A new two-dimensional anionic cadmium(II) polymer constructed through thio­cyanate coordination bridges

A new cadmium-thio­cyanate complex, poly[4-(di­methyl­amino)­pyridin-1-ium [di-[mu]-thio­cyanato-[kappa]²N:S;[kappa]²S:N-thiocyanato-[kappa]N-cadmium(II)]], {(C₇H₁₁N₂)[Cd(NCS)₃]}_n, was synthesized by the reaction of cadmium thio­cyanate and 4-(di­methyl­amino)­pyridine hydro­chloride in aqueous solution. In the crystal structure, each Cd^II ion is square-pyramidally coordinated by three N and two S atoms from five different thio­cyanate ligands, four of which are bridging. The thio­cyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd₂(NCS)₂] building blocks, while the other links the building blocks and cations via N-H...S hydrogen bonds. The N-H...S hydrogen bonds and weak [pi]-[pi] stacking inter­actions are involved in the formation of both a two-dimensional network structure and 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: 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)pyridin-1-ium [di-µ-thiocyanato-κ²N:S;κ²S:N-thiocyanato-κN-cadmium(II)]]

Crystal data

(C7H11N2)[Cd(NCS)3]	F(000) = 808
Mr = 409.82	Dx = 1.791 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3435 reflections
a = 10.319 (2) Å	θ = 3.1–27.5°
b = 15.029 (3) Å	µ = 1.84 mm^−1
c = 9.954 (2) Å	T = 293 K
β = 100.02 (3)°	Block, colourless
V = 1520.1 (5) Å^3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	2752 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 27.5°, θmin = 3.4°
ω scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→16
Tmin = 0.710, Tmax = 0.710	l = −10→12
10426 measured reflections	3 standard reflections every 180 reflections
3435 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.032P)^2 + 0.9P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3435 reflections	Δρmax = 0.53 e Å^−3
177 parameters	Δρmin = −0.59 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

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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.21827 (2)	0.609886 (15)	0.47592 (2)	0.04188 (9)
S1	0.36975 (10)	0.70641 (7)	0.33989 (11)	0.0627 (3)
S2	−0.02131 (9)	0.39397 (6)	0.72857 (9)	0.0480 (2)
S3	0.46863 (11)	0.35482 (6)	0.33571 (11)	0.0597 (3)
N3	0.1993 (3)	0.7690 (2)	0.1105 (4)	0.0675 (9)
N4	0.1213 (3)	0.5299 (2)	0.6274 (3)	0.0640 (9)
N5	0.3278 (3)	0.4879 (2)	0.4419 (4)	0.0689 (10)
C8	0.2669 (4)	0.7421 (2)	0.2062 (4)	0.0497 (8)
C9	0.0617 (3)	0.4739 (2)	0.6669 (3)	0.0467 (8)
C10	0.3881 (3)	0.4338 (2)	0.3975 (4)	0.0495 (8)
N1	0.6231 (3)	0.4695 (2)	0.1293 (4)	0.0573 (9)
H1	0.591 (4)	0.434 (3)	0.168 (4)	0.069*
N2	0.8145 (3)	0.66154 (19)	−0.0523 (3)	0.0486 (7)
C1	0.6041 (3)	0.5552 (3)	0.1556 (4)	0.0551 (9)
H1A	0.5492	0.5703	0.2169	0.066*
C2	0.6629 (3)	0.6204 (2)	0.0949 (4)	0.0504 (8)
H2A	0.6462	0.6796	0.1128	0.060*
C3	0.7500 (3)	0.5992 (2)	0.0037 (3)	0.0402 (7)
C4	0.7638 (3)	0.5074 (2)	−0.0216 (4)	0.0486 (8)
H4A	0.8169	0.4893	−0.0830	0.058*
C5	0.7012 (4)	0.4459 (3)	0.0420 (4)	0.0579 (10)
H5A	0.7127	0.3858	0.0246	0.070*
C6	0.9108 (4)	0.6388 (3)	−0.1380 (4)	0.0647 (10)
H6A	0.8667	0.6123	−0.2213	0.097*
H6B	0.9735	0.5974	−0.0906	0.097*
H6C	0.9557	0.6917	−0.1586	0.097*
C7	0.7945 (5)	0.7557 (3)	−0.0293 (5)	0.0756 (13)
H7A	0.8445	0.7728	0.0574	0.113*
H7B	0.7028	0.7666	−0.0297	0.113*
H7C	0.8230	0.7898	−0.1003	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.05421 (15)	0.03550 (13)	0.03658 (14)	0.00519 (11)	0.00972 (10)	−0.00125 (10)
S1	0.0594 (6)	0.0675 (6)	0.0604 (6)	−0.0070 (5)	0.0079 (5)	0.0224 (5)
S2	0.0493 (5)	0.0560 (5)	0.0376 (4)	0.0023 (4)	0.0044 (4)	0.0063 (4)
S3	0.0775 (7)	0.0454 (5)	0.0609 (6)	0.0141 (5)	0.0257 (5)	0.0092 (4)
N3	0.076 (2)	0.067 (2)	0.061 (2)	−0.0017 (18)	0.0148 (18)	0.0270 (18)
N4	0.073 (2)	0.078 (2)	0.0396 (17)	−0.0204 (19)	0.0075 (15)	0.0076 (16)
N5	0.0493 (18)	0.0451 (18)	0.113 (3)	0.0096 (15)	0.0161 (19)	0.0021 (18)
C8	0.062 (2)	0.0413 (18)	0.050 (2)	−0.0018 (16)	0.0217 (18)	0.0068 (16)
C9	0.0480 (19)	0.062 (2)	0.0291 (17)	0.0053 (17)	0.0027 (14)	−0.0031 (15)
C10	0.0428 (18)	0.0409 (18)	0.063 (2)	0.0023 (15)	0.0038 (16)	0.0132 (17)
N1	0.0484 (18)	0.062 (2)	0.059 (2)	−0.0142 (15)	0.0016 (15)	0.0131 (16)
N2	0.0506 (16)	0.0477 (16)	0.0478 (17)	−0.0042 (13)	0.0099 (13)	−0.0011 (13)
C1	0.0416 (19)	0.070 (3)	0.053 (2)	−0.0035 (18)	0.0076 (16)	−0.0015 (19)
C2	0.0495 (19)	0.048 (2)	0.053 (2)	0.0039 (16)	0.0072 (16)	−0.0052 (16)
C3	0.0341 (15)	0.0455 (19)	0.0388 (18)	−0.0011 (13)	−0.0002 (13)	0.0004 (13)
C4	0.0475 (18)	0.050 (2)	0.048 (2)	0.0005 (15)	0.0063 (15)	−0.0040 (16)
C5	0.059 (2)	0.045 (2)	0.066 (3)	−0.0041 (17)	−0.0008 (19)	−0.0004 (18)
C6	0.064 (2)	0.068 (2)	0.067 (3)	−0.003 (2)	0.024 (2)	0.000 (2)
C7	0.095 (3)	0.049 (2)	0.090 (3)	−0.004 (2)	0.034 (3)	0.003 (2)

Geometric parameters (Å, º)

Cd1—N5	2.211 (3)	N2—C7	1.453 (5)
Cd1—N3^i	2.289 (3)	N2—C6	1.459 (5)
Cd1—N4	2.290 (3)	C1—C2	1.349 (5)
Cd1—S2^ii	2.6148 (13)	C1—H1A	0.9300
Cd1—S1	2.6678 (11)	C2—C3	1.421 (5)
S1—C8	1.641 (4)	C2—H2A	0.9300
S2—C9	1.654 (4)	C3—C4	1.413 (5)
S2—Cd1^ii	2.6148 (13)	C4—C5	1.348 (5)
S3—C10	1.629 (4)	C4—H4A	0.9300
N3—C8	1.151 (5)	C5—H5A	0.9300
N3—Cd1^iii	2.289 (3)	C6—H6A	0.9600
N4—C9	1.151 (4)	C6—H6B	0.9600
N5—C10	1.157 (5)	C6—H6C	0.9600
N1—C5	1.332 (5)	C7—H7A	0.9600
N1—C1	1.336 (5)	C7—H7B	0.9600
N1—H1	0.77 (4)	C7—H7C	0.9600
N2—C3	1.327 (4)
N5—Cd1—N3^i	147.94 (14)	C2—C1—H1A	119.4
N5—Cd1—N4	87.69 (13)	C1—C2—C3	120.5 (3)
N3^i—Cd1—N4	86.57 (13)	C1—C2—H2A	119.8
N5—Cd1—S2^ii	102.19 (10)	C3—C2—H2A	119.8
N3^i—Cd1—S2^ii	109.83 (9)	N2—C3—C4	122.8 (3)
N4—Cd1—S2^ii	97.55 (9)	N2—C3—C2	121.9 (3)
N5—Cd1—S1	90.73 (10)	C4—C3—C2	115.3 (3)
N3^i—Cd1—S1	88.96 (9)	C5—C4—C3	121.0 (3)
N4—Cd1—S1	168.89 (8)	C5—C4—H4A	119.5
S2^ii—Cd1—S1	93.54 (3)	C3—C4—H4A	119.5
C8—S1—Cd1	103.64 (13)	N1—C5—C4	121.1 (4)
C9—S2—Cd1^ii	96.28 (12)	N1—C5—H5A	119.4
C8—N3—Cd1^iii	131.4 (3)	C4—C5—H5A	119.4
C9—N4—Cd1	158.3 (3)	N2—C6—H6A	109.5
C10—N5—Cd1	164.7 (3)	N2—C6—H6B	109.5
N3—C8—S1	177.0 (3)	H6A—C6—H6B	109.5
N4—C9—S2	178.1 (3)	N2—C6—H6C	109.5
N5—C10—S3	177.8 (3)	H6A—C6—H6C	109.5
C5—N1—C1	120.8 (3)	H6B—C6—H6C	109.5
C5—N1—H1	121 (3)	N2—C7—H7A	109.5
C1—N1—H1	118 (3)	N2—C7—H7B	109.5
C3—N2—C7	121.7 (3)	H7A—C7—H7B	109.5
C3—N2—C6	121.5 (3)	N2—C7—H7C	109.5
C7—N2—C6	116.8 (3)	H7A—C7—H7C	109.5
N1—C1—C2	121.3 (4)	H7B—C7—H7C	109.5
N1—C1—H1A	119.4
N5—Cd1—S1—C8	115.60 (17)	Cd1^ii—S2—C9—N4	162 (11)
N3^i—Cd1—S1—C8	−96.46 (17)	Cd1—N5—C10—S3	−126 (9)
N4—Cd1—S1—C8	−162.7 (5)	C5—N1—C1—C2	0.1 (5)
S2^ii—Cd1—S1—C8	13.34 (14)	N1—C1—C2—C3	−1.8 (5)
N5—Cd1—N4—C9	−57.5 (9)	C7—N2—C3—C4	177.3 (4)
N3^i—Cd1—N4—C9	154.0 (9)	C6—N2—C3—C4	−3.8 (5)
S2^ii—Cd1—N4—C9	44.5 (9)	C7—N2—C3—C2	−3.3 (5)
S1—Cd1—N4—C9	−139.5 (7)	C6—N2—C3—C2	175.6 (3)
N3^i—Cd1—N5—C10	−120.7 (12)	C1—C2—C3—N2	−176.5 (3)
N4—Cd1—N5—C10	159.5 (12)	C1—C2—C3—C4	2.9 (5)
S2^ii—Cd1—N5—C10	62.3 (12)	N2—C3—C4—C5	177.0 (3)
S1—Cd1—N5—C10	−31.5 (12)	C2—C3—C4—C5	−2.4 (5)
Cd1^iii—N3—C8—S1	−26 (7)	C1—N1—C5—C4	0.4 (5)
Cd1—S1—C8—N3	−178 (100)	C3—C4—C5—N1	0.8 (5)
Cd1—N4—C9—S2	154 (10)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S3	0.77 (4)	2.56 (4)	3.298 (3)	164 (4)