catena-Poly[[[pyrazino[2,3-f][1,10]phenanthroline]zinc(II)]-μ₄-fumarato-μ₂-fumarato]

In the title compound, [Zn(C₄H₂O₄)(C₁₄H₈N₄)]_n, the Zn^II atom is five-coordinate and exhibits a distorted trigonal–bipyramidal coordination. The Zn^II atoms are further bridged by fumarate ligands, forming a two-dimensional network parallel to the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.045
• wR factor = 0.106
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C17    -   C18    ...       1.53 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

catena-Poly[[pyrazino[2,3-f][1,10]phenanthroline]zinc(II)]- µ₄-fumarato-µ₂-fumarato]

Crystal data

[Zn(C4H2O4)(C14H8N4)]	Z = 2
Mr = 411.67	F(000) = 416
Triclinic, P1	Dx = 1.714 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8613 (14) Å	Cell parameters from 5837 reflections
b = 8.3961 (17) Å	θ = 3.0–27.3°
c = 14.610 (3) Å	µ = 1.58 mm^−1
α = 105.08 (3)°	T = 292 K
β = 98.70 (3)°	Block, colourless
γ = 94.15 (3)°	0.22 × 0.19 × 0.18 mm
V = 797.8 (3) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3472 independent reflections
Radiation source: rotor target	2651 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 10.0 pixels mm^-1	θmax = 27.3°, θmin = 2.9°
ω scans	h = −8→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.700, Tmax = 0.755	l = −18→18
7523 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 1.1513P] where P = (Fo^2 + 2Fc^2)/3
3472 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.46 e Å^−3
1 restraint	Δρmin = −0.48 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.62636 (7)	0.49775 (5)	0.40543 (3)	0.02991 (14)
C6	0.6738 (5)	0.3199 (4)	0.2068 (2)	0.0281 (8)
O1	0.5929 (4)	0.3555 (3)	0.49540 (17)	0.0306 (6)
C4	0.3865 (5)	0.3806 (5)	0.1007 (3)	0.0310 (8)
O3	0.8173 (4)	0.7024 (3)	0.46620 (18)	0.0373 (6)
N1	0.4308 (4)	0.4860 (4)	0.2773 (2)	0.0290 (7)
C11	0.6305 (6)	0.2071 (5)	0.0273 (3)	0.0337 (8)
O2	0.4594 (5)	0.1422 (4)	0.36274 (19)	0.0452 (7)
N3	0.3504 (5)	0.2694 (5)	−0.0773 (2)	0.0436 (8)
N2	0.7700 (5)	0.3434 (4)	0.3001 (2)	0.0306 (7)
C9	0.9125 (6)	0.1455 (5)	0.1433 (3)	0.0402 (9)
H9	0.9625	0.0799	0.0924	0.048*
C16	0.5214 (6)	0.0829 (5)	0.5166 (3)	0.0335 (8)
H16	0.5524	0.1301	0.5828	0.040*
N4	0.7017 (5)	0.1121 (5)	−0.0536 (3)	0.0452 (9)
C15	0.5218 (6)	0.1972 (4)	0.4510 (3)	0.0307 (8)
C10	0.7403 (6)	0.2235 (5)	0.1256 (3)	0.0322 (8)
C12	0.4579 (6)	0.2832 (5)	0.0150 (2)	0.0337 (8)
C5	0.4935 (5)	0.3987 (4)	0.1947 (2)	0.0262 (7)
C7	0.9306 (6)	0.2698 (5)	0.3151 (3)	0.0391 (9)
H7	0.9960	0.2851	0.3778	0.047*
C8	1.0060 (6)	0.1682 (6)	0.2379 (3)	0.0458 (10)
H8	1.1184	0.1165	0.2505	0.055*
O4	0.8604 (5)	0.7245 (4)	0.31906 (19)	0.0505 (8)
C17	0.8851 (5)	0.7798 (5)	0.4092 (3)	0.0327 (8)
C18	0.9999 (6)	0.9524 (5)	0.4545 (3)	0.0362 (9)
H18	1.0755	0.9957	0.4169	0.043*
C1	0.2655 (6)	0.5575 (5)	0.2676 (3)	0.0344 (8)
H1	0.2226	0.6161	0.3227	0.041*
C2	0.1513 (6)	0.5481 (5)	0.1761 (3)	0.0434 (10)
H2	0.0372	0.6010	0.1718	0.052*
C3	0.2127 (6)	0.4585 (5)	0.0930 (3)	0.0400 (9)
H3	0.1390	0.4503	0.0327	0.048*
C14	0.5941 (7)	0.1025 (6)	−0.1376 (3)	0.0522 (12)
H14	0.6349	0.0404	−0.1925	0.063*
C13	0.4202 (7)	0.1807 (6)	−0.1497 (3)	0.0510 (12)
H13	0.3530	0.1685	−0.2118	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0376 (3)	0.0269 (2)	0.0239 (2)	−0.00151 (17)	0.00068 (16)	0.00872 (16)
C6	0.0303 (19)	0.0256 (19)	0.0287 (18)	0.0007 (15)	0.0016 (14)	0.0107 (15)
O1	0.0415 (15)	0.0225 (13)	0.0297 (13)	0.0025 (11)	0.0081 (11)	0.0099 (10)
C4	0.030 (2)	0.033 (2)	0.0303 (19)	0.0024 (16)	0.0018 (14)	0.0102 (15)
O3	0.0439 (16)	0.0298 (15)	0.0337 (14)	−0.0050 (12)	0.0014 (12)	0.0066 (11)
N1	0.0299 (17)	0.0276 (16)	0.0288 (16)	0.0021 (13)	0.0034 (12)	0.0079 (13)
C11	0.040 (2)	0.030 (2)	0.031 (2)	0.0040 (17)	0.0086 (16)	0.0077 (16)
O2	0.065 (2)	0.0359 (16)	0.0307 (15)	−0.0031 (14)	0.0001 (13)	0.0091 (12)
N3	0.045 (2)	0.045 (2)	0.0387 (19)	0.0032 (17)	−0.0003 (15)	0.0129 (16)
N2	0.0341 (17)	0.0329 (17)	0.0260 (15)	0.0043 (14)	0.0013 (12)	0.0120 (13)
C9	0.039 (2)	0.040 (2)	0.043 (2)	0.0119 (19)	0.0139 (18)	0.0091 (19)
C16	0.037 (2)	0.034 (2)	0.0315 (19)	0.0065 (17)	0.0088 (15)	0.0108 (16)
N4	0.046 (2)	0.043 (2)	0.046 (2)	0.0076 (17)	0.0096 (16)	0.0093 (17)
C15	0.039 (2)	0.0244 (19)	0.033 (2)	0.0085 (16)	0.0072 (16)	0.0127 (15)
C10	0.035 (2)	0.028 (2)	0.035 (2)	0.0048 (16)	0.0051 (15)	0.0108 (16)
C12	0.042 (2)	0.032 (2)	0.0240 (18)	−0.0009 (17)	−0.0009 (15)	0.0081 (15)
C5	0.0248 (18)	0.0270 (18)	0.0280 (18)	0.0027 (14)	0.0041 (13)	0.0099 (14)
C7	0.038 (2)	0.043 (2)	0.037 (2)	0.0094 (19)	−0.0031 (17)	0.0161 (18)
C8	0.036 (2)	0.052 (3)	0.054 (3)	0.019 (2)	0.0062 (19)	0.019 (2)
O4	0.072 (2)	0.0441 (18)	0.0323 (16)	−0.0011 (16)	0.0046 (14)	0.0102 (13)
C17	0.0266 (19)	0.032 (2)	0.038 (2)	0.0055 (16)	0.0057 (15)	0.0056 (16)
C18	0.037 (2)	0.036 (2)	0.038 (2)	0.0023 (17)	0.0063 (16)	0.0133 (16)
C1	0.033 (2)	0.034 (2)	0.035 (2)	0.0080 (17)	0.0081 (16)	0.0057 (16)
C2	0.036 (2)	0.047 (3)	0.049 (2)	0.0145 (19)	0.0020 (18)	0.015 (2)
C3	0.034 (2)	0.051 (3)	0.035 (2)	0.0091 (19)	−0.0013 (16)	0.0147 (19)
C14	0.067 (3)	0.051 (3)	0.034 (2)	0.005 (2)	0.016 (2)	0.001 (2)
C13	0.060 (3)	0.060 (3)	0.027 (2)	−0.007 (2)	−0.0027 (19)	0.011 (2)

Geometric parameters (Å, º)

Zn1—O3	1.996 (3)	C9—C8	1.392 (6)
Zn1—O1	2.019 (2)	C9—C10	1.413 (5)
Zn1—N1	2.107 (3)	C9—H9	0.93
Zn1—N2	2.150 (3)	C16—C16^ii	1.344 (7)
Zn1—O1^i	2.425 (3)	C16—C15	1.522 (5)
C6—N2	1.379 (4)	C16—H16	0.93
C6—C10	1.410 (5)	N4—C14	1.313 (6)
C6—C5	1.454 (5)	C7—C8	1.416 (6)
O1—C15	1.337 (4)	C7—H7	0.93
O1—Zn1^i	2.425 (3)	C8—H8	0.93
C4—C3	1.404 (5)	O4—C17	1.258 (4)
C4—C5	1.420 (5)	C17—C18	1.528 (5)
C4—C12	1.478 (5)	C18—C18^iii	1.362 (7)
O3—C17	1.299 (5)	C18—H18	0.93
N1—C1	1.327 (5)	C1—C2	1.424 (5)
N1—C5	1.386 (5)	C1—H1	0.93
C11—C12	1.396 (6)	C2—C3	1.394 (6)
C11—N4	1.418 (5)	C2—H2	0.93
C11—C10	1.485 (5)	C3—H3	0.93
O2—C15	1.247 (4)	C14—C13	1.413 (7)
N3—C13	1.304 (6)	C14—H14	0.93
N3—C12	1.408 (5)	C13—H13	0.93
N2—C7	1.319 (5)
O3—Zn1—O1	113.16 (11)	O2—C15—C16	120.6 (3)
O3—Zn1—N1	118.42 (12)	O1—C15—C16	115.0 (3)
O1—Zn1—N1	125.98 (11)	C6—C10—C9	116.9 (3)
O3—Zn1—N2	105.43 (12)	C6—C10—C11	120.1 (3)
O1—Zn1—N2	102.26 (11)	C9—C10—C11	123.0 (3)
N1—Zn1—N2	79.02 (11)	C11—C12—N3	121.3 (3)
O3—Zn1—O1^i	84.24 (10)	C11—C12—C4	119.4 (3)
O1—Zn1—O1^i	77.65 (10)	N3—C12—C4	119.3 (4)
N1—Zn1—O1^i	92.25 (10)	N1—C5—C4	122.7 (3)
N2—Zn1—O1^i	169.21 (10)	N1—C5—C6	117.5 (3)
N2—C6—C10	123.4 (3)	C4—C5—C6	119.8 (3)
N2—C6—C5	116.5 (3)	N2—C7—C8	121.6 (4)
C10—C6—C5	120.1 (3)	N2—C7—H7	119.2
C15—O1—Zn1	114.3 (2)	C8—C7—H7	119.2
C15—O1—Zn1^i	113.2 (2)	C9—C8—C7	120.3 (4)
Zn1—O1—Zn1^i	102.35 (10)	C9—C8—H8	119.9
C3—C4—C5	117.5 (3)	C7—C8—H8	119.9
C3—C4—C12	122.0 (3)	O4—C17—O3	124.8 (3)
C5—C4—C12	120.5 (3)	O4—C17—C18	117.4 (3)
C17—O3—Zn1	117.4 (2)	O3—C17—C18	117.8 (3)
C1—N1—C5	118.3 (3)	C18^iii—C18—C17	125.1 (5)
C1—N1—Zn1	127.9 (3)	C18^iii—C18—H18	117.5
C5—N1—Zn1	113.7 (2)	C17—C18—H18	117.5
C12—C11—N4	120.6 (3)	N1—C1—C2	122.6 (4)
C12—C11—C10	120.1 (3)	N1—C1—H1	118.7
N4—C11—C10	119.3 (3)	C2—C1—H1	118.7
C13—N3—C12	116.2 (4)	C3—C2—C1	119.1 (4)
C7—N2—C6	118.8 (3)	C3—C2—H2	120.4
C7—N2—Zn1	128.0 (3)	C1—C2—H2	120.4
C6—N2—Zn1	113.2 (2)	C2—C3—C4	119.7 (4)
C8—C9—C10	119.0 (4)	C2—C3—H3	120.1
C8—C9—H9	120.5	C4—C3—H3	120.1
C10—C9—H9	120.5	N4—C14—C13	124.1 (4)
C16^ii—C16—C15	123.2 (4)	N4—C14—H14	118.0
C16^ii—C16—H16	118.4	C13—C14—H14	118.0
C15—C16—H16	118.4	N3—C13—C14	122.6 (4)
C14—N4—C11	115.2 (4)	N3—C13—H13	118.7
O2—C15—O1	124.4 (3)	C14—C13—H13	118.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3^iv	0.93	2.41	3.337 (5)	174
C13—H13···O4^v	0.93	2.37	3.204 (6)	149
C14—H14···O2^vi	0.93	2.52	3.344 (5)	148

Symmetry codes: (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x+1, −y, −z.