Bis(μ(2)-pyridine-2-carboxamide oximato)bis-[(pyridine-2-carboxamide oxime)zinc] dinitrate.

In the title dinuclear compound, [Zn(2)(C(6)H(6)N(3)O)(2)(C(6)H(7)N(3)O)(2)](NO(3))(2), the Zn(II) cation is N,N'-chelated by one pyridine-2-carboxamide oximate anion and one pyridine-2-carboxamide oxime mol-ecule, and is further bridged by an oxime O atom from the adjacent pyridine-2-carboxamide oximate anion, forming a distorted trigonal bipyramidal coordination. Two pyridine-2-carboxamide oximate anions bridge two Zn(II) cations to form the centrosymmetric dinuclear mol-ecule. Extensive O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds are present in the crystal structure.

Related literature

For similar metal complexes, see: Papatriantafyllopoulou et al. (2008 ▶); Stamatatos et al. (2006a ▶,b ▶). For the synthesis of the ligand, see: Bernasek (1957 ▶).

Experimental

Crystal data

[Zn2(C6H6N3O)2(C6H7N3O)2](NO3)2

M = 801.33

Monoclinic,

a = 7.4125 (14) Å

b = 22.201 (4) Å

c = 9.4225 (17) Å

β = 106.794 (2)°

V = 1484.5 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.70 mm−1

T = 293 K

0.51 × 0.48 × 0.39 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.478, T max = 0.557

8302 measured reflections

2632 independent reflections

2297 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.117

S = 1.03

2632 reflections

209 parameters

H-atom parameters constrained

Δρmax = 1.43 e Å−3

Δρmin = −0.97 e Å−3

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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811034908/xu5304sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034908/xu5304Isup2.hkl

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

[Zn2(C6H6N3O)2(C6H7N3O)2](NO3)2	F(000) = 816
Mr = 801.33	Dx = 1.793 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2632 reflections
a = 7.4125 (14) Å	θ = 1.8–25.1°
b = 22.201 (4) Å	µ = 1.70 mm−1
c = 9.4225 (17) Å	T = 293 K
β = 106.794 (2)°	Block, yellow
V = 1484.5 (5) Å3	0.51 × 0.48 × 0.39 mm
Z = 2

Bruker SMART 1000 CCD area-detector diffractometer	2632 independent reflections
Radiation source: fine-focus sealed tube	2297 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
Tmin = 0.478, Tmax = 0.557	k = −26→26
8302 measured reflections	l = −9→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0547P)2 + 4.2299P] where P = (Fo2 + 2Fc2)/3
2632 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 1.43 e Å−3
0 restraints	Δρmin = −0.97 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
Zn1	0.46944 (6)	0.437379 (19)	0.86499 (5)	0.02829 (17)
O2	0.3307 (4)	0.44030 (11)	1.0158 (3)	0.0305 (6)
N6	0.5478 (4)	0.52822 (14)	0.8642 (3)	0.0279 (7)
O1	0.8933 (4)	0.45773 (13)	1.0281 (4)	0.0412 (7)
H1	0.8498	0.4919	1.0208	0.062*
C12	0.4742 (5)	0.55977 (16)	0.7481 (4)	0.0290 (8)
N3	0.7493 (5)	0.41671 (15)	0.9631 (4)	0.0326 (7)
C11	0.3546 (5)	0.52544 (17)	0.6194 (4)	0.0302 (8)
N1	0.4877 (5)	0.34274 (15)	0.8238 (4)	0.0321 (7)
N4	0.3239 (5)	0.46677 (15)	0.6470 (4)	0.0311 (7)
N5	0.5021 (6)	0.61900 (15)	0.7361 (4)	0.0465 (10)
H5A	0.5739	0.6385	0.8099	0.056*
H5B	0.4482	0.6375	0.6547	0.056*
N7	0.6922 (6)	0.77875 (19)	0.9401 (5)	0.0590 (5)
N2	0.9964 (5)	0.35112 (17)	0.9759 (4)	0.0429 (9)
H2A	1.0797	0.3778	1.0161	0.051*
H2B	1.0309	0.3156	0.9583	0.051*
C5	0.6647 (5)	0.32001 (17)	0.8733 (4)	0.0298 (8)
C8	0.1400 (7)	0.4564 (2)	0.3942 (5)	0.0431 (11)
H8	0.0665	0.4321	0.3194	0.052*
C10	0.2807 (6)	0.55061 (19)	0.4812 (5)	0.0383 (10)
H10	0.3038	0.5908	0.4647	0.046*
C6	0.8138 (5)	0.36488 (17)	0.9409 (4)	0.0298 (8)
O5	0.8612 (5)	0.78443 (16)	1.0109 (4)	0.0590 (5)
O3	0.5941 (5)	0.82406 (15)	0.9079 (4)	0.0590 (5)
O4	0.6244 (5)	0.72889 (15)	0.9025 (4)	0.0590 (5)
C7	0.2194 (7)	0.43374 (19)	0.5347 (5)	0.0406 (10)
H7	0.1992	0.3934	0.5520	0.049*
C4	0.7013 (7)	0.25955 (19)	0.8636 (5)	0.0402 (10)
H4	0.8237	0.2449	0.8987	0.048*
C3	0.5540 (7)	0.22116 (19)	0.8011 (5)	0.0462 (11)
H3	0.5762	0.1803	0.7922	0.055*
C9	0.1715 (6)	0.5154 (2)	0.3668 (5)	0.0431 (11)
H9	0.1203	0.5317	0.2729	0.052*
C1	0.3466 (6)	0.30447 (19)	0.7682 (5)	0.0380 (10)
H1A	0.2242	0.3194	0.7389	0.046*
C2	0.3739 (7)	0.2436 (2)	0.7522 (5)	0.0428 (11)
H2	0.2727	0.2184	0.7092	0.051*

	U11	U22	U33	U12	U13	U23
Zn1	0.0276 (3)	0.0250 (3)	0.0300 (3)	0.00004 (17)	0.00468 (19)	−0.00044 (17)
O2	0.0287 (14)	0.0296 (14)	0.0315 (14)	−0.0055 (11)	0.0062 (12)	−0.0041 (11)
N6	0.0281 (16)	0.0260 (16)	0.0276 (17)	−0.0017 (13)	0.0049 (13)	−0.0021 (13)
O1	0.0293 (15)	0.0309 (15)	0.0560 (19)	−0.0054 (12)	0.0003 (14)	−0.0053 (14)
C12	0.030 (2)	0.0242 (18)	0.033 (2)	0.0029 (15)	0.0079 (17)	−0.0004 (15)
N3	0.0253 (17)	0.0295 (17)	0.0394 (19)	−0.0038 (14)	0.0039 (14)	−0.0009 (14)
C11	0.029 (2)	0.0298 (19)	0.032 (2)	0.0051 (16)	0.0094 (16)	0.0001 (16)
N1	0.0302 (17)	0.0287 (17)	0.0348 (18)	−0.0006 (14)	0.0053 (14)	−0.0003 (14)
N4	0.0341 (18)	0.0279 (16)	0.0286 (17)	0.0006 (14)	0.0048 (14)	−0.0003 (13)
N5	0.061 (3)	0.0255 (18)	0.042 (2)	−0.0020 (17)	−0.0027 (19)	0.0038 (15)
N7	0.0512 (11)	0.0453 (9)	0.0727 (13)	−0.0021 (8)	0.0056 (9)	−0.0090 (9)
N2	0.0279 (18)	0.0374 (19)	0.059 (2)	0.0032 (15)	0.0050 (17)	−0.0044 (17)
C5	0.033 (2)	0.0289 (19)	0.029 (2)	0.0016 (16)	0.0098 (16)	0.0010 (16)
C8	0.045 (3)	0.046 (3)	0.033 (2)	−0.002 (2)	0.0034 (19)	−0.0070 (19)
C10	0.043 (2)	0.035 (2)	0.037 (2)	0.0052 (18)	0.0099 (19)	0.0056 (18)
C6	0.029 (2)	0.030 (2)	0.029 (2)	0.0030 (16)	0.0057 (16)	0.0052 (16)
O5	0.0512 (11)	0.0453 (9)	0.0727 (13)	−0.0021 (8)	0.0056 (9)	−0.0090 (9)
O3	0.0512 (11)	0.0453 (9)	0.0727 (13)	−0.0021 (8)	0.0056 (9)	−0.0090 (9)
O4	0.0512 (11)	0.0453 (9)	0.0727 (13)	−0.0021 (8)	0.0056 (9)	−0.0090 (9)
C7	0.046 (3)	0.032 (2)	0.037 (2)	−0.0053 (18)	0.002 (2)	−0.0044 (18)
C4	0.044 (2)	0.033 (2)	0.043 (3)	0.0053 (18)	0.011 (2)	0.0009 (18)
C3	0.061 (3)	0.028 (2)	0.048 (3)	0.000 (2)	0.013 (2)	−0.0053 (19)
C9	0.043 (3)	0.051 (3)	0.032 (2)	0.006 (2)	0.0056 (19)	0.0050 (19)
C1	0.035 (2)	0.038 (2)	0.038 (2)	−0.0052 (18)	0.0059 (18)	0.0014 (18)
C2	0.050 (3)	0.039 (2)	0.038 (2)	−0.015 (2)	0.010 (2)	−0.0048 (19)

Zn1—O2	1.981 (3)	N7—O4	1.225 (5)
Zn1—N1	2.148 (3)	N7—O5	1.244 (5)
Zn1—N3	2.064 (3)	N2—C6	1.333 (5)
Zn1—N4	2.128 (3)	N2—H2A	0.8600
Zn1—N6	2.099 (3)	N2—H2B	0.8600
O2—N6i	1.411 (4)	C5—C4	1.378 (6)
N6—C12	1.281 (5)	C5—C6	1.487 (5)
N6—O2i	1.411 (4)	C8—C9	1.368 (7)
O1—N3	1.402 (4)	C8—C7	1.379 (6)
O1—H1	0.8200	C8—H8	0.9300
C12—N5	1.341 (5)	C10—C9	1.386 (6)
C12—C11	1.489 (5)	C10—H10	0.9300
N3—C6	1.286 (5)	C7—H7	0.9300
C11—N4	1.361 (5)	C4—C3	1.376 (6)
C11—C10	1.377 (6)	C4—H4	0.9300
N1—C1	1.332 (5)	C3—C2	1.374 (7)
N1—C5	1.357 (5)	C3—H3	0.9300
N4—C7	1.336 (5)	C9—H9	0.9300
N5—H5A	0.8600	C1—C2	1.381 (6)
N5—H5B	0.8600	C1—H1A	0.9300
N7—O3	1.227 (5)	C2—H2	0.9300
O2—Zn1—N3	110.42 (13)	O4—N7—O5	120.8 (4)
O2—Zn1—N6	99.93 (12)	C6—N2—H2A	120.0
N3—Zn1—N6	88.39 (13)	C6—N2—H2B	120.0
O2—Zn1—N4	117.30 (12)	H2A—N2—H2B	120.0
N3—Zn1—N4	131.62 (14)	N1—C5—C4	121.9 (4)
N6—Zn1—N4	76.45 (12)	N1—C5—C6	115.0 (3)
O2—Zn1—N1	103.55 (12)	C4—C5—C6	123.0 (4)
N3—Zn1—N1	75.87 (13)	C9—C8—C7	118.8 (4)
N6—Zn1—N1	155.12 (13)	C9—C8—H8	120.6
N4—Zn1—N1	99.58 (13)	C7—C8—H8	120.6
N6i—O2—Zn1	104.3 (2)	C9—C10—C11	119.3 (4)
C12—N6—O2i	115.4 (3)	C9—C10—H10	120.3
C12—N6—Zn1	118.6 (3)	C11—C10—H10	120.3
O2i—N6—Zn1	125.9 (2)	N3—C6—N2	124.3 (4)
N3—O1—H1	109.5	N3—C6—C5	113.8 (3)
N6—C12—N5	124.8 (4)	N2—C6—C5	121.9 (4)
N6—C12—C11	115.0 (3)	N4—C7—C8	123.3 (4)
N5—C12—C11	120.2 (4)	N4—C7—H7	118.3
C6—N3—O1	112.4 (3)	C8—C7—H7	118.3
C6—N3—Zn1	119.9 (3)	C5—C4—C3	119.0 (4)
O1—N3—Zn1	126.2 (2)	C5—C4—H4	120.5
N4—C11—C10	121.8 (4)	C3—C4—H4	120.5
N4—C11—C12	115.3 (3)	C2—C3—C4	119.5 (4)
C10—C11—C12	122.9 (4)	C2—C3—H3	120.2
C1—N1—C5	118.0 (3)	C4—C3—H3	120.2
C1—N1—Zn1	127.7 (3)	C8—C9—C10	119.1 (4)
C5—N1—Zn1	114.0 (2)	C8—C9—H9	120.4
C7—N4—C11	117.7 (3)	C10—C9—H9	120.4
C7—N4—Zn1	127.8 (3)	N1—C1—C2	123.0 (4)
C11—N4—Zn1	114.3 (2)	N1—C1—H1A	118.5
C12—N5—H5A	120.0	C2—C1—H1A	118.5
C12—N5—H5B	120.0	C3—C2—C1	118.5 (4)
H5A—N5—H5B	120.0	C3—C2—H2	120.8
O3—N7—O4	120.3 (4)	C1—C2—H2	120.8
O3—N7—O5	118.9 (4)
N3—Zn1—O2—N6i	43.2 (2)	C12—C11—N4—C7	−179.2 (4)
N6—Zn1—O2—N6i	−48.8 (2)	C10—C11—N4—Zn1	175.9 (3)
N4—Zn1—O2—N6i	−128.6 (2)	C12—C11—N4—Zn1	−3.6 (4)
N1—Zn1—O2—N6i	123.0 (2)	O2—Zn1—N4—C7	−90.2 (4)
O2—Zn1—N6—C12	−112.5 (3)	N3—Zn1—N4—C7	100.1 (4)
N3—Zn1—N6—C12	137.0 (3)	N6—Zn1—N4—C7	175.4 (4)
N4—Zn1—N6—C12	3.4 (3)	N1—Zn1—N4—C7	20.5 (4)
N1—Zn1—N6—C12	86.9 (4)	O2—Zn1—N4—C11	94.8 (3)
O2—Zn1—N6—O2i	64.1 (3)	N3—Zn1—N4—C11	−74.9 (3)
N3—Zn1—N6—O2i	−46.3 (3)	N6—Zn1—N4—C11	0.4 (3)
N4—Zn1—N6—O2i	−180.0 (3)	N1—Zn1—N4—C11	−154.5 (3)
N1—Zn1—N6—O2i	−96.5 (4)	C1—N1—C5—C4	1.8 (6)
O2i—N6—C12—N5	−1.5 (6)	Zn1—N1—C5—C4	176.4 (3)
Zn1—N6—C12—N5	175.5 (3)	C1—N1—C5—C6	−177.0 (4)
O2i—N6—C12—C11	176.8 (3)	Zn1—N1—C5—C6	−2.4 (4)
Zn1—N6—C12—C11	−6.3 (5)	N4—C11—C10—C9	0.2 (7)
O2—Zn1—N3—C6	109.2 (3)	C12—C11—C10—C9	179.6 (4)
N6—Zn1—N3—C6	−150.8 (3)	O1—N3—C6—N2	0.3 (6)
N4—Zn1—N3—C6	−80.6 (3)	Zn1—N3—C6—N2	167.2 (3)
N1—Zn1—N3—C6	9.7 (3)	O1—N3—C6—C5	179.5 (3)
O2—Zn1—N3—O1	−86.0 (3)	Zn1—N3—C6—C5	−13.7 (5)
N6—Zn1—N3—O1	14.0 (3)	N1—C5—C6—N3	10.2 (5)
N4—Zn1—N3—O1	84.3 (3)	C4—C5—C6—N3	−168.6 (4)
N1—Zn1—N3—O1	174.6 (3)	N1—C5—C6—N2	−170.7 (4)
N6—C12—C11—N4	6.5 (5)	C4—C5—C6—N2	10.6 (6)
N5—C12—C11—N4	−175.1 (4)	C11—N4—C7—C8	−1.0 (7)
N6—C12—C11—C10	−173.0 (4)	Zn1—N4—C7—C8	−175.8 (4)
N5—C12—C11—C10	5.4 (6)	C9—C8—C7—N4	1.1 (8)
O2—Zn1—N1—C1	62.8 (4)	N1—C5—C4—C3	0.4 (7)
N3—Zn1—N1—C1	170.8 (4)	C6—C5—C4—C3	179.0 (4)
N6—Zn1—N1—C1	−136.9 (4)	C5—C4—C3—C2	−1.1 (7)
N4—Zn1—N1—C1	−58.5 (4)	C7—C8—C9—C10	−0.5 (7)
O2—Zn1—N1—C5	−111.2 (3)	C11—C10—C9—C8	−0.1 (7)
N3—Zn1—N1—C5	−3.2 (3)	C5—N1—C1—C2	−3.3 (6)
N6—Zn1—N1—C5	49.1 (5)	Zn1—N1—C1—C2	−177.1 (3)
N4—Zn1—N1—C5	127.5 (3)	C4—C3—C2—C1	−0.4 (7)
C10—C11—N4—C7	0.3 (6)	N1—C1—C2—C3	2.6 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.82	1.98	2.767 (4)	162.
O1—H1···N6	0.82	2.43	3.018 (4)	129.
N2—H2A···O2ii	0.86	2.32	3.108 (5)	152.
N2—H2B···O5iii	0.86	2.35	3.180 (5)	162.
N5—H5A···O4	0.86	2.18	2.900 (5)	142.
N5—H5B···O5iv	0.86	2.18	2.985 (5)	156.

Table 1

Selected bond lengths (Å)

Zn1—O2	1.981 (3)
Zn1—N1	2.148 (3)
Zn1—N3	2.064 (3)
Zn1—N4	2.128 (3)
Zn1—N6	2.099 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.82	1.98	2.767 (4)	162
O1—H1⋯N6	0.82	2.43	3.018 (4)	129
N2—H2A⋯O2ii	0.86	2.32	3.108 (5)	152
N2—H2B⋯O5iii	0.86	2.35	3.180 (5)	162
N5—H5A⋯O4	0.86	2.18	2.900 (5)	142
N5—H5B⋯O5iv	0.86	2.18	2.985 (5)	156

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