p-Phenyl­ene­diammonium tetra­chloro­zincate(II)

The structure of the title compound, (C₆H₁₀N₂)[ZnCl₄], contains simple ZnCl₄ tetra­hedra in the bc plane creating alternating layers of organic and inorganic sublattices, a feature that is very common for compounds of this type. The two sublattices are held together by coulombic attraction of the cationic organic sublattice and anionic inorganic sublattice and also by hydrogen bonding. The anions are located on general positions. The cations, however, are located on mirror planes. As a result, there are two half-cations in the asymmetric unit.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.031
• wR factor = 0.079
• Data-to-parameter ratio = 23.7

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.398
           From the CIF: _refine_ls_abs_structure_Flack_su    0.016
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.40
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.88
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.54
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.12
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      33.00 A   3  
PLAT733_ALERT_1_C Torsion Calc   -179.4(6), Rep   -179.4(2) ......       3.00 su-Rat
              C4  -C4  -C5  -N2     4.655   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc    179.4(5), Rep    179.4(2) ......       2.50 su-Rat
              N2  -C5  -C6  -C6     1.555   1.555   1.555   4.655

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      1.542
            Tmax scaled      0.870 Tmin scaled      0.588
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.47
           From the CIF: _reflns_number_total               2867
           Count of symmetry unique reflns         1562
           Completeness (_total/calc)            183.55%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1305
           Fraction of Friedel pairs measured     0.835
           Are heavy atom types Z>Si present        yes

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

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

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2000 or??? 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Materials Studio (Accelrys, 2002).

p-Phenylenediammonium tetrachlorozinc

Crystal data

(C6H10N2)[ZnCl4]	Dx = 1.693 Mg m^−3
Mr = 317.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmc21	Cell parameters from 18412 reflections
a = 19.733 (4) Å	θ = 2.9–27.5°
b = 13.083 (3) Å	µ = 2.79 mm^−1
c = 9.6430 (19) Å	T = 293 K
V = 2489.5 (9) Å^3	Plate, green
Z = 8	0.15 × 0.10 × 0.05 mm
F(000) = 1264

Data collection

Nonius KappaCCD diffractometer	2867 independent reflections
Radiation source: fine-focus sealed tube, KappaCCD	2689 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
CCD scans	h = −25→25
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −16→16
Tmin = 0.381, Tmax = 0.564	l = −12→12
34863 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 2.3296P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2867 reflections	Δρmax = 1.13 e Å^−3
121 parameters	Δρmin = −0.53 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1305 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.398 (16)

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	0.716565 (17)	0.80014 (3)	0.18246 (6)	0.03219 (10)
Cl1	0.69760 (4)	0.63064 (6)	0.14786 (9)	0.03726 (19)
Cl2	0.69552 (4)	0.89211 (7)	−0.01282 (9)	0.0410 (2)
Cl3	0.64613 (6)	0.85483 (8)	0.34939 (11)	0.0545 (3)
Cl4	0.82861 (4)	0.83269 (7)	0.22351 (10)	0.0406 (2)
N1	0.64310 (11)	0.9155 (2)	0.6770 (3)	0.0342 (5)
H1A	0.6584	0.9217	0.7635	0.051*
H1B	0.6582	0.9676	0.6262	0.051*
H1C	0.6579	0.8570	0.6409	0.051*
N2	0.64335 (14)	0.5415 (3)	0.4362 (3)	0.0408 (7)
H2A	0.6584	0.5730	0.3604	0.061*
H2B	0.6590	0.4777	0.4378	0.061*
H2C	0.6578	0.5748	0.5110	0.061*
C1	0.53507 (17)	0.9799 (3)	0.5890 (5)	0.0497 (10)
H1	0.5589	1.0226	0.5295	0.060*
C2	0.56894 (13)	0.9160 (2)	0.6779 (4)	0.0290 (5)
C3	0.53480 (18)	0.8508 (3)	0.7650 (4)	0.0432 (9)
H3	0.5586	0.8071	0.8234	0.052*
C4	0.5351 (2)	0.6271 (3)	0.4094 (8)	0.082 (2)
H4	0.5588	0.6871	0.3916	0.098*
C5	0.56858 (16)	0.5400 (3)	0.4352 (4)	0.0336 (7)
C6	0.53522 (19)	0.4519 (3)	0.4644 (7)	0.0617 (13)
H6	0.5591	0.3924	0.4841	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03383 (17)	0.03115 (17)	0.03158 (18)	−0.00073 (13)	0.00039 (16)	−0.00044 (17)
Cl1	0.0411 (4)	0.0318 (4)	0.0389 (5)	−0.0055 (3)	−0.0005 (3)	−0.0039 (3)
Cl2	0.0449 (4)	0.0472 (5)	0.0310 (4)	0.0083 (4)	−0.0040 (3)	0.0040 (4)
Cl3	0.0649 (6)	0.0558 (6)	0.0428 (5)	−0.0027 (5)	0.0187 (4)	−0.0132 (4)
Cl4	0.0345 (4)	0.0390 (4)	0.0482 (5)	−0.0047 (3)	−0.0091 (3)	0.0037 (3)
N1	0.0269 (11)	0.0436 (14)	0.0322 (13)	0.0003 (10)	−0.0009 (12)	0.0016 (14)
N2	0.0294 (13)	0.0514 (16)	0.0416 (16)	−0.0055 (12)	−0.0008 (12)	0.0049 (14)
C1	0.0313 (17)	0.067 (3)	0.051 (2)	−0.0025 (17)	0.0047 (16)	0.027 (2)
C2	0.0229 (11)	0.0344 (13)	0.0296 (14)	0.0014 (10)	−0.0017 (13)	−0.0051 (14)
C3	0.0353 (18)	0.046 (2)	0.049 (2)	0.0046 (15)	0.0002 (16)	0.0173 (16)
C4	0.044 (2)	0.038 (2)	0.162 (7)	−0.0075 (17)	−0.003 (3)	0.030 (3)
C5	0.0277 (15)	0.0425 (17)	0.0306 (15)	0.0006 (13)	−0.0007 (13)	0.0014 (14)
C6	0.036 (2)	0.046 (2)	0.103 (4)	0.0019 (18)	0.000 (2)	0.010 (2)

Geometric parameters (Å, º)

Zn1—Cl3	2.2439 (11)	C1—C2	1.370 (5)
Zn1—Cl2	2.2729 (10)	C1—C1^i	1.384 (7)
Zn1—Cl1	2.2736 (9)	C1—H1	0.9300
Zn1—Cl4	2.2861 (10)	C2—C3	1.374 (5)
N1—C2	1.464 (3)	C3—C3^i	1.373 (7)
N1—H1A	0.8900	C3—H3	0.9300
N1—H1B	0.8900	C4—C5	1.340 (5)
N1—H1C	0.8900	C4—C4^i	1.385 (9)
N2—C5	1.476 (4)	C4—H4	0.9300
N2—H2A	0.8900	C5—C6	1.357 (5)
N2—H2B	0.8900	C6—C6^i	1.390 (8)
N2—H2C	0.8900	C6—H6	0.9300
Cl3—Zn1—Cl2	108.21 (4)	C2—C1—C1^i	119.19 (19)
Cl3—Zn1—Cl1	108.32 (4)	C2—C1—H1	120.4
Cl2—Zn1—Cl1	111.39 (4)	C1^i—C1—H1	120.4
Cl3—Zn1—Cl4	114.55 (5)	C1—C2—C3	121.4 (3)
Cl2—Zn1—Cl4	102.80 (4)	C1—C2—N1	119.1 (3)
Cl1—Zn1—Cl4	111.49 (3)	C3—C2—N1	119.4 (3)
C2—N1—H1A	109.5	C3^i—C3—C2	119.36 (19)
C2—N1—H1B	109.5	C3^i—C3—H3	120.3
H1A—N1—H1B	109.5	C2—C3—H3	120.3
C2—N1—H1C	109.5	C5—C4—C4^i	119.5 (2)
H1A—N1—H1C	109.5	C5—C4—H4	120.2
H1B—N1—H1C	109.5	C4^i—C4—H4	120.2
C5—N2—H2A	109.5	C4—C5—C6	121.4 (3)
C5—N2—H2B	109.5	C4—C5—N2	118.9 (3)
H2A—N2—H2B	109.5	C6—C5—N2	119.7 (3)
C5—N2—H2C	109.5	C5—C6—C6^i	119.0 (2)
H2A—N2—H2C	109.5	C5—C6—H6	120.5
H2B—N2—H2C	109.5	C6^i—C6—H6	120.5
C1^i—C1—C2—C3	1.2 (4)	C4^i—C4—C5—C6	−1.5 (6)
C1^i—C1—C2—N1	179.5 (2)	C4^i—C4—C5—N2	−179.4 (2)
C1—C2—C3—C3^i	−1.2 (4)	C4—C5—C6—C6^i	1.4 (6)
N1—C2—C3—C3^i	−179.5 (2)	N2—C5—C6—C6^i	179.4 (2)

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2^ii	0.89	2.31	3.180 (3)	165
N1—H1B···Cl2^iii	0.89	2.39	3.279 (3)	178
N1—H1C···Cl4^iv	0.89	2.62	3.326 (3)	137
N1—H1C···Cl3	0.89	2.82	3.258 (3)	112
N2—H2A···Cl1	0.89	2.32	3.199 (3)	172
N2—H2B···Cl1^v	0.89	2.59	3.222 (3)	129
N2—H2B···Cl4^vi	0.89	2.82	3.460 (4)	130
N2—H2C···Cl4^iv	0.89	2.39	3.270 (4)	168

Symmetry codes: (ii) x, y, z+1; (iii) x, −y+2, z+1/2; (iv) −x+3/2, −y+3/2, z+1/2; (v) x, −y+1, z+1/2; (vi) −x+3/2, y−1/2, z.