Aqua­bis(nicotinamide-κN)(thio­cyanato-κN)copper(II)

doi:10.1107/S1600536807068511

Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): m314.

Published online 2008 January 9. doi: 10.1107/S1600536807068511

PMCID: PMC2960236

Aquabis(nicotinamide-κN)(thiocyanato-κN)copper(II)

Chunyuan Li,^a^* Weijia Ding,^a and Changlun Shao^b

^aDepartment of Applied Chemistry, College of Science, South China Agricultural University, Guangzhou 510642, People’s Republic of China

^bSchool of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, People’s Republic of China

Correspondence e-mail: chunyuan-li/at/163.com

Received December 25, 2007; Accepted December 27, 2007.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

In the title compound, [Cu(NCS)₂(C₆H₆N₂O)₂(H₂O)], the Cu atom adopts a square-based pyramidal CuN₄O coordination, with the water O atom in the apical position. The pairs of N-bonded nicotinamide ligands and thiocyanate anions in the basal plane are in a trans configuration. In the crystal structure, the molecules are connected into sheets by N—H (...)

O and O—H

O hydrogen bonds.

Related literature

For related literature, see: Beatty (2001

); Aakeröy et al. (2004

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Object name is e-64-0m314-scheme1.jpg Object name is e-64-0m314-scheme1.jpg

Experimental

Crystal data

[Cu(NCS)₂(C₆H₆N₂O)₂(H₂O)]
M _r = 441.97
Monoclinic,
a = 11.078 (5) Å
b = 8.950 (4) Å
c = 18.702 (9) Å
β = 90.333 (8)°
V = 1854.3 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.43 mm⁻¹
T = 293 (2) K
0.42 × 0.35 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T _min = 0.542, T _max = 0.663
10592 measured reflections
4041 independent reflections
3292 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.090
S = 1.07
4041 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 1997

); cell refinement: SAINT (Bruker, 1997

); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008

); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008

); molecular graphics: SHELXTL (Bruker, 1997

); software used to prepare material for publication: SHELXTL.

Table 1

Selected bond lengths (Å)

Table 2

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068511/hb2684sup1.cif

Click here to view.^{(17K, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068511/hb2684Isup2.hkl

Click here to view.^{(198K, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the President’s Foundation of South China Agricultural University (grant Nos. 2006X013, 2007Y006 and 2007 K031) for financial support.

supplementary crystallographic information

Comment

Due to their inherent coordination and hydrogen bonding donor/acceptor functionalities, nicotinamide ligands have been used in crystal engineering to construct extended frameworks sustained both by hydrogen bonds and coordination bonds (Beatty 2001; Christer et al., 2004). In this paper, we report the synthesis and crystal structure of the title compound, (I).

In compound (I), the metal center occupies a general position, and is coordinated with four nitrogen atoms from two trans-nicotinamide ligands and two trans-NCS anions in a square-planar geometry, as shown in Fig 1. The amide moieties are oriented in same directions. The two pyridine rings coordinated to the Cu centre are twisted by 3.63 (2)°. The distance between Cu center and the O atom of the aqua ligand is 2.442 (4) Å, which suggests a weak non-covalent interaction (Table 1). The Cu complex units are connected via N—H···O hydrogen bonds in a head-to-head fashion, resulting in chains in the crystal. The chains are further linked via O—H···O hydrogen bonds between the coordinated water molecules and amide groups to lead to infinite sheets, as shown in Fig 2.

Experimental

CuCl₂.6H₂O (1 mmol), nicotinamide (2 mmol) and NaNCS (1 mmol) were dissolved in water and blue blocks of (I) were obtained by slow evaporation at room temperature about 5 days in 82% yield.

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids drawn at the 40% probability level (arbitrary spheres for the H atoms).

Fig. 2.

The layered hydrogen-bonded network in (I) viewed down the b axis direction. Hydrogen bonds are shown as dashed lines.

Crystal data

[Cu(NCS)₂(C₆H₆N₂O)₂(H₂O)]	F₀₀₀ = 900
M_r = 441.97	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10592 reflections
a = 11.078 (5) Å	θ = 12–18º
b = 8.950 (4) Å	µ = 1.43 mm⁻¹
c = 18.702 (9) Å	T = 293 (2) K
β = 90.333 (8)º	Block, blue
V = 1854.3 (15) Å³	0.42 × 0.35 × 0.30 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	4041 independent reflections
Radiation source: fine-focus sealed tube	3292 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.019
T = 293(2) K	θ_max = 27.2º
ω scans	θ_min = 2.5º
Absorption correction: Multi-Scan(SADABS; Bruker, 1997)	h = −14→14
T_min = 0.542, T_max = 0.663	k = −11→8
10592 measured reflections	l = −23→23

Refinement

Refinement on F²	Hydrogen site location: difmap and geom
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.045P)² + 0.9888P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.090	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.35 e Å⁻³
4041 reflections	Δρ_min = −0.36 e Å⁻³
236 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (5)
Secondary atom site location: difference Fourier map

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 (Å²)

	x	y	z	U_iso*/U_eq
Cu1	0.70192 (3)	0.10898 (3)	0.092940 (14)	0.03511 (11)
S1	0.56142 (6)	−0.14977 (7)	−0.11161 (3)	0.04101 (16)
S2	0.72370 (6)	0.27895 (8)	0.33102 (3)	0.04644 (17)
O1	0.96149 (19)	−0.1681 (2)	0.29467 (12)	0.0631 (6)
O2	0.96200 (17)	0.76310 (19)	0.03689 (11)	0.0528 (5)
O3	0.91522 (15)	0.06510 (18)	0.06824 (9)	0.0398 (4)
H3A	0.9289	−0.0271	0.0537	0.048*
H3B	0.9461	0.1164	0.0342	0.048*
N1	0.70065 (17)	−0.0949 (2)	0.14278 (10)	0.0354 (4)
N2	0.8973 (2)	−0.3974 (3)	0.32101 (14)	0.0633 (7)
H2A	0.9542	−0.4107	0.3519	0.076*
H2B	0.8453	−0.4670	0.3133	0.076*
N3	0.72932 (17)	0.3169 (2)	0.04894 (10)	0.0349 (4)
N4	1.0166 (2)	0.5956 (2)	0.12020 (13)	0.0503 (6)
H4A	1.0755	0.6508	0.1346	0.060*
H4B	1.0036	0.5107	0.1402	0.060*
N5	0.65964 (18)	0.0179 (2)	0.00029 (10)	0.0391 (4)
N6	0.7224 (2)	0.2002 (2)	0.18720 (11)	0.0467 (5)
C1	0.7870 (2)	−0.1250 (3)	0.19112 (12)	0.0351 (5)
H1A	0.8483	−0.0554	0.1981	0.042*
C2	0.7894 (2)	−0.2552 (3)	0.23123 (12)	0.0345 (5)
C3	0.6977 (2)	−0.3586 (3)	0.22028 (13)	0.0394 (5)
H3C	0.6965	−0.4475	0.2460	0.047*
C4	0.6086 (2)	−0.3276 (3)	0.17083 (15)	0.0451 (6)
H4C	0.5462	−0.3952	0.1629	0.054*
C5	0.6128 (2)	−0.1952 (3)	0.13314 (13)	0.0394 (5)
H5A	0.5523	−0.1751	0.0998	0.047*
C6	0.8898 (2)	−0.2704 (3)	0.28559 (13)	0.0404 (5)
C7	0.6561 (2)	0.3698 (3)	−0.00225 (14)	0.0429 (6)
H7A	0.5926	0.3104	−0.0182	0.052*
C8	0.6714 (3)	0.5085 (3)	−0.03205 (15)	0.0508 (7)
H8A	0.6180	0.5431	−0.0668	0.061*
C9	0.7665 (2)	0.5957 (3)	−0.00991 (14)	0.0447 (6)
H9A	0.7792	0.6889	−0.0305	0.054*
C10	0.8437 (2)	0.5437 (2)	0.04359 (12)	0.0340 (5)
C11	0.8209 (2)	0.4028 (2)	0.07201 (12)	0.0335 (5)
H11A	0.8710	0.3669	0.1082	0.040*
C12	0.9465 (2)	0.6412 (2)	0.06743 (14)	0.0379 (5)
C13	0.6193 (2)	−0.0526 (2)	−0.04580 (12)	0.0326 (5)
C14	0.7230 (2)	0.2317 (2)	0.24690 (13)	0.0353 (5)

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04718 (19)	0.02743 (16)	0.03065 (17)	−0.00594 (12)	−0.00671 (12)	0.00229 (10)
S1	0.0488 (4)	0.0379 (3)	0.0363 (3)	−0.0021 (3)	−0.0041 (3)	−0.0064 (2)
S2	0.0540 (4)	0.0510 (4)	0.0343 (3)	0.0064 (3)	−0.0001 (3)	−0.0033 (3)
O1	0.0675 (13)	0.0435 (11)	0.0777 (15)	−0.0095 (10)	−0.0353 (11)	0.0047 (10)
O2	0.0603 (12)	0.0309 (9)	0.0673 (13)	−0.0082 (8)	0.0081 (10)	0.0094 (8)
O3	0.0437 (9)	0.0324 (8)	0.0432 (9)	−0.0031 (7)	0.0032 (7)	0.0007 (7)
N1	0.0378 (10)	0.0320 (10)	0.0364 (10)	−0.0048 (8)	−0.0049 (8)	0.0045 (8)
N2	0.0633 (16)	0.0509 (15)	0.0754 (18)	−0.0085 (12)	−0.0333 (14)	0.0199 (12)
N3	0.0431 (11)	0.0284 (9)	0.0331 (10)	−0.0021 (8)	−0.0024 (8)	0.0022 (8)
N4	0.0463 (12)	0.0393 (12)	0.0653 (15)	−0.0105 (10)	−0.0087 (11)	0.0048 (10)
N5	0.0452 (11)	0.0387 (11)	0.0333 (10)	−0.0053 (9)	−0.0055 (8)	−0.0001 (8)
N6	0.0654 (14)	0.0382 (11)	0.0364 (12)	−0.0099 (10)	−0.0068 (10)	0.0004 (9)
C1	0.0358 (12)	0.0320 (11)	0.0376 (12)	−0.0039 (9)	−0.0038 (9)	0.0025 (9)
C2	0.0369 (12)	0.0320 (11)	0.0346 (12)	0.0016 (9)	0.0000 (9)	−0.0008 (9)
C3	0.0448 (13)	0.0309 (12)	0.0423 (13)	−0.0025 (10)	−0.0019 (10)	0.0066 (10)
C4	0.0436 (13)	0.0375 (13)	0.0541 (15)	−0.0115 (11)	−0.0082 (11)	0.0054 (11)
C5	0.0392 (12)	0.0364 (12)	0.0425 (13)	−0.0037 (10)	−0.0089 (10)	0.0043 (10)
C6	0.0431 (13)	0.0376 (13)	0.0405 (13)	0.0050 (10)	−0.0055 (10)	−0.0007 (10)
C7	0.0502 (14)	0.0362 (13)	0.0423 (14)	−0.0020 (11)	−0.0104 (11)	0.0031 (10)
C8	0.0602 (16)	0.0420 (14)	0.0498 (15)	0.0032 (12)	−0.0162 (13)	0.0090 (12)
C9	0.0555 (15)	0.0311 (12)	0.0475 (15)	0.0021 (11)	−0.0011 (12)	0.0092 (10)
C10	0.0392 (12)	0.0259 (10)	0.0368 (12)	0.0032 (9)	0.0061 (9)	−0.0006 (9)
C11	0.0379 (12)	0.0264 (11)	0.0362 (12)	−0.0002 (9)	−0.0012 (9)	0.0028 (9)
C12	0.0384 (12)	0.0263 (11)	0.0492 (14)	−0.0007 (9)	0.0114 (10)	−0.0009 (10)
C13	0.0363 (11)	0.0287 (11)	0.0329 (11)	0.0008 (9)	0.0018 (9)	0.0049 (9)
C14	0.0402 (12)	0.0270 (11)	0.0386 (13)	−0.0017 (9)	−0.0039 (10)	0.0040 (9)

Geometric parameters (Å, °)

Cu1—N6	1.955 (2)	N5—C13	1.156 (3)
Cu1—N5	1.969 (2)	N6—C14	1.151 (3)
Cu1—N1	2.049 (2)	C1—C2	1.386 (3)
Cu1—N3	2.058 (2)	C1—H1A	0.9300
Cu1—O3	2.442 (4)	C2—C3	1.389 (3)
S1—C13	1.635 (2)	C2—C6	1.509 (3)
S2—C14	1.629 (3)	C3—C4	1.377 (3)
O1—C6	1.223 (3)	C3—H3C	0.9300
O2—C12	1.244 (3)	C4—C5	1.380 (3)
O3—H3A	0.8821	C4—H4C	0.9300
O3—H3B	0.8574	C5—H5A	0.9300
N1—C5	1.336 (3)	C7—C8	1.372 (4)
N1—C1	1.340 (3)	C7—H7A	0.9300
N2—C6	1.318 (3)	C8—C9	1.373 (4)
N2—H2A	0.8600	C8—H8A	0.9300
N2—H2B	0.8600	C9—C10	1.393 (3)
N3—C7	1.337 (3)	C9—H9A	0.9300
N3—C11	1.342 (3)	C10—C11	1.392 (3)
N4—C12	1.317 (3)	C10—C12	1.501 (3)
N4—H4A	0.8600	C11—H11A	0.9300
N4—H4B	0.8600

N6—Cu1—N5	172.90 (9)	C4—C3—H3C	120.5
N6—Cu1—N1	87.87 (9)	C2—C3—H3C	120.5
N5—Cu1—N1	91.70 (9)	C3—C4—C5	119.3 (2)
N6—Cu1—N3	88.06 (9)	C3—C4—H4C	120.3
N5—Cu1—N3	93.28 (8)	C5—C4—H4C	120.3
N1—Cu1—N3	171.32 (8)	N1—C5—C4	122.4 (2)
O3—Cu1—N1	87.25 (7)	N1—C5—H5A	118.8
O3—Cu1—N3	85.68 (7)	C4—C5—H5A	118.8
O3—Cu1—N5	89.57 (7)	O1—C6—N2	122.5 (2)
O3—Cu1—N6	97.49 (8)	O1—C6—C2	120.1 (2)
H3A—O3—H3B	101.7	N2—C6—C2	117.4 (2)
C5—N1—C1	118.2 (2)	N3—C7—C8	122.4 (2)
C5—N1—Cu1	122.97 (16)	N3—C7—H7A	118.8
C1—N1—Cu1	118.66 (15)	C8—C7—H7A	118.8
C6—N2—H2A	120.0	C7—C8—C9	119.2 (2)
C6—N2—H2B	120.0	C7—C8—H8A	120.4
H2A—N2—H2B	120.0	C9—C8—H8A	120.4
C7—N3—C11	118.8 (2)	C8—C9—C10	119.6 (2)
C7—N3—Cu1	121.07 (16)	C8—C9—H9A	120.2
C11—N3—Cu1	120.14 (15)	C10—C9—H9A	120.2
C12—N4—H4A	120.0	C11—C10—C9	117.7 (2)
C12—N4—H4B	120.0	C11—C10—C12	123.5 (2)
H4A—N4—H4B	120.0	C9—C10—C12	118.8 (2)
C13—N5—Cu1	166.17 (19)	N3—C11—C10	122.3 (2)
C14—N6—Cu1	167.6 (2)	N3—C11—H11A	118.9
N1—C1—C2	123.1 (2)	C10—C11—H11A	118.9
N1—C1—H1A	118.5	O2—C12—N4	122.2 (2)
C2—C1—H1A	118.5	O2—C12—C10	118.7 (2)
C1—C2—C3	118.0 (2)	N4—C12—C10	119.1 (2)
C1—C2—C6	116.9 (2)	N5—C13—S1	179.0 (2)
C3—C2—C6	125.1 (2)	N6—C14—S2	179.1 (2)
C4—C3—C2	119.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.88	1.94	2.815 (3)	171
O3—H3B···O2ⁱⁱ	0.86	2.00	2.848 (3)	172
N2—H2A···O3ⁱⁱⁱ	0.86	2.09	2.944 (3)	176
N4—H4B···O1^iv	0.86	2.05	2.857 (3)	157

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2684).

References

Aakeröy, C. B., Desper, J. & Valdés-Martínez, J. (2004). CrystEngComm, 6, 413–418.
Beatty, A. M. (2001). CrystEngComm, 3, 1–13.
Bruker (1997). SMART (Version 5.6), SAINT (Version 5.06A), SADABS (Version 2.1) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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