1.369 (5) |
C4—N6 | 1.140 (5) | C14—C15 | 1.391 (5) |
C4—N5 | 1.294 (5) | C15—C17 | 1.383 (6) |
C5—N8 | 1.139 (5) | C15—H15 | 0.9300 |
C5—N9 | 1.296 (5) | C16—C17 | 1.361 (6) |
C6—N7vi | 1.119 (5) | C16—C18 | 1.373 (6) |
C6—N9 | 1.296 (5) | C16—H16 | 0.9300 |
C7—C8 | 1.503 (5) | C17—H17 | 0.9300 |
C7—N10 | 1.518 (4) | C18—C19 | 1.382 (5) |
C7—H7A | 0.9700 | C18—H18 | 0.9300 |
C7—H7B | 0.9700 | C19—H19 | 0.9300 |
| | | |
C1—N2A—C2 | 117 (2) | C14—C15—H15 | 119.9 |
C2—N2B—C1 | 118.1 (8) | C17—C16—C18 | 119.2 (4) |
N1—C1—N2A | 156 (4) | C17—C16—H16 | 120.4 |
N1—C1—N2B | 169.6 (9) | C18—C16—H16 | 120.4 |
N3—C2—N2B | 168.9 (12) | C16—C17—C15 | 121.2 (4) |
N3—C2—N2A | 157 (4) | C16—C17—H17 | 119.4 |
N4—C3—N5 | 174.0 (5) | C15—C17—H17 | 119.4 |
N6—C4—N5 | 174.2 (5) | C16—C18—C19 | 119.8 (4) |
N8—C5—N9 | 176.0 (5) | C16—C18—H18 | 120.1 |
N7vi—C6—N9 | 174.4 (5) | C19—C18—H18 | 120.1 |
C8—C7—N10 | 116.0 (3) | C14—C19—C18 | 121.7 (4) |
C8—C7—H7A | 108.3 | C14—C19—H19 | 119.1 |
N10—C7—H7A | 108.3 | C18—C19—H19 | 119.1 |
C8—C7—H7B | 108.3 | N3i—Cd1—N3ii | 180.00 (15) |
N10—C7—H7B | 108.3 | N3i—Cd1—N4iii | 87.97 (13) |
H7A—C7—H7B | 107.4 | N3ii—Cd1—N4iii | 92.03 (13) |
C7—C8—H8A | 109.5 | N3i—Cd1—N4 | 92.02 (13) |
C7—C8—H8B | 109.5 | N3ii—Cd1—N4 | 87.98 (13) |
H8A—C8—H8B | 109.5 | N4iii—Cd1—N4 | 180.0 |
C7—C8—H8C | 109.5 | N3i—Cd1—N1iii | 90.93 (13) |
H8A—C8—H8C | 109.5 | N3ii—Cd1—N1iii | 89.07 (13) |
H8B—C8—H8C | 109.5 | N4iii—Cd1—N1iii | 95.90 (13) |
C10—C9—N10 | 115.3 (3) | N4—Cd1—N1iii | 84.10 (13) |
C10—C9—H9A | 108.5 | N3i—Cd1—N1 | 89.07 (13) |
N10—C9—H9A | 108.5 | N3ii—Cd1—N1 | 90.93 (13) |
C10—C9—H9B | 108.5 | N4iii—Cd1—N1 | 84.10 (13) |
N10—C9—H9B | 108.5 | N4—Cd1—N1 | 95.90 (13) |
H9A—C9—H9B | 107.5 | N1iii—Cd1—N1 | 180.00 (14) |
C9—C10—H10A | 109.5 | N7—Cd2—N7iv | 180.0 |
C9—C10—H10B | 109.5 | N7—Cd2—N6 | 89.33 (14) |
H10A—C10—H10B | 109.5 | N7iv—Cd2—N6 | 90.67 (14) |
C9—C10—H10C | 109.5 | N7—Cd2—N6iv | 90.67 (14) |
H10A—C10—H10C | 109.5 | N7iv—Cd2—N6iv | 89.33 (14) |
H10B—C10—H10C | 109.5 | N6—Cd2—N6iv | 180.0 |
N10—C11—C12 | 116.0 (3) | N7—Cd2—N8 | 90.05 (13) |
N10—C11—H11A | 108.3 | N7iv—Cd2—N8 | 89.95 (13) |
C12—C11—H11A | 108.3 | N6—Cd2—N8 | 94.57 (13) |
N10—C11—H11B | 108.3 | N6iv—Cd2—N8 | 85.43 (13) |
C12—C11—H11B | 108.3 | N7—Cd2—N8iv | 89.95 (13) |
H11A—C11—H11B | 107.4 | N7iv—Cd2—N8iv | 90.05 (13) |
C11—C12—H12A | 109.5 | N6—Cd2—N8iv | 85.43 (13) |
C11—C12—H12B | 109.5 | N6iv—Cd2—N8iv | 94.57 (13) |
H12A—C12—H12B | 109.5 | N8—Cd2—N8iv | 180.0 |
C11—C12—H12C | 109.5 | C1—N1—Cd1 | 130.3 (3) |
H12A—C12—H12C | 109.5 | C2—N3—Cd1v | 156.1 (4) |
H12B—C12—H12C | 109.5 | C3—N4—Cd1 | 161.6 (3) |
C14—C13—N10 | 116.4 (3) | C4—N5—C3 | 120.8 (4) |
C14—C13—H13A | 108.2 | C4—N6—Cd2 | 158.9 (3) |
N10—C13—H13A | 108.2 | C6vi—N7—Cd2 | 177.7 (4) |
C14—C13—H13B | 108.2 | C5—N8—Cd2 | 128.7 (3) |
N10—C13—H13B | 108.2 | C5—N9—C6 | 120.3 (4) |
H13A—C13—H13B | 107.3 | C11—N10—C9 | 110.7 (3) |
C19—C14—C15 | 117.9 (4) | C11—N10—C7 | 107.0 (3) |
C19—C14—C13 | 122.3 (4) | C9—N10—C7 | 110.9 (3) |
C15—C14—C13 | 119.8 (4) | C11—N10—C13 | 110.2 (3) |
C17—C15—C14 | 120.1 (4) | C9—N10—C13 | 107.6 (3) |
C17—C15—H15 | 119.9 | C7—N10—C13 | 110.4 (3) |
| | | |
C2—N2A—C1—N1 | −137.1 (17) | N2B—C1—N1—Cd1 | −137 (10) |
C2—N2B—C1—N1 | 148 (7) | N2B—C2—N3—Cd1v | 48 (9) |
C1—N2B—C2—N3 | −159 (6) | N2A—C2—N3—Cd1v | 173 (7) |
C1—N2A—C2—N3 | 133 (3) | C12—C11—N10—C9 | −52.6 (5) |
N10—C13—C14—C19 | 84.0 (5) | C12—C11—N10—C7 | −173.7 (4) |
N10—C13—C14—C15 | −97.0 (4) | C12—C11—N10—C13 | 66.2 (4) |
C19—C14—C15—C17 | −1.1 (6) | C10—C9—N10—C11 | −60.6 (5) |
C13—C14—C15—C17 | 179.9 (4) | C10—C9—N10—C7 | 58.1 (5) |
C18—C16—C17—C15 | 1.5 (7) | C10—C9—N10—C13 | 179.0 (3) |
C14—C15—C17—C16 | −0.8 (7) | C8—C7—N10—C11 | 175.5 (3) |
C17—C16—C18—C19 | −0.5 (7) | C8—C7—N10—C9 | 54.6 (5) |
C15—C14—C19—C18 | 2.1 (6) | C8—C7—N10—C13 | −64.6 (4) |
C13—C14—C19—C18 | −178.9 (4) | C14—C13—N10—C11 | 56.7 (4) |
C16—C18—C19—C14 | −1.4 (7) | C14—C13—N10—C9 | 177.5 (3) |
N2A—C1—N1—Cd1 | 91 (9) | C14—C13—N10—C7 | −61.3 (4) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x+1, y, z; (vi) −x+2, −y+1, −z. |
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