(2-Meth­oxy-1,10-phenanthroline-κ²N,N′)bis­(thio­cyanato-κN)zinc(II)

In the title complex, [Zn(NCS)₂(C₁₃H₁₀N₂O)], the Zn^II ion is in a distorted tetra­hdral ZnN₂Cl₂ coordination environment. In the crystal structure, there is a weak π–π stacking inter­action between adjacent 1,10-phenanthroline rings, with a pyridine centroid–centroid distance of 3.6620 (15) Å.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.098
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.61 mm
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     -   C2      ..       6.54 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S3     -   C14     ..       6.01 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.919
            Tmax scaled      0.501 Tmin scaled      0.385

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

Derivatives of 1,10-phenanthroline play a pivotal role in the area of modern coordination chemistry (e.g. Zhang et al. 2006 and important references cited within), but no structures of complexes with 2-methoxy-1,10-phenanthroline as a ligand have been reported. Herein we report the crystal structure of the title complex (I).

The molecular structure of (I) is shown in Fig. 1. In this mononuclear complex atom Zn1 is in a distorted tetrahedral coordination geometry (Table 1). In the crystal structure, there are weak π-π stacking interactions between symmetry related 1,10-phenanthroline ligands, with the relevant distances being Cg1···Cg1ⁱ = 3.6620 (15) Å and a perpendicular distance of 3.563 Å [symmetry code: (i) 1/2-x, 3/2-y, 1-z; Cg1 is the centroid of the N1/C1/C3/C4/C5/C15 ring].

Related literature

For a related structure, see: Zhang et al. (2006). For related literature, see: McMorran & Steel (2002).

S2. Experimental

A methanol solution (15ml) of Zn(ClO₄).6H₂O (0.2951 g, 0.792 mmol) was added into a 10 ml methanol solution containing 2-methoxy-1,10-phenanthroline (0.1666 g, 0.792 mmol), and the mixture was stirred for a few minutes. Then a 10 ml methanol solution of NaSCN (0.1296 g, 1.60 mmol) was added to the above mixture. Yellow single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

S3. Refinement

H atoms were placed in calculated positions (C—H = 0.96 Å for methyl group and C—H = 0.93 Å for other H atoms) and refined as riding with U_iso = 1.5 U_eq(C) for methyl H and U_iso = 1.2 U_eq(C) for other H.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level.

(2-Methoxy-1,10-phenanthroline-κ²N,N')bis(thiocyanato-κN)zinc(II)

Crystal data

[Zn(NCS)2(C13H10N2O)]	F(000) = 1584
Mr = 391.76	Dx = 1.560 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4025 reflections
a = 26.360 (5) Å	θ = 2.2–27.6°
b = 8.5949 (16) Å	µ = 1.73 mm^−1
c = 14.814 (3) Å	T = 298 K
β = 96.266 (2)°	Bar, yellow
V = 3336.3 (10) Å^3	0.61 × 0.42 × 0.40 mm
Z = 8

Data collection

Bruker SMART APEX CCD diffractometer	3616 independent reflections
Radiation source: fine-focus sealed tube	2974 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −33→26
Tmin = 0.418, Tmax = 0.545	k = −9→10
9311 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.2305P] where P = (Fo^2 + 2Fc^2)/3
3616 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.49 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	0.130923 (10)	1.01266 (3)	0.392499 (16)	0.04081 (11)
S2	0.07232 (4)	1.52220 (8)	0.35198 (6)	0.0700 (2)
S3	0.15576 (3)	0.73246 (10)	0.13159 (4)	0.0627 (2)
N1	0.19776 (7)	0.98293 (19)	0.47711 (12)	0.0374 (4)
N2	0.10343 (6)	0.8750 (2)	0.48692 (10)	0.0372 (4)
C5	0.19054 (7)	0.8893 (2)	0.54870 (12)	0.0350 (4)
N3	0.10454 (8)	1.2204 (3)	0.38239 (13)	0.0557 (5)
O1	0.02497 (6)	0.8745 (2)	0.41868 (12)	0.0593 (4)
C4	0.22974 (8)	0.8481 (3)	0.61569 (13)	0.0415 (5)
C8	0.13985 (8)	0.8311 (2)	0.55315 (13)	0.0363 (4)
C6	0.21868 (10)	0.7477 (3)	0.68714 (15)	0.0510 (6)
H6	0.2446	0.7205	0.7320	0.061*
C12	0.05651 (8)	0.8226 (3)	0.48815 (15)	0.0446 (5)
N4	0.13885 (8)	0.9127 (3)	0.27851 (13)	0.0580 (5)
C14	0.14584 (8)	0.8383 (3)	0.21771 (14)	0.0424 (5)
C9	0.13065 (9)	0.7316 (3)	0.62413 (15)	0.0435 (5)
C2	0.09073 (8)	1.3458 (3)	0.37012 (13)	0.0422 (5)
C7	0.17119 (10)	0.6909 (3)	0.69101 (15)	0.0530 (6)
H7	0.1650	0.6244	0.7381	0.064*
C11	0.04328 (10)	0.7227 (3)	0.55773 (17)	0.0552 (6)
H11	0.0099	0.6878	0.5580	0.066*
C3	0.27856 (9)	0.9092 (3)	0.60652 (16)	0.0517 (6)
H3	0.3059	0.8854	0.6494	0.062*
C10	0.07972 (10)	0.6789 (3)	0.62360 (16)	0.0545 (6)
H10	0.0713	0.6130	0.6695	0.065*
C15	0.28561 (10)	1.0030 (3)	0.53490 (19)	0.0543 (7)
H15	0.3177	1.0435	0.5286	0.065*
C1	0.24425 (9)	1.0379 (3)	0.47095 (17)	0.0471 (5)
H1	0.2495	1.1020	0.4223	0.057*
C13	−0.02649 (9)	0.8142 (4)	0.4045 (2)	0.0721 (8)
H13A	−0.0254	0.7027	0.4012	0.108*
H13B	−0.0433	0.8548	0.3487	0.108*
H13C	−0.0449	0.8450	0.4540	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03960 (18)	0.04250 (18)	0.04019 (16)	0.00072 (11)	0.00369 (11)	0.00223 (10)
S2	0.0862 (6)	0.0478 (4)	0.0775 (5)	0.0193 (4)	0.0155 (4)	−0.0028 (3)
S3	0.0606 (4)	0.0723 (5)	0.0568 (4)	0.0133 (3)	0.0135 (3)	−0.0126 (3)
N1	0.0323 (10)	0.0394 (10)	0.0409 (9)	−0.0019 (7)	0.0053 (7)	−0.0012 (7)
N2	0.0320 (9)	0.0377 (10)	0.0427 (9)	−0.0020 (8)	0.0078 (7)	−0.0029 (7)
C5	0.0357 (11)	0.0319 (10)	0.0383 (10)	0.0010 (9)	0.0080 (8)	−0.0052 (8)
N3	0.0631 (14)	0.0480 (13)	0.0566 (12)	0.0108 (11)	0.0095 (10)	0.0064 (9)
O1	0.0332 (9)	0.0696 (12)	0.0735 (11)	−0.0053 (8)	−0.0016 (7)	0.0038 (9)
C4	0.0399 (12)	0.0424 (12)	0.0419 (11)	0.0026 (10)	0.0027 (9)	−0.0043 (9)
C8	0.0378 (11)	0.0344 (11)	0.0380 (10)	0.0001 (9)	0.0099 (8)	−0.0028 (8)
C6	0.0518 (15)	0.0577 (15)	0.0419 (12)	0.0095 (12)	−0.0021 (10)	0.0045 (10)
C12	0.0355 (12)	0.0456 (13)	0.0533 (12)	−0.0043 (10)	0.0072 (9)	−0.0080 (10)
N4	0.0637 (14)	0.0639 (14)	0.0467 (11)	0.0039 (12)	0.0065 (9)	−0.0073 (11)
C14	0.0345 (11)	0.0474 (13)	0.0448 (12)	0.0044 (10)	0.0024 (9)	0.0073 (10)
C9	0.0524 (14)	0.0397 (12)	0.0406 (11)	−0.0023 (10)	0.0145 (9)	0.0000 (9)
C2	0.0395 (12)	0.0512 (14)	0.0369 (10)	0.0001 (11)	0.0089 (8)	−0.0035 (9)
C7	0.0645 (17)	0.0512 (15)	0.0451 (12)	0.0054 (12)	0.0135 (11)	0.0098 (11)
C11	0.0421 (13)	0.0618 (16)	0.0648 (15)	−0.0143 (12)	0.0205 (11)	−0.0046 (12)
C3	0.0390 (12)	0.0560 (15)	0.0572 (13)	0.0013 (11)	−0.0072 (10)	−0.0045 (12)
C10	0.0574 (15)	0.0576 (15)	0.0522 (13)	−0.0120 (13)	0.0220 (11)	0.0036 (11)
C15	0.0366 (13)	0.0585 (17)	0.0672 (17)	−0.0106 (11)	0.0034 (12)	−0.0008 (12)
C1	0.0373 (13)	0.0486 (13)	0.0561 (13)	−0.0088 (11)	0.0083 (10)	0.0019 (10)
C13	0.0303 (13)	0.086 (2)	0.099 (2)	−0.0058 (14)	−0.0020 (13)	−0.0092 (17)

Geometric parameters (Å, º)

Zn1—N3	1.916 (2)	C6—C7	1.351 (3)
Zn1—N4	1.926 (2)	C6—H6	0.9300
Zn1—N2	2.0254 (16)	C12—C11	1.414 (3)
Zn1—N1	2.0636 (19)	N4—C14	1.136 (3)
S2—C2	1.606 (3)	C9—C10	1.416 (3)
S3—C14	1.611 (2)	C9—C7	1.419 (3)
N1—C1	1.326 (3)	C7—H7	0.9300
N1—C5	1.361 (3)	C11—C10	1.346 (4)
N2—C12	1.319 (3)	C11—H11	0.9300
N2—C8	1.349 (3)	C3—C15	1.361 (4)
C5—C4	1.398 (3)	C3—H3	0.9300
C5—C8	1.435 (3)	C10—H10	0.9300
N3—C2	1.145 (3)	C15—C1	1.397 (4)
O1—C12	1.328 (3)	C15—H15	0.9300
O1—C13	1.446 (3)	C1—H1	0.9300
C4—C3	1.410 (3)	C13—H13A	0.9600
C4—C6	1.421 (3)	C13—H13B	0.9600
C8—C9	1.397 (3)	C13—H13C	0.9600
N3—Zn1—N4	114.85 (9)	N4—C14—S3	179.9 (3)
N3—Zn1—N2	116.36 (8)	C8—C9—C10	115.7 (2)
N4—Zn1—N2	115.23 (9)	C8—C9—C7	119.8 (2)
N3—Zn1—N1	116.20 (8)	C10—C9—C7	124.5 (2)
N4—Zn1—N1	108.07 (8)	N3—C2—S2	178.9 (2)
N2—Zn1—N1	81.62 (7)	C6—C7—C9	120.8 (2)
C1—N1—C5	118.2 (2)	C6—C7—H7	119.6
C1—N1—Zn1	130.42 (16)	C9—C7—H7	119.6
C5—N1—Zn1	111.33 (14)	C10—C11—C12	119.0 (2)
C12—N2—C8	119.23 (18)	C10—C11—H11	120.5
C12—N2—Zn1	128.04 (15)	C12—C11—H11	120.5
C8—N2—Zn1	112.68 (13)	C15—C3—C4	119.9 (2)
N1—C5—C4	123.20 (19)	C15—C3—H3	120.0
N1—C5—C8	116.87 (18)	C4—C3—H3	120.0
C4—C5—C8	119.93 (18)	C11—C10—C9	121.0 (2)
C2—N3—Zn1	174.4 (2)	C11—C10—H10	119.5
C12—O1—C13	119.4 (2)	C9—C10—H10	119.5
C5—C4—C3	116.7 (2)	C3—C15—C1	119.5 (2)
C5—C4—C6	119.1 (2)	C3—C15—H15	120.2
C3—C4—C6	124.2 (2)	C1—C15—H15	120.2
N2—C8—C9	123.38 (19)	N1—C1—C15	122.4 (2)
N2—C8—C5	117.48 (17)	N1—C1—H1	118.8
C9—C8—C5	119.14 (19)	C15—C1—H1	118.8
C7—C6—C4	121.2 (2)	O1—C13—H13A	109.5
C7—C6—H6	119.4	O1—C13—H13B	109.5
C4—C6—H6	119.4	H13A—C13—H13B	109.5
N2—C12—O1	112.55 (19)	O1—C13—H13C	109.5
N2—C12—C11	121.6 (2)	H13A—C13—H13C	109.5
O1—C12—C11	125.8 (2)	H13B—C13—H13C	109.5
C14—N4—Zn1	171.4 (2)
N3—Zn1—N1—C1	−64.6 (2)	C4—C5—C8—C9	−1.0 (3)
N4—Zn1—N1—C1	66.2 (2)	C5—C4—C6—C7	0.4 (3)
N2—Zn1—N1—C1	−179.9 (2)	C3—C4—C6—C7	−178.8 (2)
N3—Zn1—N1—C5	116.32 (14)	C8—N2—C12—O1	−179.57 (18)
N4—Zn1—N1—C5	−112.90 (14)	Zn1—N2—C12—O1	−2.3 (3)
N2—Zn1—N1—C5	1.00 (13)	C8—N2—C12—C11	0.7 (3)
N3—Zn1—N2—C12	66.0 (2)	Zn1—N2—C12—C11	177.98 (16)
N4—Zn1—N2—C12	−72.75 (19)	C13—O1—C12—N2	173.2 (2)
N1—Zn1—N2—C12	−178.84 (19)	C13—O1—C12—C11	−7.1 (4)
N3—Zn1—N2—C8	−116.55 (14)	N2—C8—C9—C10	−0.6 (3)
N4—Zn1—N2—C8	104.70 (15)	C5—C8—C9—C10	−179.83 (19)
N1—Zn1—N2—C8	−1.40 (13)	N2—C8—C9—C7	179.9 (2)
C1—N1—C5—C4	−0.2 (3)	C5—C8—C9—C7	0.6 (3)
Zn1—N1—C5—C4	179.00 (16)	C4—C6—C7—C9	−0.7 (4)
C1—N1—C5—C8	−179.68 (19)	C8—C9—C7—C6	0.2 (4)
Zn1—N1—C5—C8	−0.5 (2)	C10—C9—C7—C6	−179.3 (2)
N1—C5—C4—C3	0.2 (3)	N2—C12—C11—C10	−0.8 (4)
C8—C5—C4—C3	179.70 (19)	O1—C12—C11—C10	179.5 (2)
N1—C5—C4—C6	−178.99 (19)	C5—C4—C3—C15	−0.1 (3)
C8—C5—C4—C6	0.5 (3)	C6—C4—C3—C15	179.1 (2)
C12—N2—C8—C9	0.1 (3)	C12—C11—C10—C9	0.2 (4)
Zn1—N2—C8—C9	−177.64 (16)	C8—C9—C10—C11	0.5 (3)
C12—N2—C8—C5	179.27 (18)	C7—C9—C10—C11	180.0 (2)
Zn1—N2—C8—C5	1.6 (2)	C4—C3—C15—C1	0.0 (4)
N1—C5—C8—N2	−0.7 (3)	C5—N1—C1—C15	0.1 (3)
C4—C5—C8—N2	179.77 (18)	Zn1—N1—C1—C15	−178.98 (17)
N1—C5—C8—C9	178.51 (17)	C3—C15—C1—N1	0.1 (4)