A new two-dimensional polymeric cadmium(II) complex containing dicyanamide bridging ligands

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 Cd^II cation is coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands to furnish a slightly distorted octa­hedral geometry. Neighbouring Cd^II 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.

Computing details

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)]]

Crystal data

(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) Å^3	0.18 × 0.16 × 0.12 mm

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0362P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cd1—N3^i	2.309 (3)	C8—H8A	0.9600
Cd1—N3^ii	2.309 (3)	C8—H8B	0.9600
Cd1—N4^iii	2.312 (3)	C8—H8C	0.9600
Cd1—N4	2.312 (3)	C9—C10	1.512 (5)
Cd1—N1^iii	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—N7^iv	2.307 (4)	C10—H10A	0.9600
Cd2—N6	2.320 (3)	C10—H10B	0.9600
Cd2—N6^iv	2.320 (3)	C10—H10C	0.9600
Cd2—N8	2.353 (4)	C11—N10	1.509 (4)
Cd2—N8^iv	2.353 (4)	C11—C12	1.510 (5)
N3—Cd1^v	2.309 (3)	C11—H11A	0.9700
N7—C6^vi	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—N7^vi	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
N7^vi—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	N3^i—Cd1—N3^ii	180.00 (15)
N10—C7—H7B	108.3	N3^i—Cd1—N4^iii	87.97 (13)
H7A—C7—H7B	107.4	N3^ii—Cd1—N4^iii	92.03 (13)
C7—C8—H8A	109.5	N3^i—Cd1—N4	92.02 (13)
C7—C8—H8B	109.5	N3^ii—Cd1—N4	87.98 (13)
H8A—C8—H8B	109.5	N4^iii—Cd1—N4	180.0
C7—C8—H8C	109.5	N3^i—Cd1—N1^iii	90.93 (13)
H8A—C8—H8C	109.5	N3^ii—Cd1—N1^iii	89.07 (13)
H8B—C8—H8C	109.5	N4^iii—Cd1—N1^iii	95.90 (13)
C10—C9—N10	115.3 (3)	N4—Cd1—N1^iii	84.10 (13)
C10—C9—H9A	108.5	N3^i—Cd1—N1	89.07 (13)
N10—C9—H9A	108.5	N3^ii—Cd1—N1	90.93 (13)
C10—C9—H9B	108.5	N4^iii—Cd1—N1	84.10 (13)
N10—C9—H9B	108.5	N4—Cd1—N1	95.90 (13)
H9A—C9—H9B	107.5	N1^iii—Cd1—N1	180.00 (14)
C9—C10—H10A	109.5	N7—Cd2—N7^iv	180.0
C9—C10—H10B	109.5	N7—Cd2—N6	89.33 (14)
H10A—C10—H10B	109.5	N7^iv—Cd2—N6	90.67 (14)
C9—C10—H10C	109.5	N7—Cd2—N6^iv	90.67 (14)
H10A—C10—H10C	109.5	N7^iv—Cd2—N6^iv	89.33 (14)
H10B—C10—H10C	109.5	N6—Cd2—N6^iv	180.0
N10—C11—C12	116.0 (3)	N7—Cd2—N8	90.05 (13)
N10—C11—H11A	108.3	N7^iv—Cd2—N8	89.95 (13)
C12—C11—H11A	108.3	N6—Cd2—N8	94.57 (13)
N10—C11—H11B	108.3	N6^iv—Cd2—N8	85.43 (13)
C12—C11—H11B	108.3	N7—Cd2—N8^iv	89.95 (13)
H11A—C11—H11B	107.4	N7^iv—Cd2—N8^iv	90.05 (13)
C11—C12—H12A	109.5	N6—Cd2—N8^iv	85.43 (13)
C11—C12—H12B	109.5	N6^iv—Cd2—N8^iv	94.57 (13)
H12A—C12—H12B	109.5	N8—Cd2—N8^iv	180.0
C11—C12—H12C	109.5	C1—N1—Cd1	130.3 (3)
H12A—C12—H12C	109.5	C2—N3—Cd1^v	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	C6^vi—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—Cd1^v	48 (9)
C1—N2B—C2—N3	−159 (6)	N2A—C2—N3—Cd1^v	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.