Di-aqua-bis-(pyridine-2-carboxyl-ato-κ(2) N,O)zinc di-methyl-formamide hemisolvate.

In the title compound, [Zn(C6H4NO2)2(H2O)2]·0.5C3H7NO, the Zn(II) ion is coordinated in a distorted octa-hedral N2O4 environment by two N,O-chelating pyridine-2-carboxyl-ate ligands and two cis water mol-ecules. The chelating pyridine-2-carboxyl-ate ligands create two five-membered Zn/N/C/C/O rings, which form a dihedral angle of 86.4 (2)°. In the crystal, O-H⋯O hydrogen bonds link the complex mol-ecules into a two-dimensional network parallel to (100). The di-methyl-formamide solvent mol-ecule is disordered about a twofold rotation axis.

Related literature

For background to polydentate ligands, see: Udvardy et al. (2013 ▶); Groni et al. (2008 ▶); Golenya et al. (2011 ▶); Ma et al. (2009 ▶). For related structures, see: Chen & Hu (2011 ▶); Li et al. (2008 ▶); Lumme et al. (1969 ▶); Takenaka et al. (1970 ▶); Uggla et al. (1969 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Zn(C6H4NO2)2(H2O)2]·0.5C3H7NO

M = 382.16

Monoclinic,

a = 25.777 (3) Å

b = 8.6754 (4) Å

c = 16.7916 (17) Å

β = 125.228 (15)°

V = 3067.4 (5) Å3

Z = 8

Mo Kα radiation

μ = 1.64 mm−1

T = 293 K

0.18 × 0.12 × 0.02 mm

Data collection

Agilent Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.906, T max = 1.000

4865 measured reflections

2844 independent reflections

1772 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.114

S = 1.00

2844 reflections

244 parameters

162 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.44 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813018941/lh5630sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018941/lh5630Isup2.hkl

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

[Zn(C6H4NO2)2(H2O)2]·0.5C3H7NO	F(000) = 1568
Mr = 382.16	Dx = 1.655 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 957 reflections
a = 25.777 (3) Å	θ = 3.0–28.9°
b = 8.6754 (4) Å	µ = 1.64 mm−1
c = 16.7916 (17) Å	T = 293 K
β = 125.228 (15)°	Prism, colourless
V = 3067.4 (5) Å3	0.18 × 0.12 × 0.02 mm
Z = 8

Agilent Xcalibur Eos diffractometer	2844 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1772 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 15.9914 pixels mm-1	θmax = 25.5°, θmin = 3.0°
ω scans	h = −31→25
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→5
Tmin = 0.906, Tmax = 1.000	l = −9→20
4865 measured reflections

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3
2844 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.47 e Å−3
162 restraints	Δρmin = −0.44 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	Occ. (<1)
Zn1	0.18837 (3)	0.40000 (7)	0.78138 (4)	0.0278 (2)
N1	0.18028 (19)	0.6106 (5)	0.8391 (3)	0.0273 (11)
N2	0.08845 (19)	0.3806 (5)	0.6684 (3)	0.0253 (10)
O1	0.17673 (17)	0.3193 (4)	0.8877 (2)	0.0338 (10)
O2	0.17327 (17)	0.3959 (4)	1.0115 (2)	0.0367 (10)
O3	0.18125 (17)	0.1902 (4)	0.7129 (3)	0.0335 (10)
O4	0.11570 (19)	0.0343 (5)	0.5895 (3)	0.0555 (13)
C1	0.1798 (3)	0.7558 (6)	0.8114 (4)	0.0396 (16)
H1	0.1837	0.7722	0.7603	0.048*
C2	0.1738 (3)	0.8813 (6)	0.8553 (4)	0.0433 (16)
H2	0.1739	0.9808	0.8347	0.052*
C3	0.1677 (3)	0.8573 (7)	0.9300 (4)	0.0441 (17)
H3	0.1633	0.9405	0.9606	0.053*
C4	0.1681 (2)	0.7106 (6)	0.9593 (4)	0.0336 (14)
H4	0.1646	0.6931	1.0107	0.040*
C5	0.1738 (2)	0.5873 (6)	0.9120 (3)	0.0256 (13)
C6	0.1751 (2)	0.4195 (6)	0.9396 (4)	0.0279 (13)
C7	0.0422 (3)	0.4729 (6)	0.6531 (4)	0.0364 (15)
H7	0.0529	0.5598	0.6921	0.044*
C8	−0.0215 (3)	0.4441 (7)	0.5811 (4)	0.0461 (17)
H8	−0.0529	0.5086	0.5735	0.055*
C9	−0.0372 (3)	0.3196 (7)	0.5217 (4)	0.0428 (16)
H9	−0.0794	0.2990	0.4717	0.051*
C10	0.0109 (3)	0.2248 (7)	0.5376 (4)	0.0376 (15)
H10	0.0014	0.1393	0.4980	0.045*
C11	0.0729 (3)	0.2570 (6)	0.6122 (4)	0.0268 (13)
C12	0.1270 (3)	0.1516 (6)	0.6384 (4)	0.0326 (14)
O1W	0.28549 (18)	0.3692 (5)	0.8823 (3)	0.0389 (10)
H1W1	0.3148 (18)	0.425 (5)	0.888 (4)	0.05 (2)*
H2W1	0.298 (2)	0.296 (4)	0.924 (3)	0.042 (19)*
O2W	0.2112 (2)	0.5202 (5)	0.6968 (3)	0.0413 (11)
H1W2	0.199 (2)	0.512 (5)	0.6369 (16)	0.031 (16)*
H2W2	0.2454 (17)	0.575 (6)	0.732 (3)	0.05 (2)*
O1X	0.9935 (9)	0.7274 (12)	0.7077 (8)	0.142 (8)	0.50
N1X	0.9961 (14)	0.9688 (8)	0.7567 (15)	0.065 (4)	0.50
C1X	0.9916 (9)	0.8645 (13)	0.6968 (9)	0.093 (8)	0.50
H1X	0.9865	0.8999	0.6404	0.112*	0.50
C2X	1.0023 (11)	0.9255 (17)	0.8428 (12)	0.090 (7)	0.50
H2XA	0.9611	0.9229	0.8307	0.135*	0.50
H2XB	1.0286	0.9990	0.8933	0.135*	0.50
H2XC	1.0214	0.8252	0.8629	0.135*	0.50
C3X	0.996 (3)	1.1310 (9)	0.739 (3)	0.194 (10)	0.50
H3XA	1.0385	1.1673	0.7715	0.292*	0.50
H3XB	0.9750	1.1854	0.7631	0.292*	0.50
H3XC	0.9731	1.1486	0.6700	0.292*	0.50

	U11	U22	U33	U12	U13	U23
Zn1	0.0328 (4)	0.0260 (4)	0.0265 (4)	−0.0006 (3)	0.0182 (3)	−0.0013 (3)
N1	0.034 (3)	0.026 (2)	0.026 (2)	0.001 (2)	0.020 (2)	0.002 (2)
N2	0.024 (3)	0.024 (3)	0.028 (3)	0.001 (2)	0.015 (2)	0.000 (2)
O1	0.045 (3)	0.027 (2)	0.032 (2)	−0.002 (2)	0.024 (2)	−0.0019 (18)
O2	0.046 (3)	0.041 (2)	0.032 (2)	0.005 (2)	0.027 (2)	0.0093 (19)
O3	0.024 (2)	0.033 (2)	0.034 (2)	0.0005 (19)	0.011 (2)	−0.0076 (19)
O4	0.039 (3)	0.047 (3)	0.065 (3)	0.000 (2)	0.022 (3)	−0.030 (2)
C1	0.057 (5)	0.029 (3)	0.038 (4)	−0.006 (3)	0.030 (4)	0.004 (3)
C2	0.053 (4)	0.022 (3)	0.053 (4)	−0.008 (3)	0.030 (4)	−0.006 (3)
C3	0.053 (5)	0.032 (4)	0.049 (4)	0.003 (3)	0.030 (4)	−0.011 (3)
C4	0.039 (4)	0.037 (4)	0.031 (3)	−0.002 (3)	0.024 (3)	−0.003 (3)
C5	0.019 (3)	0.029 (3)	0.020 (3)	−0.001 (3)	0.006 (3)	−0.006 (3)
C6	0.021 (3)	0.030 (3)	0.027 (3)	0.000 (3)	0.010 (3)	0.005 (3)
C7	0.039 (4)	0.028 (3)	0.041 (4)	0.008 (3)	0.023 (3)	−0.001 (3)
C8	0.036 (4)	0.045 (4)	0.062 (5)	0.019 (3)	0.031 (4)	0.013 (3)
C9	0.026 (4)	0.050 (4)	0.046 (4)	0.001 (3)	0.017 (3)	0.001 (4)
C10	0.029 (4)	0.036 (4)	0.038 (4)	−0.005 (3)	0.013 (3)	−0.010 (3)
C11	0.032 (3)	0.024 (3)	0.031 (3)	−0.002 (3)	0.021 (3)	0.001 (3)
C12	0.037 (4)	0.025 (3)	0.040 (4)	0.005 (3)	0.025 (3)	0.003 (3)
O1W	0.030 (3)	0.032 (3)	0.041 (3)	−0.005 (2)	0.013 (2)	0.012 (2)
O2W	0.049 (3)	0.049 (3)	0.026 (2)	−0.020 (2)	0.022 (2)	−0.005 (2)
O1X	0.117 (11)	0.095 (9)	0.19 (2)	0.029 (11)	0.074 (17)	−0.078 (9)
N1X	0.123 (11)	0.043 (6)	0.074 (8)	0.023 (15)	0.082 (8)	0.005 (13)
C1X	0.072 (14)	0.13 (2)	0.071 (16)	0.034 (17)	0.040 (14)	−0.035 (15)
C2X	0.132 (18)	0.084 (15)	0.072 (14)	0.015 (12)	0.069 (14)	0.015 (10)
C3X	0.45 (3)	0.055 (9)	0.26 (2)	0.02 (5)	0.31 (3)	0.03 (3)

Zn1—O1W	2.078 (4)	C7—H7	0.9300
Zn1—O1	2.094 (3)	C8—C9	1.363 (7)
Zn1—O2W	2.101 (4)	C8—H8	0.9300
Zn1—O3	2.104 (3)	C9—C10	1.379 (7)
Zn1—N1	2.134 (4)	C9—H9	0.9300
Zn1—N2	2.150 (4)	C10—C11	1.375 (7)
N1—C1	1.341 (6)	C10—H10	0.9300
N1—C5	1.343 (6)	C11—C12	1.506 (7)
N2—C11	1.329 (6)	O1W—H1W1	0.857 (18)
N2—C7	1.333 (6)	O1W—H2W1	0.857 (18)
O1—C6	1.249 (6)	O2W—H1W2	0.863 (18)
O2—C6	1.251 (6)	O2W—H2W2	0.866 (19)
O3—C12	1.271 (6)	O1X—C1X	1.1999
O4—C12	1.233 (6)	N1X—C1X	1.3069
C1—C2	1.373 (7)	N1X—C2X	1.4118
C1—H1	0.9300	N1X—C3X	1.4373
C2—C3	1.368 (7)	C1X—H1X	0.9300
C2—H2	0.9300	C2X—H2XA	0.9600
C3—C4	1.362 (7)	C2X—H2XB	0.9600
C3—H3	0.9300	C2X—H2XC	0.9600
C4—C5	1.390 (7)	C3X—H3XA	0.9600
C4—H4	0.9300	C3X—H3XB	0.9600
C5—C6	1.523 (7)	C3X—H3XC	0.9600
C7—C8	1.389 (7)
O1W—Zn1—O1	87.68 (16)	N1—C5—C6	115.4 (4)
O1W—Zn1—O2W	86.53 (18)	C4—C5—C6	123.6 (5)
O1—Zn1—O2W	167.39 (15)	O1—C6—O2	126.5 (5)
O1W—Zn1—O3	91.07 (15)	O1—C6—C5	117.2 (5)
O1—Zn1—O3	99.57 (14)	O2—C6—C5	116.3 (5)
O2W—Zn1—O3	91.74 (16)	N2—C7—C8	122.5 (5)
O1W—Zn1—N1	97.31 (16)	N2—C7—H7	118.8
O1—Zn1—N1	78.44 (15)	C8—C7—H7	118.8
O2W—Zn1—N1	91.19 (17)	C9—C8—C7	118.9 (5)
O3—Zn1—N1	171.28 (15)	C9—C8—H8	120.6
O1W—Zn1—N2	167.46 (16)	C7—C8—H8	120.6
O1—Zn1—N2	92.17 (15)	C8—C9—C10	118.4 (6)
O2W—Zn1—N2	95.90 (16)	C8—C9—H9	120.8
O3—Zn1—N2	76.58 (15)	C10—C9—H9	120.8
N1—Zn1—N2	94.94 (16)	C11—C10—C9	119.9 (5)
C1—N1—C5	118.5 (5)	C11—C10—H10	120.1
C1—N1—Zn1	129.1 (4)	C9—C10—H10	120.1
C5—N1—Zn1	112.4 (3)	N2—C11—C10	121.8 (5)
C11—N2—C7	118.5 (5)	N2—C11—C12	115.7 (5)
C11—N2—Zn1	114.0 (4)	C10—C11—C12	122.5 (5)
C7—N2—Zn1	127.4 (4)	O4—C12—O3	125.2 (5)
C6—O1—Zn1	116.2 (3)	O4—C12—C11	118.9 (5)
C12—O3—Zn1	117.7 (3)	O3—C12—C11	115.9 (5)
N1—C1—C2	122.7 (5)	Zn1—O1W—H1W1	126 (3)
N1—C1—H1	118.7	Zn1—O1W—H2W1	118 (3)
C2—C1—H1	118.7	H1W1—O1W—H2W1	116 (3)
C3—C2—C1	118.7 (5)	Zn1—O2W—H1W2	133 (3)
C3—C2—H2	120.6	Zn1—O2W—H2W2	113 (3)
C1—C2—H2	120.6	H1W2—O2W—H2W2	113 (3)
C4—C3—C2	119.5 (5)	C1X—N1X—C2X	120.7
C4—C3—H3	120.3	C1X—N1X—C3X	122.1
C2—C3—H3	120.3	C2X—N1X—C3X	117.2
C3—C4—C5	119.7 (5)	O1X—C1X—N1X	126.3
C3—C4—H4	120.2	O1X—C1X—H1X	116.9
C5—C4—H4	120.2	N1X—C1X—H1X	116.9
N1—C5—C4	121.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4i	0.86 (2)	1.86 (2)	2.715 (6)	174 (5)
O1W—H2W1···O2ii	0.86 (2)	1.89 (2)	2.723 (5)	163 (5)
O2W—H1W2···O2iii	0.86 (2)	1.98 (3)	2.768 (5)	152 (4)
O2W—H2W2···O3i	0.87 (2)	1.85 (2)	2.704 (5)	170 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O4i	0.86 (2)	1.86 (2)	2.715 (6)	174 (5)
O1W—H2W1⋯O2ii	0.86 (2)	1.89 (2)	2.723 (5)	163 (5)
O2W—H1W2⋯O2iii	0.86 (2)	1.98 (3)	2.768 (5)	152 (4)
O2W—H2W2⋯O3i	0.87 (2)	1.85 (2)	2.704 (5)	170 (4)

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