Bis(p-toluidinium) tetra­chloro­zincate(II)

The title organic–inorganic hybrid salt, bis(p-toluidinium) tetra­chloro­zincate(II), (C₇H₇NH₃)₂[ZnCl₄], crystallizes in a structure consisting of alternating ionic and organic layers. Weak C—H...π hydrogen-bonding interactions occur in the organic layer, and strong charge-assisted N—H...Cl inter­actions are present in the inorganic layer between ammonium groups and discrete [ZnCl₄]²⁻ tetrahedra.

Key indicators

• Single-crystal X-ray study
• T = 280 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.106
• Data-to-parameter ratio = 29.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Zn

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

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

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Computing details

Data collection: CrysAlis CCD 170 (Oxford Diffraction Ltd., 2003); cell refinement: CrysAlis CCD 170; data reduction: CrysAlis RED 170 (Oxford Diffraction Ltd., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.

Bis(p-toluidinium) tetrachlorozincate(II)

Crystal data

(C7H7NH3)2[ZnCl4]	Z = 2
Mr = 423.35	F(000) = 432
Triclinic, P1	Dx = 1.445 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.119 (8) Å	Cell parameters from 195 reflections
b = 11.532 (6) Å	θ = 2–31°
c = 12.490 (7) Å	µ = 1.81 mm^−1
α = 107.14 (5)°	T = 280 K
β = 95.43 (7)°	Block, dark brown
γ = 92.03 (6)°	0.30 × 0.20 × 0.20 mm
V = 973.3 (13) Å^3

Data collection

Oxford Excalibur2 diffractometer	5949 independent reflections
Radiation source: fine-focus sealed tube	3404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω–2θ scans	θmax = 31.7°, θmin = 4.5°
Absorption correction: multi-scan (Blessing, 1995)	h = −10→7
Tmin = 0.601, Tmax = 0.700	k = −16→16
9806 measured reflections	l = −17→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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0492P)^2] where P = (Fo^2 + 2Fc^2)/3
5949 reflections	(Δ/σ)max = 0.005
202 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.71 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
N1	0.2586 (3)	0.1681 (2)	−0.00008 (18)	0.0459 (5)
H1A	0.1702	0.1720	−0.0540	0.069*
H1B	0.2054	0.1406	0.0502	0.069*
H1C	0.3445	0.1178	−0.0303	0.069*
C1	0.3502 (4)	0.2894 (2)	0.0557 (2)	0.0428 (6)
C2	0.2417 (4)	0.3883 (3)	0.0708 (2)	0.0552 (7)
H2	0.1137	0.3777	0.0444	0.060 (9)*
C6	0.5389 (4)	0.3029 (3)	0.0915 (3)	0.0556 (7)
H6	0.6111	0.2356	0.0799	0.064 (9)*
C5	0.6200 (5)	0.4179 (3)	0.1463 (3)	0.0677 (9)
H5	0.7481	0.4278	0.1720	0.118 (15)*
C4	0.5140 (5)	0.5191 (3)	0.1648 (3)	0.0636 (8)
C3	0.3250 (5)	0.5026 (3)	0.1253 (3)	0.0636 (8)
H3	0.2523	0.5697	0.1363	0.089 (12)*
C7	0.6004 (6)	0.6437 (4)	0.2280 (4)	0.0961 (13)
H71	0.7325	0.6478	0.2185	0.144*
H72	0.5857	0.6605	0.3066	0.144*
H73	0.5384	0.7028	0.1993	0.144*
N2	0.7517 (3)	0.0977 (2)	0.39762 (19)	0.0487 (5)
H2A	0.6543	0.0777	0.3440	0.073*
H2B	0.7363	0.0581	0.4479	0.073*
H2C	0.8582	0.0775	0.3669	0.073*
C8	0.7620 (3)	0.2290 (2)	0.4537 (2)	0.0405 (6)
C9	0.6871 (4)	0.3051 (3)	0.3968 (2)	0.0495 (6)
H9	0.6284	0.2741	0.3236	0.058 (8)*
C13	0.8521 (4)	0.2735 (3)	0.5599 (2)	0.0583 (8)
H13	0.9041	0.2212	0.5969	0.077 (11)*
C12	0.8648 (5)	0.3964 (3)	0.6120 (3)	0.0615 (8)
H12	0.9240	0.4267	0.6853	0.092 (12)*
C11	0.7899 (4)	0.4767 (3)	0.5589 (3)	0.0521 (7)
C10	0.7014 (4)	0.4284 (3)	0.4509 (3)	0.0557 (7)
H10	0.6488	0.4804	0.4136	0.070 (10)*
C14	0.8055 (5)	0.6109 (3)	0.6170 (3)	0.0770 (11)
H14A	0.9340	0.6363	0.6483	0.116*
H14B	0.7247	0.6292	0.6764	0.116*
H14C	0.7676	0.6532	0.5637	0.116*
Zn	0.80950 (4)	0.01269 (3)	0.76682 (3)	0.04276 (10)
Cl1	0.93243 (12)	0.20514 (7)	0.82409 (8)	0.0714 (2)
Cl2	0.75839 (12)	−0.05935 (7)	0.57535 (6)	0.0618 (2)
Cl3	0.53242 (9)	−0.00867 (7)	0.83740 (6)	0.05383 (19)
Cl4	1.02362 (9)	−0.10044 (6)	0.83165 (6)	0.04822 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0474 (12)	0.0489 (13)	0.0413 (12)	0.0043 (10)	0.0052 (10)	0.0133 (10)
C1	0.0485 (14)	0.0463 (15)	0.0339 (13)	0.0020 (12)	0.0057 (11)	0.0123 (11)
C2	0.0552 (17)	0.0526 (18)	0.0547 (17)	0.0090 (14)	0.0011 (14)	0.0119 (14)
C6	0.0489 (15)	0.0565 (19)	0.0615 (19)	0.0067 (14)	−0.0005 (14)	0.0192 (15)
C5	0.0562 (19)	0.074 (2)	0.070 (2)	−0.0131 (17)	−0.0006 (16)	0.0218 (19)
C4	0.080 (2)	0.056 (2)	0.0545 (18)	−0.0147 (17)	0.0058 (17)	0.0183 (16)
C3	0.084 (2)	0.0470 (18)	0.0588 (19)	0.0085 (17)	0.0074 (17)	0.0132 (15)
C7	0.114 (3)	0.072 (3)	0.093 (3)	−0.033 (2)	−0.001 (3)	0.019 (2)
N2	0.0574 (13)	0.0474 (14)	0.0435 (12)	0.0007 (10)	0.0092 (11)	0.0161 (11)
C8	0.0389 (12)	0.0445 (15)	0.0380 (13)	0.0007 (11)	0.0071 (10)	0.0117 (11)
C9	0.0516 (15)	0.0500 (17)	0.0441 (15)	0.0054 (12)	−0.0035 (12)	0.0119 (13)
C13	0.070 (2)	0.063 (2)	0.0407 (15)	0.0032 (16)	−0.0030 (14)	0.0169 (15)
C12	0.067 (2)	0.063 (2)	0.0435 (17)	−0.0039 (16)	−0.0001 (15)	0.0032 (15)
C11	0.0415 (14)	0.0495 (17)	0.0591 (18)	−0.0025 (12)	0.0163 (13)	0.0042 (14)
C10	0.0561 (17)	0.0526 (18)	0.0622 (19)	0.0107 (14)	0.0066 (15)	0.0220 (16)
C14	0.064 (2)	0.053 (2)	0.099 (3)	−0.0045 (16)	0.0242 (19)	−0.0040 (19)
Zn	0.03820 (16)	0.04319 (18)	0.04655 (19)	−0.00089 (12)	0.00325 (13)	0.01376 (14)
Cl1	0.0840 (5)	0.0473 (4)	0.0793 (6)	−0.0166 (4)	−0.0325 (4)	0.0286 (4)
Cl2	0.0895 (5)	0.0534 (4)	0.0424 (4)	0.0012 (4)	0.0037 (4)	0.0159 (3)
Cl3	0.0378 (3)	0.0685 (5)	0.0545 (4)	0.0052 (3)	0.0110 (3)	0.0153 (4)
Cl4	0.0401 (3)	0.0520 (4)	0.0552 (4)	0.0085 (3)	0.0067 (3)	0.0191 (3)

Geometric parameters (Å, º)

N1—C1	1.464 (4)	N2—H2B	0.8900
N1—H1A	0.8900	N2—H2C	0.8900
N1—H1B	0.8900	C8—C13	1.360 (4)
N1—H1C	0.8900	C8—C9	1.375 (4)
C1—C6	1.363 (4)	C9—C10	1.378 (4)
C1—C2	1.377 (4)	C9—H9	0.9293
C2—C3	1.376 (4)	C13—C12	1.370 (4)
C2—H2	0.9300	C13—H13	0.9279
C6—C5	1.377 (4)	C12—C11	1.383 (5)
C6—H6	0.9289	C12—H12	0.9298
C5—C4	1.386 (5)	C11—C10	1.378 (4)
C5—H5	0.9292	C11—C14	1.498 (4)
C4—C3	1.375 (5)	C10—H10	0.9297
C4—C7	1.498 (5)	C14—H14A	0.9600
C3—H3	0.9292	C14—H14B	0.9600
C7—H71	0.9600	C14—H14C	0.9600
C7—H72	0.9600	Zn—Cl1	2.2386 (18)
C7—H73	0.9600	Zn—Cl3	2.270 (2)
N2—C8	1.465 (3)	Zn—Cl2	2.2769 (17)
N2—H2A	0.8900	Zn—Cl4	2.2828 (18)
C1—N1—H1A	109.5	C8—N2—H2C	109.5
C1—N1—H1B	109.5	H2A—N2—H2C	109.5
H1A—N1—H1B	109.5	H2B—N2—H2C	109.5
C1—N1—H1C	109.5	C13—C8—C9	121.3 (3)
H1A—N1—H1C	109.5	C13—C8—N2	119.1 (2)
H1B—N1—H1C	109.5	C9—C8—N2	119.6 (2)
C6—C1—C2	121.4 (3)	C8—C9—C10	118.4 (3)
C6—C1—N1	120.1 (3)	C8—C9—H9	120.7
C2—C1—N1	118.5 (3)	C10—C9—H9	120.9
C3—C2—C1	119.1 (3)	C8—C13—C12	119.3 (3)
C3—C2—H2	120.6	C8—C13—H13	120.4
C1—C2—H2	120.3	C12—C13—H13	120.3
C1—C6—C5	118.7 (3)	C13—C12—C11	121.6 (3)
C1—C6—H6	120.6	C13—C12—H12	119.3
C5—C6—H6	120.7	C11—C12—H12	119.0
C6—C5—C4	121.4 (3)	C10—C11—C12	117.4 (3)
C6—C5—H5	119.3	C10—C11—C14	121.6 (3)
C4—C5—H5	119.3	C12—C11—C14	121.0 (3)
C3—C4—C5	118.4 (3)	C9—C10—C11	121.9 (3)
C3—C4—C7	120.2 (3)	C9—C10—H10	119.0
C5—C4—C7	121.4 (4)	C11—C10—H10	119.1
C4—C3—C2	121.0 (3)	C11—C14—H14A	109.5
C4—C3—H3	119.5	C11—C14—H14B	109.5
C2—C3—H3	119.5	H14A—C14—H14B	109.5
C4—C7—H71	109.5	C11—C14—H14C	109.5
C4—C7—H72	109.5	H14A—C14—H14C	109.5
H71—C7—H72	109.5	H14B—C14—H14C	109.5
C4—C7—H73	109.5	Cl1—Zn—Cl3	112.49 (7)
H71—C7—H73	109.5	Cl1—Zn—Cl2	111.36 (6)
H72—C7—H73	109.5	Cl3—Zn—Cl2	108.28 (8)
C8—N2—H2A	109.5	Cl1—Zn—Cl4	106.91 (7)
C8—N2—H2B	109.5	Cl3—Zn—Cl4	108.31 (7)
H2A—N2—H2B	109.5	Cl2—Zn—Cl4	109.41 (7)
C6—C1—C2—C3	−1.4 (4)	C13—C8—C9—C10	−1.5 (4)
N1—C1—C2—C3	178.6 (3)	N2—C8—C9—C10	−179.0 (2)
C2—C1—C6—C5	1.6 (4)	C9—C8—C13—C12	1.5 (4)
N1—C1—C6—C5	−178.3 (3)	N2—C8—C13—C12	179.0 (3)
C1—C6—C5—C4	−0.3 (5)	C8—C13—C12—C11	−0.7 (5)
C6—C5—C4—C3	−1.1 (5)	C13—C12—C11—C10	0.0 (4)
C6—C5—C4—C7	177.8 (3)	C13—C12—C11—C14	−179.8 (3)
C5—C4—C3—C2	1.4 (5)	C8—C9—C10—C11	0.8 (4)
C7—C4—C3—C2	−177.6 (3)	C12—C11—C10—C9	0.0 (4)
C1—C2—C3—C4	−0.1 (5)	C14—C11—C10—C9	179.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^i	0.89	2.29	3.171 (4)	172
N1—H1B···Cl4^ii	0.89	2.42	3.275 (3)	161
N1—H1C···Cl3^iii	0.89	2.40	3.266 (4)	163
N2—H2A···Cl3^ii	0.89	2.41	3.273 (4)	162
N2—H2B···Cl2	0.89	2.37	3.250 (3)	168
N2—H2C···Cl2^iv	0.89	2.79	3.528 (5)	142
N2—H2C···Cl4^iv	0.89	2.77	3.417 (3)	130

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