Bis[2-(1H-1,2,3-benzotriazol-1-yl)acetic acid-κN³]dichloridozinc(II)

In the title complex, [ZnCl₂(C₈H₇N₃O₂)₂], the Zn^II atom is coordinated by two chloride ions and two N atoms in a distorted tetra­hedral coordination environment. In the crystal structure, mol­ecules are linked by inter­molecular C—H...O and O—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.100
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A    ..  O4      ..       2.69 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   3 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

Recently, we reported the structure of 2-(1H-benzo[d][1,2,3] triazol-1-yl)acetonitrile (Xu et al. (2007)). The reaction of it with ZnCl₂ in ethanol-water solution gives the title complex. The zinc(II) center is coordinated by two nitrogen atoms from the benzotriazole rings and two terminal chloride anions in a distorted tetrahedral arrangement as shown in Fig. 1. The angle between the two benzotriazole rings is 62.98 (7)°.

From Fig. 2, it is easy to see that the structure is consolidated by extensive C—H···O and O—H···O hydrogen bonds. This hydrogen bonding with the π-π stacking between neighboring results to the formation of three-dimensional structure.

Related literature

For synthesis of the organic ligand, see: Danan et al. (1997), Xu & Ye (2007).

S2. Experimental

The ligand, 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetonitrile, was synthesized by the reaction of benzotriazole and bromoacetonitrile according to the procedure described in the literature (Danan et al. (1997)).

A mixture of 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetonitrile (32 mg, 0.2 mmol), ZnCl₂(40 mg, 0.3 mmol), ethanol(1 ml) and a few drops of water sealed in a glass tube maintained at 120 °C. Colorless crystals suitable for X-ray analysis were obtained after several days.

S3. Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, O atoms to which they are bonded, with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. A packing diagram of the molecular packing of the title compound, viewed down the b axis.

Bis[2-(1H-1,2,3-benzotriazol-1-yl)acetic acid-κN³]dichloridozinc(II)

Crystal data

[ZnCl2(C8H7N3O2)2]	Z = 2
Mr = 490.60	F(000) = 496
Triclinic, P1	Dx = 1.655 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0896 (16) Å	Cell parameters from 10272 reflections
b = 9.6898 (19) Å	θ = 3.1–28.7°
c = 12.703 (3) Å	µ = 1.56 mm^−1
α = 87.48 (3)°	T = 293 K
β = 84.25 (3)°	Block, colorless
γ = 83.95 (3)°	0.3 × 0.2 × 0.1 mm
V = 984.7 (4) Å^3

Data collection

Mercury2 CCD (2x2 bin mode) diffractometer	4512 independent reflections
Radiation source: fine-focus sealed tube	4022 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.720, Tmax = 0.860	l = −16→16
10222 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 0.762P] where P = (Fo^2 + 2Fc^2)/3
4512 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.63 e Å^−3
2 restraints	Δρmin = −0.54 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 > 2σ(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	−0.24666 (3)	0.21707 (3)	0.28538 (2)	0.03130 (10)
Cl1	−0.49995 (9)	0.21702 (8)	0.23354 (6)	0.04842 (18)
Cl2	−0.17619 (9)	0.06835 (7)	0.41738 (5)	0.04511 (17)
O1	0.4086 (3)	0.4222 (3)	−0.1108 (2)	0.0764 (8)
H1C	0.4884	0.4518	−0.0874	0.115*
O2	−0.5545 (3)	0.9218 (2)	0.3737 (2)	0.0627 (6)
H2B	−0.5859	0.9846	0.3201	0.061 (11)*
O3	−0.3617 (3)	0.7988 (2)	0.26399 (16)	0.0555 (6)
O4	0.2761 (3)	0.4739 (3)	0.05103 (16)	0.0546 (6)
N1	−0.2805 (3)	0.6045 (2)	0.41091 (17)	0.0327 (4)
N2	−0.0410 (3)	0.2952 (2)	0.09576 (17)	0.0350 (5)
N3	0.0805 (3)	0.2522 (2)	0.02244 (16)	0.0338 (4)
N4	−0.3401 (3)	0.4916 (2)	0.37794 (17)	0.0350 (5)
N5	−0.0605 (3)	0.1913 (2)	0.16490 (16)	0.0334 (4)
N6	−0.2121 (3)	0.4090 (2)	0.33810 (17)	0.0330 (4)
C1	0.2918 (4)	−0.1020 (3)	0.0338 (2)	0.0470 (7)
H1A	0.3714	−0.1660	0.0004	0.048 (9)*
C2	0.1680 (4)	0.6422 (3)	0.3786 (2)	0.0465 (7)
H2A	0.2506	0.6985	0.3893	0.061 (10)*
C3	0.1993 (4)	−0.1432 (3)	0.1290 (2)	0.0504 (7)
H3A	0.2219	−0.2330	0.1565	0.056 (10)*
C4	0.0791 (4)	−0.0547 (3)	0.1816 (2)	0.0434 (6)
H4A	0.0190	−0.0820	0.2439	0.048 (9)*
C5	0.0517 (3)	0.0791 (3)	0.13594 (19)	0.0329 (5)
C6	0.1357 (3)	0.3460 (3)	−0.0639 (2)	0.0380 (6)
H6A	0.0439	0.4144	−0.0789	0.050 (9)*
H6B	0.1698	0.2937	−0.1272	0.051 (9)*
C7	0.0055 (4)	0.6881 (3)	0.4093 (2)	0.0404 (6)
H7A	−0.0256	0.7737	0.4397	0.042 (8)*
C8	0.2157 (3)	0.5130 (3)	0.3319 (2)	0.0456 (7)
H8A	0.3282	0.4876	0.3121	0.054 (9)*
C9	−0.3956 (3)	0.7224 (3)	0.4457 (2)	0.0375 (6)
H9A	−0.3464	0.7727	0.4970	0.056 (10)*
H9B	−0.4979	0.6900	0.4797	0.057 (10)*
C10	0.2827 (4)	0.4195 (3)	−0.0345 (2)	0.0391 (6)
C11	0.1012 (3)	0.4239 (3)	0.3143 (2)	0.0391 (6)
H11A	0.1325	0.3381	0.2844	0.042 (8)*
C12	0.1438 (3)	0.1188 (3)	0.0429 (2)	0.0323 (5)
C13	0.2670 (3)	0.0281 (3)	−0.0107 (2)	0.0415 (6)
H13A	0.3282	0.0552	−0.0727	0.044 (8)*
C14	−0.4354 (3)	0.8186 (3)	0.3517 (2)	0.0360 (5)
C15	−0.0664 (3)	0.4692 (2)	0.34439 (19)	0.0313 (5)
C16	−0.1116 (3)	0.5972 (2)	0.39085 (19)	0.0311 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03324 (16)	0.02833 (16)	0.03146 (16)	−0.00575 (11)	0.00609 (11)	−0.00602 (11)
Cl1	0.0373 (3)	0.0458 (4)	0.0624 (5)	−0.0034 (3)	−0.0060 (3)	−0.0035 (3)
Cl2	0.0551 (4)	0.0419 (4)	0.0363 (3)	−0.0022 (3)	0.0009 (3)	0.0019 (3)
O1	0.0671 (16)	0.100 (2)	0.0642 (16)	−0.0331 (15)	0.0161 (12)	−0.0134 (15)
O2	0.0577 (14)	0.0495 (13)	0.0762 (17)	0.0028 (10)	0.0081 (12)	−0.0038 (12)
O3	0.0670 (14)	0.0550 (13)	0.0375 (11)	0.0109 (11)	0.0131 (10)	−0.0053 (9)
O4	0.0568 (13)	0.0696 (15)	0.0398 (11)	−0.0209 (11)	0.0038 (10)	−0.0117 (10)
N1	0.0334 (10)	0.0284 (10)	0.0360 (11)	−0.0040 (8)	0.0012 (8)	−0.0081 (8)
N2	0.0393 (11)	0.0324 (11)	0.0317 (11)	−0.0044 (9)	0.0075 (9)	−0.0042 (8)
N3	0.0337 (11)	0.0345 (11)	0.0318 (11)	−0.0055 (8)	0.0071 (8)	−0.0037 (8)
N4	0.0323 (11)	0.0330 (11)	0.0400 (12)	−0.0074 (8)	0.0028 (9)	−0.0100 (9)
N5	0.0383 (11)	0.0279 (10)	0.0321 (11)	−0.0036 (8)	0.0067 (9)	−0.0025 (8)
N6	0.0320 (10)	0.0291 (10)	0.0384 (11)	−0.0068 (8)	0.0014 (9)	−0.0074 (8)
C1	0.0420 (15)	0.0468 (16)	0.0484 (16)	0.0110 (12)	0.0016 (12)	−0.0103 (13)
C2	0.0382 (14)	0.0512 (17)	0.0539 (17)	−0.0206 (12)	−0.0079 (13)	0.0027 (13)
C3	0.0575 (18)	0.0400 (16)	0.0492 (17)	0.0097 (13)	0.0000 (14)	0.0012 (13)
C4	0.0512 (16)	0.0376 (14)	0.0386 (14)	−0.0014 (12)	0.0051 (12)	0.0023 (11)
C5	0.0348 (12)	0.0324 (12)	0.0306 (12)	−0.0029 (10)	0.0031 (10)	−0.0053 (10)
C6	0.0429 (14)	0.0397 (14)	0.0303 (12)	−0.0063 (11)	0.0039 (10)	0.0002 (10)
C7	0.0463 (15)	0.0324 (13)	0.0450 (15)	−0.0125 (11)	−0.0068 (12)	−0.0032 (11)
C8	0.0297 (13)	0.0563 (18)	0.0498 (16)	−0.0046 (12)	0.0004 (12)	0.0011 (13)
C9	0.0386 (14)	0.0369 (13)	0.0352 (13)	0.0004 (11)	0.0051 (11)	−0.0115 (11)
C10	0.0445 (14)	0.0359 (13)	0.0364 (14)	−0.0084 (11)	0.0013 (10)	0.0022 (11)
C11	0.0335 (13)	0.0417 (14)	0.0411 (14)	−0.0010 (11)	−0.0007 (11)	−0.0055 (11)
C12	0.0304 (12)	0.0343 (13)	0.0319 (12)	−0.0045 (10)	0.0013 (9)	−0.0044 (10)
C13	0.0337 (13)	0.0514 (16)	0.0367 (14)	0.0003 (11)	0.0069 (11)	−0.0062 (12)
C14	0.0353 (13)	0.0332 (12)	0.0393 (14)	−0.0078 (9)	0.0051 (10)	−0.0086 (10)
C15	0.0325 (12)	0.0299 (12)	0.0318 (12)	−0.0064 (9)	−0.0015 (9)	−0.0019 (9)
C16	0.0326 (12)	0.0301 (12)	0.0310 (12)	−0.0061 (9)	−0.0014 (9)	−0.0015 (9)

Geometric parameters (Å, º)

Zn1—N5	2.041 (2)	C2—C7	1.367 (4)
Zn1—N6	2.059 (2)	C2—C8	1.410 (4)
Zn1—Cl1	2.2142 (9)	C2—H2A	0.9295
Zn1—Cl2	2.2403 (10)	C3—C4	1.369 (4)
O1—C10	1.336 (4)	C3—H3A	0.9301
O1—H1C	0.8200	C4—C5	1.402 (4)
O2—C14	1.332 (3)	C4—H4A	0.9297
O2—H2B	0.9295	C5—C12	1.394 (3)
O3—C14	1.223 (3)	C6—C10	1.533 (4)
O4—C10	1.222 (3)	C6—H6A	0.9698
N1—N4	1.340 (3)	C6—H6B	0.9703
N1—C16	1.360 (3)	C7—C16	1.402 (3)
N1—C9	1.451 (3)	C7—H7A	0.9301
N2—N5	1.318 (3)	C8—C11	1.372 (4)
N2—N3	1.331 (3)	C8—H8A	0.9298
N3—C12	1.363 (3)	C9—C14	1.521 (4)
N3—C6	1.459 (3)	C9—H9A	0.9703
N4—N6	1.314 (3)	C9—H9B	0.9702
N5—C5	1.379 (3)	C11—C15	1.400 (4)
N6—C15	1.380 (3)	C11—H11A	0.9294
C1—C13	1.363 (4)	C12—C13	1.401 (4)
C1—C3	1.422 (4)	C13—H13A	0.9300
C1—H1A	0.9292	C15—C16	1.395 (3)
N5—Zn1—N6	101.73 (9)	N3—C6—H6A	109.6
N5—Zn1—Cl1	113.50 (7)	C10—C6—H6A	109.7
N6—Zn1—Cl1	110.90 (7)	N3—C6—H6B	109.5
N5—Zn1—Cl2	107.14 (7)	C10—C6—H6B	109.4
N6—Zn1—Cl2	104.41 (7)	H6A—C6—H6B	108.2
Cl1—Zn1—Cl2	117.63 (4)	C2—C7—C16	115.2 (3)
C10—O1—H1C	109.5	C2—C7—H7A	122.6
C14—O2—H2B	119.5	C16—C7—H7A	122.3
N4—N1—C16	111.2 (2)	C11—C8—C2	122.0 (3)
N4—N1—C9	119.7 (2)	C11—C8—H8A	119.0
C16—N1—C9	128.3 (2)	C2—C8—H8A	119.0
N5—N2—N3	107.4 (2)	N1—C9—C14	110.2 (2)
N2—N3—C12	111.6 (2)	N1—C9—H9A	109.7
N2—N3—C6	120.6 (2)	C14—C9—H9A	109.7
C12—N3—C6	127.7 (2)	N1—C9—H9B	109.6
N6—N4—N1	107.55 (19)	C14—C9—H9B	109.5
N2—N5—C5	109.6 (2)	H9A—C9—H9B	108.2
N2—N5—Zn1	118.20 (16)	O4—C10—O1	125.3 (3)
C5—N5—Zn1	132.12 (17)	O4—C10—C6	120.4 (2)
N4—N6—C15	109.65 (19)	O1—C10—C6	114.2 (2)
N4—N6—Zn1	120.39 (16)	C8—C11—C15	116.2 (3)
C15—N6—Zn1	129.87 (17)	C8—C11—H11A	122.1
C13—C1—C3	122.2 (3)	C15—C11—H11A	121.6
C13—C1—H1A	118.7	N3—C12—C5	104.5 (2)
C3—C1—H1A	119.1	N3—C12—C13	133.1 (2)
C7—C2—C8	122.8 (3)	C5—C12—C13	122.4 (2)
C7—C2—H2A	118.6	C1—C13—C12	115.8 (3)
C8—C2—H2A	118.6	C1—C13—H13A	122.1
C4—C3—C1	122.1 (3)	C12—C13—H13A	122.1
C4—C3—H3A	119.1	O3—C14—O2	124.5 (3)
C1—C3—H3A	118.8	O3—C14—C9	120.8 (2)
C3—C4—C5	116.1 (3)	O2—C14—C9	114.6 (2)
C3—C4—H4A	121.8	N6—C15—C16	106.8 (2)
C5—C4—H4A	122.1	N6—C15—C11	132.0 (2)
N5—C5—C12	106.9 (2)	C16—C15—C11	121.1 (2)
N5—C5—C4	131.7 (2)	N1—C16—C15	104.7 (2)
C12—C5—C4	121.4 (2)	N1—C16—C7	132.6 (2)
N3—C6—C10	110.5 (2)	C15—C16—C7	122.7 (2)
N5—N2—N3—C12	−0.4 (3)	C16—N1—C9—C14	81.9 (3)
N5—N2—N3—C6	−177.9 (2)	N3—C6—C10—O4	−48.2 (4)
C16—N1—N4—N6	1.1 (3)	N3—C6—C10—O1	134.4 (3)
C9—N1—N4—N6	171.8 (2)	C2—C8—C11—C15	0.6 (4)
N3—N2—N5—C5	0.4 (3)	N2—N3—C12—C5	0.3 (3)
N3—N2—N5—Zn1	−176.82 (16)	C6—N3—C12—C5	177.6 (2)
N6—Zn1—N5—N2	−47.2 (2)	N2—N3—C12—C13	178.1 (3)
Cl1—Zn1—N5—N2	72.01 (19)	C6—N3—C12—C13	−4.6 (5)
Cl2—Zn1—N5—N2	−156.44 (17)	N5—C5—C12—N3	0.0 (3)
N6—Zn1—N5—C5	136.3 (2)	C4—C5—C12—N3	178.8 (2)
Cl1—Zn1—N5—C5	−104.5 (2)	N5—C5—C12—C13	−178.2 (2)
Cl2—Zn1—N5—C5	27.1 (2)	C4—C5—C12—C13	0.7 (4)
N1—N4—N6—C15	−0.4 (3)	C3—C1—C13—C12	−0.4 (4)
N1—N4—N6—Zn1	176.54 (15)	N3—C12—C13—C1	−177.6 (3)
N5—Zn1—N6—N4	148.39 (19)	C5—C12—C13—C1	−0.1 (4)
Cl1—Zn1—N6—N4	27.4 (2)	N1—C9—C14—O3	−6.9 (4)
Cl2—Zn1—N6—N4	−100.26 (19)	N1—C9—C14—O2	172.8 (2)
N5—Zn1—N6—C15	−35.3 (2)	N4—N6—C15—C16	−0.4 (3)
Cl1—Zn1—N6—C15	−156.3 (2)	Zn1—N6—C15—C16	−176.95 (17)
Cl2—Zn1—N6—C15	76.0 (2)	N4—N6—C15—C11	179.4 (3)
C13—C1—C3—C4	0.3 (5)	Zn1—N6—C15—C11	2.8 (4)
C1—C3—C4—C5	0.3 (5)	C8—C11—C15—N6	179.5 (3)
N2—N5—C5—C12	−0.2 (3)	C8—C11—C15—C16	−0.8 (4)
Zn1—N5—C5—C12	176.47 (18)	N4—N1—C16—C15	−1.3 (3)
N2—N5—C5—C4	−178.9 (3)	C9—N1—C16—C15	−170.9 (2)
Zn1—N5—C5—C4	−2.2 (4)	N4—N1—C16—C7	179.4 (3)
C3—C4—C5—N5	177.8 (3)	C9—N1—C16—C7	9.7 (5)
C3—C4—C5—C12	−0.7 (4)	N6—C15—C16—N1	1.0 (3)
N2—N3—C6—C10	92.5 (3)	C11—C15—C16—N1	−178.8 (2)
C12—N3—C6—C10	−84.5 (3)	N6—C15—C16—C7	−179.6 (2)
C8—C2—C7—C16	−0.1 (4)	C11—C15—C16—C7	0.6 (4)
C7—C2—C8—C11	−0.1 (5)	C2—C7—C16—N1	179.1 (3)
N4—N1—C9—C14	−87.0 (3)	C2—C7—C16—C15	−0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O4^i	0.82	2.20	3.015 (4)	171
O2—H2B···Cl1^ii	0.93	2.59	3.348 (3)	139
C6—H6A···O4^iii	0.97	2.69	3.586 (4)	153

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