catena-Poly[diacridinium [zinc(II)-di-μ-pyrazine-2,3-dicarboxyl-ato-κN,O:O;O:N,O]].

The crystal structure of the title compound, {(C(13)H(10)N)(2)[Zn(C(6)H(2)N(2)O(4))(2)]}(n), consists of polymeric Zn complex anions and discrete acridinium cations. The Zn cation, located on an inversion center, is N,O-chelated by two pyrazine-2,3-dicarboxyl-ate (pyzdc) anions in the basal plane, and is further coordinated by two carboxyl-ate O atoms from adjacent pyzdc anions in the axial directions with a longer Zn-O bond distance, forming a distorted ZnN(2)O(4) coordination geometry. The pyzdc anions bridge the Zn cations, forming polymeric chains running along the crystallographic b axis. The acridinium cations are linked to the complex chains via N-H⋯O and C-H⋯O hydrogen bonding. Significant π-π stacking between parallel acridinium ring systems is observed in the crystal structure, face-to-face distances being 3.311 (3) and 3.267 (4) Å.

Related literature

For the structure of a related Co(II) complex with pyzdc ligands, see: Aghabozorg et al. (2010b ▶). For the proton transfer of the carboxyl group, see: Aghabozorg et al. (2010a ▶).

Experimental

Crystal data

(C13H10N)2[Zn(C6H2N2O4)2]

M = 758.00

Monoclinic,

a = 13.2256 (12) Å

b = 6.8141 (6) Å

c = 17.9889 (16) Å

β = 111.013 (2)°

V = 1513.4 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.88 mm−1

T = 120 K

0.27 × 0.15 × 0.13 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick 1998 ▶) T min = 0.845, T max = 0.891

15968 measured reflections

2720 independent reflections

2292 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.115

S = 1.14

2720 reflections

244 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.76 e Å−3

Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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 datablocks I, global. DOI: 10.1107/S1600536810025195/xu2784sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025195/xu2784Isup2.hkl

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

(C13H10N)2[Zn(C6H2N2O4)2]	F(000) = 776
Mr = 758.00	Dx = 1.663 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 600 reflections
a = 13.2256 (12) Å	θ = 2.0–24.0°
b = 6.8141 (6) Å	µ = 0.88 mm−1
c = 17.9889 (16) Å	T = 120 K
β = 111.013 (2)°	Prism, red
V = 1513.4 (2) Å3	0.27 × 0.15 × 0.13 mm
Z = 2

Bruker SMART 1000 CCD area-detector diffractometer	2720 independent reflections
Radiation source: fine-focus sealed tube	2292 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω scans	θmax = 25.2°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick 1998)	h = −15→15
Tmin = 0.845, Tmax = 0.891	k = −8→8
15968 measured reflections	l = −21→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0644P)2 + 1.454P] where P = (Fo2 + 2Fc2)/3
2720 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.76 e Å−3
1 restraint	Δρmin = −0.47 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	1.0000	1.0000	0.5000	0.02299 (17)
N1	0.97579 (16)	0.7741 (3)	0.41650 (12)	0.0181 (4)
N2	0.92414 (17)	0.4493 (3)	0.31697 (13)	0.0235 (5)
N3	0.56207 (16)	0.2835 (3)	0.40993 (12)	0.0188 (4)
O1	0.90033 (14)	0.8249 (3)	0.53444 (11)	0.0225 (4)
O2	0.81853 (16)	0.5307 (3)	0.51045 (12)	0.0275 (5)
O3	0.71207 (14)	0.3430 (3)	0.34784 (11)	0.0231 (4)
O4	0.84996 (14)	0.1517 (3)	0.41985 (10)	0.0219 (4)
C1	0.87279 (19)	0.6642 (4)	0.49636 (15)	0.0183 (5)
C2	0.91244 (18)	0.6323 (4)	0.42725 (14)	0.0166 (5)
C3	1.0143 (2)	0.7552 (4)	0.35783 (15)	0.0213 (5)
H3	1.0591	0.8517	0.3499	0.026*
C4	0.9879 (2)	0.5930 (4)	0.30892 (15)	0.0234 (6)
H4	1.0158	0.5833	0.2684	0.028*
C5	0.88694 (19)	0.4691 (4)	0.37672 (15)	0.0174 (5)
C6	0.8114 (2)	0.3068 (4)	0.38376 (15)	0.0197 (5)
C7	0.4615 (2)	0.3287 (3)	0.35817 (15)	0.0173 (5)
C8	0.4441 (2)	0.3677 (4)	0.27753 (15)	0.0216 (5)
H8	0.5016	0.3642	0.2593	0.026*
C9	0.3419 (2)	0.4107 (4)	0.22648 (16)	0.0233 (6)
H9	0.3300	0.4348	0.1731	0.028*
C10	0.2537 (2)	0.4193 (4)	0.25332 (15)	0.0233 (6)
H10	0.1850	0.4504	0.2176	0.028*
C11	0.2682 (2)	0.3826 (4)	0.33062 (16)	0.0229 (6)
H11	0.2095	0.3882	0.3475	0.027*
C12	0.3732 (2)	0.3354 (4)	0.38588 (15)	0.0187 (5)
C13	0.3932 (2)	0.2948 (3)	0.46547 (15)	0.0183 (5)
H13	0.3366	0.3014	0.4846	0.022*
C14	0.4961 (2)	0.2445 (4)	0.51706 (15)	0.0183 (5)
C15	0.5195 (2)	0.1983 (4)	0.59890 (15)	0.0219 (6)
H15	0.4644	0.2036	0.6196	0.026*
C16	0.6211 (2)	0.1467 (4)	0.64685 (16)	0.0239 (6)
H16	0.6358	0.1182	0.7003	0.029*
C17	0.7049 (2)	0.1364 (4)	0.61494 (16)	0.0237 (6)
H17	0.7738	0.0977	0.6480	0.028*
C18	0.6877 (2)	0.1814 (4)	0.53774 (15)	0.0210 (5)
H18	0.7441	0.1759	0.5184	0.025*
C19	0.5823 (2)	0.2368 (3)	0.48739 (14)	0.0180 (5)
H3N	0.6133 (15)	0.292 (4)	0.3912 (15)	0.022*

	U11	U22	U33	U12	U13	U23
Zn1	0.0244 (3)	0.0228 (3)	0.0256 (3)	−0.00764 (17)	0.0137 (2)	−0.00581 (17)
N1	0.0126 (10)	0.0220 (11)	0.0196 (10)	0.0012 (8)	0.0058 (8)	0.0009 (9)
N2	0.0187 (11)	0.0312 (12)	0.0221 (11)	−0.0029 (9)	0.0093 (9)	−0.0022 (9)
N3	0.0152 (11)	0.0215 (11)	0.0217 (11)	−0.0001 (8)	0.0090 (9)	0.0011 (9)
O1	0.0224 (9)	0.0225 (9)	0.0252 (10)	−0.0031 (7)	0.0118 (8)	−0.0029 (7)
O2	0.0303 (11)	0.0281 (10)	0.0318 (11)	−0.0089 (8)	0.0205 (9)	−0.0043 (8)
O3	0.0149 (9)	0.0282 (10)	0.0251 (10)	−0.0018 (7)	0.0058 (8)	0.0009 (8)
O4	0.0209 (9)	0.0198 (9)	0.0234 (9)	−0.0017 (7)	0.0059 (8)	−0.0002 (7)
C1	0.0142 (12)	0.0211 (13)	0.0193 (13)	0.0010 (10)	0.0058 (10)	0.0012 (10)
C2	0.0120 (11)	0.0199 (12)	0.0177 (12)	0.0017 (9)	0.0051 (10)	0.0034 (10)
C3	0.0131 (12)	0.0285 (13)	0.0226 (13)	−0.0016 (10)	0.0067 (10)	0.0028 (11)
C4	0.0181 (13)	0.0320 (15)	0.0226 (13)	0.0014 (11)	0.0102 (11)	−0.0014 (11)
C5	0.0109 (11)	0.0223 (12)	0.0177 (12)	0.0004 (9)	0.0035 (10)	0.0003 (10)
C6	0.0164 (12)	0.0248 (13)	0.0182 (12)	−0.0031 (10)	0.0065 (10)	−0.0050 (10)
C7	0.0161 (12)	0.0150 (11)	0.0207 (13)	−0.0002 (9)	0.0064 (10)	−0.0015 (9)
C8	0.0201 (13)	0.0250 (13)	0.0226 (13)	0.0016 (10)	0.0110 (11)	0.0003 (11)
C9	0.0267 (14)	0.0232 (13)	0.0186 (13)	0.0004 (11)	0.0066 (11)	−0.0013 (10)
C10	0.0156 (13)	0.0259 (13)	0.0233 (14)	0.0011 (10)	0.0009 (11)	0.0021 (11)
C11	0.0149 (12)	0.0256 (13)	0.0284 (14)	−0.0010 (10)	0.0081 (11)	0.0008 (11)
C12	0.0165 (12)	0.0188 (12)	0.0224 (13)	−0.0008 (9)	0.0088 (11)	−0.0016 (10)
C13	0.0165 (12)	0.0187 (12)	0.0231 (13)	−0.0027 (10)	0.0112 (10)	−0.0028 (10)
C14	0.0177 (12)	0.0158 (12)	0.0223 (13)	−0.0035 (9)	0.0083 (10)	−0.0022 (10)
C15	0.0233 (13)	0.0232 (13)	0.0231 (13)	−0.0040 (11)	0.0131 (11)	−0.0009 (10)
C16	0.0250 (14)	0.0257 (13)	0.0203 (13)	−0.0065 (11)	0.0073 (11)	0.0017 (10)
C17	0.0164 (13)	0.0265 (13)	0.0247 (14)	−0.0015 (10)	0.0032 (11)	0.0050 (11)
C18	0.0152 (12)	0.0232 (13)	0.0252 (14)	−0.0020 (10)	0.0080 (11)	0.0010 (10)
C19	0.0194 (13)	0.0163 (11)	0.0199 (12)	−0.0032 (10)	0.0090 (10)	0.0000 (10)

Zn1—O1	2.0326 (17)	C7—C8	1.410 (4)
Zn1—O1i	2.0326 (17)	C7—C12	1.425 (3)
Zn1—N1i	2.093 (2)	C8—C9	1.366 (4)
Zn1—N1	2.093 (2)	C8—H8	0.9300
Zn1—O4ii	2.2435 (17)	C9—C10	1.414 (4)
Zn1—O4iii	2.2435 (17)	C9—H9	0.9300
N1—C3	1.332 (3)	C10—C11	1.357 (4)
N1—C2	1.338 (3)	C10—H10	0.9300
N2—C4	1.333 (4)	C11—C12	1.425 (4)
N2—C5	1.340 (3)	C11—H11	0.9300
N3—C7	1.358 (3)	C12—C13	1.387 (4)
N3—C19	1.359 (3)	C13—C14	1.388 (4)
N3—H3N	0.86 (2)	C13—H13	0.9300
O1—C1	1.273 (3)	C14—C19	1.422 (3)
O2—C1	1.240 (3)	C14—C15	1.427 (4)
O3—C6	1.263 (3)	C15—C16	1.357 (4)
O4—C6	1.249 (3)	C15—H15	0.9300
C1—C2	1.528 (3)	C16—C17	1.422 (4)
C2—C5	1.399 (3)	C16—H16	0.9300
C3—C4	1.377 (4)	C17—C18	1.359 (4)
C3—H3	0.9300	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.414 (4)
C5—C6	1.526 (3)	C18—H18	0.9300
O1—Zn1—O1i	180.0	O3—C6—C5	114.1 (2)
O1—Zn1—N1i	99.32 (7)	N3—C7—C8	120.4 (2)
O1i—Zn1—N1i	80.68 (7)	N3—C7—C12	119.5 (2)
O1—Zn1—N1	80.68 (7)	C8—C7—C12	120.1 (2)
O1i—Zn1—N1	99.32 (7)	C9—C8—C7	119.3 (2)
N1i—Zn1—N1	180.0	C9—C8—H8	120.4
O1—Zn1—O4ii	86.88 (7)	C7—C8—H8	120.4
O1i—Zn1—O4ii	93.12 (7)	C8—C9—C10	121.2 (2)
N1i—Zn1—O4ii	89.71 (7)	C8—C9—H9	119.4
N1—Zn1—O4ii	90.29 (7)	C10—C9—H9	119.4
O1—Zn1—O4iii	93.12 (7)	C11—C10—C9	120.8 (2)
O1i—Zn1—O4iii	86.88 (7)	C11—C10—H10	119.6
N1i—Zn1—O4iii	90.29 (7)	C9—C10—H10	119.6
N1—Zn1—O4iii	89.71 (7)	C10—C11—C12	120.1 (2)
O4ii—Zn1—O4iii	180.000 (1)	C10—C11—H11	120.0
C3—N1—C2	118.8 (2)	C12—C11—H11	120.0
C3—N1—Zn1	129.49 (17)	C13—C12—C11	122.9 (2)
C2—N1—Zn1	111.71 (16)	C13—C12—C7	118.5 (2)
C4—N2—C5	116.2 (2)	C11—C12—C7	118.6 (2)
C7—N3—C19	122.7 (2)	C12—C13—C14	121.2 (2)
C7—N3—H3N	115.6 (19)	C12—C13—H13	119.4
C19—N3—H3N	121.6 (19)	C14—C13—H13	119.4
C1—O1—Zn1	115.63 (15)	C13—C14—C19	119.0 (2)
C6—O4—Zn1iv	145.70 (16)	C13—C14—C15	122.8 (2)
O2—C1—O1	126.6 (2)	C19—C14—C15	118.2 (2)
O2—C1—C2	117.0 (2)	C16—C15—C14	120.8 (2)
O1—C1—C2	116.4 (2)	C16—C15—H15	119.6
N1—C2—C5	119.9 (2)	C14—C15—H15	119.6
N1—C2—C1	115.5 (2)	C15—C16—C17	119.6 (2)
C5—C2—C1	124.7 (2)	C15—C16—H16	120.2
N1—C3—C4	120.1 (2)	C17—C16—H16	120.2
N1—C3—H3	119.9	C18—C17—C16	122.1 (2)
C4—C3—H3	119.9	C18—C17—H17	118.9
N2—C4—C3	123.1 (2)	C16—C17—H17	118.9
N2—C4—H4	118.5	C17—C18—C19	118.7 (2)
C3—C4—H4	118.5	C17—C18—H18	120.6
N2—C5—C2	121.9 (2)	C19—C18—H18	120.6
N2—C5—C6	115.7 (2)	N3—C19—C18	120.4 (2)
C2—C5—C6	122.3 (2)	N3—C19—C14	119.1 (2)
O4—C6—O3	126.0 (2)	C18—C19—C14	120.5 (2)
O4—C6—C5	119.9 (2)
O1—Zn1—N1—C3	179.3 (2)	N2—C5—C6—O4	83.9 (3)
O1i—Zn1—N1—C3	−0.7 (2)	C2—C5—C6—O4	−98.6 (3)
O4ii—Zn1—N1—C3	92.5 (2)	N2—C5—C6—O3	−93.2 (3)
O4iii—Zn1—N1—C3	−87.5 (2)	C2—C5—C6—O3	84.3 (3)
O1—Zn1—N1—C2	−1.26 (16)	C19—N3—C7—C8	−177.2 (2)
O1i—Zn1—N1—C2	178.74 (16)	C19—N3—C7—C12	2.4 (4)
O4ii—Zn1—N1—C2	−88.05 (16)	N3—C7—C8—C9	179.3 (2)
O4iii—Zn1—N1—C2	91.95 (16)	C12—C7—C8—C9	−0.4 (4)
N1i—Zn1—O1—C1	−177.15 (17)	C7—C8—C9—C10	0.8 (4)
N1—Zn1—O1—C1	2.85 (17)	C8—C9—C10—C11	−0.8 (4)
O4ii—Zn1—O1—C1	93.66 (17)	C9—C10—C11—C12	0.2 (4)
O4iii—Zn1—O1—C1	−86.34 (17)	C10—C11—C12—C13	−179.4 (2)
Zn1—O1—C1—O2	175.2 (2)	C10—C11—C12—C7	0.2 (4)
Zn1—O1—C1—C2	−3.8 (3)	N3—C7—C12—C13	−0.1 (3)
C3—N1—C2—C5	−0.7 (3)	C8—C7—C12—C13	179.5 (2)
Zn1—N1—C2—C5	179.80 (17)	N3—C7—C12—C11	−179.8 (2)
C3—N1—C2—C1	179.3 (2)	C8—C7—C12—C11	−0.2 (3)
Zn1—N1—C2—C1	−0.2 (2)	C11—C12—C13—C14	178.3 (2)
O2—C1—C2—N1	−176.4 (2)	C7—C12—C13—C14	−1.4 (4)
O1—C1—C2—N1	2.7 (3)	C12—C13—C14—C19	0.7 (4)
O2—C1—C2—C5	3.6 (4)	C12—C13—C14—C15	−178.8 (2)
O1—C1—C2—C5	−177.4 (2)	C13—C14—C15—C16	178.9 (2)
C2—N1—C3—C4	0.7 (4)	C19—C14—C15—C16	−0.6 (4)
Zn1—N1—C3—C4	−179.85 (18)	C14—C15—C16—C17	−0.7 (4)
C5—N2—C4—C3	−0.7 (4)	C15—C16—C17—C18	1.6 (4)
N1—C3—C4—N2	0.0 (4)	C16—C17—C18—C19	−1.2 (4)
C4—N2—C5—C2	0.7 (4)	C7—N3—C19—C18	176.9 (2)
C4—N2—C5—C6	178.2 (2)	C7—N3—C19—C14	−3.1 (4)
N1—C2—C5—N2	−0.1 (4)	C17—C18—C19—N3	179.8 (2)
C1—C2—C5—N2	179.9 (2)	C17—C18—C19—C14	−0.2 (4)
N1—C2—C5—C6	−177.4 (2)	C13—C14—C19—N3	1.6 (3)
C1—C2—C5—C6	2.6 (4)	C15—C14—C19—N3	−178.9 (2)
Zn1iv—O4—C6—O3	−171.95 (18)	C13—C14—C19—C18	−178.4 (2)
Zn1iv—O4—C6—C5	11.3 (4)	C15—C14—C19—C18	1.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O3	0.86 (2)	1.78 (2)	2.634 (3)	172 (3)
C13—H13···O2v	0.93	2.38	3.211 (4)	149
C16—H16···O3vi	0.93	2.49	3.377 (3)	159

Table 1

Selected bond lengths (Å)

Zn1—O1	2.0326 (17)
Zn1—N1	2.093 (2)
Zn1—O4i	2.2435 (17)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O3	0.86 (2)	1.78 (2)	2.634 (3)	172 (3)
C13—H13⋯O2ii	0.93	2.38	3.211 (4)	149
C16—H16⋯O3iii	0.93	2.49	3.377 (3)	159

Symmetry codes: (ii) ; (iii) .