Download citation
Download citation
link to html
The structure of the title compound, [Zn(C12H10N4)2(H2O)4](ClO4)2, determined at 110 K, reveals a unique layered supramolecular aggregation stabilized by a combination of coordination, hydrogen-bonding and π–π forces. Disordered mol­ecules of solvent (methanol or a mixture of methanol and water) occupy the channel-like voids formed between the layers. The zinc cations have \overline{1} site symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805008962/hb6169sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805008962/hb6169Isup2.hkl
Contains datablock I

CCDC reference: 265638

Key indicators

  • Single-crystal X-ray study
  • T = 110 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in solvent or counterion
  • R factor = 0.058
  • wR factor = 0.152
  • Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of . 199.00 A   3
Author Response: Indeed, high residual electron-density peaks obtained in conventional refinement indicate presence of severely disordered solvent in these voids (probably methanol), which could not be reliably modeled and refined. The current CIF data represent SQUEEZE treated structure (Spek, 2003), with the undefined solvent excluded from the structural model.

Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for CL20A PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.28 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 38.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 Cl O4
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 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 4 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski and Minor, 1997); data reduction: DENZO (Otwinowski and Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DS ViwerPro 5.0 (Accelrys, 2002), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.

Tetraaquabis(1,4-di-4-pyridyl-2,3-diaza-1,3-butadiene)zinc(II) bis(perchlorate) top
Crystal data top
[Zn(C12H10N4)2(H2O)4](ClO4)2Z = 1
Mr = 756.81F(000) = 388
Triclinic, P1Dx = 1.290 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2316 (3) ÅCell parameters from 2237 reflections
b = 10.5151 (4) Åθ = 2.0–27.0°
c = 13.4031 (5) ŵ = 0.83 mm1
α = 90.500 (2)°T = 110 K
β = 103.127 (3)°Prism, yellow
γ = 100.5940 (18)°0.35 × 0.30 × 0.20 mm
V = 974.28 (7) Å3
Data collection top
Nonius KappaCCD
diffractometer
4113 independent reflections
Radiation source: fine-focus sealed tube3171 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 56 microns pixels mm-1θmax = 27.0°, θmin = 2.0°
φ and ω scansh = 09
Absorption correction: multi-scan
(Blessing, 1995)
k = 1313
Tmin = 0.758, Tmax = 0.851l = 1716
7657 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.076P)2 + 0.407P]
where P = (Fo2 + 2Fc2)/3
4113 reflections(Δ/σ)max = 0.001
236 parametersΔρmax = 0.83 e Å3
8 restraintsΔρmin = 0.77 e Å3
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
Zn11.00000.50001.00000.02663 (19)
N20.9514 (4)0.3460 (3)0.88707 (19)0.0280 (6)
C30.9870 (4)0.3667 (3)0.7933 (2)0.0282 (7)
H31.05220.45000.78110.034*
C40.9335 (4)0.2731 (3)0.7152 (2)0.0287 (7)
H40.96100.29210.65030.034*
C50.8384 (4)0.1496 (3)0.7312 (2)0.0282 (7)
C60.8081 (5)0.1259 (3)0.8288 (2)0.0312 (7)
H60.74970.04200.84390.037*
C70.8642 (5)0.2261 (3)0.9035 (2)0.0303 (7)
H70.84010.20940.96940.036*
C80.7728 (5)0.0466 (3)0.6507 (2)0.0303 (7)
H80.70570.03540.66440.036*
N90.8049 (4)0.0659 (3)0.5619 (2)0.0342 (6)
N100.7281 (4)0.0457 (3)0.4947 (2)0.0343 (6)
C110.7551 (4)0.0246 (3)0.4059 (2)0.0303 (7)
H110.82080.05800.39240.036*
C120.6856 (4)0.1265 (3)0.3234 (2)0.0285 (7)
C130.7039 (5)0.0998 (3)0.2246 (2)0.0308 (7)
H130.76580.01640.21050.037*
C140.6316 (5)0.1951 (4)0.1470 (2)0.0352 (8)
H140.64370.17490.07960.042*
N150.5448 (4)0.3152 (3)0.1623 (2)0.0328 (6)
C160.5318 (5)0.3414 (3)0.2582 (2)0.0323 (7)
H160.47400.42670.27060.039*
C170.5976 (5)0.2516 (3)0.3402 (2)0.0309 (7)
H170.58320.27450.40680.037*
O180.7059 (3)0.4656 (2)0.99862 (17)0.0352 (5)
H18A0.61930.41480.94260.080*
H18B0.67040.43741.05580.080*
O190.9341 (5)0.6284 (3)0.88066 (18)0.0536 (8)
H19A0.84490.68300.88250.080*
H19B1.05160.65230.85580.080*
Cl20A0.4652 (4)0.2389 (2)0.17497 (16)0.0462 (6)0.747 (6)
O21A0.3491 (9)0.1874 (4)0.1147 (4)0.0689 (16)0.747 (6)
O22A0.6590 (6)0.2038 (4)0.1141 (3)0.0693 (14)0.747 (6)
Cl20B0.3747 (12)0.2396 (5)0.1920 (4)0.0475 (18)0.253 (6)
O21B0.4788 (17)0.1654 (11)0.1003 (8)0.049 (3)*0.253 (6)
O22B0.1738 (16)0.2328 (15)0.2223 (11)0.083 (5)*0.253 (6)
O230.4033 (5)0.3757 (2)0.1857 (2)0.0581 (8)
O240.4485 (4)0.1833 (3)0.27130 (19)0.0536 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0322 (3)0.0250 (3)0.0219 (3)0.0049 (2)0.0053 (2)0.00318 (19)
N20.0289 (14)0.0288 (15)0.0264 (13)0.0072 (11)0.0053 (11)0.0015 (11)
C30.0312 (16)0.0282 (17)0.0258 (15)0.0045 (13)0.0087 (13)0.0026 (12)
C40.0300 (16)0.0341 (18)0.0228 (14)0.0067 (13)0.0074 (13)0.0004 (13)
C50.0260 (16)0.0311 (18)0.0271 (15)0.0074 (13)0.0043 (13)0.0059 (13)
C60.0327 (17)0.0273 (17)0.0334 (16)0.0054 (13)0.0077 (14)0.0036 (13)
C70.0345 (17)0.0296 (18)0.0264 (15)0.0057 (14)0.0069 (13)0.0027 (13)
C80.0316 (17)0.0298 (18)0.0291 (16)0.0053 (13)0.0071 (13)0.0089 (13)
N90.0348 (15)0.0329 (16)0.0324 (15)0.0039 (12)0.0051 (12)0.0144 (12)
N100.0349 (15)0.0347 (16)0.0315 (15)0.0043 (12)0.0063 (12)0.0116 (12)
C110.0298 (16)0.0324 (18)0.0286 (16)0.0086 (13)0.0044 (13)0.0028 (13)
C120.0265 (16)0.0321 (18)0.0264 (15)0.0101 (13)0.0021 (13)0.0034 (13)
C130.0320 (17)0.0306 (18)0.0279 (15)0.0055 (13)0.0036 (13)0.0004 (13)
C140.0355 (18)0.043 (2)0.0252 (15)0.0085 (15)0.0032 (14)0.0028 (14)
N150.0344 (15)0.0364 (17)0.0262 (13)0.0089 (12)0.0030 (11)0.0058 (12)
C160.0304 (17)0.0307 (18)0.0355 (17)0.0066 (14)0.0065 (14)0.0040 (14)
C170.0375 (18)0.0329 (18)0.0238 (15)0.0096 (14)0.0079 (13)0.0007 (13)
O180.0308 (12)0.0367 (14)0.0350 (12)0.0019 (10)0.0058 (10)0.0094 (10)
O190.098 (2)0.0346 (15)0.0279 (12)0.0209 (15)0.0071 (14)0.0003 (11)
Cl20A0.0628 (14)0.0340 (9)0.0385 (9)0.0103 (10)0.0040 (9)0.0051 (6)
O21A0.119 (5)0.049 (3)0.068 (3)0.040 (3)0.063 (3)0.015 (2)
O22A0.078 (3)0.052 (3)0.064 (3)0.015 (2)0.014 (2)0.005 (2)
Cl20B0.083 (5)0.029 (2)0.025 (2)0.014 (3)0.022 (3)0.0045 (17)
O230.104 (2)0.0272 (14)0.0502 (16)0.0097 (14)0.0349 (16)0.0035 (12)
O240.078 (2)0.0456 (17)0.0404 (14)0.0092 (14)0.0207 (14)0.0145 (12)
Geometric parameters (Å, º) top
Zn1—O18i2.087 (2)C12—C131.387 (4)
Zn1—O182.087 (2)C12—C171.396 (5)
Zn1—O19i2.130 (2)C13—C141.379 (5)
Zn1—O192.130 (2)C13—H130.9500
Zn1—N22.131 (3)C14—N151.342 (5)
Zn1—N2i2.131 (3)C14—H140.9500
N2—C71.346 (4)N15—C161.337 (4)
N2—C31.350 (4)C16—C171.380 (4)
C3—C41.368 (4)C16—H160.9500
C3—H30.9500C17—H170.9500
C4—C51.396 (5)O18—H18A0.9476
C4—H40.9500O18—H18B0.8979
C5—C61.391 (4)O19—H19A0.9425
C5—C81.457 (4)O19—H19B0.9736
C6—C71.385 (4)Cl20A—O241.411 (3)
C6—H60.9500Cl20A—O231.422 (3)
C7—H70.9500Cl20A—O22A1.432 (5)
C8—N91.274 (4)Cl20A—O21A1.455 (4)
C8—H80.9500Cl20B—O241.385 (5)
N9—N101.419 (4)Cl20B—O21B1.426 (8)
N10—C111.264 (4)Cl20B—O22B1.432 (9)
C11—C121.467 (4)Cl20B—O231.483 (6)
C11—H110.9500
O18i—Zn1—O18180.0N10—C11—C12120.5 (3)
O18i—Zn1—O19i86.50 (12)N10—C11—H11119.7
O18—Zn1—O19i93.51 (12)C12—C11—H11119.7
O18i—Zn1—O1993.50 (12)C13—C12—C17117.7 (3)
O18—Zn1—O1986.49 (12)C13—C12—C11120.1 (3)
O19i—Zn1—O19180.0C17—C12—C11122.1 (3)
O18i—Zn1—N289.59 (9)C14—C13—C12119.5 (3)
O18—Zn1—N290.41 (9)C14—C13—H13120.2
O19i—Zn1—N290.65 (10)C12—C13—H13120.2
O19—Zn1—N289.35 (10)N15—C14—C13123.1 (3)
O18i—Zn1—N2i90.41 (9)N15—C14—H14118.4
O18—Zn1—N2i89.59 (9)C13—C14—H14118.4
O19i—Zn1—N2i89.35 (10)C16—N15—C14117.1 (3)
O19—Zn1—N2i90.65 (10)N15—C16—C17123.7 (3)
N2—Zn1—N2i180.0N15—C16—H16118.1
C7—N2—C3117.4 (3)C17—C16—H16118.1
C7—N2—Zn1120.3 (2)C16—C17—C12118.7 (3)
C3—N2—Zn1122.0 (2)C16—C17—H17120.6
N2—C3—C4123.0 (3)C12—C17—H17120.6
N2—C3—H3118.5Zn1—O18—H18A117.8
C4—C3—H3118.5Zn1—O18—H18B117.9
C3—C4—C5119.7 (3)H18A—O18—H18B107.0
C3—C4—H4120.1Zn1—O19—H19A120.8
C5—C4—H4120.1Zn1—O19—H19B105.6
C6—C5—C4117.7 (3)H19A—O19—H19B124.8
C6—C5—C8119.7 (3)O24—Cl20A—O23111.5 (2)
C4—C5—C8122.6 (3)O24—Cl20A—O22A110.7 (3)
C7—C6—C5119.1 (3)O23—Cl20A—O22A111.2 (3)
C7—C6—H6120.4O24—Cl20A—O21A111.3 (3)
C5—C6—H6120.4O23—Cl20A—O21A107.8 (3)
N2—C7—C6123.0 (3)O22A—Cl20A—O21A104.1 (3)
N2—C7—H7118.5O24—Cl20B—O21B106.7 (7)
C6—C7—H7118.5O24—Cl20B—O22B103.1 (7)
N9—C8—C5120.3 (3)O21B—Cl20B—O22B115.0 (10)
N9—C8—H8119.8O24—Cl20B—O23109.4 (4)
C5—C8—H8119.8O21B—Cl20B—O23110.7 (7)
C8—N9—N10111.5 (3)O22B—Cl20B—O23111.6 (8)
C11—N10—N9111.1 (3)
Symmetry code: (i) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O18—H18A···N15ii0.951.802.748 (3)179
O18—H18B···O23ii0.902.012.911 (3)179
O19—H19A···O22Aiii0.941.962.903 (5)180
O19—H19B···O22Biv0.971.842.690 (14)144
O19—H19B···O21Aiv0.972.433.246 (7)141
Symmetry codes: (ii) x+1, y, z+1; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds