Poly[[diaquadi-μ-dicyanamido-nickel(II)] bis-(pyridinium-4-olate)].

The title compound, {[Ni(C(2)N(3))(2)(H(2)O)(2)]·2C(5)H(5)NO}(n), is a centrosymmetric two-dimensional coordination polymer with a layer (4,4) network structure. The asymmetric unit is compossed of an Ni(II) atom, which sits on an inversion center, a μ-1,5-bridging dicyanamide anion, a water mol-ecule, and a free 4-hydroxy-pyridine mol-ecule present in the zwitterionic pyridinium-4-olate form. The Ni(II) atom is coordinated in a slightly distorted N(4)O(2) octa-hedral geometry by four bridging dicyanamide ligands and two trans water mol-ecules. In the crystal, the two-dimensional networks are linked via N-H⋯O and O-H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For coordination polymers involving dicyanamide (dca), see: Manson et al. (1998 ▶, 2001 ▶); Batten et al. (1998 ▶). For nickel(II)–dca complexes, see: Van der Werff et al. (2004 ▶); Armentano et al. (2006 ▶). For dicyanamide complexes with a co-ligand, see: Batten & Murray (2003 ▶); Manson et al. (1998 ▶, 2001 ▶); Miller & Manson (2001 ▶). For dicyanamide complexes with 4-cyano­pyridine as co-ligand, see: Dalai et al. (2002 ▶); Du et al. (2006 ▶).

Experimental

Crystal data

[Ni(C2N3)2(H2O)2]·2C5H5NO

M = 417.02

Monoclinic,

a = 7.8598 (6) Å

b = 12.8199 (10) Å

c = 9.1080 (7) Å

β = 96.7530 (10)°

V = 911.37 (12) Å3

Z = 2

Mo Kα radiation

μ = 1.10 mm−1

T = 293 K

0.23 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.788, T max = 0.848

6950 measured reflections

1788 independent reflections

1606 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.073

S = 1.08

1788 reflections

136 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048880/su2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048880/su2153Isup2.hkl

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

[Ni(C2N3)2(H2O)2]·2C5H5NO	F(000) = 428
Mr = 417.02	Dx = 1.520 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1788 reflections
a = 7.8598 (6) Å	θ = 2.6–26.0°
b = 12.8199 (10) Å	µ = 1.10 mm−1
c = 9.1080 (7) Å	T = 293 K
β = 96.753 (1)°	Block, green
V = 911.37 (12) Å3	0.23 × 0.18 × 0.15 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	1788 independent reflections
Radiation source: fine-focus sealed tube	1606 reflections with I > 2σ(I)
graphite	Rint = 0.016
φ and ω scans	θmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
Tmin = 0.788, Tmax = 0.848	k = −15→15
6950 measured reflections	l = −10→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0362P)2 + 0.2827P] where P = (Fo2 + 2Fc2)/3
1788 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.30 e Å−3
4 restraints	Δρmin = −0.16 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	1.0000	1.0000	0.0000	0.03617 (12)
C1	0.9985 (2)	0.59861 (12)	0.1821 (2)	0.0424 (4)
C2	0.9988 (3)	0.75355 (14)	0.0636 (2)	0.0500 (5)
C3	0.6251 (3)	0.38083 (17)	0.1568 (3)	0.0771 (7)
H3	0.7156	0.4248	0.1417	0.092*
C4	0.6426 (3)	0.27675 (16)	0.1384 (3)	0.0657 (6)
H4	0.7434	0.2503	0.1088	0.079*
C5	0.5095 (2)	0.20841 (13)	0.1638 (2)	0.0458 (4)
C6	0.3615 (3)	0.25592 (16)	0.2048 (3)	0.0678 (7)
H6	0.2686	0.2145	0.2216	0.081*
C7	0.3507 (3)	0.36025 (17)	0.2205 (3)	0.0683 (6)
H7	0.2513	0.3896	0.2486	0.082*
N1	0.9923 (2)	0.84211 (11)	0.05067 (19)	0.0499 (4)
N2	1.0097 (3)	0.65203 (13)	0.0627 (2)	0.0801 (7)
N3	0.9881 (2)	0.54506 (12)	0.28000 (17)	0.0481 (4)
N4	0.4816 (3)	0.42170 (13)	0.1960 (2)	0.0641 (5)
O1	0.52314 (18)	0.10983 (10)	0.15018 (18)	0.0600 (4)
O1W	1.26183 (19)	0.99136 (10)	0.01412 (19)	0.0535 (4)
HN4	0.473 (4)	0.4871 (14)	0.214 (4)	0.091 (10)*
H1WA	1.330 (2)	1.0346 (15)	0.057 (2)	0.070 (7)*
H1WB	1.313 (2)	0.9513 (14)	−0.039 (2)	0.061 (6)*

	U11	U22	U33	U12	U13	U23
Ni1	0.0457 (2)	0.02211 (17)	0.0425 (2)	−0.00065 (11)	0.01317 (14)	−0.00113 (11)
C1	0.0567 (11)	0.0236 (7)	0.0491 (10)	0.0012 (7)	0.0155 (8)	−0.0022 (7)
C2	0.0751 (14)	0.0337 (10)	0.0449 (10)	−0.0002 (9)	0.0223 (9)	0.0043 (8)
C3	0.0755 (16)	0.0437 (12)	0.117 (2)	−0.0220 (11)	0.0303 (15)	−0.0086 (12)
C4	0.0528 (12)	0.0457 (11)	0.1031 (18)	−0.0087 (9)	0.0282 (12)	−0.0134 (11)
C5	0.0489 (10)	0.0324 (8)	0.0575 (11)	−0.0035 (7)	0.0118 (8)	−0.0082 (8)
C6	0.0577 (13)	0.0430 (11)	0.1088 (19)	−0.0096 (9)	0.0355 (13)	−0.0184 (11)
C7	0.0627 (14)	0.0477 (11)	0.0971 (18)	0.0079 (10)	0.0204 (13)	−0.0200 (11)
N1	0.0674 (11)	0.0284 (8)	0.0565 (9)	−0.0011 (7)	0.0182 (8)	0.0034 (7)
N2	0.163 (2)	0.0272 (8)	0.0577 (11)	0.0077 (10)	0.0439 (12)	0.0057 (8)
N3	0.0675 (11)	0.0315 (8)	0.0472 (9)	0.0000 (7)	0.0144 (7)	0.0043 (7)
N4	0.0811 (14)	0.0302 (9)	0.0808 (13)	0.0004 (8)	0.0082 (11)	−0.0084 (8)
O1	0.0604 (9)	0.0298 (6)	0.0932 (11)	−0.0021 (6)	0.0234 (8)	−0.0126 (7)
O1W	0.0447 (7)	0.0448 (8)	0.0725 (10)	−0.0022 (6)	0.0135 (7)	−0.0208 (7)

Ni1—O1Wi	2.0498 (15)	C4—C5	1.405 (3)
Ni1—O1W	2.0498 (15)	C4—H4	0.9300
Ni1—N3ii	2.0769 (16)	C5—O1	1.276 (2)
Ni1—N3iii	2.0769 (16)	C5—C6	1.402 (3)
Ni1—N1	2.0785 (15)	C6—C7	1.349 (3)
Ni1—N1i	2.0785 (15)	C6—H6	0.9300
C1—N3	1.136 (2)	C7—N4	1.335 (3)
C1—N2	1.297 (3)	C7—H7	0.9300
C2—N1	1.142 (2)	N3—Ni1iv	2.0769 (15)
C2—N2	1.304 (2)	N4—HN4	0.858 (16)
C3—N4	1.330 (3)	O1W—H1WA	0.834 (9)
C3—C4	1.354 (3)	O1W—H1WB	0.840 (9)
C3—H3	0.9300
O1Wi—Ni1—O1W	180.0	C3—C4—H4	119.8
O1Wi—Ni1—N3ii	91.34 (7)	C5—C4—H4	119.8
O1W—Ni1—N3ii	88.66 (7)	O1—C5—C6	122.59 (18)
O1Wi—Ni1—N3iii	88.66 (7)	O1—C5—C4	121.93 (18)
O1W—Ni1—N3iii	91.34 (7)	C6—C5—C4	115.49 (17)
N3ii—Ni1—N3iii	180.00 (2)	C7—C6—C5	121.6 (2)
O1Wi—Ni1—N1	90.65 (6)	C7—C6—H6	119.2
O1W—Ni1—N1	89.35 (6)	C5—C6—H6	119.2
N3ii—Ni1—N1	86.80 (6)	N4—C7—C6	120.5 (2)
N3iii—Ni1—N1	93.20 (6)	N4—C7—H7	119.7
O1Wi—Ni1—N1i	89.35 (6)	C6—C7—H7	119.7
O1W—Ni1—N1i	90.65 (6)	C2—N1—Ni1	171.49 (17)
N3ii—Ni1—N1i	93.20 (6)	C1—N2—C2	120.69 (18)
N3iii—Ni1—N1i	86.80 (6)	C1—N3—Ni1iv	157.84 (15)
N1—Ni1—N1i	180.0	C3—N4—C7	120.46 (18)
N3—C1—N2	174.66 (19)	C3—N4—HN4	121 (2)
N1—C2—N2	173.5 (2)	C7—N4—HN4	118 (2)
N4—C3—C4	121.5 (2)	Ni1—O1W—H1WA	125.4 (15)
N4—C3—H3	119.2	Ni1—O1W—H1WB	122.9 (14)
C4—C3—H3	119.2	H1WA—O1W—H1WB	110.3 (15)
C3—C4—C5	120.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N4—HN4···O1v	0.86 (2)	2.00 (2)	2.792 (2)	153 (3)
O1W—H1WA···O1vi	0.83 (1)	1.91 (1)	2.732 (2)	167 (2)
O1W—H1WB···O1vii	0.84 (1)	1.90 (1)	2.715 (2)	164 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—HN4⋯O1i	0.858 (16)	2.00 (2)	2.792 (2)	153 (3)
O1W—H1WA⋯O1ii	0.834 (9)	1.912 (11)	2.732 (2)	167 (2)
O1W—H1WB⋯O1iii	0.840 (9)	1.898 (11)	2.715 (2)	164.0 (19)

Symmetry codes: (i) ; (ii) ; (iii) .