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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o459–o460.
Published online 2010 January 27. doi:  10.1107/S1600536810002564
PMCID: PMC2979915

4,7-Phenanthrolinium perchlorate–5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one–water (1/1/2)

Abstract

The asymmetric unit of the title compound, C12H9N2 +·ClO4 ·C6H6N4O·2H2O, contains a monoprotonated 4,7-phenanthrolinium (47phen) cation, a perchlorate anion balancing its charge, a neutral mol­ecule of 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO) and two inter­stitial water mol­ecules. In the crystal structure, the acidic H atoms of 47phenH+ and HmtpO form strong hydrogen bonds with the water mol­ecules, which in turn act as hydrogen-bond donors, forming links between them and towards the carbonyl O atom of HmtpO, the non-protonated N atom of 47phen+ and one of the O atoms of the anion.

Related literature

For other structures containing perchlorate and protonated 4,7-phenanthroline, see: Shang et al. (2006 [triangle]); Gillard et al. (1998 [triangle]). For other structures containing neutral and non-coordinated 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one, see: Navarro et al. (1997 [triangle]); Salas et al. (1996 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o459-scheme1.jpg

Experimental

Crystal data

  • C12H9N2 +·ClO4 ·C6H6N4O·2H2O
  • M r = 466.84
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o459-efi1.jpg
  • a = 8.6082 (8) Å
  • b = 14.7723 (14) Å
  • c = 16.8079 (17) Å
  • β = 104.609 (2)°
  • V = 2068.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 298 K
  • 0.42 × 0.38 × 0.13 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1999 [triangle]) T min = 0.764, T max = 0.969
  • 12883 measured reflections
  • 4653 independent reflections
  • 3687 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.152
  • S = 1.03
  • 4653 reflections
  • 302 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 1999 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: Xtal_GX (Hall & du Boulay, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002564/lh2981sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002564/lh2981Isup2.hkl

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

Acknowledgments

We acknowledge financial support from the Spanish Ministerio de Ciencia y Tecnología (project CTQ2008–00037/PPQ) and from the Junta de Andalucía (research group FQM 195). ABC is grateful for a FPU grant from the Spanish Ministerio de Educación y Ciencia.

supplementary crystallographic information

Comment

The title compound was obtained as a by-product when trying to synthesize a copper complex containing both heterocycles, as indicated in the preparation section. The formula of the compound is (47phenH)(HmtpO)(ClO4).2H2O (47phen = 4,7-phenanthroline and HmtpO = 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-7(4H)-one), which also correspond to the contents of the asymmetric unit which is shown in Figure 1. The geometrical parameters of both heterocycles do not significantly differ from other compounds with protonated 47phen (Shang et al., 2006, Gillard et al., 1998) or neutral HmtpO (Navarro et al., 1997, Salas et al. 1996). The species are linked in the crystal mainly by hydrogen bonds, water molecules being the main actors of the H-bond network. One of the independent water molecules (O1W) accepts an H-bond from the extra proton of 47phen (N4P—H) and donates towards the carbonyl O-atom (O7) of the triazolopyrimidine moiety and towards the other water molecule (O2W). The later also accepts an H-bond from the acidic H-atom of HmtpO (N4—H) acting as donor for the perchlorate anion and for the non-protonated N atom of 47phen (N7P). This builds a two-dimensional hydrogen bond network, which includes, among other motifs, centrosymmetric (HmtpO)2(H2O)4 boxes, with both HmtpO molecules stacked with a separation of 3.4 Å and linked by two chains with two water molecules each, starting at N4P of one of the heterocycles and ending at O7 of the other: N4P—H···O1W—H···O2W—H···O7.

Experimental

The compound was fortuitously obtained as a by-product when trying to synthesize a ternary complex of Cu(II) with 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-7(4H)-one (HmtpO) and 4,7-phenanthroline (47phen). An aqueous solution (10 ml.) of Cu(ClO4)2.6H2O (0,75 g, 2 mmol), another aqueous solution (20 ml.) of HmtpO (0,61 g, 4 mmol) and a ethanolic solution (10 ml.) of 47phen (0,73 g, 4 mmol) were mixed and the mixture was refluxed for 2 h, a green precipitate (a Cu-Hmtpo complex) appearing which was filtered off. The mother liquor was left to stand at room temperature for two weeks, when a mixture of green and pale yellow crystals was obtained, which was filtered off. It was possible to separate both types of crystals under a lens, the green crystals turning out to be a Cu-phen complex whereas the pale yellow ones are the title compound, the structure of which is presented in this article. Elemental analysis data for C18H19ClN6O7. % Found (Calc.): C 46.17 (46.31), H 4.52 (4.10), N 17.79 (18.00).

Refinement

Hydrogen atoms of the organic moieties were idealized with distances to their parent atoms of 0.93 (C) or 0.86 (N) Å, the location of acidic (N—H) H atoms being obvious from previous ΔF maps. Free rotation was allowed for the methyl group. Water hydrogen atoms were easily located in ΔF maps and refined with restrained O—H distances (0.82 (1) Å). Displacement parameters of all H atoms were fixed at 1.2 times the Ueq of their parent atoms.

Figures

Fig. 1.
View of the asymmetric unit of the title compound with the displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H9N2+·ClO4·C6H6N4O·2H2OF(000) = 968
Mr = 466.84Dx = 1.499 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3841 reflections
a = 8.6082 (8) Åθ = 2.4–24.6°
b = 14.7723 (14) ŵ = 0.24 mm1
c = 16.8079 (17) ÅT = 298 K
β = 104.609 (2)°Irregular, pale yellow
V = 2068.2 (3) Å30.42 × 0.38 × 0.13 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer4653 independent reflections
Radiation source: fine-focus sealed tube3687 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 8.26 pixels mm-1θmax = 28.3°, θmin = 1.9°
[var phi] and ω scansh = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 1999)k = −18→16
Tmin = 0.764, Tmax = 0.969l = −22→13
12883 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: mixed
wR(F2) = 0.152H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.080P)2 + 0.7P] where P = (Fo2 + 2Fc2)/3
4653 reflections(Δ/σ)max = 0.001
302 parametersΔρmax = 0.40 e Å3
4 restraintsΔρmin = −0.37 e Å3

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 (Å2)

xyzUiso*/Ueq
Cl0.45313 (6)0.33264 (4)0.31768 (3)0.04631 (18)
O10.3034 (3)0.31480 (17)0.33511 (15)0.0894 (7)
O20.4656 (3)0.42667 (14)0.30285 (15)0.0838 (6)
O30.4615 (4)0.28347 (18)0.24717 (16)0.1138 (10)
O40.5784 (3)0.30880 (19)0.38506 (17)0.1111 (9)
N10.0430 (2)0.68226 (12)0.53673 (12)0.0482 (5)
C20.0189 (3)0.67004 (16)0.61003 (16)0.0521 (6)
H2−0.03480.71300.63360.063*
N30.0760 (2)0.59263 (13)0.65035 (12)0.0470 (4)
C3A0.1429 (2)0.55371 (13)0.59692 (12)0.0372 (4)
N40.2222 (2)0.47442 (11)0.60339 (10)0.0390 (4)
H40.22870.44040.64560.047*
C50.2917 (3)0.44833 (14)0.54280 (13)0.0416 (5)
C510.3840 (3)0.36204 (17)0.55767 (17)0.0591 (6)
H510.41430.34440.50870.071*
H520.31840.31560.57250.071*
H530.47860.37040.60160.071*
C60.2757 (3)0.49988 (15)0.47456 (13)0.0456 (5)
H60.32130.47910.43340.055*
C70.1924 (3)0.58373 (15)0.46251 (13)0.0438 (5)
O70.1771 (2)0.63513 (13)0.40383 (10)0.0629 (5)
N80.1250 (2)0.60466 (11)0.52801 (10)0.0375 (4)
C1P0.2195 (3)0.60343 (16)0.13977 (14)0.0509 (6)
H1P0.25550.66150.13250.061*
C1AP0.2186 (2)0.53636 (14)0.08008 (12)0.0388 (4)
C2P0.1672 (3)0.58385 (19)0.20817 (15)0.0608 (7)
H2P0.16820.62830.24750.073*
C3P0.1126 (3)0.49785 (19)0.21863 (15)0.0565 (6)
H3P0.07580.48470.26480.068*
N4P0.1128 (2)0.43452 (14)0.16298 (11)0.0480 (5)
H4P0.07840.38140.17070.058*
C4AP0.1650 (2)0.44961 (14)0.09408 (13)0.0401 (5)
C5P0.1638 (3)0.37718 (15)0.03805 (14)0.0488 (5)
H5P0.12700.32020.04820.059*
C6P0.2157 (3)0.39210 (15)−0.02966 (14)0.0501 (5)
H6P0.21930.3440−0.06480.060*
C6AP0.2661 (2)0.47963 (15)−0.04881 (13)0.0423 (5)
N7P0.3086 (3)0.48934 (14)−0.12090 (12)0.0548 (5)
C8P0.3516 (3)0.57049 (19)−0.14009 (16)0.0611 (7)
H8P0.38000.5776−0.18960.073*
C9P0.3551 (3)0.64575 (18)−0.09078 (16)0.0617 (7)
H9P0.38640.7016−0.10710.074*
C10P0.3139 (3)0.63783 (17)−0.01789 (15)0.0539 (6)
H10P0.31550.68800.01570.065*
C0AP0.2681 (2)0.55214 (14)0.00543 (13)0.0397 (5)
O1W0.0223 (2)0.26333 (13)0.18493 (13)0.0679 (5)
H11W−0.045 (3)0.237 (2)0.1499 (15)0.081*
H12W0.095 (3)0.2279 (18)0.2039 (19)0.081*
O2W0.2656 (3)0.37456 (12)0.74489 (11)0.0640 (5)
H21W0.335 (3)0.3355 (16)0.7542 (19)0.077*
H22W0.275 (4)0.4077 (17)0.7846 (13)0.077*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0445 (3)0.0470 (3)0.0486 (3)−0.0056 (2)0.0139 (2)−0.0066 (2)
O10.0712 (13)0.1078 (18)0.1028 (18)−0.0295 (12)0.0472 (13)−0.0301 (14)
O20.0952 (16)0.0500 (11)0.1048 (17)−0.0044 (10)0.0228 (14)0.0031 (11)
O30.171 (3)0.0986 (18)0.1052 (18)−0.0598 (18)0.0961 (19)−0.0507 (15)
O40.0844 (17)0.1027 (19)0.120 (2)0.0050 (14)−0.0229 (15)0.0294 (16)
N10.0501 (11)0.0397 (10)0.0580 (12)0.0076 (8)0.0193 (9)0.0062 (8)
C20.0545 (13)0.0445 (12)0.0642 (15)0.0067 (10)0.0273 (12)−0.0001 (11)
N30.0546 (11)0.0445 (10)0.0475 (11)0.0028 (8)0.0232 (9)0.0028 (8)
C3A0.0364 (10)0.0377 (10)0.0383 (10)−0.0050 (8)0.0109 (8)0.0017 (8)
N40.0458 (9)0.0350 (9)0.0354 (9)0.0014 (7)0.0089 (7)0.0048 (7)
C50.0440 (11)0.0378 (11)0.0431 (11)0.0009 (9)0.0110 (9)−0.0030 (9)
C510.0713 (16)0.0464 (13)0.0624 (15)0.0156 (12)0.0223 (13)0.0041 (12)
C60.0550 (13)0.0458 (12)0.0388 (11)0.0042 (10)0.0174 (10)−0.0018 (9)
C70.0468 (11)0.0483 (12)0.0363 (11)0.0011 (9)0.0109 (9)0.0023 (9)
O70.0826 (13)0.0654 (11)0.0457 (9)0.0198 (9)0.0254 (9)0.0208 (8)
N80.0400 (9)0.0337 (8)0.0385 (9)0.0012 (7)0.0094 (7)0.0034 (7)
C1P0.0661 (15)0.0418 (12)0.0479 (13)0.0001 (11)0.0200 (11)−0.0025 (10)
C1AP0.0404 (10)0.0384 (11)0.0378 (11)0.0008 (8)0.0101 (9)0.0010 (8)
C2P0.0820 (18)0.0600 (15)0.0460 (13)0.0092 (13)0.0266 (13)−0.0063 (12)
C3P0.0645 (15)0.0705 (17)0.0407 (12)0.0067 (13)0.0250 (11)0.0086 (12)
N4P0.0493 (10)0.0505 (11)0.0458 (11)−0.0016 (8)0.0153 (8)0.0108 (9)
C4AP0.0383 (10)0.0419 (11)0.0396 (11)0.0020 (8)0.0090 (9)0.0051 (9)
C5P0.0572 (13)0.0363 (11)0.0530 (13)−0.0077 (10)0.0140 (11)0.0004 (10)
C6P0.0644 (14)0.0394 (12)0.0474 (13)−0.0040 (10)0.0157 (11)−0.0078 (10)
C6AP0.0454 (11)0.0429 (11)0.0396 (11)−0.0017 (9)0.0127 (9)−0.0007 (9)
N7P0.0691 (13)0.0574 (12)0.0421 (11)−0.0034 (10)0.0217 (10)−0.0055 (9)
C8P0.0750 (17)0.0690 (17)0.0456 (13)−0.0101 (14)0.0271 (13)0.0053 (12)
C9P0.0794 (18)0.0540 (14)0.0570 (15)−0.0140 (13)0.0271 (14)0.0073 (12)
C10P0.0715 (16)0.0418 (12)0.0513 (13)−0.0093 (11)0.0210 (12)−0.0009 (10)
C0AP0.0405 (10)0.0399 (11)0.0390 (11)−0.0018 (8)0.0106 (9)−0.0001 (9)
O1W0.0710 (13)0.0532 (11)0.0702 (13)−0.0163 (9)0.0007 (10)0.0043 (9)
O2W0.1006 (15)0.0453 (10)0.0443 (10)0.0124 (10)0.0149 (10)0.0037 (8)

Geometric parameters (Å, °)

Cl—O41.398 (2)C1AP—C0AP1.442 (3)
Cl—O31.407 (2)C2P—C3P1.381 (4)
Cl—O11.416 (2)C2P—H2P0.9300
Cl—O21.420 (2)C3P—N4P1.323 (3)
N1—C21.313 (3)C3P—H3P0.9300
N1—N81.374 (2)N4P—C4AP1.362 (3)
C2—N31.357 (3)N4P—H4P0.8600
C2—H20.9300C4AP—C5P1.424 (3)
N3—C3A1.315 (3)C5P—C6P1.341 (3)
C3A—N41.346 (3)C5P—H5P0.9300
C3A—N81.357 (3)C6P—C6AP1.426 (3)
N4—C51.361 (3)C6P—H6P0.9300
N4—H40.8600C6AP—N7P1.359 (3)
C5—C61.354 (3)C6AP—C0AP1.404 (3)
C5—C511.489 (3)N7P—C8P1.318 (3)
C51—H510.9600C8P—C9P1.382 (4)
C51—H520.9600C8P—H8P0.9300
C51—H530.9600C9P—C10P1.364 (3)
C6—C71.420 (3)C9P—H9P0.9300
C6—H60.9300C10P—C0AP1.411 (3)
C7—O71.225 (3)C10P—H10P0.9300
C7—N81.402 (3)O1W—H11W0.816 (10)
C1P—C2P1.367 (3)O1W—H12W0.819 (10)
C1P—C1AP1.409 (3)O2W—H21W0.818 (10)
C1P—H1P0.9300O2W—H22W0.816 (10)
C1AP—C4AP1.402 (3)
O4—Cl—O3111.1 (2)C4AP—C1AP—C0AP118.41 (19)
O4—Cl—O1110.00 (17)C1P—C1AP—C0AP123.79 (19)
O3—Cl—O1108.70 (14)C1P—C2P—C3P119.8 (2)
O4—Cl—O2108.15 (15)C1P—C2P—H2P120.1
O3—Cl—O2109.56 (15)C3P—C2P—H2P120.1
O1—Cl—O2109.35 (15)N4P—C3P—C2P119.9 (2)
C2—N1—N8101.11 (17)N4P—C3P—H3P120.3
N1—C2—N3117.5 (2)C2P—C3P—H3P119.8
N1—C2—H2121.3C3P—N4P—C4AP123.0 (2)
N3—C2—H2121.2C3P—N4P—H4P118.5
C3A—N3—C2101.16 (18)C4AP—N4P—H4P118.5
N3—C3A—N4128.72 (19)N4P—C4AP—C1AP119.04 (19)
N3—C3A—N8111.43 (18)N4P—C4AP—C5P119.39 (19)
N4—C3A—N8119.85 (17)C1AP—C4AP—C5P121.57 (19)
C3A—N4—C5119.71 (17)C6P—C5P—C4AP119.3 (2)
C3A—N4—H4120.1C6P—C5P—H5P120.4
C5—N4—H4120.2C4AP—C5P—H5P120.3
C6—C5—N4120.29 (19)C5P—C6P—C6AP121.7 (2)
C6—C5—C51124.0 (2)C5P—C6P—H6P119.0
N4—C5—C51115.68 (19)C6AP—C6P—H6P119.2
C5—C51—H51109.7N7P—C6AP—C0AP122.4 (2)
C5—C51—H52109.4N7P—C6AP—C6P117.6 (2)
H51—C51—H52109.5C0AP—C6AP—C6P119.99 (19)
C5—C51—H53109.4C8P—N7P—C6AP118.0 (2)
H51—C51—H53109.5N7P—C8P—C9P123.3 (2)
H52—C51—H53109.5N7P—C8P—H8P118.3
C5—C6—C7123.46 (19)C9P—C8P—H8P118.3
C5—C6—H6118.2C10P—C9P—C8P119.9 (2)
C7—C6—H6118.3C10P—C9P—H9P120.1
O7—C7—N8120.9 (2)C8P—C9P—H9P120.0
O7—C7—C6127.1 (2)C9P—C10P—C0AP118.7 (2)
N8—C7—C6111.98 (18)C9P—C10P—H10P120.6
C3A—N8—N1108.82 (16)C0AP—C10P—H10P120.6
C3A—N8—C7124.57 (17)C6AP—C0AP—C10P117.58 (19)
N1—N8—C7126.40 (17)C6AP—C0AP—C1AP118.92 (19)
C2P—C1P—C1AP120.4 (2)C10P—C0AP—C1AP123.5 (2)
C2P—C1P—H1P119.8H11W—O1W—H12W108 (3)
C1AP—C1P—H1P119.8H21W—O2W—H22W111 (3)
C4AP—C1AP—C1P117.80 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4···O2W0.861.892.743 (2)173
N4P—H4P···O1W0.861.842.699 (3)175
O1W—H11W···O7i0.82 (1)1.96 (2)2.733 (3)158 (3)
O1W—H12W···O2Wii0.82 (1)2.10 (1)2.913 (3)173 (3)
O2W—H21W···O3iii0.82 (1)2.09 (1)2.875 (3)162 (3)
O2W—H22W···N7Piv0.82 (1)1.96 (1)2.771 (3)177 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2981).

References

  • Bruker (1999). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Winsconsin, USA.
  • Gillard, R. D., Hursthouse, M. B., Abdul-Malik, K. M. & Paisey, S. (1998). J. Chem. Crystallogr.28, 611–619.
  • Hall, S. R. & du Boulay, D. (1997). Xtal_GX University of Western Australia, Perth, Australia.
  • Navarro, J. A. R., Romero, M. A., Salas, J. M., Faure, R. & Solans, X. (1997). J. Chem. Soc. Dalton Trans. pp. 2321–2326.
  • Salas, J. M., Romero, M. A., Rodríguez, J. A. & Faure, R. (1996). J. Chem. Crystallogr.26, 847–851.
  • Shang, R.-L., Du, L. & Sun, B.-W. (2006). Acta Cryst. E62, o2920–o2921.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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