3-[3-(3-Pyrid­yloxy)pyrazin-2-yl­oxy]­pyridinium perchlorate

In the crystal structure of the title compound, C₁₄H₁₁N₄O₂⁺·ClO₄⁻, the cations are connected by inter­molecular N—H...N hydrogen bonds to form one-dimensional chains along the a axis, while weak inter­molecular C—H...O hydrogen bonds connect the cations to the perchlorate anions. In the cation, the dihedral angles between the pyrazine ring and the two pyridine rings are 71.00 (16) and 64.59 (16)°, and the dihedral angle between the two pyridine rings is 12.02 (16)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.064
• wR factor = 0.233
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.777
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.30
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

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

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

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S1. Comment

Compounds containing pyrazine and pyridine rings have play an important role in coordination chemistry (McMorran & Steel, 2002) and it was originally hoped to synthesize a Zn^II complex of 2,3-bis(pyridin-3-yloxy)pyrazine and phosphorate as multi-dentate ligands, but instead the title compound was obtained and its crystal structure is reported herein.

The asymmetric unit is shown in Fig. 1. Geometric parameters are in the usual rangs (Allen et al., 1987). In the cation, the dihedral angles between the pyrazine ring and the two pyridine rings are 71.00 (16)° and 64.59 (16)°, and the dihedral angle between the two pyridine rings is 12.02 (16)°. In the crystal structure, intermolecular N—H···N hydrogen bonds link cation molecules to form one-dimensional chains along the a axis. In addition, weak C—H···O hydrogen bonds connect perchlorate anions bound to the cations.

Related literature

For a related structure, see: McMorran & Steel (2002). For related literature, see: Allen et al. (1987).

S2. Experimental

5 ml me thanol solution of 2,3-bis(pyridin-3-yloxy)prazine (0.0521 g, 0.196 mmol) was added into 10 ml H₂O solution containing Zn(ClO₄)₂.6H₂O (0.1430 g, 0.384 mmol) and NaH₂PO₄.2H₂O (0.0602 g, 0.386 mmol), and the mixture was stirred for a few minutes. Yellow single crystals were obtained after the solution had been allowed to stand at room temperature for one week.

S3. Refinement

The H atoms were placed in calculated positions and refined as riding, with C—H = 0.93 Å, U_iso(H) = 1.2_eq(C), N—H = 0.86 Å, U_iso(H) = 1.2_eq(N). The larger than normal anisotropic displacement parameters associated with the O atoms of the perchlorate anion may be due to a small amount of disorder with repect to these atoms. The disorder was not modelled.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. Partial packing plot with hydrogen bonds shown as dashed lines.

3-[3-(3-Pyridyloxy)pyrazin-2-yloxy]pyridinium perchlorate

Crystal data

C14H11N4O2^+·ClO4^−	F(000) = 752
Mr = 366.72	Dx = 1.565 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1097 reflections
a = 11.557 (3) Å	θ = 2.6–20.3°
b = 9.815 (2) Å	µ = 0.29 mm^−1
c = 13.955 (3) Å	T = 298 K
β = 100.444 (4)°	Prism-like, yellow
V = 1556.8 (6) Å^3	0.23 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3365 independent reflections
Radiation source: fine-focus sealed tube	2041 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
φ and ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
Tmin = 0.937, Tmax = 0.955	k = −12→12
9181 measured reflections	l = −15→17

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.233	H-atom parameters constrained
S = 0.78	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
3365 reflections	(Δ/σ)max = 0.003
226 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.25 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
Cl1	0.21688 (9)	0.66871 (9)	0.09517 (7)	0.0516 (3)
O2	0.50784 (18)	0.9667 (2)	0.12191 (17)	0.0451 (6)
O1	0.31002 (18)	1.0866 (2)	0.14694 (17)	0.0410 (6)
N1	0.5197 (2)	0.8455 (3)	0.2650 (2)	0.0433 (7)
N3	0.8152 (2)	0.9357 (3)	0.1091 (2)	0.0453 (7)
N4	−0.0023 (2)	1.1068 (3)	0.1394 (2)	0.0481 (7)
H2	−0.0623	1.0535	0.1327	0.058*
N2	0.3098 (2)	0.9658 (3)	0.2899 (2)	0.0425 (7)
C8	0.3580 (3)	0.9940 (3)	0.2154 (2)	0.0363 (7)
C9	0.4649 (3)	0.9316 (3)	0.2024 (2)	0.0369 (7)
C6	0.3666 (3)	0.8749 (4)	0.3551 (3)	0.0510 (9)
H6	0.3344	0.8522	0.4094	0.061*
C5	−0.0182 (3)	1.2402 (4)	0.1459 (3)	0.0497 (9)
H5	−0.0935	1.2740	0.1451	0.060*
C14	0.7113 (3)	0.9855 (4)	0.1218 (3)	0.0445 (8)
H14	0.7056	1.0766	0.1387	0.053*
C7	0.4695 (3)	0.8163 (4)	0.3429 (3)	0.0488 (9)
H7	0.5062	0.7546	0.3892	0.059*
C2	0.2006 (3)	1.1387 (3)	0.1528 (2)	0.0359 (7)
C10	0.6132 (3)	0.9047 (3)	0.1105 (2)	0.0377 (7)
C13	0.8222 (3)	0.8059 (4)	0.0853 (3)	0.0459 (9)
H13	0.8946	0.7715	0.0768	0.055*
C1	0.1045 (3)	1.0532 (3)	0.1427 (3)	0.0438 (8)
H1	0.1139	0.9595	0.1383	0.053*
C3	0.1868 (3)	1.2755 (4)	0.1582 (2)	0.0417 (8)
H3	0.2515	1.3333	0.1647	0.050*
C4	0.0738 (3)	1.3278 (4)	0.1539 (3)	0.0509 (9)
H4	0.0617	1.4213	0.1564	0.061*
C11	0.6194 (3)	0.7710 (4)	0.0858 (3)	0.0460 (9)
H11	0.5531	0.7155	0.0778	0.055*
C12	0.7274 (3)	0.7203 (4)	0.0728 (3)	0.0523 (10)
H12	0.7353	0.6295	0.0558	0.063*
O5	0.1759 (3)	0.5676 (3)	0.0247 (2)	0.0879 (11)
O4	0.2440 (4)	0.7893 (3)	0.0502 (3)	0.0944 (12)
O3	0.3166 (5)	0.6217 (6)	0.1546 (5)	0.168 (2)
O6	0.1339 (5)	0.6938 (5)	0.1538 (4)	0.150 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0620 (7)	0.0423 (5)	0.0517 (6)	−0.0002 (4)	0.0137 (5)	−0.0013 (4)
O2	0.0263 (11)	0.0570 (15)	0.0549 (14)	0.0092 (10)	0.0150 (10)	0.0168 (11)
O1	0.0222 (11)	0.0449 (13)	0.0572 (14)	0.0044 (9)	0.0110 (10)	0.0112 (11)
N1	0.0259 (14)	0.0576 (18)	0.0461 (16)	0.0052 (12)	0.0059 (12)	0.0043 (13)
N3	0.0268 (14)	0.0515 (18)	0.0599 (18)	0.0016 (12)	0.0135 (13)	0.0034 (14)
N4	0.0251 (14)	0.0525 (18)	0.0676 (19)	−0.0042 (12)	0.0103 (13)	0.0030 (15)
N2	0.0340 (14)	0.0482 (17)	0.0476 (16)	0.0050 (12)	0.0132 (13)	0.0007 (13)
C8	0.0236 (15)	0.0379 (17)	0.0468 (18)	−0.0016 (13)	0.0048 (14)	−0.0015 (14)
C9	0.0260 (15)	0.0420 (18)	0.0426 (17)	0.0000 (13)	0.0061 (13)	0.0015 (14)
C6	0.050 (2)	0.059 (2)	0.0467 (19)	0.0069 (18)	0.0163 (17)	0.0038 (17)
C5	0.0296 (18)	0.049 (2)	0.070 (2)	0.0105 (15)	0.0083 (17)	0.0060 (18)
C14	0.0331 (18)	0.0378 (18)	0.065 (2)	0.0001 (14)	0.0166 (16)	−0.0034 (16)
C7	0.044 (2)	0.062 (2)	0.0399 (18)	0.0121 (17)	0.0061 (15)	0.0089 (16)
C2	0.0250 (15)	0.0397 (18)	0.0438 (17)	0.0027 (13)	0.0082 (13)	0.0042 (13)
C10	0.0277 (16)	0.0467 (19)	0.0410 (17)	0.0022 (13)	0.0125 (13)	0.0039 (14)
C13	0.0394 (19)	0.053 (2)	0.049 (2)	0.0096 (16)	0.0186 (16)	0.0029 (16)
C1	0.0297 (17)	0.0364 (18)	0.067 (2)	0.0027 (14)	0.0127 (16)	0.0034 (16)
C3	0.0307 (17)	0.0438 (19)	0.0499 (19)	−0.0007 (14)	0.0055 (15)	0.0037 (15)
C4	0.044 (2)	0.0373 (19)	0.073 (3)	0.0074 (15)	0.0140 (19)	0.0064 (17)
C11	0.043 (2)	0.049 (2)	0.046 (2)	−0.0131 (16)	0.0109 (16)	−0.0006 (16)
C12	0.066 (3)	0.045 (2)	0.052 (2)	0.0078 (18)	0.0251 (19)	−0.0021 (17)
O5	0.128 (3)	0.0568 (19)	0.081 (2)	−0.0236 (19)	0.026 (2)	−0.0157 (16)
O4	0.155 (4)	0.0531 (18)	0.078 (2)	−0.026 (2)	0.030 (2)	0.0002 (16)
O3	0.137 (4)	0.155 (5)	0.179 (5)	0.026 (4)	−0.061 (4)	0.032 (4)
O6	0.186 (5)	0.119 (4)	0.185 (5)	−0.023 (3)	0.139 (5)	−0.045 (3)

Geometric parameters (Å, º)

Cl1—O3	1.372 (5)	C6—H6	0.9300
Cl1—O4	1.402 (3)	C5—C4	1.357 (5)
Cl1—O5	1.417 (3)	C5—H5	0.9300
Cl1—O6	1.391 (4)	C14—C10	1.369 (5)
O2—C9	1.352 (4)	C14—H14	0.9300
O2—C10	1.396 (4)	C7—H7	0.9300
O1—C8	1.361 (4)	C2—C3	1.356 (5)
O1—C2	1.381 (4)	C2—C1	1.378 (5)
N1—C9	1.295 (4)	C10—C11	1.362 (5)
N1—C7	1.353 (4)	C13—C12	1.366 (5)
N3—C13	1.323 (4)	C13—H13	0.9300
N3—C14	1.337 (4)	C1—H1	0.9300
N4—C5	1.328 (5)	C3—C4	1.395 (5)
N4—C1	1.334 (4)	C3—H3	0.9300
N4—H2	0.8600	C4—H4	0.9300
N2—C8	1.296 (4)	C11—C12	1.387 (5)
N2—C6	1.356 (4)	C11—H11	0.9300
C8—C9	1.420 (4)	C12—H12	0.9300
C6—C7	1.359 (5)
O3—Cl1—O4	108.9 (3)	C10—C14—H14	119.4
O3—Cl1—O5	108.8 (3)	C6—C7—N1	121.6 (3)
O4—Cl1—O5	110.7 (2)	C6—C7—H7	119.2
O3—Cl1—O6	107.3 (4)	N1—C7—H7	119.2
O4—Cl1—O6	110.3 (3)	C3—C2—O1	119.2 (3)
O5—Cl1—O6	110.7 (3)	C3—C2—C1	120.5 (3)
C9—O2—C10	116.3 (2)	O1—C2—C1	119.9 (3)
C8—O1—C2	117.8 (2)	C14—C10—C11	120.5 (3)
C9—N1—C7	116.9 (3)	C14—C10—O2	117.1 (3)
C13—N3—C14	118.8 (3)	C11—C10—O2	122.4 (3)
C5—N4—C1	121.7 (3)	N3—C13—C12	122.8 (3)
C5—N4—H2	119.2	N3—C13—H13	118.6
C1—N4—H2	119.2	C12—C13—H13	118.6
C8—N2—C6	116.9 (3)	N4—C1—C2	119.1 (3)
N2—C8—O1	121.7 (3)	N4—C1—H1	120.4
N2—C8—C9	121.4 (3)	C2—C1—H1	120.4
O1—C8—C9	116.9 (3)	C2—C3—C4	118.7 (3)
N1—C9—O2	121.3 (3)	C2—C3—H3	120.6
N1—C9—C8	121.7 (3)	C4—C3—H3	120.6
O2—C9—C8	117.0 (3)	C5—C4—C3	118.9 (3)
C7—C6—N2	121.5 (3)	C5—C4—H4	120.5
C7—C6—H6	119.2	C3—C4—H4	120.5
N2—C6—H6	119.2	C10—C11—C12	118.0 (3)
N4—C5—C4	121.0 (3)	C10—C11—H11	121.0
N4—C5—H5	119.5	C12—C11—H11	121.0
C4—C5—H5	119.5	C13—C12—C11	118.8 (3)
N3—C14—C10	121.2 (3)	C13—C12—H12	120.6
N3—C14—H14	119.4	C11—C12—H12	120.6
C6—N2—C8—O1	−178.2 (3)	C8—O1—C2—C1	−63.0 (4)
C6—N2—C8—C9	0.5 (5)	N3—C14—C10—C11	−0.1 (5)
C2—O1—C8—N2	−7.4 (4)	N3—C14—C10—O2	−177.8 (3)
C2—O1—C8—C9	173.9 (3)	C9—O2—C10—C14	−109.9 (3)
C7—N1—C9—O2	−179.7 (3)	C9—O2—C10—C11	72.4 (4)
C7—N1—C9—C8	0.9 (5)	C14—N3—C13—C12	0.2 (5)
C10—O2—C9—N1	0.3 (4)	C5—N4—C1—C2	−0.3 (5)
C10—O2—C9—C8	179.8 (3)	C3—C2—C1—N4	−0.7 (5)
N2—C8—C9—N1	−1.0 (5)	O1—C2—C1—N4	−173.7 (3)
O1—C8—C9—N1	177.7 (3)	O1—C2—C3—C4	173.4 (3)
N2—C8—C9—O2	179.5 (3)	C1—C2—C3—C4	0.4 (5)
O1—C8—C9—O2	−1.8 (4)	N4—C5—C4—C3	−2.0 (6)
C8—N2—C6—C7	0.1 (5)	C2—C3—C4—C5	1.0 (5)
C1—N4—C5—C4	1.7 (6)	C14—C10—C11—C12	0.1 (5)
C13—N3—C14—C10	−0.1 (5)	O2—C10—C11—C12	177.7 (3)
N2—C6—C7—N1	−0.2 (6)	N3—C13—C12—C11	−0.2 (6)
C9—N1—C7—C6	−0.3 (5)	C10—C11—C12—C13	0.0 (5)
C8—O1—C2—C3	124.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H2···N3^i	0.86	1.81	2.669 (4)	175
C12—H12···O5^ii	0.93	2.54	3.410 (5)	155

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